Estudios Geotermicos Con Tecnias Isotopicas y Geoquimicas en America Latina

IAEA-TECDOC-641
Estudios geotrmicos
con tcnicas isotpicas y geoquimicas
en America Latina
Actas de una Runion final de coordination de investigaciones
celebrada en San Jos, Costa Rica, 12-16 de Noviembre de 1990
Geothermal investigations
with isotope and geochemical techniques
in Latin America
Proceedings of a Final Research Co-ordination Meeting
held in San Jos, Costa Rica, 12-16 November 1990
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ESTUDIOS GEOTERMICOS CON TECNICAS ISOTOPICAS Y GEOQUIMICAS

EN AMERICA LATINA
GEOTHERMAL INVESTIGATIONS WITH ISOTOPE AND GEOCHEMICAL TECHNIQUES
IN LATIN AMERICA
OIEA, VIENA, 1992
IAEA-TECDOC-641
ISSN 1011-4289
Impreso por el OIEA in Austria
Marzo de 1992
PREFACIO
Publicamos en el prsente volumen

las memorias
presentadas en
la ultima Reunion para
coordinar las
investigaciones del Programa Coordinado de Investigacion
(PCI) del OIEA para America Latina sobre empleo de tcnicas
sotopicas y geoquimicas en la exploracin de recursos
geotrmicos. La reunion se clbr en San Jos de Costa Rica
del 12 al 16 de noviembre de 1990 y se organize con la
cooperacin del Institute Costarricense de Electricidad, al
cual
expresamos
nuestro
profundo
agradecimiento.
Anteriormente se celebraron reuniones para coordinar las
investigaciones con el fin de examinar la labor en curso, en
diciembre de 1986 en el Instituto de Asuntos Nucleares de
Bogota (Colombia) , y en noviembre de 1988 en el Instituto
Ecuatoriano de Electrificacin de Quito (Ecuador).
Cientificos
de
nueve paises
de America
Latina
(Argentina,
Bolivia,
Colombia,
Costa
Rica,
Ecuador,
Guatemala, Mexico, Peru y Venezuela), que participaron en el
PCI, presentaron los resultados de sus estudios sobre el
terreno en la reunion de San Jos.
Ademas de stos,
cientificos
de otros
trs
paises
latinoamericanos con
importantes recursos geotrmicos, que no participaron en el
PCI (Chile, El Salvador y Nicaragua), y expertos de Italia,
Nueva Zelanda y los Estados Unidos de America, que cooperaron
en la ejecucin del programa, asistieron a la reunion y
presentaron informes sobre sus actividades.
En trminos gnrales, las investigaciones cientificas
realizadas en el marco del PCI del OIEA constituyen el primer
estudio geoquimico sistemtico de los recursos geotrmicos de
America Latina. La reunion de San Jos permitio obtener una
panormica actualizada de las exploraciones de recursos
geotrmicos que se vienen efectuando en la rgion utilizando
la geoquimica e istopos ambientales, que constituyen tambin
un instrumente geoquimico.
Los resultados estn ahora a la disposicion de las
autoridades nacionales interesadas, que deben decidir acerca
de la continuacin de las investigaciones, especialmente en
el caso de aquellos campos geotrmicos en los que se han
obtenido resultados particularmente prometedores, habida
cuenta de una posible explotacin con fines de generacion de
energia.
La ejecucin de la siguiente etapa de las
investigaciones, que es mas costosa, y que puede incluir
sondeos exploratorios, podria demorar un tanto en aquellos
paises que disponen de fuentes de energia mas economicas,
taies como petrleo o centrales hidroelctricas, o cuyos
campos geotrmicos estn ubicados en regiones remotas,
escasamente pobladas. Aun asi, consideramos que vali la pena
llevar a cabo las investigaciones dado que contribuyeron a la
evaluacin de los posibles recursos energticos que podrian
utilizarse en el futuro, asi como a la capacitaciOn de un
numro de geoquimicos latinoamericanos en el empleo de las
tcnicas isotopicas y geoquimicas.
FOREWORD
We are publishing in this volume the papers presented at

the last Research Co-ordination Meeting of the IAEA Co-ordinated
Research Programme (CRP) for Latin America on the Use of Isotope
and Geochemical Techniques in Geothermal Exploration.
The
meeting was held in San Jos de Costa Rica from 12 to 16 November
1990, and was organized with the co-operation of the Institute
Costarricense de Electricidad, which is warmly acknowledged.
Previous Research Co-ordination Meetings to discuss the work in
progress were held in December 1986 at the Institute de Asuntos
Nucleares in Bogota, Colombia, and in November 1988 at the
Institute Ecuatoriano de Electrificacion in Quito, Ecuador.
Scientists from nine Latin American countries, i.e.
Argentina, Bolivia, Colombia, Costa Rica, Ecuador, Guatemala,
Mexico, Peru and Venezuela, which took part in the CRP, presented
the results of their field studies at the San Jos meeting. In
addition to these, scientists from three other Latin American
countries with important geothermal resources, which did not take
part in the CRP, i.e. Chile, El Salvador and Nicaragua, and
experts from Italy, New Zealand and the United States of America,
who co-operated in the programme implementation, were present and
reported on their activities.
On the whole, the scientific investigations carried out
within the frame of the IAEA CRP constitute the first systematic
geochemical survey of the geothermal resources of Latin America.
The San Jos meeting provided an updated picture of the current
explorations of geothermal resources in the region using
geochemistry and environmental isotopes, which are also a
geochemical tool.
The results remain now at the disposal of the interested
national authorities, which have to decide about the continuation
of the investigations, especially for those fields where the
results have been particularly promising, in view of a possible
exploitation for power production.
The next, more expensive
stage of investigation, which may include exploratory drillings,
might not take place soon in those countries which dispose of
cheaper sources of energy like oil or hydroelectric plants, or
where the geothermal fields are located in remote, scarcely
populated regions.
Even so, however, we believe that the
investigations have been useful and worth being carried out,
because they helped to assess potential energy resources which
may be used in future, and to form and train a number of Latin

American geochemists in the use of isotope and geochemical
techniques.
NOTA EDITORIAL
Al preparar esta publication para la imprenta, el personal correspondiente del Organismo
International de Energa Atmica ha montado y paginado los manuscritos originales facilitados par
los autores y ha procurado una prsentation satisfactoria.
Las opiniones expresadas en las mernorias, las declaraciones formuladas y el estilo general
adoptado son propios de los autores citados. Dichas opiniones no reflejan necesariamente las de los
Gobiernos de los Estados Miembros o las de las organizations bajo cuyos auspicios se han elaborado
los manuscritos.
Las denominaciones concretas de pases o territorios empleadas en esta publication no implican
juicio alguno par parte del OIEA sobre la condition juridica de dichos pases o territorios, de sus
autoridades e institutions, ni del trazado de sus fronteras.
La mention de determinadas empresas o de sus productos o mar cas comer dales no implica
ningun gnra de aprobacin o recomendacin por parte del OIEA.
Corresponde a los autores obtener el permiso necesario para reproducir textos ajenos sujetos a
derechos de propiedad intelectual.
EDITORIAL NOTE
In preparing this material for the press, staff of the International Atomic Energy Agency have
mounted and paginated the original manuscripts and given some attention to presentation.
The views expressed do not necessarily reflect those of the governments of the Member States or
organizations under whose auspices the manuscripts were produced.
The use in this book of particular designations of countries or territories does not imply any
judgement by the publisher, the IAEA, as to the legal status of such countries or territories, of their
authorities and institutions or of the delimitation of their boundaries.
The mention of specific companies or of their products or brand names does not imply any
endorsement or recommendation on the pari of the IAEA.
INDICE
Resumen del Programa coordinado de investigation ..................................................

Summary of the Co-ordinated Research Programme ..................................................
Reservoir characteristics of the vapor dominated geothermal field of Copahue, Neuqun,

Argentina, as established by isotopic and geochemical techniques ..............................
J.L. Sierra, F. D'Amore, H. Panarello, G. Pedro
Isotopic and geochemical study of the Domuyo geothermal field, Neuqun, Argentina ........
H. Panarello, J.L. Sierra, F. D'Amore, G. Pedro
Flow patterns at the Tuzgle-Tocomar geothermal system, Salta-Jujuy, Argentina:
An isotopic and geochemical approach ................................................................
H. Panarello, J.L. Sierra, G. Pedro
Informe geoquimico sobre la zona geotrmica de Laguna Colorada, Bolivia .....................
G. Scandiffio, M. Alvarez
Geochemical report on the Empexa geothermal area, Bolivia .......................................
G. Scandiffio, W. Cassis
Geochemical report on the Sajama geothermal area, Bolivia ........................................
G. Scandiffio, J. Rodriguez
Geochemical and isotopic exploration of the geothermal area of Paipa, Cordillera Oriental,
Colombia ....................................................................................................
R. Bertrami, A. Camacho, L. De Stefanis, T. Medina, G.M. Zuppi
Isotopic composition and origin of thermal and non-thermal waters from the
Miravalles geothermal field, Costa Rica ..............................................................
W.F. Giggenbach, R. Corrales, L. Vaca
Modelo geotrmico preliminar de areas volcnicas del Ecuador, a partir de estudios
quimicos e isotpicos de manifestaciones termales .................................................
E. Almeida, G. Sandoval, C. Panichi, P. Noto, L. Bellucci
Avance de las pruebas de radiotrazado en el campo geotrmico de Ahuachapn,
El Salvador .................................................................................................
W.J. McCabe, E. May en, P. Hernandez
Isotopic and chemical composition of water and gas discharges from the Zunil
geothermal system, Guatemala ..........................................................................
W.F. Giggenbach, D. Paniagua de Gudiel, A.R. Roldn Manzo
Investigaciones geoqufmicas realizadas en los campos geotrmicos de Zunil
y Amatitln, Guatemala ..................................................................................
A.R. Roldn Manzo
Caracterfsticas geoqufmicas e isotpicas de los fluidos producidos por los pozos
de Los Humeros, Puebla, Mexico .....................................................................
E. Tello Hinojosa
Geochemical report on the Challapalca and Tutupaca geothermal areas, Peru ...................
G. Scandiffio, D. Verastegui, F. Portilla
9
11
13
31
57
77
115
141
169
201
219
237
245
279
307
345
Geothermal exploration by geochemical methods of the thermal area El Pilar-Mundo Nuevo,

State of Sucre, Venezuela
377
F D'Amore, G Gianelh, E Corazza, J Jauregui, P Varela
Origins of acid fluids m geothermal reservoirs
423
A H Truesdell
IAEA mterlaboratory comparative geothermal water analysis program
439
W F Giggenbach, R L Goguel, WA Humphries
Lista de participantes
457
RESUMEN DEL PROGRAMA COORDINADO DE INVESTIGACION
El PCI para la America Latina sobre el empleo de tcnicas

isotpicas y geoquimicas en la exploracin de recursos
geotermales se inici en 1984.
Los recursos financires para
la ejecucin del programa fueron facilitados por el Gobierno
italiano,
al
cual
el
Organismo
desea
expresar
su
agradecimiento.
La primera actividad realizada fue el
seminario
sobre
el
empleo
de
tcnicas
isotpicas
y
geoquimicas en la exploracin geotrmica, celebrado en junio
de 1984 en Morelia (Mexico) , en las instalaciones de la
Comisin Federal de Electricidad, Gerencia de Proyectos
Geotermoelctricos. Durante el seminario, al cual asistieron
reprsentantes de
las
instituciones
que posteriormente
participaron en el programa, se examinaron los objetivos, las
principales lineas de investigacin y los campos geotrmicos

que se estudiarian durante el PCI.
Los primeros contratos de investigacin se adjudicaron
hacia finales de 1984. Los trabajos de campo empezaron en
1985 y continuaron hasta 1990.
Durante la ejecucin del PCI
se estudi un numro considrable de campos geotrmicos, en
los nueve paises participantes.

Mas adelante figura una
relacin de dichos campos.
Las investigaciones efectuadas
fueron bastante amplias desde el punto de vista geoquimico,
en la mayoria de los casos, pero en algunos otros se
encontraban todavia en una etapa de reconocimiento cuando
finalize el PCI; estos Ultimos estudios no son tema del
prsente documento, pero, en principio, se puede tener acceso
a los datos obtenidos solicitndolos a las instituciones
nacionales correspondientes.
Si bien las investigaciones
utilizando tcnicas geoquimicas convencionales ya se habian
iniciado en varios de los campos antes de 1985, los mtodos
isotpicos se aplicaron por primera vez en todos los casos
durante este PCI.
Debido a la localizacin de muchos de los campos
estudiados en lugares remotos y de gran elevacin y a las
condiciones
meteorolgicas
adversas
durante
prolongados
priodes
del
ano, las
investigaciones
no
avanzaron
rpidamente; esa es la principal razn de la duracin
anormalmente prolongada del PCI, que solo pudo concluir tras
mas de cinco anos de haberse iniciado.
Las zonas geotrmicas investigadas en el transcurso del
PCI son las siguientes:
Argentina; Volcan Copahue, Volcan Domuyo, Epulafqu, todos en

la provincia de Neuqun, zona occidental de Argentina;
Tuzgle-Tocomar en el altiplano del norte de Argentina,
provincias de Salta y Jujuy;
Bolivia: Laguna Colorada, Empexa y Volcan Sajama, en el
extremo occidental del altiplano boliviano y en la cordillera
occidental, cerca de la frontera con Chile;
Colombia; Paipa en la Cordillera Oriental;
Colombia-Ecuador ;
Nariro-Tufino-Chiles-Cerro
Negro:
lo
que
constituye un solo campo geotermico compartido por los dos

paises;
Costa Rica; Volcan Miravalles en la Cordillera de Guanacaste;
Ecuador; Chachimbiro, Papallacta, Tungurahua,
Cuenca, todos en la Cordillera Central;
Chimborazo
Guatemala; Lago Amatitlan, Zunil, San Marcos y Tecuamburo, en

la Sierra Madr al noroeste de la Ciudad de Guatemala;
Mexico; Los Humeros, Estado de Puebla;

Peru; Challapalca, Paucarani, Calacoa, Calientes y Tutupaca,
Todos en la Cordillera Andina en el sur del Peru;
Venezuela; Las Minas, Mundo Nuevo y Aguas Calientes en el
Estado de Sucre, nordeste de Venezuela; Merida, Tachira y
Trujillo en la region andina en el oeste de Venezuela.
para
Los isotopos ambientales se utilizaron principalmente

identificar el origen de los componentes del fluido
geotermico, la mezcla de aguas geotermicas con otras aguas, y

los
procesos
que
ocurren
en
profundidad
que
producen
fraccionamiento
isotopico,
como
por
ejemplo,
las
interacciones agua-roca y las perdidas de vapor. Por primera

vez se sugirio la presencia de una hipotetica
"agua
andesitica",
definida,
de
una
derivada
subduccion
composicion
del
junto
con
agua
de
sedimentos
isotopica
mar
bastante
bien
transportada
por
marinos
en
subduccion (vease memoria de Giggenbach y otros,

sistema geotermico de Miravalle, Costa Rica).
zonas
de
sobre el
La geotermometria isotopica se limito a unos pocos

casos,
posiblemente
debido
a
la
complejidad
de
las
mediciones; no obstante, los pocos resultados disponibles
(Colombia, Mexico y Peru) confirman que el sistema de
sulfato-agua constituye un buen geotermometro, mientras que
los
sistemas
basados
en
componentes
fluidos
gaseosos
(metano-CO2 y metano-hidrogeno) probablemente reflejan el

equilibrio isotopico a la temperatura de formacion, que es
superior a la de la zona de almacenamiento geotermico.

Los
analisis
quimicos
de
los
fluidos
geotermicos
se
utilizaron ampliamente en geotermometria, asi como paia el

estudio
del
origen y
la historia geoquimica
de
los
componentes fluidos.
Otra actividad que vale la pena mencionar, organizada
poco despues del inicio del PCI, fue la intercalibracion de
los analisis quimicos de aguas geotermicas entre los
laboratories participantes en el PCI. Asimismo, laboratorios
de instituciones geotermicas de otros paises pudieron tomar
parte
en
el
ejercicio.
intercalibracion se dan
este volumen.
10
Los
resultados
a conocer en
de
dicha
la ultima memoria
de
SUMMARY OF THE CO-ORDINATED RESEARCH PROGRAMME
The CRP for Latin America on the Use of Isotope and

Geochemical Techniques in Geothermal Exploration started in
1984.
The financial resources to implement the programme were
assured by the Italian Government, to which the Agency would like
to express here its gratitude. The first activity carried out
was a Seminar on isotope and geochemical techniques in geothermal
exploration, which took place in June 1984 in Morelia, Mexico, at
the premises of the Comision Federal de Electricidad, Gerencia de
Proyectos Geotermoelctricos. During the seminar, which was
attended by representatives of the institutions which later took
part in the programme, the objectives, main research lines, and
geothermal fields to be studied during the CRP were discussed.
The first research contracts were awarded towards the end

of 1984.
The field work started in 1985 and continued through
1990.
During the implementation of the CRP a considerable number
of geothermal fields, the list of which is reported below, were
studied in the nine participating countries. The investigations
carried out were geochemically quite comprehensive in most cases,
but in some others they were still in a reconnaissance stage when
the CRP ended: the latter studies are not reported in these
proceedings, but the data obtained are in principle available
from the relevant national institutions. While investigations
with conventional geochemical techniques had already started in
several fields before 1985, isotope methods were applied for the
first time in all cases during this CRP.
Due to the remoteness and high elevation of many of the

fields studied and the adverse meteorological conditions during
long periods of the year, the investigations could not proceed
rapidly: this is the main reason for the unusually long duration
of the CRP, which could be concluded only after more than five
years after its inception.
The geothermal areas investigated in the course of this
CRP are:
Argentina: Volcan Copahue, Volcan Domuyo, Epulafqun, all in the
Neuqun Province, western Argentina; Tuzgle-Tocomar in the
altiplano of northern Argentina, provinces of Salta and Jujuy;
Bolivia; Laguna Colorada, Empexa and Volcan S a jama, on the

western edge of the Bolivian altiplano and on the Western
Cordillera, close to the border with Chile;
Colombia: Paipa in the Cordillera Oriental;

Colombia- Ecuador ; Narino-Tufino-Chiles-Cerro Negro: this
constitutes a single geothermal field shared between the two
countries;
11
Costa Rica: Volcan Miravalles in the Cordillera de Guanacaste;

Ecuador: Chachimbiro, Papallacta, Tungurahua, Chimborazo and
Cuenca, all in the Central Cordillera;
Guatemala: Lake Amatitlan, ZuniL San Marcos and Tecuamburo, on
th Sierra Madr north-west of Ciudad de Guatemala;
Mexico: Los Humeros, state of Puebla;

Peru: Challapalca, Paucarani, Calacoa, Calientes and Tutupaca,
all in the Andean Cordillera in southern Peru;
Venezuela: Las Minas, Mundo Nuevo and Aguas Calientes in the
state of Sucre, north-eastern Venezuela; Mrida, Tchira and
Trujillo in the Andean region in western Venezuela.
Environmental isotopes were mainly applied to identify the
origin of the geothermal fluid components, mixing of geothermal
water with other waters, and processes occurring at depth which
produce isotopic fractionations, such as water-rock interactions
and vapour losses. The occurrence of a hypothetical "andesitic
water", with a rather well defined isotopic composition, deriving
from sea water subducted together with marine sediments in
subduction zones, was suggested for the first time (see paper by
Giggenbach et al. on Miravalle geothermal system, Costa Rica).
Isotopic geothermometry was limited to a few cases,

possibly because of the complexity of the measurements:
nevertheless, the few results available (Colombia, Mexico, Peru)
confirm that the sulphate-water system constitutes a good
geothermometer, while the systems based on gas fluid components
(methane-CCU and methane-hydrogen) probably reflect the
isotopic equilibrium at the temperature of formation, which is
higher than that of the geothermal reservoir.
Chemical analyses of geothermal fluids were extensively
used for geothermometry, and for studying the origin and
geochemical history of the fluid components.
Another activity worth mentioning, organized shortly after
the beginning of the CRP, was the intercalibration of geothermal
water chemical analyses among the laboratories taking part in the
CRP.
Also, laboratories of geothermal institutions of other
countries could take part in the exercise. The results of this
intercalibration are reported in the last paper of these
proceedings.
12
RESERVOIR CHARACTERISTICS OF THE VAPOR

DOMINATED GEOTHERMAL FIELD OF COPAHUE,
NEUQUEN, ARGENTINA, AS ESTABLISHED BY
ISOTOPIC AND GEOCHEMICAL TECHNIQUES
J.L. SIERRA*, F. D'AMORE**,
H. PANARELLO***, G. PEDRO*
* Ente Provincial de Energa del Neuqun,

Neuqun, Argentina
**Istituto Internazionale per le Ricerche Geotermiche,
Consiglio Nazionale delle Ricerche,
Pisa, Italy
*** Institute de Geocronologia y Geologfa Isotpica,
Buenos Aires, Argentina
Resumen-Abstract
CARACTERISTICAS DE ALMACENAMIENTO DEL CAMPO GEOTERMICO DOMINADO FOR LA
FASE VAPOR DE COPAHUE, NEUQUEN, ARGENTINA, ESTABLECIDAS MEDIANTE TECNICAS
ISOTOPIC AS E GEOQUIMICAS.
El caiapo geotrmico de Copahue-Caviahue, se puede dfinir

como
del tipo "dominado por vapor" con estratificacin horizontal y capas
conectadas por fracturas y buena permeabilidad
vertical dentro del
reservorio.
Los istopos oxigeno-18 y deuterio, asociados con anlisis de
gases y el estudio de la evolucin de la relacin gas/vapor,
permitieron demostrar la existencia de por lo menos dos nivels productives: el was superficial a unos 800-1000 m y el mas profundo a mas de
4000 m (todas las medidas respecte de la boca de pozo).
Las temperaturas obtenidas por mtodos quimicos e isotpicos rondan los 200 y 250C para la capa mas superficial y mas profunda
respectivamente.
Los valores de carbono-13 y las concentraciones de NZ, He y Ar
caracterisaron los gases acompanantes como principalmente magmaticos.
RESERVOIR CHARACTERISTICS OF THE VAPOR DOMINATED GEOTHERMAL FIELD OF COPAHUE,

NEUQUEN, ARGENTINA, AS ESTABLISHED BY ISOTOPIC AND GEOCHEMICAL
TECHNIQUES.
he geothenal field of Copahue has been defined has vapor dominated field tiith stratified layers connected by fractures ith good vertical peneability vithin the reservoir.
2
H and J< 0, associated gas analysis and the study of the gas vapor ratio, alloyed to prove the existence of at
least i?o productive layers, the shallower at ca. 800-1000 t and the deeper at sore than 1400 a (both bellon the
sell top level).
Isotopic and geotheraosetric teeperatures are rounding 260'C and 250'C respectively, HC, H}, r and Se analyses
allotted to hypothesise the origin of geothertal gases.
13
l.
INTRODUCTION
1.1. LOCATION AND GEOLOGY

The area of Copahue is located in the AW sector of the Neuqun
province (Argentine Republic) near the border with Chile. The latitude
is ca. 37 deg 50' S. and the longitude about the 71 deg 0.5' N. It
cover a zone on the Andean Cordillera between 1600 and 2300 m a.s.l.
Domuyo
Copahue \*fj^";,'
FIG. 1.
The climate is Patagonic, and that of high mountain, depending of
the altitude, with snow and rain precipitations from autumn to spring,
and vinds prevailing from the AW. (Pacific ocean).
The effusive
complex Copahue-Caviahue started to develope in
Pliocene and its eruptions originated the large lavic mantle of
Hualcupen Formation.
This episode Mas over with the formation of a
the
the
17
km average radius calders.

Because of the draining, result of the continous magmatic activi-
ty and to the great explotions produced by variations in the dynamic,

all the volcanic building was seated. This fact determined that the
bottom was constituted by numerous fragmented
14
blocks that originate an
area of high permeability. Latter a diastrophyc phase allowed the accumulation of lacustrine sediments in the base of the caldera. A further magmatic evolution originated an effusive
focus that produced
lavic flows covering the bottom of the system. The location of this
effusive
focus would have been in the nearness of the volcano Copahue
and is known as Las Mellizas Formation.
During the Pliocene-Holocene the magmatic activity continued,
leading to new effusive
points, favoured by the deep dislocations in
the border of the caldera that produced a set of priphrie eruptions.

This postcaldera volcanism can be classified into three effusive
stages. The last one is represented by the Copahue volcano.
In the area two wells have been drilled: COP-1 and COP-2.
The
former was drilled in March 1982 reaching 1414 m depth and lead to the
discover of a gothermie reservoir producing dry vapor. Two productive
levels have been detected, one between 800-900 m and a second into the
well bottom. The COP-2 was finished in 1986 with a total depth of 1236
m and is producing dry vapor of similar characteristics of COP-1

the shallower layer.
2.
from
METHODOLOGY
Information
available in
the ENTE PROVINCIAL
DE ENEBGIA DEL NEU-
QUEN (EPEN) i.e. production curves, build ups, pressure and temperature records of COP-1, COP-2 as well as chemical analyses of geothermal
manifestations and wells was recovered.
During three field trips performed in the 1985/1987 period,

were
sampled and analysed COz, H2S, HZ, CH4, NZ, Ar, He and CO on gaseous
samples (tab. 1 and 2).
pH, alkalinity, majoritary ions, Fez +, Fe3 + , SiO? and Li+, stable
isotopes-' deuterium, oxygen-18 and tritium contents were determined on
vapor condenstes, cold and hot waters (tab. 3 and 4). In addition
carbon-13 was measured in C2 coming with gas in wells and selected
toani fes ta ti ons.
The large number of analysis and the high precision achieved,
allowed to distinguish the productive layers,
to calculate the
physicochemical conditions within
the reservoir,
and to
reformulate
the geothermal field model. Based on this model, a third exploration

well is being drilled (COP-3) and is intended to reach 1800 m below
top well level in order to verify the results of this work.
15
o
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REFERENCES:
CO
m
>
i: C
a. a.
S
j
T
X
I.
u.
u.
n
a.
.
--
<_p
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<J
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in
in
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CJ
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i"
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UJ
r^
irf
;>,
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OC
UJ
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u.
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16
rH
rx
o
rH
pH
JURI
pH
..o
pH
CO
o
pH
ro
pH
rH
lu
(M
ijj
in
_i
CO
""
t-t
CE
I
pH
T'eu
rH
UJ
L-
fH
rH
CL'
o
o
l/V
pH
0
O
o
CT'
CL
UJ
rH
OJ
"J
--
--
;-j
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T
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CL.
CL
l-*
l.
<X
a.
CL
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i.
--
n
a
.
\^
i*^
LOCRION
: SAMPLE i
icopH-i s: L
; r
rUqumit
3:
CHtniCfiL
: rvPE
: <o :
! H ..1.1
; 130 I Y.por
1 242 I Vpoi-:
ICOPfl-2 ft! Poro COP I
flND ISOTOPIC flNflLVSIS OF CONDENSEES ONO COLD ONO HOT UWrERS
2000
e.V.. >
; <T.u.y
: ng/l : g/l : g/i : q,a : .3/i1
-10,8
:-84,2
!O,8+/-0,7:
-9,6 ;
-82,7
:o,6/-o,7i
! 8S ! V*por
-10,6
I-85,1
:o,o/-o,6:
: COP-
: Ffrrugi no**
'
51 Liquid
2000
-11,9 :
-84,7
: t,7/-C,7:
5,9
! 489
13
:copfl-5
; Sulûro*
61
2020
-11,9 :
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:2.5>/-0,7!
6,6
1 474
12
:CPfi-3 H! L
riiqum-
"
: copfl-e.
; d-i rut
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2020
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5,9
282
1 < 1
: copfl-7
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2010 ;
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:3,3/-0,7l
5,9
287
: copn-6
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20-40
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286
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2010 :
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1
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20 : 3,6 : 1,7 ! < o,os
Isotop] c flnlyin: INGEIS.
ISOTOPIC HNftLVSIS OF COP-1 RNO COP-2 UELLS.
COP-1
COP-i
: u/86 :
: INGEIS :
-8.3 :
;
:
-78 :
:< 0,05
if,8/-o,7:
1 1/86 !
IIRG
: INGEIS
-8. .2 :
-76
1/87
-9.1
i 1/86 :
REFERENCES; INGEIS ! INGEIS :
-7.6 ;
-10.8 :
QHyg.n-16 :
Dutr-jLUM ;
-es ;
-si ;
DOTE
3/86
11/86 :
IIRG
: o,0b
: < u.os
;3.6/-o,s: 6,8
DfirE : s/ei : i/85

REFERENCES: OURIO ; INGEIS
Oxyg.n-13 :
-10.5 !
-9.6
ou-t*i-i ,JM ;
-81 :
-33
19
so
6,2
-8i,9
TRBLE N" 1:
23
o,iu:
:4.s*/-o,4i 6,6 !
!1,3/-0,4:
:-90,1
! n.n.ntll
30
-11,3 :
Ch-nicl ftnlylis: flPft-EPEM.
-12,5
!WF-3
SI
! nnntll
: , o, i :
1670 ;
! WF-2
29
13
! 8
Excondzd* I
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19
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12
;ciwi-i
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1/87
; INGEIS
-7.7 ;
-83 :
-lO.l
3.
RESULTS AND DISCUSSION
3.1. METEORIC WATER LINE

As established by Panarello et al., 1988,
cold samples
CAVI-1-2-
3-4,
VAF-1 and COPA-4-5-6-7-8-9 fit closely the average world meteoric
water line defined by Craig (1961) i.e.
62H - 8
+ 10 o/oo
Othervj.se doesn't exist a good correlation between isotopic

position and altitude due mainly to the following:
com-
- Precipitation mainly as snow.

- Hest origin (Pacific) of the vapor mass that make the altitude
gradient reverse.
- Small altitude differences
that do not allow the sampling of
the water at a well established height. (Panarello et al . , op
ci t)
Vapor condensate samples
line that intercepts
the m.w 1.
are shifted
in
oxygen-13 and define
in the isotope composition of
feeding the system This waters would have infiltrated

tured area known as "El Anfiteatro" (fig. 8).
3.2. CALCULATION
RESERVOIR
As it
OF THE PHYSICOCHEMICAL
waters
at highly frac-
CONDITIONS
INTO
THE
is showed in fig. 2, static pressure and temperature profi-
les in the bottom of the COP-1

well (the well then has collapsed)
it
is possible to differenciate
two zones into the reservoir. The former
PRESSURE
P (bar)
T
-200 -
D
e
P
t
h
-400
-600
i
n
-800
0
t
r
8
-1000 -
-1200 -
-1400
90
110
130
150
170
ont or i
BAKU Qias* nun BM i
190
210
230
Temperature ( C)
FIG. 2. COP-1 static pressure and temperature profiles
18
250
between 800-1000 m ith a temperature between 195'C and 220'C and
the
second at 1400 m, a temperature of about 250"C and static pressure of

4 MPa. This is
the last information available that is then compared
with those obtained through chemical and isotopic considerations.
Q ( In/h)
g/t (IN/K yapor)
80
25
50
20
i
40
15
BX\
^
10
Eb
20
P- 8 ata
10
C
i
0
3/8 1
1/82
1/83
- Q (tn/h)
30
1/84 1/85
1/88
1/87
YEARS
g/v (m/Kg vapor)
FIG. 3. COP-1: production and gas/vapor ratio.
Q (ta/h)
I/Y (IN/Ki vapor)
5 -
3/86
(IN/Kg vapor)
FIG. 4. COP-2: production and gas/vapor ratio.
19
-IO
.45
HSH = 3 log I H 2 S / H 2 0 J - t o g ( H 2 / H 2 0 >

FIG.
5. FT-HSH diagram (D'Amore and Truesdell, 1985).
In the FT-HSH diagram
(fig. 5)
(D'Amore
& Truesdell,
1985) all
gas analyses and gas to vapor ratio available are plotted in order
calculate temperature (TC) and vapor fraction
to
(Y) simultaneously.
It should be taken into account that the gas/vapor ratios are not
accurate because oftently
are measured in the well without to stabili-
ze. In addition the method reflects

a very located situation and not
that of the whole reservoir, since it is based in the gas/vapor ratio
in the influence
20
area of the well.
The advantages are that there is no need of measuring the CO concentration to calculate the temperature, and the method shows an approximate historical evolution.
For the ell COP-1 at the beginning of
the production (1982)
temperature T= 175C and a vapor fraction Y= 1 is computed. This
fact
can be interpreted as a "gas cap" as observed in The Geysers, geothermal field (Box, 1987).
That cap has been consumed, probably,
during
the first months of production.

The results in February,
1985 were: T= 195-200'C, Y= 0.7. This
situation came as a consequence of the
loss of the "gas cap" and
the
further production from a biphasic system. Then the yield of this well
fall down in
40 % and simultaneously a shift
towards more positive
values in deuterium
and oxygen-18 was observed, indicating that
the
shallow reservoir was becoming exhaust.
In November, 1986, when the well was reopened, after
to be closed
by 10 months, a temperature of 200-205C and a Y= 0 25 are calculated,

an increase in the production was observed. This could be explained as
the contribution to the production of the residual
liquid from
the
precedent exploitation. The calculated value of temperature doesn't
indicate a deep contribution. This hypothesis is in agreement with the
more positive values of oxygen-18. Also

value is
must be noticed that the
H 2$
the same in 1982 and 1985 (0.4-0.5 %) .
In April, 1987 an strong increase in the HzS content (1.0 %) was

observed. The calculated temperature T= 245-250C, Y= 0 45, and a return to more negative oxygen-18 values correspond to the depletion
of
the residual liquid (the yield also declines) and to the existence
of
a deep contribution. The discharge declined because there is no good

connection between both reservoirs. The gas/vapor ratio increased to
2-5 % due to the deep contribution of gas and vapor
First migrate the
residual liquid, then the vapor and the deeper gas (fig. 6).
Q (lu/h)
30
20
rJdaal l
2/83
dp contribution
xhaarta
4/VI
HZ* - 1.0 (COP-2 nlu 11/6)
T T wo c
10
-11
2/88
-10.5
-10
-9.5 -9
-8
-B.5
-7.5
Delta Oxyieu-18 (X.)
FIG. 6. COP-1: production vs oxygen-18.
21
For the ell COP-2 on March, 1986, a value of T= 200C and Y= 1

is obtained (similar to the beginning of COP-1) and is also producing
from a shallow reservoir
On November,
1986 when the
well was reopened and assuming
Bg/v-
1.6 x 10-3 a temperature T= 235"C an Y= 0.03 is calculated. This values do not correspond to the "gas cap" but to a residual liquid characterized by high oxygen-18 values and a deep contribution of gas and
vapor.
In April, 1987 an strong decrease in the discharge was observed

A temperature T= 235"C and a vapor fraction Y= 0.35 is computed.
Taking into account the analytical error the COP-1
and COP-2 show the
same local origin; mainly deep (vapor and gas).
In addition, also in the
COP-2, the oxygen-18 value became
negative, indicating that the residual
liquid has been fastly
more
removed
In fig.
7 the evolution of the gas/vapor ratio vs the delta
gen-18 is showed for the COP-1 and COP-2 wells. The evolution for
from the beginning (vapor
cap) until November,
1986 (when they
reopened) fits on a straight line (I)
oxyboth
were
Ca/Vnpor (IN/Kg vnpor)

60
v
3/6
'
Tpor cap
.S/W
40 dwp xmlrlbuliem
of f uid Tmpor
30 -
20
10 rmidiua Uifoll
production
____o
-11
-10.5
-10
-9.5 -9
\\
"/ ^ o
-8.5
-8
-7.5
Delta Oxygen-18 (X.)

A
COP-1
COP-2
FIG 7. Gas/vapor ratio vs oxygen-18.
In fig.
8 (o*H
vs $1*0 plot) the
evolution for
the COP-1 well,
starting from its

drilling until
it was reopened
November, 198fi
is
plotted. COP-1 follows a line with a slope of about 200C and then the
values became more negatives. The same evolution is observed for

the
COP-2 well, but with a slope of 210-220'C, in shorter intervals, indicating that the shallower reservoir is smaller
Using the chemical analysis of gas sampled in November, 1986 some
physicochemical parameters of the fluid in the reservoir were computed
with a methodology proposed by D'Amore et al, 1987

22
Delta Deuterium (%.)
-60
-70
11/88
-80
-90
-100 -
-110
-18
-17
-16
-15
-14
-13
-12
-11
-10
-9
-B
Delta Oxygen-18 (%.)
'"
Las Maquinitas
COP-1
COP-2
FIG. 8. Deuterium vs oxygen-18.
They are: minim T("C), maxim T('C), C02 pressures (PC02),

vapor
fraction (Y), gas/total water ratio (g) and redox conditions (pO2 and
pS2).
In table 5
maxim and
minim temperatures
calculated through
CO
analysis are presented. It roust be noticed that all the samples shot?
the temperature of the shallower reservoir, excepting that of the COP2 (T= 240C) that was already producing from the deeper layer
Table 6 exhibits the maxim values (method without CO to fixed
temperatures). Two temperature values are presented: that without (*)
is a assumed one, that with (*) is a maxim value. The value of
the
gas/total water ratio in. the reservoir has two different
significate
according to the temperature considered. The corresponding to max T
represent an almost total evaporation into the reservoir, for instance
at the COP-1 is
similar to the gas/vapor
ratio measured at the well
top.
The maxim temperature calculated for November, 1986 for the COP-1
is 200 C in agreement with that estimated by other methods, as resulted from a shallow production. Conversely for the COP-2, Tmax= 270"C is
accounting for the deep contribution. A value of Y- 0.046 (Sl = 0.30)
complete the conditions of the deeper reservoir (1400 m).
"Las Maquinitas" and "Las Maquinas", exhibit a Tmax= 208-216C

indicating that the main contribution is from the shallower reservoir.
At the area of the "Termas de Copahue" the value of Tmax- 245C indicate a strong deep con tri bution.
By using the diagram PC02 vs T (fig. 9) for the sampling of November, 1986 for "Las Maquinitas", COP-1 and COP-2 is possible to see
that the points are aligned on the equilibrium straigh line:

Muscovite (and clay minerals) + Calcite + Quartz =
K-Feldespar + Epi do ta
(Xps- 0.275)
in full agreement with the minerals observed during the drilling above
850 m. Assuming the PC02 calculated using the gas/vapor ratio from
23
L>
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ce
r
o
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24
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OBSERVRTIONS
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R E F E R E N CES
COP l
LAS MAQUINI1AS
LAS M AQUINAS
COP l
11/86
DEEP RESERVOIR P(C02)
SIMULATED g/v 1987-2SQOC
10
1987 and T= 250 C a reaction of equilibrium where PCO^ would be controlled by the equilibria of the alteration minerals Epidota and Pre-
nhite is obtained (cross in the diagram)
3.3. HYPOTHESIS ON THE ORIGIN OF THE INERT GASES

The values of 813C obtained in 1985 from Las Maquinas - -10 7
o/oo,
Las Maquinitas --68 o/oo and COP-1 - -10 9 o/oo range between -7 and -11 o/oo approximately These values are typical of active
volcanic zones, where could have existed the following interaction
during the magmatic activity
Calcite + Silicates = C02 + Hollastonite (Ca-Silicate)
Epstein and O Neil showed that this reaction produce a carbon
isotope fractionation leading to more depleted values in the ramaining
cal cite The shifting to more negative values depend on the degree of
progress of the reaction
If the relative
quantities of N2
Ar and He
are considered
is
possible to see the following
1 The Nz/Ar ratio, taking into account all the sampled manifestations and wells range from 300 to 1000 The value for the meteoric
water recharging the system is close to 40
Therefore could be said
that the N2 and the Ar are not from atmospheric origin

2
In the diagram (fig 10)
the position for the points
ponding to all the samples indicates a strong deep magmatic

tion that can explain the primary origin of the N2
N 2 /1CO
COP I
2 COP a
3
LAS MAQUNIJAS
LAS MAQU NAS
Hex 10
FIG 10 Relative N2, He and Ar contents m geothermal gas discharges
26
corres-
contribu-
4.
CONCLUSIONS
Based on isotopic and chemicals considerations and on the production data, the following conclusion can be established:
- Copahue is a typical vapor dominated geothermal field, where
the pressure into the reservoir is fixed by a biphasic (vapor/
liquid) system (Sierra. 1981).
- This kind of reservoir have been proposed by D'Amore (1979) and
confirmed in deep perforations at the Geysers by Box (1987) and
in Santa Lucia Island by Aqua ter. They are characterized as

stratified systerns.
The reservoir is constituted by several productive layers separated by low permeability zones. The productive layers have
diffrents
physicochemical characteristics and productions. For
the Copahue field, a first level with the following characteristic have been established:
Depth - ---------- - 850 to 1000 m
Temperature ---------- 200 to 215'C (excluding the primary
gas cap)
v _ __ _ _ __ _ _
_ _ __ nL / .nff
1
L / C I y-,-i
O C ' Ln/ . *?j
PC02 --- ---------- 50 kPa
Production data for the COP-1 and COP-2 indicate that the system has been quickly depleted.
The shallow reservoir would have a low lateral permeabylity,
thus the original fluid, near COP-1, would have undergone a
strong drop of pressure, gas and vapor loss (lowering of the

gas/vapor ratio and the discharge) due to the exploitation.
Also shows an isotopic enrichment, mainly in oxygen-18, and a
relative decrease of soluble gases.
After the reopening of the COP-1 and COP-2 wells in November,

1986 the first fluid produced by the COP-1 was originated in a
local residual liquid (condensate) that migrates laterally towards the well. In addition for the COP-2 a deep gas and vapor
source contributed to the production.

The local liquid is
fastly
consumed, and after
five months both
COP-1 and COP-2 fluids exhibits characteristics belonging to

the deep level (below 1400 m) with the following thermodynamic
pa rame t ers '
Temperature ----- - _ _ _ _ 250-260 C

Discharged vapor temperature ----- 200-220C
Vapor fraction ------------ 0.03-0.05
G/V ratio ----------------------- 20-30 L.N./kg
T>nn _ _ _ _ _ _ _
IT \~t\J %
H2S/H2
018Q
_ _
_ _ _ _ _ _ _
_______
_ ~~ J_1 nn~
?nn
I-Pêt
U U
&
U U
J\.JT
-------------------------- > i
---------------------------
-10.0 0/00
The future COP-3 well would must find a fluid with this
characteristics typical for a vapor dominated system of high
enthalpy. In order to explain the present discharges of COP-1
and COP-2 a system with good vertical permeability must be
assummed (fig. 11).
27
PHASE I
VHPUR
ERS
i '" """"" ' "
":
FIRST LEUEL
y +
==J>
^^
3=
=l>
T =3an-2Q5
V: D.QS -D.2
_ r : 3,5
<F=
jm
xxy--vfoxxfi;:xxxx:^>fixxrex*>y^
SECOND LEUEL
L <J * G
PHASE II
y
LEVEL
V = U dti
's-..
X^RESIPUBL LIQUID
SECDrtD LEytL
'_ U G
.^ R?-.
T =2SD-SBD_ n
v = D -3 - Q..5
L: LIQUID
G:
Y:
GRS
URPDR
FIG. 11. COP-1 well (evolution).
ciaosledgtKstts - Tiis sork has been perforted sithin the fraiesork of tie lSt Coordinated Research Prograne on the
application of Isotope and Geocheiical Techniques in Geothertsl Exploration in Latin iierica (Research Contract N'
39S8/IG), financially supported by the Gorerntent of Italy.
REFERENCES
Bolognas! L. , Noto P. e Nuti S.
(1986) Studio chimico ed isotopico
della solfatara di Pozzuoli: ipotesi sull 'origine e sulle temperature profonde dei fluidi. Ftendiconti Soc. It. Min. e Petr. , 41 (2),
pp. 281-295.
Box H. T.,
D'Amore F. and Nuti S. (1987) Chemical and isotopic composition of the fluid sampled during drilling at The Geysers (Ca,
USA). Int. Symp. on Development and Exploitation of Geothermal Besources, Cuernavaca, Mexico, oct. 5-10, in press.
D'Amore F. and Truesdell A. H. (1979) Models for steam chemistry at

Larderello and The Geysers. Proc. 5th Workshop Res. Eng.,
University, pp. 283-293.
28
Stanford
D'Amore F., Celati B. and Galore C. (1982) Fluid geochemistry applications in reservoir engineering (vapor dominated systems). Proc.
8th Workshop Res. Eng., Stanford University, pp. 295-308.
D'Amore F. and Gianelli G. (1984) Mineral assemblages and oxygen and
sulphur fugacities in natural water-rock interaction processes. Geochim. et Cosmochim. Acta, 48, pp. 847-857.
D'Amore F. and Pruess K. (1985) Correlations between vapor saturation, fluid composition and well decline in Larderello. 10th Workshop Bes. Eng., Stanford University, pp. 113-121.
D'Amore F. and Truesdell A. H. (1985) Calculation of geothermal reservoir temperatures and steam fractions from gas compositions. GBC
Symp. on Geothermal Energy, Kona, Hawaii, 9, pp. 303-310.

D'Amore F., Fancelli R. and Saracco L. (1986) Development of a methodology for measuring CO and its geothermometric applications.
Part J. Model development. CNR Report to European Communities (Contract 0022-1).
D'Amore F. and Truesdell A. H. (1986) A review of solubilities and
equilibrium constants for gaseous species of geothermal interest.
Appendix to CNR 1987 Report to European Communities (Part II),
(Proposal A2/083/I, Contract 0022-1).
D'Amore F. , Fancelli R. , Mussi M. , Saracco L. , Caprai A. , Calvi E. ,

Del Chicca G. (1987) Development of a methodology for measuring
carbon monoxide and its geothermometric applications (Part II). CNR
Report to European Communities (Proposal A2/083/I, Contract 0022-1).
D'Amore F. (1987) Some geochemical techniques for reservoir temperature computation. Int. Symp. on Development and Exploitation of Geothermal Resources, Cuernavaca, Mexico, oct. 5-10, in press.
D'Amore F., Fancelli R. and Saracco L. (1987) Gas geothermometry

based on CO content. Application in Italian geothermal fields. Proc.
12th Workshop Res. Eng., Stanford University, in press.
D'Amore F., Sierra J. L., Panarello H. (1988) Informe

Contra to de Investigacin 01EA N 3988/IG.
Avance del
Jurio R. L. (1977) Caracteristicas geoquimicas de los fluidos

les
de Copahue (Neuqun
terma-
- Argentina). Principales implicancias geo-
trmicas. Apartado de la revista "Mineria", N" 172, 11 pp.
Mas L. C. (1986) Estudios petrogrficos de minrales de alteracin y

algunos parmetros fisicos sobre rouestras de roca de perforaciones.
Informe CNR - Int. School of Geo thermies. IIRG, Pi sa.
Panarello H. 0. , Levin M. , Albero M. C.,
Sierra J. L. and Gingins M.

0. (1986) Isotopic and geochemical study of the vapor dominated geothermal field of Copahue (Neuqun, Argentina). Int. Meeting on Geothermics and Geothermal Energy, Guaruja, Brasil, 10-14 ug. 1986, 16
PP. (A).
Panarello H. O. , Sierra J. L. , Gingins M. O. , Levin M. y Albero M.
C. (1986) Estudio geoquimico e isotpico de los sistemas geotermales

de la Provincia del Neuqun, Repblica Argentina, primera parte:
area Copahue. Informe anual de avance del contrato OIEA N" 3988 IG.
(B).
Saracco L. and D'Amore F. (1988) C02B, a computer program for
applying a gas - geothermometer to geothermal systems. Submitted to
Computers and Geosciences (Pergamon Press).
29
Secretara del COPADE (Provincia del Neuqun) (1982) Consideraciones

brves sobre antcdentes hidroqumicos de vertientes, condensados
acuosos y gases no condensables del area geotrmica de Copahue
(Neuqun - Argentina). Informe LATINOCONSULT - ESIN S.A., 59 pp.
Secretara del COPADE (Provincia del Neuqun), LATINOCONSULT - ELC.
Estudio de factibilidad geotrroica en Copahue: primera etapa. Informe COP-I-5284.
Sierra J. L., Gingins M. 0. , Panarello H. 0., Levin M., D'Amore F. y

Gianelli G. (1986) Estudio geoquimico e isotpico de los fluidos
geotermales de la Provincia del Neuqun.
(Convenio N 3988/IG),
Informe
de avance OIEA
nov. 1986, 15 pp.
Truesdell A. H., Haizlip J. P., Box H. T. and D'Amore F. (1987)

Fieldwide chemical and isotopic gradients in steam from The Geysers.
Proc. 12th Workshop Res. Eng., Stanford University, in press.
30
ISOTOPIC AND GEOCHEMICAL STUDY OF THE DOMUYO

GEOTHERMAL FIELD, NEUQUEN, ARGENTINA
H. PANARELLO*, J.L. SIERRA**,
F. D'AMORE***, G. PEDRO**
*Instituto de Geocronologfa y Geologfa Isotopica,

Buenos Aires, Argentina
**Ente Provincial de Energfa del Neuqun,
Neuqun, Argentina
***Istituto Internazionale per le Ricerche Geotermiche,

Pisa, Italy
Resumen-Abstract
ESTUDIO ISOTOPICO Y GEOQUIMICO DEL CAMPO GEOTERMICO DE DOMUYO, NEUQUEN,

ARGENTINA.
Se realizaron analisis isotpicos y anlsis quimicos en slidos
disueltos y gases con el objeto de establecer un modelo de circulacin
y determinar la temperatura de reservorio.
De acuerdo a 2 os nivels de tritio registrados y los va lores de
los istopos estables deuterio y oxigeno-18, la recarga del sistema se
produce a una al tara de a. 2900 m s.n.m. en la falda oeste del cerro
Domo.
El agua muestreada en un geyser, "El Humazo", se reconoce como la

proporcin de agua meterica reciente. La temperatura del reservorio de dond proviene "El Humazo", sria de unos 225 C de acuerdo con el geotermmetro de Na-K-Ca. Asimismo se puede infrir la existencia de otro
reservorio mas superficial con temperaturas de alrededor de 176C de
donde provendrian las aguas de "Las Olletas" y "Los Tachos", tambin
afectados por procesos de dilucin y prdida de vapor.
mas relacionada al agua primaria, aunque contiene una pequena
Finalmente las manifestaciones templadas como "Aguas Calientes" y

"Banos de agua caliente", serian el resultado de mezclas entre aguas
del tipo de "Las Olletas" con acuiferos frios superficiales.
La termometria gaseosa y las temperaturas obtenidas a travs de

consideraciones termodinmicas sobre el equilibrio entre flui dos y
minrales arro.jan temperaturas entre 220-248 "C para el reservorio mas
profundo en concordancia con la temperatura quimica. Asimismo sugieren
un valor cercano a cero de la fraccin de vapor en el reservorio (Y)
confirmando el estado liquido del fluido en el reservorio.
ISOTOPIC AND GEOCHEMICAL STUDY OF THE DOMUYO GEOTHERMAL FIELD, NEUQUEN,

ARGENTINA.
Snvironental isotopes, 2S, II0 and }S as sell as cheiical analyses of dissolved solids and gases have
been perfoned in order to establish a circulation todel and reservoir teiperature

according to tritiai levels and isotope content, recharge occurs 2900 i above sea level on the vest slope of the
Doio volcano.
Hater fro* a geyser, "El Buiazo", sas recognised as the tore related to the pritary deep geothenal fluid, altough
sith a linor proportion of fresh sater.
31
Reservoir temperature as estimates by the Na-K Ca geotheraoaeter on this tamfestation yield a value of 225'C
A shallower reservoir mth temprature of about l'C (Ha tf Ca geotheraoaeter) is evidenced in "Las Olletas" and
'Los achos" also affected by dilution and steaa loss processes
finally, teaperate Manifestations as "/tguas Calientes" and "SaSos de tguas Calieates" are the result of sizing bet
veen Las Olletas type eaters vith fresh eeteoric shallover vaters
Gas theraotetry and coiputation of fluid and sineral equilibria yield teaperatares betveen 220-248'C for the deep
reservoir, in agreement sith sore classical techniques and suggest a value near to zero for the vapor fraction (7)
at depth and confire the liquid state of the fluid into the reservoir
1.
INTRODUCTION
The Domuyo geothermal area is located at AW of the Neuquen Province c a 36 45' S and 70 47
W, 40 km away from the Andes Cordillera
The climate is defined as Semiarid Patagonic in the lower
and as Andino high mountain type in the upper areas
zones
The basement is constituted by acid plutonites, metamorphites and

Jurasic sediments from the Neuquenian Basin The upper part is covered
by tertiary vulcanites (Pliocene) and quaternary lava, the last correspond to emissions of domic vulcanism whose magmatic chamber is responsible of a thermic anomaly
Domuyo
Copahue
FIG 1.
32
Great regional faults cross the zone with E-W. N-S and N-M direction. In these faults intercepts, wain thermal manifestations as thermal spring and geysers are found.
The study of the zone began in 1982 hen a geological interpretation of satellitary images and air photography was made. An area of 40
km2 was selected at the west of the Domuyo mount. On this area a geological survey was performed. In adittion geochemistry, gravimetry,
heat flow measurements, geoelectric and seismic prospections were
done.
2.
METHODOLOGY
During 1985 and 1988 two field trips were performed. In the first
pH. conductivity, Na + , K+. Ca2 + , Mg2 + , Li+, Al , Si02, NH3, B, Cl~,
SO42-, 32-, F-, 1*0, 2H and 3ffwere analysed.
In the second one a more detailed chemistry of water and gases in
selected manifestations was made.
The information obtained during the first stage allowed the chemistry and isotopic classification of water samples, geothermometry,
determination of mixture of waters, altitude and area of recharge,
extension of the reservoir and to establish a circulation model. With
data of the second stage saturation indexes and physicochemical conditions within the reservoir were modelled.
3.
3.1. CHEMICAL COMPOSITION OF THE HATERS

In table 1 results of chemical analyses are presented. According
to their temperature and conductivity, water can be classified into 3
groups :
Group I: Comprises the samples corresponding to "El Humazo'

"Las Olletas" (LO) and "Los Tachos"
(LTD, they are alkaline
clorurated, mainly Na + , K+, with low concentration of Ca2+ and Mg2 + .
Conductivity oscilate between 5.38 and 6.42 mS/cm. Emergence temperature is near to the boiling point at these altitude (~93C).
pH round 8.2.
(EH1),
Group II: Cold waters, MAF 3,4, 5, 6, 8, 10, 11. 12, 13 are
cluded. They are HC03- Na + Caz+ . Conductivities are lower than
uS/cm. Surface temperature is less than 13C. pH ranges between
and 8.1.
in102
4.5
Group III: Aguas Calientes (AC) 4, 5, 6, Banos de Aguas Calientes

7), LT12 and MAF 1, 5 and 7 These samples present intermediate
values between group I and II i.e. conductivities between 629 and 4200
US/cm, temperatures of 16 to 64C and pH of 5.9 to 7.9.
(BAC
Tritium values showed in table 3 confirm the existence of this 3

groups being of (0 to 1) T.U. for the first, (1 to 6.5) T.U. the
cond and (1 to 3.5) T.U. for the third.
33
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VI
3.2.
LIQUID PHASE THERMOMETRY
Table 6 presents the temperature values obtained by mean of different geothermometers Silica, Na/K, Na-K-Ca,
Na-K-Ca corrected by
Mg, Na-Li, Mg~Li, K-Mg and in
figure 2 the graphic method of Giggenbach (1986) is presented
Assuming as more reliable the Na-K-Ca geothermometer, the highest
temperature correspond to EH1, 225,5C
On LO and LT1 similar temperatures of 176"C and 179 C respectively are obtained AC and BAC 7
yield lower values of 150 and 156C
The triangular diagram of Giggembach (op cit) (fig
2) shows
groups of samples, aligned on two isotherms EH1 and LT12 lie on
isotherm of 245C, LO, LT1 and all
two
the
AC on the isotherm of about 190C
Sample EH1 fits close to the full equilibrium curve, however it

shows a dilution since it is not on the curve, LT12 is more diluted
The position of LO and LT1 on the 190C isotherm suggests the reequilibration of the system to a lower temperature As can be seen in fig
2, all the remaining manifestations are more diluted
The silica geothermometers yield lower temperatures for EH1 than

those obtained by the Na-K-Ca one, they are 191 C for the quartz equilibrium, without steam loss, and 177C if
steam loss is
considered
Thus boiling with SiU2 precipitation is evidenced
TABLE
N* 6: 6EOTHERHONETERS
BEOTHERHOI1ETERS
AC4
ACS
AC6
Na/K (F)
178,9
187,4
188,5
Na/K (T)
140,9
151,0
Na-K-Ca
177,5
Na-K-Ca (q>
LO
LT1
EH1
RP
198,6
173,3
176,0
228,2
232,4
175,9
152,5
164,7
134,2
137,4
201,8
207,1
136,7
177,5
183,4
186,6
176,0
178,7
211,3
225,5
159,7
161,6
168,9
159,1
137,6
172,8
174,2
206,1
225,5
29,7
Na-Li
148,1
134,6
138,3
145,3
141,0
138,6
144,6
143,0
227,7
K-tlg
131,2
133,4
129,8
118,8
151,1
149,8
168,9
212,8
101,2
Hq-Li
209,9
198,2
194,3
175,6
242,7
236,1
233,1
297,5
151,1
TQC
174,3
165,4
178,2
172,0
177,5
181,6
168,8
191,2
149,6
TQfi
163,6
156,2
166,7
161,6
166,2
169,5
159,0
177,3
143,8
TCH
152,4
142,2
156,8
149,7
156,0
160,8
146,0
171,9
124,3
BAC7
LT12
Na/K (Fl: FOURNIER

Na/K ( ) : TRUESDELL
Na-K-Ca (ttq): CORRECTION BY HAGNESIU
TQC: QUARTZ CONDUCTIVE

TCH: CHALCEDONY
~ NOTE: TEHPERAURES ARE IN 'C
37
Na/1000
%-Na"=c N /10S
'o-Mg" = 100 Vct
.<:, in mg/kg
LO
EHI
LTI
a 12
20
<U
10
70
/ 90
',
"V.-Ma'
enbach, G r a p h i c a l Techniques, 11B6.-
MAE 7
S1O2 (ppm)
600
400 -
300 -
ZOO -
100
20
40
00
80
100
120
140
180
180
200
220
Rnthalpj (Koal/Kf)
FIG. 3. Enthalpy silica.

1
HLBITE
L[1
^rj^'
a
HC5.^'"^LT1?
K
_^-''
No-nBMT
a
"
MICRDCLINE
KHOLINITE
__
.ÎT,
-H
SVST. Hci,Hea
t ana oC i q oH;J',tiH: -a 3 5 = û
FIG. 4. Activity diagram.
38
IQ
240
Mg
FIG. 2.
LITHIUM VS CHLORIDE
BORON VS CHLORIDE
20
Lithium (ppm)
Boron (ppm)
12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
mi
+
15 -
...........................................
10
KBl
+..+. .
. +. . . . . . . . . . . . .
B
10 -
+ U>
?
+LT1
LT1Z
1C*
+
"
+
aicrqk-
+1C6
5 -
1C8
BlCTfWl
2 - ' ' * ' '+' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2 -H +
0
)
zoo
500
1000
ZO00
1500
()
500
1000
Chloride (ppm.)
Chloride (ppm)
SULFATE VS CHLORIDE
SODIUM VS CHLORIDE
Sulfate (ppm)
+
150
1200
LO
LO
1000
BOO
les
1C
100
600 -
50
ZO
Sodium (ppm)
1400
EB1
1500
8
+
uiz
400 -
200 -
ll+-
0-1
500
1000
Chloride (ppm)
1500
2000
500
1000
Chlorid* (ppm)
FIG. 5.
1500
2000
-fees
MAGNESIUM VS CHLORIDE
POTASSIUM VS CHLORIDE
Potuilum (ppm)
UH ani nrn
ppm)
""* fU>F
^
"u.
m+
1*0
4120
100
+ 7
BO
to
LT1
80
ACS
AC AC*
BAC7
40
*-
++
.K
k+
j
i
1
2 (i
i
4-
4.
-r
-f
-f-
4+ AC*
-r
">
0T
500
1000
1500
2000
i i i
500
1000
SILICA VS CHLORIDE
En.th.alpy (Kcl/kg)
m
4
BAC7
"tin
T_^
LO
LT12
BAC7
i-
<
'
_P
ACe
ACS
f
S 7
20. r
I+ 2
1"^
'4-2
Ol
0
0
40r
S-f
50 ' ;
AC*
4- ACS
60k
H-
li
80-
150 1-
2000
ENTHALPY VS CHLORIDE
Silica (ppm)
100
1500
Chloride (ppm)
Chloride (ppm)
20
ttl
+
m2
T"
0
0
ACS
,
AC
20
500
1000
1500
ZOOO
Chloride (ppm.)
I
i i i I
500
1000
Chlorid (ppm)
FIG. 6
1500
2000
Enthalpy (Kcal/leg)
300 i -*
500
1000
2500
1500 2000
3000
Chloride (ppm)
FIG. 7 Enthalpy vs chloride
-100
-21
-20
-19
-18
-17
-16
-15
-13
Delta Oxyfen-18 (X.)
FIG 8 Deuterium vs oxygen-18
3.3. GAS GEOTHEBMOMETBY
A.
METHOD l
Starting with the composition of the

reservoir parameters Here determined
t,
(PCOs),
vapor fraction
sample EH3, the following

partial pressure of C2
(Y) and gas to water ratio
The used methodology is that proposed by D'Amore et al

(1987)
It is reliable for reservoirs with temperatures over 140C and take
into account the gaseous species C02, HzS, CH4, H2 and CO The follo-
41
wing reactions are consideredH20 = H2 + 1/2
02
H3S - H 2 +1/2 S z
CH4
+ 2 H20
= 4 H? + C02
CO ? -f- H 2 = CO + H20
1/2
Fe304
CO
+ S z - FeS2 + 2/3
02
MP
Taking into account

this 5 equation and the equilibrium constants, partial pressures of 82 and 02 can be eliminated and the following equations to be written:
4 log P(H2) + log P(C02)
log AV + 2 log P(H20)
- log P(CH4)
3 log P(H2S) -log P(Hz) 2 log KH - 3 log Ks - 3/2 log KMP
+ 2 log P(H20)
4 log P(CO) - 3 log P(C02)
- log P(CH4)
4 log Kco + log KC - 2 log P(H20)
The partial pressure of every gas specie may be written as a

function of its molar concentration ( n ) respect water in the dischar-
ge point (d), the molar fraction of the vapor (Y) and the molar
ficient
log Pi = log
where
and
(nl/nH20)d
- log A, + log P(H2O)
A, - Y + (1 - Y)
log
coef-
of distribution between vapor and liquid -S2
B1 - a + b t
for
Y > 0
for
Y < 0
where t - temperature
a,
( "C )
b = constant for
each
gaseous specie.
Replacing in the
expression we have:
3 equations above,
partial pressures by
4 log(H2/CU2)
- log(CH4/C02)
~ fi(t)
+ fi(t,Y)
- 4 logP(C02)
3 log(H2S/C02)
- log(H2/C02)
= f2(t)
+ f2(t,Y)
- 2 logP(CO2)
4 log(CO/CO2)
- log(CH4/C02)
- f3(t)
+ f3(t,Y)
their
fi(t), f2(t) and fs(t) are functions expressing the dependence of

the equilibrium constants with temperature and fj(t,Y),
f2(t,Y)
and
f y f t , Y) represent the termins A^ that are function of both, temperature and vapor fraction
42
Solving this system for EH3 we obtain:
t - 220'C reservoir temperature

PC02 =300 kPa
Y = 0.003 vapor fraction
log H2/H20 - - 6
Gas/water = 4.7 x 10-*
logP(Oz) = - 39.9
B.
METHOD 2
In this method is taking into account the system C02. CH4, H2 and
CO. H2S is excluded, thus one constant must be assumed; in this case
Y=0.
The obtained results for EH3 are the following:

t - 240'C
log P(C02) - - 38.3
PCO2 - 300 kPa
In the manifestation at the border of the geothermal field Rincn
de las Papas (RP) we obtain:
t - 210"C
log P(02) - - 41.2
PCO? - 2 MPa
C.
METHOD 3 (D'Amore et al., 1989)
In this method the reservoir
temperature is calculated by
the simultaneously composition of
the va ter and the
the concentrations of CE4. H2 and

red.
In the reaction:
CO refered to the CO2 are
CO + 3 H2 = CH4 + H20
using
gas. in the
gas
conside-
(1)
considering Y=0 we have:

log
Pj
log
n2/nC02
log
B! -
log
B(CO2)
log
P(C021
(?)
Taking into account equations 1 and 2 we arrive to an

only depending on T and P/cost-
expression
In the same ay is no possible with aid of computer programs

calculate the P(co2) from the water composition, alkalinity and pH at
different temperatures. At the equilibrium temperature both pressures
calculated from water and gas must be equals.
With water from EH1 and gas from EH3, it was obtained:
t - 248C
P(co2) =150 kPa
As can be observed the three methods yield values between 220 and
248C in agreement with those obtained by classic thermometry.
The
obtained value for Y, virtually equal to zero define the field as liquid dominated.
43
3 4.
ENVIRONMENTAL
A.
ISOTOPES RESULTS
COLD HATER SAMPLES
Samples representatives of
meteoric water line o^H - 8 <5 1 0
exhibits more depleted in 2H and
tude of the recharge Conversely
to MAF 1 5 and 8
In fig
cold water springs

2 1 close to
the
+ 10 o/oo MAE 1U 11, 12 13 and
14
l S0 values indicating a higher altithe more enriched samples correspond
14 the oxygen- 18 contents of cold va ter springs are plot-
ted as a function of altitude An altitude effect

o/oo/lOO m is estimated fitting the equation
6160
(18 2) x 10 * /fn
with a coefficient
CIO 8 + 05)
of correlation r-0
of
(0 18 0 02)
o/oo
In similar form (fig 15) an altitude effect

of (1 3+0 2)o/oo
per 100 m is found for deuterium The regression equation is
2H - (13 2) x 10 3 /m
(80 98 0 Ob) o/oo
r~ 0 83
One pole of
these lines are
determined by samples
MAb 1 and
with high tritium contents representing

local recent precipitation
Conversely the other pole is represented by samples MAF 3 10 11,
13
and 14 with lower tritium contents corresponding

the west slope of
to spring located
the Domo mount over 2900 m a i l
at
assumed as the re
charge area
HOT HATER SAMPLES
In figures 9A and 9B the isotope content 01S0 and 62H of

samples
EH LO and LT show to be near of the isotopic equilibrium at the
temperature of emergence
This fact and the Cl' enthalpy diagram allow to
calculate the isotopic composition prior to the steam separation
LO
LT1 and HI
O^H vs
Cl ~ and 6 1 *O vs Cl - diagrams (fig 10 and
11),
lead to the calculation of the composition of the deep reservoirs HI*
and LO*LT*
From the 62H vs 8iaO diagram can be concluded that watei

recharged at the Domo mount recharge the reservoirs corresponding to El Humazo ( H I * ) and that of Las Olletas-Los Tachos (LO*LT*) with the
major
oxygen-18 shift for HI* AC and BAC manifestations are produced by the
mixing of waters LO type with local recent meteoric waters
Tritium contents of hot water samples indicate a minor meteoric
water proportion for
EH1 and a significative
contribution of
fresh
water to AC and BAC samples
44
Temperature { C)
250
200
150
100
50
8
10E3 In
10
12
14
16
FIG 9a Oxygen-18 enrichment as a function of the emergence temperature
Temperatur ( C)
250
200
150
100
50
-10
10
20
30
10E3 In
40
50
60
70
FIG 9b Deuterium enrichment as a function of the emergence temperature
45
-100
Delta Deuterium (% )
500
1000
1500 2000
Chloride (ppm)
3000
FIG 10 Deuterium vs chloride.
Delta Oxygen-IB (X)
500
1000
1500 2000
Chloride (ppm)
FIG. 11 Oxygen-18 vs chloride
46
3000
Tritium (T.U. +/-
0.6)
8
7
i
6
5
4ir.12
13
11
2'-
ACE
ice
1-
BAC?
C4
KH1
LO
0
0
500
1000
1500 2000
Ht
2500
3000
consist of
Chloride (ppm)
FIG.
3.5. CIRCULATION
12. Tritium vs chloride.
MODEL
In figure 13, a circulation model
is presented. It
central area with a fluid HI* feeding the manifestation of El Humazo y

Los Tachos and a second system less hot, responsible of Las 01 le tas
and Banos de Aguas Calientes (LO*LT*) diluted with cold water in different proportion.
All
the system is recharged in the neighboring of the Domo mount.

3.6. HYPOTHESIS
ON THE ORIGIN OF GASES
13C composition of gases from EH1, EH3 and PP are -7.6, -7.3 and
-8.2 o/oo respectively, indicating magmatic or atmospheric origin.
This results would be partially confirmed by the study of concentration of non reactive gases (Giggenbach, 1983).
The source of
the Ar, N2 and He can be characterized as follows:
1. Recent waters, air

saturated, with low He content and N^/Ar
ratio depending on the quantity of gases withdrawn from waters. It can
range between 78 (low proportion of extracted gas) and 38 (all the gas
extracted).
2. A deep magma tic contribution with low He content, N 2/He
ter than 3000 and Nz/Ar ratio higher than 500.
3. Cortical
component typically
circulation. They have an He content
observed in
systems with
increasing as a function of
greaslow
the
residence time of the fluid at the crust.

In figure 16 these parameters are presented as a triangular
dia-
gram.
47
FIG. 13. Circulation model
-13.0
2000
2500
3000
Altitude (m)
FIG. 14. Delta oxygen-18 vs altitude.
-95
-100
-105
-110
'7
-115
-120
1500
2000
2500
3000
Altitude (m)
FIG. 15. Delta deuterium vs altitude.
49
M - Mantle
N^/IO
C Cruitul
ASW - Air Saturate Water at JO'C
COIWUL
Ar
i - --
FIG 16 Triangular diagram N2-Ar-He for some geothermal fields of the world (D'Amore et al , 1989)
The PP sample shows a clear origin in air saturated groundwater

Conversely EH3, with higher values of He is shoving a deeper origin
EH3 gases can be considered as a mixture between a cortical and a man
tie contribution The sample from Copahue exhibits a typical
composi
tion of gases coming from the mantle It must be noted that is possible, at the Domuyo area, not far from El Humazo the existence of a
basaltic magmatic chamber This chamber would contain gases of similar
characteristics to those of Copahue The further circulation through
methamorfic and granitic rocks, could explain the high He concentration making the crustal component became important
3 7
SILICATE SOLUBILITY PRODUCT
The most of problems related to the suitability of a given geothermometer on aqueous samples is frequently due to the unknown interaction between the host rock and water, and to the value of the pH at
depth Also to the difficulty for reaching the equilibrium in low enthalpy systems local cooling effects and mixing processes
The use of secondary mineral equilibrium fixing the water chemistry, could eliminate any unknown related to the estimated
temperature
for the aquifer
It can be achieved by determining the monomeric aluminium
(A1+3)
and (Al(xy)H)z with x= OH- F~, 504 =, etc and z~ (3 wy) In the pro
cess of leaching of the host rock into microfractured system d certain
quantity of polimeric aluminium is produced in addition to other
anions and cations Only a part of this polimeric aluminium produces
monomeric aluminium, being the latter a function of the solution composition and temperature This monomeric aluminium participates in the
formation of hydrothermal altered silicates in equilibrium
50
Using adecuate computer programs and field data like pH, temperature and alkalinity as well as laboratory chemical data, it is possible to calculate the composition of the fluid at depth and the saturation indexes (S.I.) of several minerals at any temperature (Arnonson &
Sigurson, 1982; Worley, 1979).

The S.I. are computed and plotted for a selected group of minerals that are compatible with the local minralogie matrix For each
mineral, the intercept of the line S.I.= 0 vs temperature yield the
calculated equilibrium temperature.
Taking into account the uncertainty in the thermodynamic data,
the interval considra ted as
"in equilibrium' for a given mineral
falls into a range of S I. = 0 0.25
In table 7 the value of S.I. for selected alteration minerals of
the manifestation EH1 are presented. The program was run assuming the
system descompression occured at 180C.
fflBLE N 7:
S*tur.tion ind*nI of on* lt#r.tion Hin*r*l*

**l*ct*d tnp*r*tijrs CfroM U*tch 3 progrM for
d*scoposition tnpr-atur-* td 180 O.

EH1 hot
spring, DoMuyo.
t -c
tllNERRL
200
225
250
275
for
5.1 . 0
1>
rig-Chlorit
-2. 11
-0.96
1.20
3.16
236
2~>
Zoisit*
-2.51
-1.52
-0.26
1. 17
251
3") Epidot
-0.96
-1.06
-0.29
1.40
254
4>
-0.57
0. 16
1.31
2.6-4
220
-0.3$
0.04
0.48
0.90
223
-tluscovi t
-0. 10
-0.05
O.'J
0.90
225
flrihydrjt.
+ Fluorit
-0.44
-0. 19
0.05
0.27
245
5")
Pr*hnit
Rlbit-
-KF*1 dsp*r
6>
7)
KF.ld*pr-
t - 237 +/-
15 C
Cfor S.I. - 0 . 0 5
t -
17 C
Cfor S . I . " 0.0 /-
238 +/-
0.253
Supr**turation with rpct to Ctlcit*.

Urdrs*tur*-fcl on MI th
In figure
r**pct to2 U*ir*kit* f
LuoMontit*^
MontNori 11 orri t
17 an average temperature of 238+ 17C is
obtained
The recalculated pH is 6.8 for

a PC02= 120 kPa, for each temperature
value, the silica concentration corresponding to quartz saturation was
assumed. The obtained results are in agreement with those calculated
by the triangular diagram (Giggenbach op. cit ), classical geothermometers and gas geothermometers.
The computed pH- 6.8 is lower than such measured at the field=
8.2. It can be explained as a descompression phenomena with C02 loss.
In figure 19 the pH= 6.8 at a temperature of 240C is
with the K-feldespar and K-mica-quartz and the salinity.
consistent
In table 8 are presented the values of S I.

for Pinon de las
Papas (RP) manifestation and in figure 18 a temperature of 166 17
'C for the mentioned sample is obtained.
51
_4
-2 -
150
175
200
225
250
275
Temperature ( C)
k-chlor.
Zolstte
Prhenlte
JUb-KFeld
<>
Kpldote
FIG. 17. Saturation indexes at selected temperatures,

El Humazo (EH1).
SI
(1) Qwt*
(t) Cttuomtta
(3)
&l
(4) UrwoorlU
(8)
UfCblmiU(UUU)
(8)
_<
-3
25
50
75 100 125 150 175 200 225 250 275

Temperature ( C)
'
(D
(2)
0)
(4)
(6)
(6)
FIG. 18. Saturation indexes vs temperature,

Rincn de las Papas (RP).
52
Solution pH
8
. BTrir<il(O.OOB)
T KopU(O.OOe)
m(N+K)-0 01
Hl DOUUTO-1988
(0.060)
m(N+K)-0.1
lrlcl(0 044)
Js Brodln4(0 034)
lfoblo(0 1)
ahobra(0 07)
Crro Prllo(0.2B)
(12)
200
150
250
300
350
Temprature ( C)
FIG. 19. pH vs temprature.
TR8LE N 8
Saturation indH*s fot~ SOM*

lctd tnprtur*.
RP hot
spring, Dowuyo.
t ->c
t C
MT MP*DCII
125
ISO
175
200
0. 165
-0.01
-0.37
148
100
0.41
15 Ou*i-tr
for
S.I .-
25 2 Muscowit-3 L*UMontit*
2. -120
1.5-1
-0.27
-1.94
171
35 Huscoî t*- 3 fllfc.it*
0.45
0.6S
-0.25
-1.13
i&e
*O tluscoyi'fc*
-Zoisi t
3.65
1.82
0.10
-1.52
177
55 Muscoî t*
+ n^Chlorit
-1.32
0.05
2.97
119
0.95
0. 15
-0.52
181
65 riuffcovi t*~
- 2 fldul^ri
t - 16& +/-
14 &C
t 166 +/-
17 C
1.36
<for S.I. - 0.05

Cfor S.I. - 0.0 */- 0.255
SuperA^tur *tl on HI irh r*p*c^ t

Undrst'jrtlon MI th r**pct to!
Epldot,
Prehnlt,
Uirkit,
flnhidrit*.
53
4,
CONCLUSIONS
The important number of hot and cold springs and their relatively
high discharge, allowed to get a great number of data to formulate
an
hydrologies! model
By mean of chemical data, isotope analysis and enthalpy data
possible to calculate
the chemical
and isotopic
as
composition of
the
composition of gases
and
parent water as well as the recharge altitude
The methodology based

saturation indexes have led
the geothermal field
field
in
the chemical
to a better and more accurate knowledge of
The Domuyo geothermal field have a Hater dominated reservoir

has a central zone between
El Humaô v Los Tachos
having
The
the
parent water the following characteristics
2H (o/oo)
Oi*0 (o/oo)
t CO
-115
-13 U
220-248
O 03
PC02 (kPa)
150-300
Cl
2500
(ppm)
A second zone with a shallower reservoir comprising a more extent

area with a similar isotopic
composition
a temperature of about
170
C and a chloride concentration of ca 2000 ppm
In addition a third zone
bicarbonated waters,
typical
(Rincon de las Papas)

of
the
exhibit
strongly
boundary of geothermal aiea^
The
more reliable temperature is that obtained by using the S I

166 17C Gas geothermometers and classic geothermometers yield
higher and erratic values
Acknoiledgeients - fhis vork has been perforied mtbia the fraievork of the Hlk Coordinated Research Prograste on the
application of Isotope and Geocheaical techniques ID Geotberial Exploration in Latin tterica (Research Contract K'
3988/IG), financially supported by the Governtent of Italy
REFERENCES
Cramer S D
(1982) The solubility of methane
carbone dioxide
oxygen in brines from 0 to 300C U S Bureau of mines Report of
vestigation N 8706
and
in-
D Amore F , Celati R and Cal ore C (1982) Fluid geochemistry applications in reservoir engineering (vapor-dominated
systems)
Proc
8th
Worshop Geothermal Res Eng , Stanford University, pp 295-307
D Amore F and Celati R (1983) Methodology for
lity in geothermal reservoirs Geothermics, 12
calculating steam quapp 129-140
D Amore F and Gianelli G

(1984) Mineral assemblages and oxygen
and
sulfur fugacities in natural water-rock interaction processes
Geo-
chim Cosmochim
Acta 48, pp
857-857
D Amore F and Truesdell A H (1985) Calculation of geothermal reservoir temperatures and steam fractions from gas compositions G R
C
Symp
on Geothermal Energy
Kona, Hawaii, Transactions, 9, Part 1, pp
305-310
54
D'Amore F. (1987) Some geothermal techniques for reservoir temperature

computation. Istituto Internazionale Ricerche Geotermiche, Pisa, Italia. International
Symposium on the Development and Explotation
of
Geothermal Resources. Cuernavaca. Morelos, Mexico.
D'Amore F., Fancelli fi. and Caboi K. (1987) Observations on the application of chemical geothermometers to some hydrothermal systems in
Sardinia. Geothermics, 16, N 3 in press. 3994/IG, 55 pp.
D'Amore F. and Panichi C. (1987) Geochemistry in geothermal exploration. Applied Geothermics, Ed. by M. Economides and P. Ungemach, pp.
69-89.
D'Amore F., Nuti S., Fancelli R., Michard J. . and Paces T. (1989) Recent methamorphic and hydrothermal fluids in
Variscan structures in
Europe. Proc. 6th In term. Symp.
Hater-Rock Interation, Malvern,
UK, in
press.
D'Amore F. and Truesdell A. H. (1989) A review of solubilities and
equilibrium constants of gaseous species of geothermal interest.
Sciences Gologiques.
EPEN-INGEIS
(1987).
Informe
de avance Convenio OIE A 3988/IG.
Gianelli G., Passerini P. , Troisi C. and Zan L. (1989) Geothermal deep

exploration in Djibouti:
Stratigraphy, authigenic mineral assemblage
and temperature data of the drilled wells. Structural data from the
Asal rift. Geothermics. In press.
Giggembach W. F. (1980) Geothermal gas equilibria.
Acta 44, N 12, pp. 2021-2032.
Geochim.Cosmochim.
Giggembach H. F. (1986) Graphical

techniques for
the evaluation of
water/rock equilibration conditions by use of Na, K, Mg and Ca contents of discharge waters. Proc.
PP. 37-43.
8th New Zealand Geothermal
Horshop,
Gingins, Mario (1986) Estudio Geoquimico-Isotopico de los Fluidos Geotermales de la Provincia del Neuqun (Convenio OIEA 3988/IG).
Ente
Provincial de Energia del Neuqun, Neuqun,Argentina.
Helgenson H. C., Delany
Summary and critique of
minerals. Amer. Journal
J. M., Nesbitt H. . and Bird D. K. (1978)

the thermodynamic properties of rock-forming
of Science, Vol. 278, A, pp.
729-804.
Henley R. M . , Truesdell A. H. and Barton P. B. , with a contribution of

Whitney J. A. (1984) Fluid Mineral Equilibria in Hidrothermal systems.
Reviews in Economic Geology, 1. Published by the Society of Economic
Geologists.
JICA-COPADE (1982-1984) Proyecto de Desarrollo Geotrmico en la
Norte de la Provincia del Neuqun-Domuyo.
Zona
Michard G., Ouzounion G. , Fouillac C. and Sarazin G. (1979)

Contrle
des concentrations d'aluminum dissous dans les
eaux thermales. Geochim.Cosmochim. Acta 43. pp. 147-156.
Michard G. and Roekens E. (1983) Modeling of the chemical
of alkaline hot waters. Geothermics, 12, pp. 161-169.
composition
Panarello H. , Albero M. and Levin M. (1987) Informe preliminar de los

resultados isotpicos del Area de Domuyo. Convenio OIEA 3988/IG.
Institute de Geocronologa y Geologia Isotpica, Buenos Aires, Argentina.
55
Sierra J.L
and Pedro G. (1987) Estudio Geoquimico e Isotopico de los
Fludos Geotermales de la Piovincia del Neuquen-Domuyo
(Convenio OIEA
3988/IG)
Wolery
aqueous
Ente Provincial de Energa del Neuquen, Neuquen, Argentina

J
(1979)
solution and
Livermore Laboratory
56
Calculation
minerals
of
chemical
the EQ3/6
equilibrium
software
package
between
Laurence
FLOW PATTERNS AT THE TUZGLE-TOCOMAR GEOTHERMAL

SYSTEM, SALTA-JUJUY, ARGENTINA
An isotopic and geochemical approach
H. PANARELLO
Institute de Geocronologia y Geologfa Isotpica,
Buenos Aires
J.L. SIERRA, G. PEDRO

Ente Provincial de Energia del Neuqun,
Neuqun
Argentina
ResumenAbstract
MODELO DE FLUJO EN EL CAMPO GEOTERMICO DE TUZGLE-TOCOMAR, SALTA-JUJUY,

ARGENTINA: ESTUDIO ISOTOPICO Y GEOCHIMICO.
En este trabajo se han ernpleado tcnicas isotpicas

(tritio.
deuterio y oxigeno-181 asi como anlisis quimicos de aniones y cationes mayoritarios y minoritarios y anlsis de gases para establecer
las condiciones hidrogeolgicas y las tempera taras de reservorio.

Los contenidos en isotopos estables exhiben una buena correlacin
con la altitud y permiten diferenciar las areas posibles de recarga.
Debido a las condiciones climticas altamente rigurosas del
ambiente Puneno, como gran ampli tad trraica, baja humedad y prs ion atmosfrica y escasa precipitacin,
se producen importantes fraccionamientos cinticos fundamentalmente en oxigeno-18.
La termometria gumica de slidos disueltos y gases, definen

area como un sistema de baja a media entalpia con temperaturas de
servorio del orden de 90 a 140C.
el
re-
FLOW PATTERNS AT THE TUZGLE-TOCOMAR GEOTHERMAL SYSTEM, SALTA-JUJUY, ARGENTINA: AN ISOTOPIC AND GEOCHEMICAL APPROACH.
Environiental isotopes '#, *ff and J'O, aajor and linor anions aad cations, and gas analysis have been
lade in order to establish hydrological conditions and reservoir tetperatures.
Isotope contents of gaters, 2S, ISO shon good correlation sith altitude and alloy to differentiate the possible
recharge areas.
Due to the rigorous feather conditions prevailing at the high altitud in the Puna environtent i.e. great theraic
amplitude, los precipitation, los huaidity and ataospheric pressure, gross kinetic fractionation aainly in oiygenIS has been found.
Chetical of dissolved solids and gas geotheraoieters define the area as a lov to lediui entalpy mth reservoirs
teiperatures range fron 30 to 140'C.
Circulation of cold and bot water shots a pattern vhere are recreated tost of cases of stable isotope fractionation.
57
l.
INTRODUCTION
The area under study is

located in
the border zone of
the
provinces of Sal ta and Jujuy at the AW of the Argentine Republic
The
geographic coordinates are aproximately
24 S and 66 30 H The area
covered is ca 400 km2, where the thermal manifestations of El Tuzgle,
Tocomar and Pompeya are located
The higher picks, correspond to the
Tuzgle Volcano (5500 m) and to
the Colorado creek (5220 m) The zone
is extremely arid and the basin have no drainage
field
The climate is particular, since that the average ctltitLide of the

is more
than 4500 m a s l
Tempratures are
very low all
the
year long, showing a daily
amplitude
as big as 36C
The main town is San Antonio de los Cobres, if ff m a s l

distant
25 Km from the geothermal field
A 4 yeat record of the meteorological
conditions for
this town
Average annual
account
for
the following
temperature
ti 8C
Average annual atmospheric pressure

Highest temperature
Lowest, temperature
649 hPa
27C
16"C
Average annual precipitation
13 mm
Freezing frequence
223 day/year
In the gothermie area studied

800 m above, the climatic condi
tions are by far
more rigurous Hinds prevailing fiom H-NW and W-SW
have a velocity between 2-20 m/s, blowing during 10 to 18 hours per
day
ifrom
the geological point of
view the region presents metamorphic
and cristaline rocks from the Proterozoic Eruptive rock with great
significance have been originated
in four
principal
phases,
i e
Dacitic eruption
of
the Upper
Miocene
(old dacites),
eruption
of
andsites during
the early
to medium Pliocene,
early Pleistocene
dacites (new dacites) and finally, eruption of basalts in the Bolocene All this metamorphic
cristaline sedimentary and eruptive
rocks
were affected
by tectonic movements
Tertiary
diastrofism
of great
intensity, have masked the less important effects
of other precedent
diastrophic cycles
2.
METHODOLOGY
The samples for
this work were collected at an area of about
400
km2 comprising all

the thermal manifestation
of Tuzgle, Toc^nar
and
Pompeya (map 1) on October, 1989 and January
1990 9 cold waters and
17 hot water samples
8 corresponding to hi Tuzgle, 6 to Tocomar, 3 to
Pompeya and 7 samples from creeks
pH and conductivity were determinated at field
Fe, Mn, Al
Na+,
+
::
K+, Ca2 + , Mg2 + , Li . As. NH3 , S = , S04 . C03=. HCO3~, Cl~, FBand
SiC>2 at
the Administracion Provincial del
Agua (APA) and tritium,
deuterium and oxygen-18 at the Institute de Geocronologia y Geologia
Isotpica (INGEIS)
(Tables 1, 2, 3 and 5)
58
Toeomar
TOP 3 (4262. I SO) r?
TOFt(4324.13B)
MAP 1
59
TRBLE N
1:
CHErilCHL RNftLVSIS OF UfiTER SRHPLES FROH FUZGLE.
i ruc-i : ruc-2 : ruc-3 : ruc-1: TUC-S : ruc-6 : ruc-7 : Tuc-8 : TU
56
6630
3220
3950
6.2
6.7
6.1
; 111
: 1110 : 2120
: us ; 101
110
100
808
9i
: mo
; 89
: 0.70
; 0.72
Na
900
; 0.37 : 0.37
: sso ! 690
13l
C*
Hg
:
:
Si 02
:
:
101 i
is
:
72
:
68
;
13
:
Rx
10
; o. 17
T CO
19
coNDUcr. : soo o
pH
HC03
Cl
501
F
lin
M2S
NH3
6.1
370
; 18.5 ;
15
12
39
: 6710
6170
6.0
6. i
126
2220
80
11
! 6300
:
:
: 6.1 ;
: 118 : 132 :
: 2000 : 2000 ;
1
7l
63
13
7.9
72
13
ls
98
;
:
ig
73
ei
17
:
:
83
17
72
is
12
13
5.20
3.90
12
7.2
91
2.6
6.3
2.3
2.2
:
:
6.5
2.2
:
i
51
39
11
11
2.8
10
1238
80
;
;
:
88
22
75
;
;
;
6i
11
10
:
:
:
95
:
:
76
16
: 2.5
: 0.30
;
:
11
; 0.08 :
7.10
; 7.20
: i. 80 : o. 10 : 0.32 l 0.23 ! 0.32 : < o . i :

: 2.20 ; 2.00 l 0.57 ; 0.68 : i.io ; 1.30 : 1.10 : <o.os :
: 0.22 ; 0.22 ; <o. i 1 <0. 1 l 0.29 : <o. i ; <o. i :
:
;
; i.io ; 1.30 : 0.16 : 0.58 : i.oo : 0.92 : i.oo ;
Corfrn-fcr-ti on*
311
:
;
:
22
75
31
190 :
73
:
75
;
;
7.9
; 11
: 75
; 32
: 11
; 7.10 ; 9.20
9.5
62
21
71
6.1
111 :
123
750
1250
: 0,10 : 0.15 l 0.62 : <0.20 :

: 1260 : mo
; 1120 : 13
;
; 137 ; 123 : 129 : 9.3 :
1230
0.12
:
:
16
10
11
: o.si ; 1.7
: 0.01 : 0.17
: <o.02 : 0.08
: 0.22
r in
TUF-I
:
:
:
;
:
:
;
13
592
36
ruF-2 ; ruF-3 :
12
;
8
:
;
108 : 183 ; 329 :
6.1 : 6.7 l 7.6 !
36
: 182 : 113 :
7 . 1 : 18
: 11
:
: 32
;
5.9 : 33
<o.20 ; <0.20 : <0.20 !
f l r -i: TU flr-2!
'
122
7.0
so
6.1
11
<0.20
; 0.63
; 0.13
: 0.01 : 0.03
: <o.02 : <o.o2
:
'
'
'
TflBLE N 2: CHEniCRL HNRLVSI5 OF UHTER SRMPLES FROH TOCOHRR.
! TOC-3 : TOC-4 : TOC-5 : TOC-6 !TO flr-1! PO flr-2! TO flr-3! TO fir-4! TOF-l i TOF-3 ! TOF-4 ! TOF-5
! TOC-1 TOC-2
i
;
CONDUCT . :
:
pH
HC03
:
Cl
:
S04
:
F
:
T CC>
N*
:
:
:
;
:
:
:
:
:
:
:
C*
ng
Si02
8
Li
R*
F*
n r,
H2S
NH3
i 62
: 57 : 55 : 60
35
: 45
3680 : 3640 ! 3640 ! 3640 ! 3640 : 3300
6.7 ; 6.5 ; 6.8 i 6.6 ; 6.6 : 6.8
725 : 730 ! 740 ! 720 : 720 : 700
808 : 828 i 828 ! 828 : 828 : 727
192 : 185 : 187 i 183 : 166 i 176
1.40 : 2.80 : 2.40 ! 1.50 i 2.50 ; 2.30
740
: 730
65 : 64
7.3 i s.e
4.2 : 4.2
67
: 67
42 : 43
10 : 10
o.64 : 0.87
0.12 : o.ii
<o.os : <o.os
0.35 ; 0.67
8.40 : 8.00
740
! 740
:
:
:
:
:
:
66
12
: 66
: 8.6
: 3.7
i 66
; 44
: 10
:
:
;
:
:
i
: 0.64
3.7
69
44
10
i 0.79
725
17
: is
1734 : 1190
7. s ; ?.i
352 : 247
339 ; 218
104 : 199
i . 70 :1.20
342 : 215
30 : 20
17
: 28
6.4 ! 5.2
:
20 : 13
69
: 61
12 : 5.8
3.6 : 5.6
6i : 55
44
; 38
10 : 9 ; 4.50 i 2.80
0.50 : 0.73 : 0.44 ! 0.23
: 0.18 ; <o.i : 0.29 :

; <o.os : <.o.os : <o.os :
! 0.55 : 0.67 : i.io :
: 8.80 I 8.80 ! 7.60 :
r in ng/1.
650
;
;
:
;
;
:
;
;
:
i
:
:
:
0.16
<0.05
0.42
7.60
:
:
:
i
'
'
: 14
: 4970
: 6.2
0.5
1013
! 8.2
! 965 ! 321
! 1162
: 154
i 229 ! 52
1 i.oo
: 1.40
1 1125
: 175
: 98 : is
: 4.4 : 22
! 5.1
: 18
:
:
: 64
12
: is
: 2.90
: 1. 10 : 2.30
i
:
'
!
;
'
;
'
!
i
: 104
: 7.3
: 44
: 6. i
: 5.9
: <o.20
: 5.5
: 2.4
: 11
: 1.8
: 6.7
: 0.33
: 0.03
! <o.o2
: 0.13
; <o.os
: <0.1
i
11
: 420
: 8. l
: 197
; 14
: 47
: 0.25
: 27
: 4.2
: 24
: 24
! 222
104
: 7.2 !
: 76
:
; 11 :
; 30
6.5
<o.20
; 16
: 2.8
: 23
: 2.9
!
:
: 0.90 ; 0.76
: 0.24 : 0.07
: <o.o2 ; 0.05
:
:
:
:
:
:
;
:
:
:
:
l
!
:
i
:
:
:
fflBLE N 3: CHEniCflL HNfiLVSIS OF UflfER SRHPLES FROh

POHPEVR - niNfi BETTV - SEV
r c<C3
CONDUCT.
: pool : POC-2 !
:
so
: 35
!
: SEID : 6110
52
5670
: 6.7
: 1210
: 1262
: 298
:
:
1120
1338
0.80
1187
:
:
;
:
:
;
111
Li
; 0.70 i 0.90
: 1200 : 1350
; 109 ; 128
: 8.9 : 11
: 21
: 25
; 11
; 16
: si
: 60
: 11
: 13
fll
: 7.30
i 7.80
i 9.20
: i.io : 0.30
: 0.12 ; 0.22
: 0.16 : o. 16
! 2.60
: i.eo
1 <0.1
pH
HC03
Cl
S01
F
N*
K
C*
rig
Si02
B
Hn
H2S
NH3
: 6.5
: lose
: 136
: 25:
on* -r
6.8
251
SEV
12
230
:
:
7.0
57
:
:
26
28
: <o.2
i
15
121
23
1.6
22
3.7
:
:
7.7
26
:
:
53
25
15
:
:
11
23
61
51
56
II
1.8
12
12
2. 10
; <o.o2
0.56
<0.1
: <o. i
11
i 0. 15
:
:
; PO flr-i; ne
; 19
: 20
: 5950 ; 1307
: e . i ; 6.7
: 1077 : 162
; 1161 : 317
: 278 ; 31
: o.80 : <0.2
: 1325 : 180
; 7.10 ;
i <o.i :
; <o.os :
<0.05 i
<0.02
<0.05
0.55
; <0. 1
1.30
; <0. 1
: <o.i
<0. 1
l n Mg/1 .
FfiBLE N 1:
GRS RNHLVSIS FROH
ruc-ii
TUC-2
ruc-s
roc-3
TOC-1
roc-5
98.11
99.10
C<0.093
95.80
99. 1
0.093
C<0.093
99.35
C69.323
95.93
C<0.093
ND
C-3
<0.0002
C-3
0.035
c-o
0. 16
<->
C80.9S3
0.16
C68.713
3.99
C87.683
7.22
C37.373
0.31
C21.993
02
0. 16
C18.733
0. 11
C31.033
0. 17
Cll. 86)
0. 10
C7.573
CH1
0.01
CO. 285
<0.022
CO. 253
0.0305
CO. 11>
0.53
H2
<0.001
CO. 00 13
<0.001
CO. 0025
H.
0.01
CO.O351
<0.002
CO. 01?
C02
C<0.093
H2S
<0.0002
C-3
N2
62
POC-3
1.11
0.01
C-3
POC-1
91. 18
'KO.og 1
POC-2
91.11
C<0.093
0.03
C-3
0 . 005
C-3
3.51
C82.25J
5.56
C91 .96)
C93.S83
0. 13
C2.013
0.06
Cll. 893
0. 18
t?. 573
0.20
C5. 753
C5.013
0.0201
C3.593
0.3733
C5.813
0.0399
CO. 123
0.011
CO. 313
0.001
CO. 00 13
<0.001
CO. 0063
0.001
(0.08793
<0.001
CO. 0123
<0.001
CO. 0005)
<0.001
C<0.001)
0.0031
0.0012
C.O113
<0.002
fO. 00973
0.002
CO. 0363
O.O2
CO. 018)
0.0072
C<0.063
co.osn
a. 61
TOBLE N 5:
ISOTOPIC ftNflLVSIS OF THERflflL fiND COLD UfiTERS.
! SflrtPLE : LOCflTION !flLTITUDE!OKVGEN-l!3 DEUTERIUH ! TRITIUM

.> + /-! : CTU>/-0.6
a . s . 1 :X.3X-0.2!
. .' (
! H
: Tuc-i
: Turgl*
! 1190
: TUC-2
! Turgl*
: TUC-3
! Turgl*
: TUC-I
! Turgl
! TUC-S
! Turgl*
: TUC-6
! Turgl*
! 1190
! 1190
! 1190
! 1220
! 1220
: TUC-7
! Turgl*
! 1190
1218
1218
!TU ftr-l ! Turgl v
: TU ftr-2 ! Turgl*
: Toc-i
! TocoHar
! 1230
: TOC-2
TocoMar
1230
-9.6
!
: -9.2
; -10.2
: -9.9
: -9.1
: -9.2
i
-8.9
: -9.0
: -9.5
: -lo.i
: -10.3
:
:
;
:
:
:
:
:
!
:
;
-76
-76
0.0
-77
0.0
-77
-77
-76
-77
-72
-77
-81
-81
-81
-si
:
:
:
:
:
:
-86
-79
-79
:
:
0.0
0.0
: TOC-3
! TocoHar
! 1230
: -10.2
: TOC-I
! Tocowar-
' 1250
-10.2
: TOC-5
! Toconar
! 1250
: TOC-6
! Toconar
! 1250
-10.3
-lo.o
:
:
!TO fir-l ! TocoMar
-9.1
: TO flr-2 ! TocoHar
:
:
:
:
-79
: TO fir-3 ! TocoMar
-8.1
-8.2
-79
-7.0
-79
-lo.i
-10.2
-10.6
-9.1
-9.8
:
:
:
:
:
-81
-82
-83
-79
:
:
:
:
-76
0.0
-76
0.6
:
:
-75
1.5
-79
2.1
-83
0.0
:
:
:
:
:
-83
0.0
-83
2.1
-76
o.o
-77
0.1
-77
0.0
!TO flr-1
! TocoHar
IPOC-1
! PoHp*ya
! 3838
: POC-2
: poc-3
! Ponp*u.a
! 3836
I PoHp#y
3838
!PO flr-1
! Pop.ya
i 3838
: TUC-S
i Turgl*
1160
TUF-2
! Turgl*
TUF-3
! Turgl*
i TUF-1
! Turgl*
1160
1261
1700
: MB
JSEV
Mi n* B*fc-ty !
:s*y
1025
i TOF-1
\ TocoM*r-
1701
! TOF-3
Tocoh**r-
1262
! TOF-1
! TocoHar
1321
: TOF-5
! TocoHar
! 1380
: -10.0
: -10.2
: -10.1
: -10.1
! -11.7
; -11.7
-9.3
!
: -9.5
! -10.7
63
3.
3.1. PHYSICOCHEMICAL
CHARACTERISTIC OF THE HATERS
3.1.1. TZGLE
There is chemical similitude between hot water samples TUC-1. 2,
3, 4, b, 6, 7 snd the
TU Ax - 1 creek obtained down stream the
thermal
manifestations
They are alkaline clorurated and can be classified
according the salt content into two subgroups:

I. Conductivity between 5000 and more than 6700 uS/cm. samples TUC-1 ,' 2, 5, 6 and 7
11. Conductivity between 3200 and 4250 uS/cm. samples TUG 3,
4 and TU Ar-1
pH of samples belonging the subgroup I is slighty lower (6.0-6.2)
than those of the subgroup II (6.4-7 9) The temperature of all hot
waters oscilate between 39 and 56C.
The other set of samples are of
cold
water
TUF 2,
3.
and
the
TUC-8.
All
they
are
alkaline
bicarbonated, pH between 6.1 and 7.6 and conductivities between

and 592 uS/cm, with exception of TUF-4 (122 uS/cm)
329
Finally the sample of the TU Ar-2 creek sampled upstream

thermal manifestations is bicarbonated aIka1ine-terrea1 alkaline.
pH is 6.4 and the conductivity 108 uS/cm.
Concerning TUC-8, it was sampled and classified as thermal water,
but latter due to its physicochemical caracteristics, was considered
like a cold water with superficial circulation.
3.1.2. TOCOMAB
Hot waters at Tocomar TOC-1, 2, 3, 4 and 6 constitute an homogeneous group from the chemical point, of view. They are sodium clorurated. Temperatures oscilate between 35 and 62C and conductivites bet
ween 3300 and 3700 uS/cm. Their pH range from 6.b tc 6.8. Creeks samples TO Ar-1, 2, 3 and 4 are the result of a mixing among thermal and
cold waters.
TO Ar-3 is still more concentrated than the thermal manifestations
It
can
as
be
explained
as
result
of
the
process
of
evaporation,
demostrated by the iso topic content of the samples (see forward)
Cold water samples TOF-1, 3, 4 and 5 are bicarbonated-terreal

alkaline. Their conductivity oscilates between 5600 and 6450 uS/cm
Temperatures range 35
to 52C
Sample
of the creek
PO Ar-1
is
more
alkaline (pH= 8.1), 5950 uS/cm and a temperature of 19C

In addition two sampled
waters at Mina Betty
and Sey, have
the
following characteristics:
Mina Betty: alkaline clorurated, high calcium and magnesium, pH~

temperature 20C and a conductivity of 1.3 uS/cm.
Sey: Ca -Mg-Bicarbona ted, pH- 7, T- 12"C and a conductivity of 230
fi S/cm.
6.7,
3.2. ISOTOPE HYDROLOGY

3.2.1. METEORIC LINE AND MIXING LINES.
With data of rain samples taken at Mina Providencia at similar

altitude and climatic conditions the local meteoric water line is
obtained. Points fit on a straight line whose parameters are
64
slightly
diffrents to those of the world meteoric water line defined bj(1961)
o/oo
2H- 7 8 1&U + 13
Samples falling
t> )
Craig
They are
The remaining
closer this meteoric line are TOF-1 and SEY (fig
samples are located
under the m l
evaporation phenomena after precipitation

of 3-6 characteristics of very dry zones
-6
They fit
mainly due
lines with
to
slopes
Delta Oxygen-18 (% )
4
D
3
2
D
I
n
(y-o oa)
10
3-t
2-8
11
12
200
400
600
800
1200
1000
1400
Chloride (ppm)
TOF
4- TOC
POC
TOAR
TUF
FIG 1 Chlonde-oxygen-18
-75
' 28
XX
-77
4
-79
n__ru
ErmporvtloQ
-81
(Y--0 08)
-83
-ffZ-3-4
-85
-f
-87
200
TOF
400
600
BOO
Chloride (ppm)
TOC
POC
1000
TOAR
1200
1400
< TUF
FIG 2 Chloride-deuterium
65

-8.3 i
-fl.8
-9 3 L',
2
-9.8 r-x'
-10 3,
-10.8
-11 3
-11.8
1000
1500 2000
Chloride (ppm)
500
TOF
TUF
TUC
2500
TUAR
FIG. 3. Chloride-oxygen-18.

-72 0 -
-84.0
500
1000
Chloride (ppm)
' TOF
TUF
+ TUC
FIG. 4. Chloride-deuterium.
66
1500
n
TUAR
2500 2000
-65 -
-12
-115 -11
TOF
-105
-10
Delta Oxygen-18 (% )
TUF
-95 -9
-8 5
WORLD METEORIC WATER
FIG. 5. Oxygen-18-<Jeuterium
Samples of hot Hater from

El Tuzgle
(fig 6), have a trend
towards more positive values of S^Ô, however the limit between cold
and hot waters is not sharp No oxygen-18 shift is observed due to the
relative low reservoir temperature and to the kind of rock of matrix
mainly siliceous
Samples at Tocomar and Pompeya (fig 7) are diffrents to

of El Tuzgle with an apparent oxygen-18 shift
those
In the 6180 vs Cl - and O^H vs Cl- plots (fig I and

2)
corresponding to the Tocomar-Pompeya zone, two diffrents groups one
for each zone is evidenced There are no evidences of mixing between a
ffeothermal fluid and shallow waters, neither in Tocomar nor in Pompeya Only samples at the Tocomar creek and their tributaries allow to
see clearly that TO Ar-1 is the sum of the contributions of TO Ar-2
3, 4 and cold waters (fig 2) but they are separated from the source
thermal manifestation due to a strong evaporation process This fact
is also evidenced in the ^H, i *0 plot (fig 7)
At the Tuzgle area a mixing line between a geothermal fluid as

TUC 2, 6, 5 and 7 with shallow cold water (isotopically similar to
that of the creek) is evidenced Concerning samples of the TU Ar-2
creek, this would correspond to a shallow circulation, while TU Ar-1
to a mixing of TU Ar-2 type waters with a geothermal fluid The slope
of the mixing line is higher, since is repeated the phenomena described in Tocomar due to the evaporation of the creek With dashed line
the evolution due to this phenomena is indicated
67
-59 0
-640
--69 0
l
D
-740
+V
-79 0
3 3-
-84 0
- -L
-69 0
-13
-12 5
-12
-115
-11
95
-105 -10
B5
DelU Oxygen-18 (7. )
TOF
TUC
TUF
TUAR
FIG 6 Oxygen-18-deuterium
-60 0 -65 0 -
IJ D
-85 0
- 9 0 0 'L L -
' '
*
'
i
-13-125-12-115-11-105-10-95
-t
-i
_i
J -i
-9-85-8-75-7
65
Delta Oxygen- 18 (X.)
TOF
TOC
POC
TOAR
>
TUf
FIG 7 Oxygen-18-deuterium
J ^. 2
RECHARGE AREAS
In fiff
8 the 62H is
plotted a fa in the dltitude of zechazge
If
samples corresponding to Mina Betty and El S?y ?2~e not considered (the
altitude of the recharge is not veil known)
the following equation j s
obtained
62HIt
68
by linear regression a
1 47 x 10 2 h - 11 3 o/oo
means a variation of about 1 b o/oo per
1 OU m altitude
Recharge altitude (m x 1000)

5.4 -
-88
84
-88
-82
-80
-78
76
-74
-72
-70
TOP
TUF
FIG. 8. Deuterium-altitude.
In the case of the oxygen-18 vs altitude plot (fig. 9) also samples TUF-4, TOF-3 and 4 have been excepted due to the evaporation that
affects
mainly the oxygen-18 content.
The resulting equation is:
Oi8O= - 0.30 x 10-2 h + 2.9 o/oo
With a variation of
0.3U 180/100 m.
As result of this correlations the following altitude of recharge
were determined:
62H
0180
4500 m
5000 m
Tuzgle --------- 4400 m
Tocomar -------- 4900 m

Mina Betty ----- 4800 m
Sey ------------ 4800 m
Recharge altitude (m x 1000)
5.4 -
5.2
-12.5
-12
-11.5
-11
-10.5 -10
-9.5 -9
-8.5
-8
Delta Orygen-lB (%.)
TOF
TUF
FIG. 9. Oxygen-18-altitude.
69
Tritium (T.U. +/-
0.6)
3 r
TUF-4-rOF-l
2
TUF-3
TUF-2
TOF-4
TOr-3
TUC-5
TUC-8
TUC-3
TUC-7
ffr
500
1000
1500 2000
Chloride (ppm)
2500
FIG. 10. Chloride-tritium.
The altitude of
the sampling point of Nina Betty suggest
that
water emerge from a point distant to the recharge zone The tritium
content T- O T.U. confirm the hypothesis.
The same consideration is
valid for El Sey.
In the map 2, the probable recharge zone in accordance with the
isotope data are located. In map 3 the possible recharge areas having
into account the hidrology are indicated
3.3. AQEOS PHASE THERMOMETRY

In table 6 maximum, minimum and average reservoir temperatures as
computed by diffrents
geothermometers in liquid phase are showed. The
following conclusions may be outlined:
- The Na-K geothermometers yield excesively high
temperatures
because the equilibrium Na-Feldespar
-K-Feldespar is
not achieved.
These thermometers are reliable only
to temperatures over 150C,
not
probable in this case.
The Na-K-Ca is
not applicable too because although more complete than the Na-K. also require equilibrium between feldespars.
- Temperatures obtained from K-Mg geothermometer may be
conside-
red as reasonables. The K-Mg couple equilibrates faster and at
lower
temperatures than the couple Na-K In addition the measured activities

are not
in
correspondence
with a high
temperature system,
being
correct the interpretation of such equilibrium.
- Temperatures
yielded by the Na-Li
geothermometer are rather
high. This fact is due to their calibration in granitic systems.
70
AREA 06 RKARGA PROBABLE
AREA DE RKAR&A PROBABLE
PARA
AGUA CALI6NTE DEL
PARA ZONAS DE ' TOCOMAR r POMPEYA'
MAP 2
71
3ASAMEN 0
MLY PERMEABLE
FA A ERJPT A
FCRMACON CO C*
FORM AC ON PJNCC"i!SCÂ
, BASAL O
FORMAL ON
MEDIANAKNTE
POCO PERMEABLE
MpfRMEAatE
ANCCSinS
Q A C I T A S Y SLBuPUPO P
F O R M A C ^ ^ CAUCH^PI
F RMAC ON PASTOS CHCOS
MAP 3
72
RINCHERA
TABLE No. 6. GEOTHERMAL RESERVOIR TEMPERATURE BY

CHEMICAL GEOTHERMOMETERS
GEOTERMOMETROSJ
AC4
AC5
Na/K (F)
178.9
187.4
188.5
198.6
173.3
176.0
228.2
232.4
175.9
NA/K
140.9
151.0
152.5
164.7
134.2
137.4
201.8
207.1
136.7
177.5
177.5
183.4
186.6
176.0
178.7
211.3
225.5
159.7
Na-K-Ca (Mg)161.6
168.9
159.1
137.6
172.8
174.2
206.1
225.5
29.7
Na-Li
134.6
138.3
145.3
141.0
138.6
144.6
143.0
227.7
131
133.4
.2129.8
118.8
151.1
149.8
168.9
212.8
101.2
(T)
Na-K-Ca
K-Mg
148.1
AC6
BAC 7
LO
LTI
LTI2
EHI
RP
Mg-Li
209.9
198.2
194.3
175.6
242.7
236.1
233.1
297.5
151.1
TQC
174.3
165.4
178.2
172.0
177.5
181.6
168.8
191.2
149.6
TQA
163.6
156.2
166.7
161.6
166.2
169.5
159.0
177.3
143.8
TCH
152.4
142.2
156.8
149.7
156.0
160.8
146.0
171.9
124.3
Na/K (F):
Fournier
Na/K (T):
Truesdell
Na-K-Ca (Mg): Correction for Mg
TQC:
TCH:
Quartz without vapour loss

Chalcedony
The temperature is expressed in C.
- Silica geothermometers shows a probable equilibration with

chalcedony for El Tuzgle and Tocomar, while that in Pompeya the equilibrium is controlled by the christobalite, if is considered that the
water produced by the well have a temperature similar to that of the
reservoir.
3.4. GAS PHASE THERMOMETBY
The sami empirical geothermometer developed by Panichi, D'Amore
(1981) is used. Its error is 15C and gave reasonable values at
high temperature geothermal manifestations. In addition,

ratio (fas measured on thermal manifestations zones.
gas/water
Pompeya: The calculated temperature is 71 15C and the maxichemical composition is typical of low
enthalpy manifestation, and probably connected to the boundaries of
the geothermal field.
mum possible is 91C. The gas
73
Tocomar The geothermometer indicates a temperature of 139 15

The gas/water ratio decreases from west to east, in agreement with
the reservoir geometry
Although,
the gas/water ratio
is low in
all
the area along, in agreement with the calculated temprature

Tuzgle The calculated temperature are lower (80 C) than those
of Tocomar area In this zone, there are interferences with a shallow
cold water acuifer The gas/water ratio increase from north to south
CONCLOSIONES
Nina Betty The origin of the thermal anomaly is a deep circulation, with a heat exchange between rock and water The calculated re
charge altitude is 4800 m a s l
It is not completely explained the relatively high value of t80
Sey In this point,
the sample has got an isotopic composition
similar to TOF-1 The chemical analysis indicates that it was not
heated during its circulation
The calculated recharge altitude is
4800 m a s l , therefore the distance between the infiltration zone
and the discharge point is big
Tocomar Is a medium enthalpy geothermal reservoir,
with a
calculated deep temperature of 134~143C and a low gas/water ratio
the fluid conductivity of 3300 3680 uS/cm
The calculated recharge
altitude 5000 m a s l There are neither mixed geothermal fluids nor
shallow water detected
Tuzgle The conditions seems to be similar to those of the Toco
mar area a calculated deep temperature of 132-142"C A low gas/water
ratio but a higher fluid conductivity (up to 6 7 mS/cm) The recharge
altitude is 4500 m a s l The sampled water is a mixture between re
servoir fluid and shallow cold water
Pompeya The sampled water is similar to the well water in the

vicinity from a chemical and isotopical point of view In that way is
possible to say, they originate in the same reservoir
with a
temperature close to that measured at the well head (52"C)
ackaotledgefeats - Part of this sort has been perfoned mthin the fraiesor of the lS Coordinated Research Prograite
on tie Application of Isotope and Seochetical Techniques in Geotherial Exploration in Latin Aienca (Research Contract
' im/IG), financial!? supported b? the Coteraient of Italy
REFERENCES
Arias J (1979) Areas hidrotermales de las piovincias de Salta y

Jujuy
V Convencion Anual Nacional de la frederacion Argentina de
Geologos
D Amoie F and Panichi C (1980) Evaluation of deep temperatures of

hydrothermal systems by a new gas geothermometer Geochim cosmochim Acts vol 44, pp 549-556
D Amore F and Panichi C (1987) Geochemistry in geothermal exploration Applied Geothermics, Ed by M Economides and P Ungemach,
pp 69-89
74
4. Hidroproyectos S.A. SETEC S. P L -CEP1C S C con la colaboracion de

Geologia de Servicios S A (1985) Estudio de la Segunda Fase de
Prefactibilidad Geotrmica del Area denowinada Tuzgle, Departamento
de Susques.
International Atomic Energy Agency (1981) Stable isotope hydrology

Deuterium and oxigen-18 in the water cycle
TRS N 210, pp 103142, 223-240. 241-271.
6. International Atomic Energy Agency (1983) Isotope techniques in the

hydrogeological assessment of potential sites for the disposal of
high-level radiactive wastes. TRS N 228, pp 44-57
7. Vilela C. (1969) Descripcin geolgica de la Hoja 6C, San Antonio

de los
Cobras, Provincias de Salta y Jujuy
Direccion General de
Geologia y Mineria, bole tin N 110
75
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA

DE LACUNA COLORADA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per l'Energia Elettrica,
Pisa, Italia
M. ALVAREZ
Universidad Mayor de San Simon,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE LAGUNA COLORADA, BOLIVIA.

La zona geotrmica de Laguna Colorada esta situada en el extremo sur de
Bolivia, cerca de la frontera con Chile y con la Argentina.
Hasta la
fecha
se han perforado cinco pozos de sondeo:
API, SM1, SM2,
SM3 y SM4; salvo el ultimo, todos los dems son productives.

La composicin quiraica e isotopica de los fluidos obtenidos es casi idntica a la
del
campo geotrmico de El Tatio (Chile), que se encuentra a poco
mas de 20 km de alli.
La verdadera diferencia entre los dos campos consiste en las actividades
de superficie:
contrariamente a lo que ocurre en El Tatio, ninguno de los
caudales trmicos de Laguna Colorada muestra una penetracin importante en la

fase liquida profunda;
tan solo unos cuantos manantiales trmicos al borde
del salar de Challviri, a unos 10 km al SE de los pozos, tienen una ligerisima

contaminacin.
vada de la
Sin embargo, hay varias zonas con entrada de vapor y gas deri-
separacion en la
fase profunda:
estanques calientes y fumarolas
forman sistemas irapresionantes que se localizan cerca de los pozos SM1, SM2 y
SM3 (zona de Sol de Mariana), y a 10 km al 0 de los pozos (zonas de Huaylla Ja-
ra y Aguita Brava).
GEOCHEMICAL REPORT ON THE LAGUNA COLORADA GEOTHERMAL AREA, BOLIVIA.
The
geothermal
area
of
Laguna
Colorada
is
located
at
the
southern end of Bolivia, near the border with Chile and Argentina.
To date five boreholes have been drilled: A P I , SM1,
and SM4; except the last one all
SM2,
of them are productive.

77
SM3
Chemistry and isotopic composition of the produced fluids are

almost
identical
to those of the geothermal
field
of El Tatio
(Chile), just over 20 km away from there.
The
real
difference between
the two
fields
regards
surface
manifestations: otherwise than at El Tatio, no thermal discharge

of
Laguna
phase;
Colorada
only
shows
few
thermal
substancial
springs
at
inflow
the
of
edge
deep
of
liquid
Salr
de
Challviri, some 10 km to the SE of the wells, have a very little

contamination.
Several
are
instead
the
zones with
an
inflow
of
steam and gas derived from phase separation at depth: impressive

systems
formed
by
hot
pools
and
fumaroles
occur
in
the
neighbourhood of SM1, SM2 and SM3 wells (Sol de Manana area) , and
10 km to the W of the wells (Huaylla Jara and Aguita Brava areas).
1. Lineamiento
historico
della
exploracin
geotermica
en
Bolivia
Como todos los paises de la cordillera Andina, Bolivia pose
condiciones
geolgicas
muy
favorables
para
la
explotacin
de
fuentes geotrmicas para generar energia. El gobierno de Bolivia,

tomando
en
cuenta
tal
potencial,
promovi
las
actividades
de
exploracin desde 1974.

Casi todos stos estudios fueron llevados acabo con cooperacin
internacional por expertos en Geotermia, en 1976 el gobierno de
Italia envi una firma de consultores Italianos para un estudio de

reconocimiento
realizado
por
de
las
el
areas
Programa
al
oeste
de
las
de
la
codillera
Naciones
Unidas
Andina,
para
el
Desarrollo (U.N.D.P ) dentro el proyecto BOL/71/532.

Posteriormente fue hizo un estudio de prefactibilidad en dos
areas
seleccionadas
en
base
los
estudios
de
reconocimiento:
Salar de Empexa y Laguna Colorada/Salar de Challviri distantes una

de la otra
78
aproximadamente 150 Km.
Como una consecuencia de los resultados favorables obtenidos y

en base a consideraciones econmicas se escogi Laguna Colorada
como area para empezar la factibilidad del proyecto. El estudio de

factibilidad
fu
despus
ejecutado
en
el
arnbito
del
BOL/84007 [1] de las Naciones Unidas entre los anos 1985
Proyecto
- 1990.
Todas las informaciones de caractr geolgico que se presentan
en continuacin han sido tomadas del informe citato.

1.1.
Desarrollo geolgico de la zona en estudio
El area del proyecto forma parte de un arco volcnico de edad

mioceno-pleistocnica y esta
situada en
la parte mridional
de
Bolivia cerca del limite con Chile.

La
morfologia
es
tipicamente
volcnica,
caracterizada
por
grandes extensiones ignimbriticas, que han nivelado las asperezas
morfolgicas, y sucesivamente modelada por fenmenos de rosion

glacial.
Las estructuras prdominantes en escala
rgional tienen dos
direcciones principales: una aproximadamente N-S
cadena
una
NO-SE
que
muestra
un
componente
paralela
a la
transcurrente
izquierdo.
La evolucin geolgica de la zona puede esquematizarse de la

siguiente manera:
-
en
el
Plioceno,
ignimbriticas,
actividad
probablemente
por
encima
de
plataformas
estaban prsentes unos aparatos volcnicos
escencialmente
efusiva
que
emitian
productos
con
de
composicin dacitica y andesitica;

- en el Pleistoceno inferior el rea examinada fu cubierta
por grandes volumenes de ignimbritas de composicin dacitica y

andesitica que nivelaron la morfologia preexistente;
despus
de
las
erupciones
ignimbriticas
la
actividad
volcnica continua hasta el prsente con edificios situados a

lo largo del eje N-S de la cadena. La actividad es mixta pero
79
prevalece aquella
de
tipo
efusivo
de
composicin
andesitico-
dacitica;
- en la parte mas elevada del area son evidentes las huellas
de una
glaciacin
post-ignimbritica
occurrida
probablemente
hace 35000 y 16000 anos;

- en el periodo post-glacial
tectnica
evidenciada
plataformas
fluides
por
fallas
ignimbriticas
calientes
que
se mantiene una actividad nco-
activas
que
que
permiten
alimentan
las
el
afectan
ascenso
varias
las
de
los
manilestacines
termales de la zona.
Todos los datos geolgicos, vulcanolgicos y estructurales, y
en particular: 1) la persistencia de la actividad volcnica por un
largo
periodo
con
pocas
variacines
de
la
composicin
de
los
productos emitidos, 2) el gran volmen de las igniinbritas y 3) las
caracteristicas
subactuales
sugieren
quimicas
similares
la
existencia
petrogrficas
las
de
de
los
cmaras
de
productos
magmaticas
los
productos
mas
antiguos,
volumtricamente
importantes situadas por debajo del eje volcnico activo, y por lo
tanto,
la
localizada
persistencia
de
inmediatamente
una
al
importante
Oeste
de
fuente
la
de
zona
calor
de
las
manifestaciones.
En
lo
encuentra
que
en
se
refiere
formaciones
al
reservorio
volcnicas
geotrmico,
profundas
como
este
ha
se
sido
confirmado por el pozo SM1 .

2. Muestreo, determinaciones de campo y de laboratorio
2.1 Generalidades
Los datos que se refieren a las manifestaciones superficiales
muestreadas en 1986 provienen de] Informe Final sobre Exploracin
de Superficie realizado para
el proyecto BOL 84/007
[1],
y del
reporte de la IAEA [2]. Tambin los datos de 1989 relatives a las
80
manifestaciones fueron obtenidos en el ambito del programa de la

IAEA, el mismo que permiti todas las determinaciones isotpicas
de las muestras de los pozos.

Estn
actualmente
disponibles,
adems
de
las
informaciones
sobre las manifestaciones y drenaje superficial, los datos de los

pozos API, SM1 y SM2. Los resultados incluyen anlisis realizados
en el campo o en laboratorio de muestras de vapor
condensado,
fluido total, liquido en el vertedero, admas de dos muestras de

fondo pozo.
El estudio de los datos quimicos de Laguna Colorada tuvo el
objeto de dfinir de manera preliminar las caracteristicas de los

fluidos geotrmicos
la
extension
del
asi como de proponer algunas hiptesis sobre
reservorio
los
procesos
de
circulacin
procedencia de los fluidos profundos.

La ubicacin de los pozos y manifestaciones superficiales es
reportada en la fig. 1. La fig. 2 muestra el esquema de aparato de

cabezal de pozo con los puntos de muestreo.
2.2. Metodologia de muestreo y anlisis

Los
liquides
fueron recogidos en
6 distintas muestras para
analizar los prinipales costituentes y aquellos in traza, alumino
monomerico, silica, isotopos stables ( O y D) y tritio.

Se realizaron en el campo las determinaciones de temperatura,
Eh, Ph, condutividad elctrica, alcalinidad y cido suifihidrico.
Las muestras de fluidos seleccionados fueron analizadas en los

laboratories
de
determinando
los
ENEL
(Ente
Nazionale
siguientes
per
paramtres :
l'Energia
pH,
Elettrica)
Conductividad
Elctrica, Alcalinidad, a, Mg, K, Li, Rb, Cs, Sr, Fe Total, B, As
Total,
Zn
Total,
Pb
Total,
Alcalinidad,
Sulfates,
Cloruros,
Fluoruros, Bromuros, Acido Brico, Silice.
81
//
,'_'-->
*wa, jf^ -
^-
Ô-i
^rX-A^
~ >~.
J
__>^v*
sfe^Mt^"1"^^
âss*^SHJ
^l^^- /
5>V V-" ^ ^<A-^
J("
=- / / /OV^r h-<,oJ
^t^ f^^ ^-^k i S-^! ^ ^ f / <-^-V4r^

^^s^^Ci^^^^
^^1^^
Û^'^S^rtpx <V^
J / ^-i~
^~-Ci'->(/LT!X-vi Sî-
_, ^^>yA
K_
^-,
cfd-yiscACMis ^/KT.,1 \i=
^>Ro",<riCAMo'>;vO'raro^ .aa^fo^ -'KJ XT
,/nv S^l
^^{SM^Â1 "i1 fHJ? i^^^^^^^fe^^sTir^
^1^-^
LODOS CALIENTES
SURGENTES
rs^sjT ^-
POZOS
SUPERFICIALES
Escala 1 250000
FIG
82
1 ' MAPA DE IDS PUNTOS
DE HUESTREO
LEYENDA
Boca pozo
Punto de m u e s t r e o de fluido t o t a l y liquido de condensado
despues del separador p o r t a t i l
Separador a t m o s f e r i c o
Punto de muestreo de liquide de veriedero
Uertedero
Fluido t o t a l y gas
( D e s p u e s de
separation con separador p o r t a t i f )
Fig. 2
En
lo que
se
/(5)
Lit|uido s e p a r a d o a c o n d i c i o / i e s a t m o s l e n c a s ( V e r t e c l e r o )
Esquema de los puntos de muestreo
refiere
los
componentes
isotpicos
fueron
analizados en su totalidad en Viena por la Agenda Internacional

de Energia Atmica a travs del programa que se habia mencionado
anteriormente.
En las tablas 1-5
de
agua
estn reportados los datos de las muestras
consideradas,
en
las
cuales
se
presentan
general-
mente desviaciones porcentuales < 10 %.

En la tabla 6 estn reportados los datos de las muestras de
gases.
Text cont. on p. 93.
83
Tabla 1 - Analisis quimico de los pozos AP1.SM1, y SM2(mg/l)

T.M. = ST (vertedero), = FT (fluido total)
oo
-t-
T.M. = UB (en pozo), = C (condensado)
Muestra
Fecha
T. M.. T.c. pH.c. Con.c. Alc.c. 1r.l. pH.l.

Cod.
MS
meq/l
20.0
6.41 3820
74.5
17.0
18.5
7.2017400
5.95
7100
7.3218300
0.6
0.8
0.8
0.5
03/02/89 979 ST
80.5
23/06/89 1697 ST
23/06/89 1695 FT
83.0
20.0
0.0017500
7.35 19300
7.0018100
0.5
0.5
0.5
AP1
AP1
AP1
SM1
SM1
SH1
SM2
SM2
SM2
AP1
SM1
SM2
Muestra
20/12/88 15 FT
07/01/89 965 ST
04/01/89 958
FT
03/02/89 980 FT
15/10/89 2921 UB
06/01/89 963 C
03/02/89 978 C
14.5
20.5
5.45
5.18
23/06/89 1696 C
13.0
5.15
Codigo
H2S
Li
MS meq/l
20 6.18
158
112
45
0.6
0.3
0.2
20
20
20
20
20
20
20
20
20
20
20
Rb
Cs
NH4
13/10/89 2922 WB
Con.l. Alc.l. Rlc.l.
6.78
6.89
6.73
6.27
6.75
6.89
6.75
6.70
6.64
6.48
5.57
Sr
3500
12700
6780
16300
6910
18600
17700
16900
1570
261
Mg
Na
0.140
0.075
0.040
0.060
0.160
0.079
0.076
770.0
3620.0
1640.0
4560.0
1390.0
5230.0
5230.0
128.0
631.0
269.0
707.0
180.0
829.0
925.0
0.1
47,.0
186,.0
76,.6
212,.0
56,.0
249,.0
232,.0
189,.0
10,.3
.6
1,
0..2
0..0
Sb
Pb
0.5
0.5
0.4
1.7
0.4
0.4
0.2
1.6
72
Ba
Zn
Cl
S04
SM1
SM1
SM2
SH2
SM2
AP1
SM1
SM2
15
965
958
14 .00
5.10
1.80
980
2921
979
1697
1695
3.90
0 .66
0.00
0.00
3 .90
3 .30
10.60
15.70
2922
963
978
1696
14.30
16.70
12.30
1.36
6.80
10.20
8.20 1.50 3.10 5 .800

37.00
3.110
16.80 2.90 5.40 4 .820
48.50 8.30 15.90 2 .040
12.30 1.80 5.20 11 .700
47.50
2 .680
53.00
2.300
45.00 8.20 14.90 1 .890
3.60 0.41 1.20 7.300
0.280.04
9.110
0.09
0.20 3 .590
5 .110
0.4
0.2
0.0
0.1
2.6
0.4
0.1
0.050 4130.0 675.0
0.070 296.0 37.5

0.006 28.5 4.2
0.000
9.4
1.7
0.000
3.3
0.0
As
Fe
Al. T
Al. M
0.48 0.002 0.900
0.280 0.005
0.99 0.080 0.023

3.70 0.330 0.010
2.20 0.500 0.220
0.270 0.000 3.30 0.680 0.060 0.000

0.630 0.000 25.90 0.120 0.320 0.000
0.140 0.030 0.72 4.400 1.500 0.720
3.50 0.320
0.12 0.060
0.02 0.002 0.019
Si 02
H3B03
Br
1270.0 80.240.5 251.0 245.0 1.40

6500.0 168.0
37.6 617.0 806.0 0.00
2770.0 82.053.0 301.0 394.0 2.60
8400.0 30.022.5 665.0 980.0 8.50
2340.0 24.6
106.8 1100.0 231.0 2.50
9560.0 35.524.9 686.0 1070.0 0.00
9310.0 35.9 7.4 755.0 1070.0 0.00
7830.0 30.727.6 678.0 936.0 8.30
347.0 119.0 170.2 372.0 48.9 0.54
4.6
3.0 0.00
43.3 4.4 46.7
12.8 2.0 41.1
2.4
4.5 0.00
0.0
4.1 0.00
5.5
0.0 38.6
TDS
TAN
meq/l
AP1
AP1
AP1
SM1
HC03
meq/l
0.6
0.7
0.4
0.6
2.8
0.4
0.1
0.1
252
1:a
0.720
0.020
0.012
0.004 0.210
0.000
5.80 1.200 0.096 0.000
0.000 25.90 0.120 0.280 0.000

1.20 0.350 2.800 2.400
0.010
0.000 0.16 0.310
0.000 0.06 0.060
0.000 0.05 0.000
TCAT
meq/l
2840 38.3
12569 187.0
0.00
0.00
0.34
0.89
0.29
0.00
0.00
0.84
0.17
0.00
0.00
0.00
018 Deut.
Trit.
Prof.
o/oo
U.T.
m.
0/00
40.6
188.0
5584 80.5
84.7
15689 247.0 234.0
536S 66.5 70.3
-9.69
-5.94
-5.55
-83.5
-67.8
-83.3
0.12
-6.39
-7.27
17724 270.0 268.0 -5.53
-79.5
-79.6
-72.8
0.04
17630 277.0 270.0

14596 227.0 213.0
-74.9
1255
12.3
102
1.4
45
0.5
29
0.3
-8.82
-6.26 -78.1
15.3 -6.88 -74.5
2.0 -11.81 -99.4
0.7 -11.29 -103.9
0.4 -11.25 -102.1
1000
1240
Tabla 2 - Analisis quimico de todos calientes y fumarolas

T.M. = HP (lodos calientes), = F (fumarolas)
Muestn3
Fecha
Cod. T. M. T.c. pH.c. (:on.c. A Ic.c. T.I. pH.l. Con. l. Ale. 1. Rlc.l.
c
HAB1
HAB2
HHJ2
HHJ3
HSM
HSM3A
HSM4
HSH7
HSH8
FAB
FAB3
FAB6
FHJ
FHJ1
FHJ2
FSM1
FSM2
FSM5
FSM6
FSHA
FSMB
FSHD
SMO
SMO
oo
(J\
15/03/86
15/03/86
15/03/86
16/02/89
17/01/89
13/03/86
13/03/86
13/03/86
13/03/86
15/01/89
15/03/86
15/03/86
16/01/89
12/03/86
12/03/86
13/03/86
13/03/86
13/03/86
13/03/86
17/01/89
17/01/89
17/01/89
17/01/89
13/03/86
867 HP
868 HP
14 HP
996 HP
988 HP
10
11
12
13
HP
HP
HP
HP
999 F
1002 F
1001
1000
15
16
17
18
19
20
1001
1002
1003
1004
21
F
F
F
F
F
F
F
F
F
F
F
F
F
4.58
3.57
82.9 3.14
70.0 2.44
81.5 3.04
53.6 2.25
84.0 3.38
67.2 6.57
73.2 2.16
15.0 5.10
84.5
84.4
17.0 5.53
84.6
84.6
84.5
84.5
84.7
84.7
12.0 4.10
20.0 4.80
19.0 5.00
16.0 4.30
118
79.0
81.0
MS meq/l
1670
2650
1830
3600
2010
4030
1580
841
3140
250
"C
23
23
20
20
20
Ca
Mg
Na
Cl
S04
HC03
S i 02 H3B03
3.4
8.2
0.0
21.6
44.5
10.8
31.0
1.1
1.6
1.4
1.000
3.300
0.001
8.600
13.900
14.000
18.400
0.800
0.090
0.014
2.3
3.4
0.0
19.8
36.4
18.4
87.0
12.9
1.8
0.4
1.4
2.8
0.0
572.0
1010.0
0.0
1530.0
941.0
1740.0
732.0
276.0
600.0
4.6
0.0
0.0
30.5
21.1
2.9
0.0
1.0
0.6
0.0
1.4
5.5
0.8
34.8
5.4
0.7
0.5
43.3
1.0
0.7
103.0
0.0
0.0
286.0 70.4
300.0
2.9
9.0
0.0
0.0 63.0
0.0 598.0
0.0 130.0
0.2
0.0
fiS meq/l meq /l
4.09
3.12
3.22
2.04
2.40
2.21
1590
2680
1830
4050
2130
0.8
20 6.12
0.6
20 6.88
58
0.3
108
4.5
20 6.62
89
0.6
0.3 0.005
0.5
0.1
0.7
41
6
114
2
20
20
20
20
58
117
18
0.3
0.3
0.3
0.0
0.8
0.2
0.1
0.2
2.3
0.3
0.8
0.4
0.1
0.1
0.1
1.6
0.5
0.2
0.3
6.58
6.10
6.42
4.48
0.6
7.9
16.4
12.5
0.013
0.013
0.002
0.005
0.4
0.0
0.2
0.0
0.0
0.0
0.0
0.0
49.7
0.0
65.9
4.6 285.6
5.9
3.4
23.4
6.3
19.2
80.5
83.0
0.0
0.1
0.0
3.9
1.7
1.0
0.8
0.6
0.8
0.0
0.3
Tabla 2 - ( cont.)
Muestra Codigo
HAB1
HAB2
HHJ2
HHJ3
HSM
HSM3A
HSM4
HSM7
HSM8
FAB
FAB3
FAB6
FHJ
FHJ1
FHJ2
FSM1
FSM2
FSM5
FSM6
FSMA
FSMB
FSMD
SMO
SMO
867
866
14
996
988
10
11
12
13
999
H2S
NH4
219.00
284.00
0.010
89.600
109.00
129.00
125.00
9. 640
54.400
29.10 7.600
TDS
TAN
TCAT
meq/l
meq/l
373
2035
1470
1935
1122
926
792
45
11. 9
21. 0
0.0
31.9
19.7
36.2
16. 2
5.9
12. 5
0.4
1002
1001
1000
15.10
13.600
40
0.5
44.20
29.10
0.48
27.20
0.130
8.200
15.800
0.630
60
46
42
36
0.2
0.2
0.5
0.2
15
16
17
18
19
20
1001
1002
1003
1004
21
018 Deut. Trit. Altitud
o/oo
o/oo U.T. s.n.m.
0..78 -42. 0
4890
-0..28 -43.2
4890
-0..60 -42. 2
4760
7.8 1..47 -36.9 0.42 4760
11.4 -2..27 -46. 2 0.13 4850
10.0
5..89 -34. 0
4850
14.6 1..27 -37. 1
4850
1.8
4850
3.3 3..72 -37. 8
4850
0.5 -10,.36 -80. 8
4890
4890
0.0 -9..66 -77. 2
0.0 -12..78 -87. 3 6.5
4890
0.8
4760
-8,.49 -79. 5
4760
-9.95 -86. 2
4760
-9.,32 -81. 9
4850
-9.,14 -80. 8
4850
-9.30 -83. 6
4850
4850
-10. ,38 -90. 2
0.2 -8.,79 -77. 8
4850
0.5 -8.82 -78. 7
4850
0.9 -9.,05 -80. 2
4850
0.1 -9.,13 -80. 1
4850
-8.,64 -79. 7
4850
12.5
16.6
0.0
Tabla 3 - Analisis quimico de las surgentes (mg/l)
Muestra Fecha
Cod. T.M. T.c. pH.c. Con.c. Alc.c. T.l. pH.l. Con.l. Alc.l. Rlc.l.
* meq/l
LC1
LC1
LC11
LC11
LC4
LC4
LC5
LC5
SAB7
SC1
SC1
SC11
SC11
SC2
SC21
SC21
SC4
SC4
SHJ1
SHJ2
SHJ3
SHJ4
SPB1
SPB1
SPB2
SPB3
WP1
11/01/89
18/07/86
23/02/89
17/03/86
11/01/90
18/07/86
28/02/89
18/07/86
15/03/86
10/01/89
18/07/86
10/01/89
18/07/86
18/07/86
10/01/89
18/07/86
18/07/86
10/01/89
14/02/89
17/03/86
17/03/86
17/03/86
21/01/89
16/03/86
16/03/86
16/03/86
22/01/89
993
1
998
7
994
2
995
3
0869
989
0861
991
0865
0862
992
0866
0863
990
997
4
5
6
986
0870
0871
0872
983
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
22.5
21.5
31.0
30.1
22.0
21.1
21.0
20.8
8.2
40.0
40.0
36.5
36.2
41.0
30.5
29.3
33.9
34.5
30.0
29.4
26.7
27.5
12.0
10.9
12.0
10.6
37.0
7.19
7.71
7.03
7.31
7.61
7.74
8.20
8.10
7.68
7.50
7.79
7.84
8.25
7.69
7.78
8.50
8.25
7.50
7.05
7.22
7.65
7.09
7.48
6.05
6.95
6.60
7.66
377
381
1480
512
447
820
946
264
1150
1140
485
496
1180
487
376
701
650
400
440
189
375
86
362
130
98
374
1.1
1.2
3.1
3.2
1.1
1.2
0.7
0.8
1.1
1.6
1.5
0.7
0.8
1.9
0.8
0.9
1.1
1.6
4.3
4.6
0.8
3.1
0.6
0.6
0.4
0.3
0.9
us
20
24
20
20
20
24
20
24
23
20
24
20
23
24
20
23
24
20
20
20
20
20
20
21
21
21
20
6.50
6.48
6.95
7.23
6.90
6.38
6.90
6.29
6.57
6.67
7.15
6.60
6.71
7.15
6.81
6.48
7.03
6.67
7.09
7.34
6.87
7.23
6.32
7.10
6.67
6.58
6.65
Hg
Na
Cl
S04
HC03
59.1
57.7
337.0
358.0
106.0
71.2
202.0
201.0
3.6
160.0
125.0
3.6
2.6
180.0
6.4
2.6
59.4
65.0
3.2
1.2
1.0
1.0
3.6
3.0
4.1
2.0
3.4
30.1
28.6
145.0
149.0
42.6
32.6
104.0
104.0
42.4
267.0
271.0
190.0
180.0
250.0
118.0
113.0
174.0
175.0
56.4
50.9
69.5
68.2
13.3
12.9
15.0
12.6
126.0
67.1
71.4
189.2
194.6
70.2
70.2
43.3
45.2
67.1
97.0
92.7
43.3
47.6
112.9
51.3
56.1
65.3
S02 H3B03
Br
4.4
5.1
20.2
20.9
6.5
5.6
15.1
15.1
1.2
24.2
19.9
1.9
2.2
30.0
2.9
2.9
10.8
10.2
0.7
1.6
1.6
1.9
1.1
1.5
1.6
1.2
6.9
0.00
0.00
0.27
0.00
0.00
0.00
0.00
0.18
0.00
0.17
0.14
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
meq/l meq/l
362
391
1470
1670
523
447
903
1000
253
1120
1130
484
501
0.9
1.1
3.1
3.5
1.2
1.2
0.7
0.7
1.4
1.6
1.5
0.7
0.8
0.9
1.1
3.1
370
377
727
670
517
509
158
432
94
98
89
74
370
0.9
0.9
1.1
1.1
4.3
4.6
0.8
3.4
0.5
0.5
0.4
0.4
0.9
0.9
0.9
1.1
1.1
4.2
1.1
1.2
0.7
0.7
1.4
1.4
1.5
0.7
0.8
0.5
0.5
0.4
0.4
0.9
8.4
7.5
37.1
38.0
9.4
7.9
6.8
6.2
19.0
51.5
54.7
36.4
36.6
51.6
16.8
16.7
29.8
28.9
43.3
38.5
4.8
31.0
7.2
7.0
6.8
5.9
22.2
3.600 63.4
3.800 56.0
21.400 259.0
24.100 246.0
5.500 99.4
4.000 66.9
4.200 187.0
4.200 172.0
8.000 16.8
6.300 188.0
6.700 160.0
2.900 66.8
2.900 60.0
6.800 190.0
0.480 66.1
0.440 59.0
2.900 102.0
2.800 110.0
24.300 34.2
25.000
28.7
2.550 19.0
19.200 28.5
2.000
9.8
2.100 9.0
1.700 5.6
1.600 3.9
2.900 59.8
8.1
9.0
28.8
35.6
10.9
9.6
12.6
14.4
9.9
30.0
26.0
4.4
1.1
31.0
3.1
2.8
14.0
15.5
8.7
11.4
5.9
9.0
1.5
1.6
3.1
2.5
6.6
97.0
262.4
280.1
45.8
189.2
33.6
34.8
24.4
19.5
56.1
80.9
74.0
96.9
116.0
80.9
76.0
89.8
82.0
52.0
141.0
133.0
60.7
70.0
139.0
71.2
69.0
107.0
104.0
116.0
122.0
92.0
116.0
21.5
31.8
47.8
41.2
83.5
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
oo
oc
Tabla 3 - ( cont.)
Muestra Cod i go
LC1
LC1
LC11
LC11
LC4
993
1
998
7
LC4
LC5
LC5
995
SAB7
SC1
0869
989
0861
991
0865
0862
992
0866
0863
990
SC1
SC11
sen
SC2
SC21
SC21
SC4
SC4
SHJ1
SHJ2
SHJ3
SHJ4
SPB1
SPB1
SPB2
SPB3
WP1
994
997
U
5
6
986
0870
0871
0872
983
0.00
0.42
0.28
0.22
0.00
0.44
0.00
0.34
0.00
0.63
0.64
0.26
0.26
0.66
0.22
0.21
0.52
0.44
0.00
0.00
0.28
0.16
0.00
0.21
0.00
0.00
0.25
Li
0.21
0.19
1.00
0.12
0.33
0.23
0.68
0.64
0.00
0.87
0.63
0.05
0.03
0.77
0.07
0.03
0.32
0.42
0.03
0.06
0.06
0.06
0.00
0.01
0.01
0.00
0.05
Rb
0.00
0.00
0.09
0.03
0.00
0.00
0.00
0.00
0.00
0.17
0.10
0.00
0.00
0.13
0.00
0.00
0.08
0.08
0.00
0.05
0.06
0.06
0.00
0.00
0.00
0.00
0.00
Cs
0.00
0.00
0.00
0.00
0.00
0.21
0.00
0.00
0.00
0.26
0.33
0.00
0.00
0.33
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
NH4
0.000
0.011
0.000
0.011
0.000
0.011
0.120
0.012
0.050
0.000
0.009
0.000
0.010
O.OO
0.000
0.008
0.010
0.000
0.000
0.007
0.008
0.008
0.000
0.015
0.020
0.010
0.000
Sr
Ba
Sb
Pb
0.00 0.000 0.000 0.000

0.08 0.000 0.000 0.000
0.39 0.010 0.000 0.000
1.50 0.018 0.000 0.002
0.00 0.000 0.000 0.000
0.08 0.000 0.000 0.000
0.00 0.000 0.000 0.000
0.11 0.000 0.000 0.000
0.10 0.010 0.000 0.000
0.34 0.020 0.000 0.012
0.36 0.020 0.012 0.000
0.08 0.000 0.000 0.028
0.08 0.000 0.024 0.000
0.34 0.020 0.000 0.000
0.03 0.020 0.011 0.000
0.02 0.020 0.032 0.000
0.20 0.010 0.024 0.000
0.20 0.000 0.000 0.000
0.00 0.000 0.000 0.000
0.14 0.000 0.000 0.000
0.07 0.000 0.000 0.000
1.30 0.000 0.000 0.000
0.00 0.000 0.000 O.OO
0.04 0.000 0.000 0.000
0.05 0.000 0.000 0.000
0.04 0.000 0.000 0.000
0.09 0.000 0.000 0.000
As
Fe Al. T
0.16 0.000
0.17 0.000
0.40 0.000
0.50 0.000
0.18 0.000
0.17 0.027
0.38 0.000
0.44 0.000
0.00 0.047
0.40 0.000
0.66 0.026
0.03 0.000
0.02 0.000
0.73 0.044
0.10 0.000
0.05 0.012
0.41 0.000
0.37 0.000
0.03 0.000
0.00 0.000
0.00 0.000
0.00 0.000
0.00 0.000
0.00 0.260
0.00 0.000
0.00 0.000
0.03 0.000
0.000
O.OO
0.017
0.000
O.OO
0.035
0.000
0.000
0.059
0.150
0.000
0.028
0.000
TDS
TAN
T CAT
meq/l
meq/l
326
3.4
314
3.4
15.6
16.4
5.0
3.8
1137
1185
432
345
666 8.6
646 8.6
220 2.1
968 11.7
892 10.7
0.000
4.8
4.6
12.1
3.5
3.4
567 6.4
610
7.1
549 5.6
0.000
560
0.000
0.018
0.040
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
410
403
994
337
323
243
466
94
104
110
90
368
5.7
2.2
4.5
0.9
0.9
0.8
0.6
3.7
018 Deut. Trit. Altitud

o/oo
o/oo
3.7 -12.55
3.4 -12.38
15.8 -10.48
-95.9
-93.4
-76.6
15.5 -10.57 -74.6
5.6 -12.42 -94.6
3.9 -12.48 -92.7
9.2 -11.51 -85.8
8.6 -11.36 -85.5
2.6 -9.09 -67. Z
12.2 -11.01 -88.4
11.0 -11.01
5.1 -10.94
4.7 -10.94
12.3
3.8 -10.94
3.5 -10.96
6.6
-88.4
-86.6
-86.6
U.T.
4280
4280
0.04
0.00
0.00
7.50
0.00
0.00
-83.8
-82.7 0.00
6.9
5.9 -10.45
5.5
-68.8
1.4 -11.35
-75.5
s.n.m.
0.25
4280
4280
4280
4280
4280
4280
4890
4400
4400
4400
4400
4400
4400
4400
4400
4400
4640
4640
4620
4.6 -10.51 -70.5 0.70

1.0 -11.85 -94.3 0.00
1.0 -12.06 -91.4 0.16
4580
4700
0.8 -11.57
-89.7
0.7
4.1 -9.70
4700
4700
-79.0
0.20
4700
4860
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o o o o o r*. o o 0
o o o o o
o o
Kl Kl
Kl PJ
s4
O
o
o
0 0 0 CD
PJ
o o
O O Os Kl
O O O o
Os 0
O O O
PJ
O 0
03
R
O O
O PJ 00 PJ
CD sT PJ PJ
0 O O 0
(->
89
Tabla 4 - A n a l i s i s quimico de aguas supcrficiales (mg/l)

T - M . = LA (lagunas), = R (rios), = N (nieve)
Muestra
Fecha
Cod. T. M. T . c .
pH.c.
Con.c. A l c . c . T . l .
MS
meq/l
pH.l . Con. I. A l e . I . R l c . l .
MS
206
8.42 200000
31.
meq/ 1
Ca
Mg
Na
276.0 669.00
41000
27.2
17/03/86 8
LA
19.2
8.05
RAB
22/01/89 985
16.0
6.95
189
0.8
20
6.44
196
0.8
0.8
17.8
RHJ
19/01/89 984
2.0
8.50
241
3.5
20
7.37
439
3.4
3.4
33.9 19.800
RS
21/01/89 987
16.5
7.50
288
2.3
20
6.79
224
2.3
2.3
15.2
SC10
18/07/86 0864 LA
24.0
8 . 2 5 31600
2.7
23
7.51
2.6
2.1
Pb
As
Muestra Codi go
Cl
S04
HC03
S i 02
H3B03
3580 53900 .0
6.100 14.3 2.8

7.200
22600 1909.8
2 .2
55,.6
33.8 9.0
2 .9
64,.6
30.7 3.0
4 .4
336.0 174.00 5700.0 236.0
93.0 4180.0
4 5 . 8 62.2
0.6
0.00
91.7
0.8
0.00
7,.0
139.7 57.4
1.7
0.00
8780 .0 1790,.0
162.3 76.4
210.5
4 1 0 . 0 3.60
Li
Rb
Cs
NH4
Sr
Ba
Zn
Sb
Fe
ALT
TDS
TCAT
018
Deut.
meq/ 1
meq/ 1
o/oo
o/oo
2020 1970.0
Tri t . A l t i t u d
U. T
s. n. m.
LC12
0.89 165.0
0.000
0 . 0 00.084 0.080
0.020 0.100
-0.51
-28.1
985
0 . 0 0 0 . 0 0 0.00
0.00 0.200
0.00 0.000 0.000
0.000 0.000
0.01 0.000 0.000
208
2.0
2.1 -10.22
-75.5
0. 6
4760
RHJ
984
0.00 0.03 0.00
0.00 0.210
0.00
0.000 0.000
0.000 0.000
0.03 0.000 0.000
467
5.1
5.0
-54.2
0. 5
4310
RS
987
0 . 0 0 0 . 1 5 0.00
0 . 0 0 0 . 1 3 0 0.000.000 0.000
0.000 0.000
0.13 0.000 0.000
267
2.6
-96.1
0. 2
SC10
0864
1 . 5 0 2 . 6 0 1.60
3 . 4 0 0.900
0.000 0.000
3 . 5 0 0.230 0.460
SNOW
8.800.000 0.060
76.00 1.230 0.500 128486
TAN
RA8
12.80 21.30
Br
meq/l
LC12
SNOW
17691 288.0
-7.68
2.8 -12.10
285.0
4275
4340
-8.04
-68.3
4600
-8.00
-47.4
5000
Tabla S - Analisis quimico de fluidos del Tatio (mg/l)

T.M. = FT (fluido total), = S (surgentes)
T.M. = HP (lodos calientes), = H (nieve)
Muestra Fecha
l.M.
T.c. pH.c. T.I. pH.l. Ale. I.
C
H28
H324
H347
HC1
HC3
HC4
S227
S241
S319
S56
S65
SA4
SA5
SA7
SA9
SNOW
W1
U2
W3
W5
01/11/68
01/10/69
01/10/69
01/11/68
01/11/68
01/11/68
01/11/68
01/11/68
01/11/68
01/11/68
01/11/68
01/08/70
01/08/70
01/08/70
01/08/70
01/11/68
01/12/69
01/06/70
01/10/70
01/03/71
HP
HP
HP
HP
HP
HP
S
S
S
S
S
S
S
S
S
N
FT
FT
FT
FT
78.0
78.0
56.0
20.0
86.0
85.0
85.0
85.0
83.0
85.0
86.0
14.0
25.0
12.0
55.0
211
227
254
212
Ca
Mg
Na
Cl
53
32
28
16
44
15
4600
4320
3000
3060
2880
35
6
52
540
18
9
5
8
15
10
520
525
367
150
145
4
1
4
64
0
0
0
0
0
0
8220
7870
5370
5380
5240
53
0
90
760
3340
3430
2570
3760
310
431
127
519
5820
6020
4490
6690
S04
HC03 S02 H3B03
Li
Rb
Cs
NH4
TDS
018
Deut.
404 -0.90
535 7.50
392 6.30
362 -8.60
474 -3.70
236 -3.30
15106 -5.50
14381 -5.70
9889 -6.00
9927 -6.10
10061 -6.50
203 -8.20
59 -8.80
253 -7.70
2547 -8.40
-9.70
10796 -6.00
11221 -6.30
8259 -6.80
12527 -5.60
-44.0
-26.0
-31.0
-55.0
-49.0
-44.0
-69.0
-68.0
-67.0
-68.0
-67.0
-58.0
-53.0
-48.0
-0.6
-55.0
-73.0
-78.0
-75.0
-72.0
meq/l
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
15 6.70
15 3.60
15 4.90
15 7.10
15 6.90
15 6.40
15 7.40
15 7.40
15 6.30
15 7.60
20 0.00
15 7.50
15 6.70
12 8.40
15 8.20
6.80
6.80
6.60
6.70
15
15
15
15
7.46
7.36
7.65
7.40
0.5
0.0
0.0
2.7
0.2
0.1
0.7
0.7
1.1
1.4
1.6
0.5
0.1
0.6
14.3
37
37
26
99
45
280
278
171
232
225
4
4
8
28
0.00
0.00
0.00
0.00
0.00
0.00
0.30
0.00
0.00
0.00
7.20
0.00
0.00
0.00
0.00
0.3
0.6
0.1
0.8
196
197
198
219
0.81
0.54
1.52
0.80
27
180 28.1
345
0.0
245
1.2
14 164.7
228 15.3
180
3.7
38 45.2
26 43.9
22 64.7
46 87.3
42
0 31.7
5
4.9
6 37.2
5 860.3
47
33
44
34
20.7
34.8
9.2
48.2
88
112
87
60
127
0
256 1070
280 972
149 704
207 726
777 704
11
64
38
0
33
23
188
97
293
298
173
343
727
727
612
858
47 6.70 15.80
2.900
45 6.40 14.90
27 4.20 10.30
27 2.10 9.90
28 2.10 10.00
0 0.01 0.00
0 0.00 0.00
0 0.01 0.00
4 0.30 0.70
23
28
21
32
3.50 11.30 1.400

4.80 12.30 2.170
1.70 9.50 0.000
5.60 13.10 1.500
Tabla 6 - A n a l i s i s quimico de gases, res = gases residuales
1 = Chiodim and C i o n i , 1989. 2 Giggenbach, 1989.
Muestra
FSMO
FSHA
FSMB
Cod
93.98
95.38
91 .08
96.59
94.63
95.34
13/03/86
12/03/86
13/03/86
16/03/86
16/03/86
16/03/86
15/03/86
15/03/86
12/03/86
12/03/86
96.03
97.35
97.48
95.01
95.90
95.36
96.48
1968a 02/02/89
0999
1000
FSMO
FSM2
21
18
FSH3
FSM5
FSM6
FSM9
19
20
SM1
SM1
C02%
18/01/89
17/01/89
17/01/89
17/01/89
15/01/89
11/01/89
1004
1001
1002
1003
FSMD
FAB
FHJ
FAB3
FAB5
FHJ1
FHJ2
Fecha
15
16
1968b 02/02/89
H2S%
CH4%
2.79
0.83
2.17
2.65
3.21
0.69
1.00
1 .67
0.86
0.59
0.20
0.00
97.61
95.57
1.12
0.73
1.08
0.86
1.09
1.23
0.82
0.83
0.36
0.22
0.01
0.75
0.22
0.63
0.28
0.81
0 10
0.11
93.80
96 91
0 90
1 32
1 .33
1.67
95.42
1.17
1.39
H 2%
N2*
02%
co%
fH20%
0 . 1 1 0 .0000 0 .00160
2.03 0 .0000 0 .00174
6.17 0 .0000 0 .00062

1 . 76 0.0000 0 .00058
2.32 0 .0000 0 .00245

3 22 0.0000 0 .00078
0.36
0.13
0.07
0.30
0.58
0.30
0.35
0.39
0.28
0.24
2.07
0.91
1 22
2.22
2.23
2.82
1 .71
2.12
0 .0081
0..0035
0..0100
0..0085
0..0091
0..0120
0..2800
0..0150
0 .00073
0..00018
0..00012
0..00028
99.17
98.21
98.16
98.37
97.92
98.86
0..00130 98.62
97.90
1 00 0. 0030
97.76
1.23 0..0040
97.89
6.30 0. 0000 0. 00238

0.43 0..0000 0..00267
N2%
02%
res
res
CH4% H2%
res
res
He%
Ar%
res
res
C
1
73.2 0.0 13.70 12.30 0.025 1 . 1 1 0

73.2 0.0 13.30 15.80 0.036 0.411
74.1 0.0 18.60 6.91 0.029 0.330
74.7 0.0 12.30 12.80 0.024 0.464
78.9 17.2 0.62 1.52 0.006 0.000
80.8 0.0 6.90 14.80 0.036 0.389
PC02
bar C
1
2
240
250
220
220
300
240
248 1 .07 290

207 4.15 267
201 5.30 244
211 2.80 256
271 11 .93 310
267
262
3. Pozos, reconstruction del fluido profundo y equilibracin
con el reservorio
Los pozos productives SM1, SM2 y SM3, que no estan ubicados
lejos
de
las
manifestaciones
de
Sol
de
Mariana,
tienen
una
profundidad variable entre 1200 y 1500 m aproximadamente. Durante

el periodo de perforacin ha sido reconocidos distintos nineles
productivos
con
permeabilitad
temperatura
diferentes.
La
temperatura maxima encontrada ha sido de 244C y en las prevuas de
producin la entalpia se ha mantenido siempre entre 1050 y 1060

KJ/Kg. El pozo API profundo 1600 m, que se encuentra a unos 5 km a
SO de los anteriores tiene una temperatura maxima de 260C y una
permealidad mas reducida. Durante las prevuas la entalpia era, en

principio, muy elevada, luego se establiz
en 1380 KJ/Kg. Esto
indica la existencia de fenomenos de ebullicin en las cercanias

de la zona de producin.
Tenendo en cuenta solamente los pozos SM1 y SM2, de los quales

existe
un
numro
suficiente
de
datos
(considerando
que
el
reservorio es del tipo liquido dominante y que el fluido producido
es el resultado de un
proceso isoentlpico) con un balance de
masa y energia del sistema puede ser calcolada
la composicion
total del fluido del reservorio y de esta el pH y el estado de

saturacin del mismo, respecte a un grupo de minrales (Ver fig. 3
Y 4) .
Para esta reconstruccin fueron utilizados los valores medios
de los anlisis de agua de vertedero, de vapor condensado y de gas
separado muestreados en el periodo enero-junio 1989; en el periodo

considerado
la
entalpia
del
fluido
variaciones, manteniendose en el rango
producido
no
ha
sufrido
1055 KJ/Kg (244C).
93
Pozos SW 1 y SM 2
Fluido de reaervorio
Carbon total:
13.07 mmol/Kg
120
160
200
240
280
320
Temprature
FIG. 3
INTERACCION AGUA-ROCA. LOG (SI) Vs TEMPERATURA
(CON CONTENIDO DE CARBON TOTAL = 13 mg/1)
Pozos S M ~ 1 y SM2
Fluido de reservorio
Ccrbon totol:
80 mmol/Kg
160
200
Temprature
FIG. 4
94
INTERACCION AGUA-ROCA. LOG (SI) Vs TEMPERATURA

(CON CONTENIDO DE CARBON TOTAL = 80 mg/1)
Debido al tipo de quipe usado durante las pruebas los datos

analiticos disponibles se refieren a 2 tipos de muestras:
a) liquido en la salida del separador atmosfrico funcionando a
84 C y 0.56 bar (vertedero) , tales muestras ha sido indicadas en
la tabla 1 con el codigo ST;

b) fluido total tornado en un punto del equipo que tiene una
temperatura de 123-132C y presion de 2.2-2.7 bar, tales muestras
ha sido indicadas en la tabla 1 con el

Para
porque
esto
como
tipo
de
muestras
consequencia
de
codigo FT.
fueron
realizadas
fenomenos
de
correciones,
canalizacin
en
la
planta, la fraccin de agua muestrada resultaba major de aquella
teoricamente
possible
aquellas
condiciones
temperatura.
Los anlisis de gas
de
presion
(ver tabla 6) se refieren a
muestras tomadas en el mismo punto.
El valor de la relacin gas/vapor se refiere al mximo medido

en el periodo considerado y es de
1.1 NL/kg.
La reconstruccin efectuada utilizando un programa de clculo,
estudiado para este objeto, entrega como resultado per i pozzi SM1
e SM2 a una temperatura de reservorio de 244C, un fluido con un
valor de pH = 6.31 y una alcalinidad total de 1.69 meq/1.

La composicion total, (valores en mg/kg), esta representada en
la siguiente tabla:
Pozo
Condicion
SM1-,
SM2J
Reservorio
La
asociacin
reservorio
pH
6.31 175
Mg
Na
0.056
3807 579
Cl
6615 25
mineralgica
(Ver fig. 3
S04
4),
HC03
H3B03
Si 02
TDS
802
779
500
13350
rsultante
esta
la
temperatura
de
acuerdo
en
solucin
con
de
aquella
observada en las muestras de perforacin.

Los
minrales
que
llevan
Calcio
(Calcita
Anortita) estn sobresaturados.
95
Si se acepta un modelo mineralgico del reservorio en el cual

la calcita es un minral secundario que se produce de la reaccion
del tipo:
Anortita + CCu + H2O -->
CaCC>3 + "arcilla"
el echo del desequilibrio con la calcita, para una temperatura

de la solucin de 244C, no es consistente.
Para llevar la calcita a un nivel de saturacicn compatible con

el modelo es necesario anadir CCu al fluido de reservorio.
La cantidad necesaria rsulta ser 80 mmol/kg, con una prcsin
parcial de CO2 en reservorio de 7.95 atm.

4.
Quimica del aqua
4.1.
Clasificacin quimica de las muestras de agua
Los resultados ana]iticos de los fluidos muestreados durante la
investigacin en esta rea son reportados en las tablas 1, 2, 3,

4,
5,.
La
diagramas
clasificacin
de
de
correlacin
las
aguas
utilizando
fu
cfectuada
concentraciones
mediante
de
const ituyentes mas fundamentales: Ca, Mg, Na, K, HCO3 , SO4

Durante
la
interpretacin
no
fueron
consideradas
los
y Cl.
aquellas
surgentes muestreadas en el ano 1986, quimicamente eran idc-nticas
a las muestreadas en 19B9, (Ver tablas 2, 3, 4).

Fueron
utilizadas
caracteristicas para
2921
sin
embargo
comparar
para el pozo Sol
los
datos
de Mariana!
2922 para el pozo Sol de Manana2
las
que
de
(SM1), de
tenian
distintas
las muestras,
969
las muestras 1695 y
(SM2) y la mucstra 958 para el
Pozo Apachetal (API), (Ver tabla 1).

En las figuras 5, 6, 7 son reportados los clsicos diagramas de
Piper. En la figura 5 podemos observar que esta dividida en cuatro

cuadrances, en
el cuadrante Sud-Este
Alcalino-Cloruradas.
En
el
Alcalino-Trrea-Bicarbonato,
96
cuadrante
encontramos
Nort-Oeste
generalmente
aguas del tipo

son
coligadas
del
tipo
circula-
100
Cl-
-.
Q)
fPBl
+
(D
IQ
feie
- pozos
100
FIG.
HC03- + S04
DIAGRAMA DE PIPER CON Cl~
504
0
COMO ION SEPARADO.
100
+
4-
POZOS
100
FIG. 6
HC03- + Cl0
DIAGRAMA DE PIPER CON 504 COMO ION SEPARADO.
97
100
Cl- + S04--
ra
100
HC03- + C03
FIG.
clones
superficiales,
DJAGRAMA DE PIPER.
finalmente
en
el
cuadrante
Nort-Este
del
tipo Suifato-Calcica.
Como habiamos considerado las muestras colectadas del area en
estudio, 19 de ellas, las que se ubican en el primer cuadrante son

del
tipo Alcalina-Clorurada, cuatro
en
el
cuadrante Nort-Este
quedan ocho, ubicadas mas abajo en el cuadrante Nort-Oes'e
(ver
fig. 5) .
Todo esto mejor se visualiza en las fig.
6 y 7 los diagramas
fueron construidos de modo tal que el ion aislado fuese SO^ en una
de las figuras y Cl en la otra.

Por comparacin de esos diagramas, trs grupos de agua son bien
individualizados,
98
(el primero de los cuales como se vera despus
puede ser
ulteriormente dividido en dos) las caracteriscas de
ellos se pueden resumir como sigue:

GRUPO A conformado por las muestras SHJ1, SJH2, SHJ4, RHJ,
SAB7, SPB1, SPB2, SPB3, RS y RAB. Las trs primeras son fuentes
tibias situadas al Nort-Oeste del rio Huaylla Jara (RHJ), emergen

de lava
ignimbritas y son caracterizadas por
la temperatura y
conductividad variable en los rangos que se indican a continuacin: 27.5C-30C y 430/iS-520/iS. La muestra SAB7, 8.2C y 250/iS,
es ubicada al Sud- Este de las fumarolas de Aguita Brava, las

surgentes
frias
SPB1,
aproximadamente
100/xS
Finalmente
muestras
las
SPB2
ubicadas a
RAB
SPB3
con
1.5-2 Km del
RS
aguas
conductividad
Cerro
Lagunitas.
superficiales
del
Rio
Aguita Brava y del Rio Silala, esta ultima esta ubicada muy lejos
del
area
en
estudio.
Todas
las
muestras
de
agua
se
pueden
considerar como una mezcla de porcentajes variables de los trs

componentes Bicarbonato-Alcalino Trreo, Sulfato-Alcalino Trreo y
Bicarbonato-Alcalino.
COTOO ya se habia afirmado, el grupo A se puede todavia
subdividir,
tienen
bajos y
porque
componentes
un
las
muestras
RAB, SAB7,
Bicarbonato-Alcalino
componente
Sulfato-Alcalino
SPB1, SPB2
Trreos
Trreo
SPB3
levemente
mayor
que
mas
SHJ1,
SHJ2, SHJ4, RHJ y SPB1.
La muestra del Rio Silala se caracteriza por un elevado compo-
nente Bicarbonato-Alcalino.
GRUPO B esta formado por las muestras SHJ3, WP1, SC2, SC4,
SC11 y SC21, estas tienen conductividad y temperatura en el rango
de valores: 158-1130juS y 26.7-41C.
Este grupo se diferencia del prcdente por la falta total del

componente
Bicarbonato-Alcalino
prdominante
el
componente
Trreo;
quimicamente
Sulfato-Alcalino-Alcalino
Trreo
es
con
una contribucin de Sodio-Bicarbonato. En las muestras SCI, SC2, y
99
de
SC4
hay
tambin
una
considerable
cantidad
de
Sodio
tibia
modesta
Potasio
Cloruro.
La
muestra
SHJ3
es
una
fuente
de
(158jiS) ubicada cerca de las otras caracterizadas
salinidad
con la misma
sigla y discutida anteriormente en el grupo A , mientras que la

muestra WP1 (30C y 370/iS) proviene de un pocito profundo de 127m,
esta ubicada a un Km al sud del pozo Sol de Manana.
Las otras cinco fuentes stan ubicadas en la esquina Oeste de

la Laguna Salada
(area del Salar de Challviri) y se encuentran
localizadas a un nivel mas alto de la laguna, excluyendo asi un

primer grado de contaminacin directa.
De las numerosas fuentes, cuyo caudal de agua es de 100 1/seg y
cuya conductividad y temperatura disminuyen progresivamente hacia

el Norte, solo las mas importantes fueron muestreadas.
Es
interesante
observar
los
datos de muestreo
realizados en
Laguna Salada, la temperatura es inversamente proporcional a los

porcentajes
del
componente
Suifato-Alcalino
directamente
proporcional al Alcalino-Clorurado, con la sola excepcin de SC11.
(Ver
fig. 8 y 9)
42
SC2
40-
.SCI
SC 11
(1989)
38-
36-
SC11
'SCII C989)
SC4 (1989)
SO.
O)
32-
SC21
(19891
30SC21
28-
26-
25
20
I
30
i
35
NQ-K-S04
FIG.
100
TEMPERATURA
i
40
Vs.
Na - K - SO,
50
42
SC2
.SCI
40-
"SC 1(1989)
38-
36
SC 11 (1989)
"
.SC 4 (1989)
SC4
I 32
SC 21 (1989)
30-
28-
26-
15
10
FIG.
20
25
Na-K-Cl (%)
TEMPERATURA
30
35
Vs. Na - K - Cl
GRUPO C Formado de LC1, LC4, LC5, LC11, LC12, SC10 y las
muestras
de
los
pozos.
Este
grupo
de
muestras
es
del
tipo
Alcalino-Clorurado se puede dividir en dos subgrupos: el primero

comprende
las muestras
LC12 (Laguna
Colorada),
SC10 (Salar de
Challviri) y cuatro fuentes tibias LC1, LC4, LC5, LC11 localizadas
alrededor de Laguna Colorada. La temperatura y la conductividad de

estas
ultimas
varian
respectivamente
entre
28.1-30.1C
390-
1670/zS.
El quimismo consiste principalmente en el componente AlcalinoClorurado mayor al 50%, en las lagunas puede aumentar mas del 75%.
El
componente
restante
puede
ser
subdividido
en
Bicarbonato-
Alcalino, y Sulfato-Alcalino Trreo. En alguna de estas muestras
hay cierta interaccin con las aguas de Laguna Colorada.

El
segundo
subgrupo,
como
ya
se
ha
mencionado,
comprende
fluidos de pozos profundos gu, a excepcin de SM2 (2922), tienen
un componente Clorurado-Alcalino mayor del 95%. La muestra SM2

(2922) que ha sido muestreada del pozo a una profundidad de 1240
m, rsulta mas compleja
presentando una suma total
de los dos
componentes Bicarbonato-Alcalino y Sulfato-Alcalino mayor del 15%.
101
4.2. Consideraciones gnrales de las caracteristicas del agua

La evaluacin de la composicion quimica de las muestras tomadas
fines
del
corresponde
1986 ponen
a
tipos
en
de
evidencia
circuitos
que
cada
superficiales
una
de
ellas
ninguna
mostrado mezcla con una fase liquida originada por la interaccin
a altas temperaturas con un reservorio de naturaleza volcnica.

El calentamiento de las aguas discutidas en el prrafo anterior
podria explicarse por el flujo de vapor; en el rea en estudio
existen
numerosas
manifestaciones
localizadas
diverses
kilometros unas de las otras (Sol de Manana, Huaylla Jara y Aguita

Brava), originadas por fenmenos de ebullicin.
La investigacin de componentes trazas como Amoniaco y Acido
Brico excluyen esta hiptesis. Por ejemplo las muestras SCI y SC2
(en el rea de Salar de Challviri) tienen una temperatura de 30C

mayor a la temperatura estacional promedio. Un flujo de vapor del
9%
en
peso,
200 "C,
es
la
cantidad
requerida
para
calentar
convectivamente el agua de 10 a 40C. En ese caso se tiene que
tomar en cuenta el contenido de NH3 en las "Steaming pools" y en

las fumarolas respectivamente. Un tal flujo de vapor produciria en
SCI y SC2 una concentracin de NH3 500 veces mayor a los valores
observados.
mismo
Las mismas consideraciones
mecanismo
deberia
son
implicar
aproximadamente 500 mg/1 contra
para
el H 3 BO 3 , este
concentraciones
de
los 30 mg/l de los actualmente
encontrados. Un proceso de este tipo necesariamente
implica una
proporcionalidad directa entre la temperatura y el porcentaje de

sulfates
(oxidacin
del H2S prsente
en
el
vapor),
la
fig. 9
muestra que esta proporcionalidad existe solo con el componente

Clorurado-Alcalino.
Por otra parte teniendo en cuenta la pequena extension de rea

y
la
cantidad
de
agua
caliente
confluiente
en
la
laguna,
la
temperatura de esos fluidos no puede ser explicada solo por el
102
mcanisme
de
conducin.
La
disponibilidad
de
los
anlisis
del
fluido de pozos a permitido aclarar mejor el origen de las fuentes

calientes del
Salar de
Challviri; si
se
considra
el diagrama
triangular Li, Rb, Cs (ver fig. 10), los puntos representativos de

SCI y SC2 resultan extremadamente vecinos a los pozos profundes.
LEYENDA
o
Muestras de L Colorado
Muestras del Talio
i i i i i i i l : l l i l i l l l i M
ri l i i i l l r M
l l l l l i l l l l l i l i
Rb (mg/l) * 4
FIG. 10
DIAGRAMA TRIANGULAR
Li, Rb, Cs.
La presencia de stos componentes en agua asi diluida no puede
ser atribuida a procesos de interaccin agua roca superficiales a

una
baja
temperatura,
contaminacin
del
se
acuifero
puede
en
explicar
cuestin
por
unicamente
parte
del
por
fluido
profundo.
Un aporte del 3-4 % de un fluido con las mismas caracteristicas
de
aquellas
encontradas
en
la
perforacin
profunda
no
solo
justificaria el contenido de Cl, Li, Rb, y Cs encontrados en estas
fuentes termales, sin tambin un incremento en su temperatura de

103
aproximadamente 1CTC. Reconsiderando la Fig. 9 si se extrapola a

cero el components Clorurado-Alcalino, la temperatura teorica del
acuifero
resultaria
aproximadamente
28C,
con
un
incremento
respecto a la temperatura estacional media de aproximadamente 15 a

20C. Esto es debido probablemente al mecanismo de conducion.
Para
concluir
tambin
la
temperatura
de
las
otras
fuentes
termales que emergen alrededor de Laguna Colorada y Cerro Huaylla

Jarita deben ser ligadas a factores conductivos.
Las
caracteristicas de las fuentes frias SPB1, SPB2 y SPB3
muestreadas a dclive en el cerro Lagunitas son definitivamente
anomalas: estas ultimas, no obstante tienen una temperatura baja y

muestran cantidades de NH4 y H3BO3 mucho mayor de aquellas que se
deberian esperar razonablemente con respecto a los solidos totales
podrian
ser
efectivamente
contaminadas
por un
lev
flujo
de
vapor. Finalmente en la fig. 10 fueron indicados con triangulos

pequenos las muestras de pozos y manifestaciones del campo geotermico
del
Tatio
(Chile),
la
casi
perfecta
sobreposicion
de
puntos representativos, da una vez mas la estrecha similitud de
los
fluidos geotermicos originados en los dos campos distintos
(Sol de Mariana y El Tatio) distantes entre si 20 Km.
5. Geotermometros
5.1. Consideraciones gnrales
Por
lo
que
se
menciono
anteriormente
no
es
posible
hacer
ninguna evaluacion basada en la composicion quimica de los puntos

de agua
superficiales disponibles,
porque ninguna de ellas
fue
reconocida como un fluido de origen profundo; tambien las muestras

SCI y SC2 son contaminadas seguramente a un nivel mas bajo y no
pueden ser utilizadas para tal objeto.
En lo que se refiere a fluidos profundos la interpretacion es

simplemente hecha usando el diagrama ternario de Giggenbach
104
[3]
(ver
Fig. 11)
basado
simultaneamente
en
dos
funciones
termomtricas Na/K y K/Mg.
LEYENDA
7 _ Na/1000
On
Agua superficial
Muestras de fluido total
Muestras de vertedero
<>
Muestras de pozo
Muestras del Tatio
Curya de full
equilibrio
2 x Dilucio'n
10 * Dilucio'n
K/100
% Mg
Fig 11- Diagrama de Giggenbach
Na, K, Mg
Los puntos representativos de pozos profundes del area Sol de

Manana se colocan todos sobre la isoterma t Na/K de 280C., la
mayor parte, ya sea muestras tomadas al vertedero (ST) o de fluido
total
(FT) , se encuentran a la izquierda de la curva de "full
equilibrium". Una posible explicacin es que durante la salida del
fluido
profundo
se
verifica
un
fenmeno
de
precipitacin
que
reduce la concentracion inicial de Mg.

Las muestras tomadas en los pozos, SM1(1000 m) y SM2(1240 m)
que
respecto
diluidas
la
composicin
terica
del
reservorio
son
mas
(aproximadamente 2.2 y 10 veces), en este diagrama se
colocan mas alto y en el caso del pozo SM2 tambin a la derecha

respecto a la posicion que deberian tener si fueran diluidas con
105
agua destilada en la proporcion encontrada por los anlisis. Todo

esto nos hace considerar que los pozos presentan distintos nivels
de permeabilidad, caracterizados por fluidos con temperaturas y

composiciones
estticas
distintas;
son
una
las
muestras
mezcla, con
tomadas
relaciones
en
condiciones
distintas
respecte
aquellas muestreadas en el curso de la produccin.

La
temperatura
obtenida
de
la concentracin
de SiO2
en el
vertedero, corregida por la prdida de vapor [4], rsulta para SM1

y SM2 respectivamente 249 y 258C. Estos valores son cercanos a
los medidos directamente en los pozos, mientras los obtenidos de
las funciones geotermomtricas inicas t K/Na y K/Mg indican de

hecho temperaturas superiores de 40-50C.
La hiptesis mas probable es que el fluido producido en el area
de Sol
de Mariana
proviene
de
horizontes
mas
profundos
de
las
fracturas productivas que se encontraron en la perforacin.

La temperatura en la parte mas profunda del reservorio esta
dada por
potasio,
la relacin
mientras
la
Na/K,
reequilibrandose
temperatura
en
la
zona
lentamente
donde
se
sodio y
produce
actualmente estaria por la concentracin de Sicu. La relacin K/Mg

indica
una
explicar con
temperatura
un
mayor
fenomeno
de
que
la
anterior,
ebullicin
esto
podriase
degasificacin
en
el
reservorio.
Esta hiptesis se confirma:

- por la presencia fisica de numerosas fumarolas y "hot pools"
en
el
rea
Sol
de
Manana
cuya
extension
superficial
esta
necesariamente ligada a un gran fenomeno de separacin de fases.

- por calcules tericos, considerando que la Anortita es el
nico minral prsente en el reservorio que proporciona calcio en
solucin. A
la temperatura de 240C, con
la cantidad de calcio
prsente en el reservorio (175 mg/1) la presin parcial de C02 que
106
dtermina el equilibrio entre la Anortita y la Calcita es de 7.9

atm,
mientras que la calculada de los datos analiticos de los
fluidos producidos en el
pozo es de 1.37 atm.
La concentracin de SiCu queda en cambio inaltrable y esta de

acuerdo con las medidas de temperatura efectuadas.
6. Geoquimica isotpica
6.1.
Reconstruction
isotpica
del
fluido
de
reservorio,
generalidades y mtodos
Como
ya
indicado
anteriormente,
durante
las
pruebas
de
produccin no ha sido posible efectuar un muestreo representativo
del condensado de los pozos. Esto obviamente, hizo imposible el
calcule de la composicion isotpica del fluido en el reservorio,

por simple balance de masa entre el vertedero y el condensado.
Esta problemtica fu afrontada utilizando el anlisis del fluido
total (muestras FT) oportunamente corregido como ya hemos indicado

en el capitulo 3. La comparacin entre el contenido analitico de
Cloruro en el fluido total y el resultado terico calculado a
partir de los cloruros prsentes en la muestra
del vertedero
indican de hecho que las muestras furon tomadas a una fraccin de
agua mayor
de aquellas tericas.
Los resultados asi obtenidos furon controlados con los valores

calculados a travs de la composicion isotpica en el vertedero
(ver fig. 2 punto 2) hipotetizando que el proceso en la produccin

sea reconducible a dos mecanismos fundamentales: un fenmeno de
separacin de vapor que ocurre entre el reservorio y el boca pozo

(asimilable a una continua prdida de vapor) y a un proceso de
"single stage steam loss" lo que opra entre el boca pozo y el
separador atmosfrico.
107
En la siguiente tabla aparecen los resultados obtenidos:

METODO 1
METODO 2
POZO
<518O
<S180
SM1
-7.05
-81.7
-6.70
-77.3
SM2
-6.85
-80.8
-6.77
-79.9
MEDIA
-6.95
-80.9
-6.73
-77.6
6 D
6 D
Considerando la medida de valores calculados se verifica una

diferencia muy
reducida, estos valores son
adems estrechamente
cercanos aquellos postulados por Giggenbach
[5]
para
el vecino
campo geotrmico de El Tatio (618O = - 6.9, 5D= - 78).

Fueron escogidos como valores de referenda para el fluido de
reservorio 618O = -6.9 y <5D = -78; sobre esta base se elaboraron
las consideraciones relativas a las manifestaciones superficiales.
En el caso del pozo Apachetal
(API) no fu posible ap] icar
estas metotologias porque el exceso de entalpia medido esta casi
seguramente ligado a fenomenos de segregacin de fase con o sin

cesin de calor de parte del reservorio.
Esta circunstancia se traduce en el flujo en el pozo de una

cierta
cantidad
disponibles
no
de
es
vapor,
cuya
valuable.
consistente con los valores de
composicion
Tal
18
mecanismo
con
no
los
datos
obstante
es
y D los cuales en Apacheta 1
(API) son resultados mucho mas negatives que los correspondientes

a las muestras de los pozos SM1 y SM2.
6.1. Fuentes termales y frias

En
la
figura
12
son
reportados
los
resultados
analiticos
pertinentes a los istopos, observamos variaciones en el contenido

de <S18O y 6D las cuales no son fcilmente explicables frente a la
altitud.
108
Las
variaciones
parecen
bastante
regulres
con
una
Agua residua despues

de Single step poilmg
enlre 2<0 y
85C
L E Y E N D A
Vapor pnmano de agua

de reservor'o pnmaria
diluida con agua de tipo
LW
Agua superficial ( Rios, Lagunas. Nieve)

Vapor pnmaoo de agua
de
no dtluid
Vapor pnmano de agua

de reservofio primana
diluida con agua de tipo
R W
Surgentes de aguas termales y f r i e s

Muestras de fumarolas corregidas por el fraccionamient
en el curso de la condensacidn
Muestras de fumarolas sin correccion

Lodos calientcs Laguna Colorada
Aguas profundes
FIG.
12
DIAGRAMA <S 18 O Vs 5D EN AGUA.
tendencia hacia de valores ms negativos en la direccin N-E (esta

tendencia puede llegar tambin al Salar de Empexa).
No es fcil entender la razn de ese desarrollo probablemente
ligado a fenmenos metereolgicos (debido a la masa de nubes que
originan
la precipitacin).
Esas
ultimas
pueden
venir
predomi-
nantemente del Oceano Pacifico.

En particular
considerando
los datos pertinentes de Huaylla
Jara y Aguita Brava, nieve del Volcan Michina (N) y el Rio Huaylla
Jara (RHJ), los puntos muestreados, en absoluto los mas positivos,
se
unen
con
el
punto
D,
que
sria
el
agua
meteorica
local
postulada por Giggenbach para el campo geotermico del Tatio [5].

RAB , SHJ3, WP1, LC11 y de modo menor, SHJ1, SHJ4 y SAB7 tienen
una
composicion
pudiera ser
mas
negativa.
Por
el
contenido
de
deuterio,
considerada como una posible recarga de los campos
geotrmicos de Chile y Bolivia. La interseccin de la paralela al

eje de la absisa que pasa por el punto DW (composicin isotpica
de los pozos) con
la recta meterica da el punto RW
(agua de
recarga).
Los puntos de agua muestreados al norte de Laguna Colorada RS,
LC1,
LC4, y aquellas mas al sud SPB1, SPB2 en proximidad al Cerro
Lagunitas, resultan pues en absoluto mas negativas del area entera
en estudio.
Por lo que se refiere a las surgentes en torno a Laguna Salada
y la muestra LC5 sus composiciones son intermedias a aquellas dos
de los grupos anteriores.
No
obstante
los
puntos
de
aguas
frias,
de
origen
local
sublocal, son muy pocas, por lo tanto es dificil dar un cuadro de
la distribucin de los valores isotpicos, haciendo asi una vez

mas,
complicada la explicacin de las variaciones observadas.

La impresin final es que las variaciones isotpicas y quimicas
no son vinculadas a las anteriores, son mayormente causadas por

mecanismos metereolgicos.
110
Resumiendo, las variaciones de
18
O y deuterio identifican una
linea local meterica con la ordinaria pendiente de 8 pero con una
interseccin menor de 10 probablemente 5. Ciertamente la falta de

cambios isotpicos en las fuentes, sugiere que ninguno de esos
fluidos reaccionan con el reservorio a alta temperatura.
6.2 Fumarolas, "steamed pools" y aguas profundas

El vapor de las "hots pools" en el lado derecho de la grfica
6O
vs 6D del diagrama
(ver fig.
12) , esta bien alineado a lo
largo de una recta con una pendiente alrededor de 1.6; este valor
es el misrtio que
caracteriza el campo de El Tatio [5].
En la interseccin de esa linea con la linea de las aguas
metericas se obtiene el punto LW (local ground). Este punto, muy

cerca a los puntos N (nieve del Volcan Michina) y RHJ (Rio
Jara) , puede
ser
considerado
representativo
de
la
Huaylla
composicion
isotpica de aguas freticas en la zona donde estn prsentes

estas manifestaciones.
La fumarolas, cuyas composiciones fueron corregidas por causa
del fraccionamiento durante la condensacin, (solamente para las

muestras tomadas en el area de Huaylla Jara y Sol de Mariana de
1986
y para las muestras SMO tomadas en 1989), se encuentran a lo
largo de la linea con una pendiente alrededor de 8, extendindose

3
unidades
518O a
la
derecha,
lejos
de
la
linea
meteorica
interceptada a +10.
El punto DW reprsenta la composicion media del liquido del
reservorio que alimenta los pozos de Laguna Colorada, similar al
que al prsente alimenta el campo fronterizo de El Tatio. La recta
reprsenta
la
composicion
de
los
liquidos
residuos
que
se
originan en DW por "single stage boiling".

La ausencia de puntos representativos debajo de la linea C esta
de acuerdo con la falta de muestras representativas del liquido

profundo en el area investigada.
111
Con
la excepcin de FAB6
fraccionamiento
durante
la
(que no ha sido corregida por el
condensacin),
todas
las
fumarolas
estn localizadas dentro la region comprendida entre las curvas A,

B y B1 como se puede observar en la figura 12.
En las mismas curvas estn tambin incluidos todos los vapores

que teoricamente se pueden formar:
- por ebullicin del liquido primario DW a temperaturas mas
bajas de 240C por un enfriamiento conductivo (curva A).

- por
dilucin
ebullicin
con
de
un
diferentes
liquido
primario
porcentajes
DW
de
despus
agua
de
de
la
recarga
representadas por el punto RW (curva B).

- por
dilucin
ebullicin de un
con
diferentes
liquido primario
porcentajes
de
DW, sucesiva
agua
fretica
a la
local
representada por el punto LW (curva B 1 ).

7. Geotermometria de los gases
Durante la produccin de los pozos SM1 y SM2 fueron tomadas

muestras de gas
natural
con modalidades distintas
entre
ellas
(salida del separador atmosfrico y muestreo de fluido bifase).

Las
muestras
contaminacin
mas
de
representativas
aire
sobre
fueron
estas
corregidas
fueron
aplicadas
por
la
tcnicas
geotermomtricas. La composicin del gas producido por el pozo SM1

esta presentada en la tabla 6; la Fraccin de Vapor calculada por
el Flash de 244 a B5C y la relacin Gas/Vapor
son respectiva-
mente O.304 y 1.10 NL/Kg.
Desafortunadamente no existe medidas
de H2
para el pozo en
examen, por lo tanto es posible aplicar solo el geotermometro que
utiliza el CO de Giggenbach
fumarolas
puede
Chiodini
ser
Cioni
[6]; por
utilizado
[7],
lo que se
tambin
esto
ultimo
el
refiere a las
geotermometro
permite
contemporaneamente, la presin de CO2 en el reservorio.
112
de
de
obtener,
En la tabla 6 estan representados los resultados por el pozo

SM1 (265C) y las fumarolas.
Estos
risultados,
existe una
a pesar que entre
diferencia costante de 50C
los dos
geotermometros
aproximadamente, de toda
manera indican que la temperatura y la presin de CO2 mas elevadas

se encuentran en la zona de Aguita Brava muy cercana al Volcan
Micina. Este ultimo es, sin lugar a dudas, la fuente de calor mas
importante de toda el area estudada.
Como
se
puede
representan
muestras
los
de
observar
contenidos
gas,
aun
en
la
relatives
sendo
figura
de
13,
N2/
contaminadas
en
Ar
la
y
por
que
He,
una
se
estas
componente
meteorica, parecen indicar un origen de los gases mas crustal que

magmatica.
No/100
IOOO
30
10He
FIG.
13
CONTENIDOS RELATIVOS DE N
Ar y He.
1
113
REFERENCIAS
[1] ENEL - Estudio de factibilidad geotrmica en el area de

Laguna
Colorada,
Naciones
Unidas/PTCD,
proyecto
BOL
84/007, 1986.
[2]
ENEL
- Final
report
of the
ENEL technical
mission
to
Bolivia (Laguna Colorada), 10-16 March 1986.

[3] Gigghenbach,
Derivation
of
W.F.
Geothermal
Na-K-Mg-Ca
solute
geoindicators.
equilibria.
Geochimica
et
Cosmochimica Acta, 52, 2749-2765, 1988.

[4] Fournier,
expanded
R.O. and
silica
Potter,
quartz
R.W. -
revised
geothermometer.
and
Geothermal
Research Council Bullettin, v. 11, 3-9, 1982.

[5] Gigghenbach, W.F. - The isotopic composition of waters
from
El
Tatio
geothermal
field.
Geochimica
et
Cosmochimica Acta, V. 42, 979-988, 1978.
[6] Gigghenbach,
analysis
of
W.F. and
geothermal
Goguel
and
R.L. -
volcanic
Collection
waters
and
and
gas
geobarometry
for
discharges. DSIR Report n. CD2401, 1989.
[7] Chiodini
G.
and
Cioni
R.
Gas
hydrothermal systems and its application to some Italian

geothermal
1989.
114
areas.
Applied
Geochemistry,
v.
4,
465-472,
GEOCHEMICAL REPORT ON THE EMPEXA

GEOTHERMAL AREA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per 1'Energia Elettrica,
Pisa, Italy
W. CASSIS
Empresa Nacional de Electricidad,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE EMPEXA, BOLIVIA.

La zona de Empexa esta situada cerca de la frontera con Chile, en la provincia de Daniel Campos, Departamento de Potosi, a aproximadamente 6830' de
longitud y 2022' de latitud.
Se caracteriza la zona por la presencia de un
vasto salar en una cuenca volcnica a una altura de 3 717 m sobre el nivel del
mar.
Muchas de las actividades trmicas tienen lugar en los limites de este
salar, pero las mas calientes se encuentran en una zona limitada;
la cantidad
y la circulacin de gases libres son muy reducidas.

Toda
la
parte
sur
de la
zona es
riquisima en azufre y cido borico.
Existen diversas minas de las que se extraen grandes cantidades de azufre.
La
presencia de estas materias y la intensa filtracin de los depsitos salinos

evaporiticos, causada por el continuo retroceso del salar, hacen muy dificil
caracterizar las muestras de agua y calcular la composicion original del fluido termal profundo.
La temperatura maxima calculable del
depsito a juzgar
por las muestras de superficie, no deberia sobrepasar los 180C.
GEOCHEMICAL REPORT ON THE EMPEXA GEOTHERMAL AREA, BOLIVIA.
The area of Empexa is

the
province of
Daniel
situated near the border with Chile in
Campos,
Department
of
6 8 3 0 ' of longitude and 2 0 2 2 ' of latitude. It
Potosi,
at
roughly
is characterized by
the presence of a vast salar in a volcanic basin at an altitude of

3717
m above the
sea level. Many of the thermal manifestations are
located at the edges of this salar, but the hottest are found in a
restricted area; the presence and the
flowrate of free
gases is
very limited.
115
All the south of the area is highly rich in sulphur and boric
acid.
There
are
various mines
from
which
high
quantities
of
sulphur are extracted. These occurrences and the strong leaching
of
the
saline
evaporitic deposits,
receding of the
caused
salar, make very diffucult
by
the
progressive
to characterize the
water samples and to estimate the original composition of the deep
thermal fluid. The maximum computable temperature in the reservoir

from surface sample should not exceed 180C.
1. Sample collection and field determinations
The sampling in the Rio Empexa Valley was carried out over a
period of four days, from the 17th to the 20th of March 1986.
total of 18 samples of hot and cold springs were taken, 2 of free

gas,
3 of residual gases collected
from two water points and one
fumarole in the sulphur mine Mina conception.

The limited amount of time did not allow the carrying out of a
complete survey.
surveys,
Some of the water points recorded
conducted
in
1976
and
1977,
were
not
in previous
found
[1],
the
location of these points was imprecise and the organization of the

field work did not permit an inventory of all the water points
present in this area and the collection of a suitable brine sample
of the salar.
The analysis of the fluids sampled during the 1986 survey are
shown in tables 1 (waters) and 2 (gases) . During the elaboration
of this report, the data from previous studies on water points not
found
at
the
time
of
collection,
have
been
also
taken
into
consideration.
Samples location
(fig- 1) defines an area of about 300 km2 ;
the most significative manifestations are

edge
of
the
salar.
The
flow
rate
of
located on the southern
the
water
points
at
the
highest temperatures (t > 65C) varies between 0.3 and 4 1/s for a
116
i =.--'-. ^_ CmCX ALTAM1KA Z
/iM-*"?*^ r S1,1
. E.ne,.w,i
"' ~
=?
*'(- --
MM "CAUEJONl *f>t-
~'SALAR DE EMPEXA
= Surface water points

A = Test holes
fe- = Mina conception (fumarole)
Fig.l - Location map of Empexa area samples.

117
Table 1 - Empexa water samples analyses

s = spring, r = stream, w = well, b = brine
Sample;
Date
Cod. S. T. T. f. pH. f. Con. f. /Uc.f.
E01
E02
E03
E04
E05
E 06
E07
E 08
E 09
E10
E11
E12
E13
EH
17/03/86
17/03/86
17/03/86
07/05/78
17/03/86
29/04/78
17/03/86
29/04/78
01/05/78
29/04/78
10/05/78
10/05/78
20/03/86
20/03/86
07/05/78
12/05/78
07/05/78
0841 S
0840 S
0839 S
S
0842 S
S
0843 S
R
S
S
S
S
0853 S
0852 S
S
S
U
E15
E16
E17
E18
E19
E20
E21
E22
E23
E24
E25
E26
E27
E 28
E29
E30
E31
E32
E33
UE1
WE2
WE4
UE5
WEG
19/03/86 0850 S
02/05/78
S
02/05/78
S
20/03/86 0855 S
26/04/78
W
01/01/78
U
01/01/79
W
01/01/79
W
01/01/79
W
01/01/79
W
SE135
01/09/76 135
SEUO
SEK1
01/09/76 140
01/09/76 141
8
B
20/03/86 0854 S
18/03/86 0848 S
18/03/86 0846 S
18/03/86 0847 S
19/03/86 0849 S
17/03/86 OS44 S
18/03/86 0845 S
04/05/78
27/04/78
S
19/03/86 0851 S
27/04/76
S
11.0
14.0
14.0
13.0
22.0
30.0
35.0
15.0
15.0
13.0
18.0
25.0
25.0
34.0
32.0
75.0
17.0
18.0
16.0
68.0
22.0
69.0
86.0
87.0
45.0
9.0
11.0
10.0
/'S
7.18
7.86
7.25
6.50
3.34
4.30
4.85
4.15
6.80
5.70
7.50
6.70
6.60
6.61
6.80
1.70
0.90
7.04
4.50
5.90
5.70
5.75
8.27
7.67
5.80
7.40
141
520
370
690
1190
15200
13000
7550
15100
2490
8910
10500
6260
6160
8080
49500
57700
6730
4190
24500
6940
6550
6070
7.08
4910
621
35.0
15.0
13.0
6.70
6.75
8.20
7.50
5920
1550
125
1960
11.0
36.0
64.0
29.0
111
23.0
20.0
20.0
20.0
3.80
7.50
8.40
6.90
6.80
7.60
7.00
7.00
7.00
1240
8000
8000
5400
7100
5400
meq/l
1.1
1.8
1.4
0.7
0.2
0.8
12.0
5.5
5.6
9.4
2.1
7.3
15.9
4.7
5.1
7.2
0.8
0.2
0.5
1.1
2.9
6.3
2.7
1.7
9.1
1.3
r. l.
pH. l. Con. l. /MC. l.
c
25
25
25
25
25
25
25
25
25
25
25
25
23
23
25
25
25
24
23
25
25
23
25
23
25
25
23
25
23
25
25
24
25
25
25
25
25
25
20
20
20
Rlc.l.
meq/ 1
meq/ 1
6.24
6.60
6.66
155
463
372
0.8
0.8
1.0
1.7
1.0
1.7
3.50
1160
4.78
12700
6.99
6.84
6450
7050
Ca
Mg
Na
12.5 6.00 8.9
5.6
Cl
6.73
6.73
6.58
8.72
8.11
0.00
67.J
4560
26400
43100
54100
6580
6370
S i 02
H3B03
7.4
30.3 0.0
51.8
40.4
59.6
60.0
71.0
38.0
20.0
58.0
65.0
53.0
41.0
4.5
2.4
3.6
4.0
7.6
39.6
38.0
25.0
43.5
25.4
13.5
37.8
41.0
45.0
50.2
792.0
1100.0
38.6
62.0 11.60 2 4 . 7 6.8

7.6 196.0 67.1
40.0 11.80 2 0 . 4 9.8
14.4 97.4
107.4
56.3 12.80 30.1
12.0 13.0 194.0
86.6
120.0 13.00 108.0 110.0
156.0 391.0 0.0
965.0 131.00 2440.0 71.4 4750.0 1620.0
0.0
930.0 107.00 2350.0 64.0 4580.0 1600.0
0.0
518.0 56.70 1030.0 40.9 1890.0 1150.0
0.0
696.0 187.00 2230.0 131.0 4300.0 1410.0 2013.6
186.0 26.30 136.0 6.8
121.0 682.0
0.0
769.0 103.00 940.0 30.0 2960.0 179.0 4 5 . 7
5.4
5.4
252.0 196.00 1780.0

390.0 118.00 898.0
89.7 2960.0 907.0

74.0 1440.0 1150.0
5.4
5.4
390.0 130.00 1030.0
8 4 . 0 1660.0
732.2
335.6
1140.0 341.7
1310.0 573.6
36.4 0.0
5 7 . 1 0.0
446.0
128.1
589.0
0.0
105.0
112.0
118.0
563.0
330.0
82.0
105.0
956.0
445.4
174.0
15.2 509.0 405.00 8500.0 310.0 13600.0 2340.0
970.2
286.8
146.0
164.0
385.0 161.00 1280.0 108.0 2040.0

753.0 405.00 6750.0 646.0 13500.0
1260.0 240.00 9000.0 913.0 18800.0
6.78
5.81
HC03
S04
2.0
0.6
7.0
15.4
4.6
4.4
4.9
2.0
0.6
6.8
4.6
3.8
4.5
0.00
6.51
642
0.8
0.8
0.00
6.50
0.00
0.00
0
1830
0.0
0.5
0.0
0.5
4.22
0.00
0.00
0.00
0.00
0.00
0.00
7.00
7.00
7.00
210
171.0 92.00 1110.0 67.0 1910.0

290.0 48.60 580.0 74.0 1160.0
83.0 203.00 5100.0 187.0 8100.0
125.0 522.00 11100 412.0 17900.0 2020.0

3.0
0.25 1410.0 5 3 . 0 1800.0 338.0
87.3
6.6
0.17 1380.0 5 2 . 5 1760.0 326.0 274.6
7.4
2.80 1320.0 4 4 . 8 1700.0 342.0 4 4 4 . 8
196.0 13.50 338.0 4 3 . 3 759.0 226.0 4 5 . 6
5 2 . 2 12.60 4 5 . 0 20.8 2 7 . 2 202.0
0.0
266.0 16.90 486.0 59.2 1040.0 301.0 12.9
128.0 8.30 201.0 23.4 459.0 128.0 30.5
6.4
2 . 6 0 5.0
2.7
4.4
1 5 . 4 63.5
80.7 47.00 118.0 2 3 . 4 262.0 159.0 176.3
13.6
2.60 11.6 5.8
4.7
69.6 0.0
83.8 12.00 58.4 8.9
8.8 372.0
0.0
421.0 133.00 1060.0 121.0 1740.0 1430.0 380.7
150.0 59.00 1380.0 7 4 . 0 1840.0 1150.0 55.3
261.0
37.50
736.0 101.0 1280.0
672.0
103.7
28.1
2.90 1430.0 50.8 1740.0 399.0 536.9
341.0 21.80 644.0 74.3 1380.0 437.0
78.1
420.0 3000.0 60000 9200 131000 13400 17085
580.0
10000
440.0
11000 85000
90000
6100
8500
200000
190000
1630020746
11000 14034
80.2
244.0
278.0
400.0
80.0
78.6
7.0
118.0
38.0
78.0
72.0
108.0
246.0
397.0
90.0
246.0
90.1
65.0
177.0
280.0
288.0
120.0
115.0
164.0
32.0
9.0
41.9
23.0
3.4
60.9
3.2
8.5
54.9
74.2
74.2
124.0
74.1
Br
0.00 0.00
0.00 0.00
0.00 0.00
0.15 0.00
1.40 0.42
0.42 0.31
0.49 0.31
0.90
2.00
3.20
4.60
4.40
2.40
2.40
0.31
0.54
0.84
1.00
0.77
0.97
0.84
0.00 0.00
0.74 0.42
Table 1 - ( cont.)
Sample Code
Li
Rb
E01
E02
E03
E04
0841 0.00
0840 0.00
0839 0.00
0.00 0.00
0.00 0.00
0.00 0.00
E05
E 06
E07
E08
E09
E10
E11
E12
E13
EH
E15
E16
E17
E18
E19
E20
E21
E22
0842 0.44
0.140.06
0843
1.40
4.20 0.32
0853 0.75
0852 0.76
2.00 0.21
2.40 0.26
0854
0848
0846
0847
0849
0844
0845
0.00 2.20 0.18

0.22 2.70 0.40
0.96 13.40 0.96
1.70 21.40 1.80
0.67 25.00 1.80
2.60 6.00 0.49
2.60 6.?0 0.44
E27
E 28
E29
E30
E31
0851
0.00
0.01 0.05
0850 0.42
1.00 0.08
E32
0855 0.00
0.00 0.00
E23
E24
E25
E26
E33
UE1
WE 2
WE 4
WE5
WEC
SE135
SEKO
SE141
135
140
141
190.0
260.0
440.0
Cs
NH4
Sr
Ba
Zn
0.00 0.000 0.10 0.020 0.000

0.00 0.014 0.29 0.010 0.000
0.00 0.007 0.24 0.020 0.000
0.010
0.00 0.018 0.36 0.010 0.046
0.056
0.35 0.068 8.10 0.020 0.043
0.011
0.006
0.020
3.017
0.020
0.00 0.200 4.60 0.020 0.000
0.00 0.005 4.80 0.020 0.000
0.005
0.288
0.000
0.00 0.061 1.60 0.020 0.007
0.24 0.300 1.60 0.010 0.018
1 .30 0.300 2.70 0.210 0.033
2.40 0.100 6.60 0.170 0.034
1 .60 0.504 2.70 0.130 0.230
1 .10 0.056 1.40 0.040 0.000
1 .40 0.043 2.60 0.190 0.000
0.041
O.OOU
0.00 0.041 0.34 0.020 0.000
0.020
0.22 0.012 2.20 0.000 0.000
0.007
0.006
0.00 0.000 0.04 0.010 2.600
0.001
0.063
0.167
0.198
0.324
0.054
Sb
As
Fe AI. T Al. H
0.000 0.00 0.000 0.000 0.000

0.000 0.00 0.000 0.000 0.000
0.019 0.00 0.000 0.000 0.000
TDS
127
TAM
T CAT
,5180
SO
meq/l
meq/l
o/oo
o/oo
0.8
Trit. 5180/S04 534S/S04 Alt.

U. T.
o/oo
1.6 -14.82 -117 .2
5.3
352 5.4
259 4.2
4.1
384 5.8
5.5
0.020 0.00 0.025 4.200 2.000 982 12.5 14.6
10055 168.0 167.0
0.000 0.12 1.600 0.570 0.260 9708 162.0 159.0
4769 77.3 76.4
9096 184.0 150.0
1236 17.6 17.5
5036 88.0 88.5
6315 114.0 108.0
0.000 0.42 0.011 0.050 0.000 4225 70.1 70.1
0.000 0.50 0.010 0.050 0.000 4601 76.2 77.1
5462 94.2 90.9
23446 382.0 381.0
31700 531.0 497.0
0.000 0.26 0.000 0.000 0.000 3919 65.3 66.1
0.011 1.40 0.000 0.000 0.000 2921 45.0 45.6
0.056 4.70 0.012 0.070 0.000 15009 256.0 247.0
0.016 8.10 0.130 0.000 0.000 26138 448.0 436.0
0.023 4.30 0.180 0.080 0.000 32573 552.0 543.0
0.069 4.40 0.000 0.039 0.020 3989 59.3 62.9
0.070 4.10 0.000 0.039 0.020 3937 61.0 61.7
3988 62.4 59.2
1688 26.9 26.7
.0.000 0.02 0.000 0.048 O.OUO 448 5.0
6.1
2218 35.8 37.3
0.000 1.70 0.000 0.000 0.000 1096 16.1 16.4
0.8
79
1.5
832 13.6 13.6
1.6
186 1.6
0.000 0.00 0.039 0.032 0.000
660 8.0
7.9
5212 85.1 81.2
5125 76.8 74.3
3254 51.8 50.7
4030 66.2 65.1
3064 49.3 48.7
234510 4250 3110.0
344040 6320 4920.0
320380 5820 4840.0
-14.75 -113 .6
-14.01 -108 .8
0.3
0.2
-15.30 -118 .2
-14.94 -114 .4
-11.41
-11.62
-89 .0
-87 .9
-14.73
-13.68
-12.96
-8.45
-12.52
-13.06
-12.77
-110.5
-102 .8
-98 .7
-80 .6
-V6 .8
-99 .3
-100 .3
0.4
-15.42 -113 .8
0.4
-15.06 -106 .8
-9.16
-85 .3
9.30
4.90
0.3
0.4
7.00
-1.20
o/oo
m.
4250
4100
4100
3800
3900
375
3900
3710
3780
3760
3750
3750
3750
7.60 3750
3750
3750
3750
3750
3750
8.30 3750
3750
8.90 3750
9.10 3800
3800
3800
3835
3900
3870
3950
4010
3630
4000
4270
Table 2 - Empexa gas samples analyses

Total gases (vol. %)
E8a
FE
FE(Aquat. )
C02
H 2S
H:>
CH4
N2
96. 30
95. 70
98. 66
0 .00
4 .00
1 .11
0. 000
0. 000
0. 001
0.018
0.004
0.001
3,.60
0..30
0..20
He
(ppm)
CO
(ppm)
3.3
415.0
8.0
38.9
Residual gases (vol. %)

C02
E6b
E8b
FE
97. 50
95. 10
92. 30
H2S
<0.05
<0.05
4.20
total of roughly 11 l/s.
H2
CH4
<0 .005
<0 .005
0 .034
CO. 005
<CO. 005
<CO. 005
N2
2 .10
4. 60
3. 30
02+Ar
NH3
0.06
0.08
0. 58
0. 27
0. 03
The total flow rate of other less warm
springs, still having temperatures exceeding 30C, is more than 40

1/s.
The emission of gases, associated principally with water points

at the
highest temperatures,
is very weak; a
fumarole
(FE)
is
present in the Mina Conception with a temperature of 85.6C.

Water samples were collected generally in 6 separate aliquots
for analyses of major and trace constituents, monomeric aluminum
silica, stable isotopes (18O and D) and tritium.
Temperature, pH, conductivity and alcalinity were determined in

the field. Major and trace chemical costituents
were analyzed in
ENEL laboratory in Italy; isotopes were analyzed in IAEA and DSIR
laboratories.
2) Previous studies
As mentioned above, in the period April-May 1977,
a prefeasi-
bility study was carried out by the Italian company Aguater [1],
24 water points and some gases were sampled.
120
Subsequently,
in 1978,
some springs and
fluids encountered
during the drilling of 6 thermal gradient test holes were resampled. The temperatures could not be measured with exactitude,
but at least in two cases they were above 100C (WE3 = 121, WE5 =
115) .
The geochemical interpretation of collected data was based on
statistical factors and on the individuation of leakage anomalies.

No particularly favorable results emerged in this connection.
In the summer of 1976 a geological study was conducted [I], the
most
important
results
of
which
are
summarized
in
the
next
paragraphs.
2.1 Stratigraphy
The stratigraphie sequence in the area is made up of Miocene to

Recent
age
formations,
essentially
volcanics
or
sediments
of
volcanic origin.
The lowest unit of the sequence is the "Quemez Formation" with
a radiometric age of 16.1, 9.4 m.y. This is made up of numerous
ignimbritic units with an estimated maximum thickness of 300 m.

The
probably
base
of
made
the
up
of
"Quemez
older
Formation",
volcanites
not
(lower
outcropping,
Miocene)
of
is
the
Formation of Yoza which outcrops east of Rio Empexa.
At the summit of the "Quemez Formation", Pleistocene volcanites

occur which are linked to the renewed andesitic volcanic activity
during
the
Quaternary
period
with
differentiated
dacitic
and
rhyolitic products.
In heteropia with the products of the Quaternarian volcanism,
sedimentary lacustrine and fluvial series of a prevalently muddy

and
conglomerate
nature
with
local
peat
intercalations
are
present.
121
Volcanics cover the entire period of the Quaternary glaciations

during which they were intensively moulded. The related morainic
deposits are associated to the glacial phases.
The only post-glacial volcanites are found between the Cerro

Milluri and the Cerro Pilaya Khollu.
2.2 Tectonics
A compressive phase of the lower Pliocene (Quechua phase) has
weakly
folded
tensional
the
phase
"Quemez
with
Formation".
the
This was
development
of
followed
hrst
and
by
graben
structures. The latter one gave origin to closed basins during the
isostatic uplift of the erogenic chain and, as a result of the

progressive development of evaporitic processes, have become the
present Salars (Empexa and Uyuni).
Two
principal
systems
of
regional
fractures
can
be
indi-
viduated: the first and the oldest with W-NW, N-NE direction, and
the second, still active, with a NE, NW direction.
Locally, structures of vertical collapse connected to volcanic

activity may be individuated.
2.3 Volcanism and geothermal implications

The area of recent post-glacial volcanism is located between
Cerro Milluri and Abra de Napa. A number of acid volcanoes occur
here: C. Pico Loro, C. Cayti, C. Mucellcani. The volcanic products
of this area
dacites
show
an evident evolutive
-< rhyolites
in
relation
to
trend
from
process
of
andsites -
subsurface
differentiation caused by fractional crystallization. This seems
to
suggest
cooling
the
presence of
a magmatic body
in the process
(the dating of an ignimbrite sample of the volcanites of
the Cerro Pico Loro and Huallcani gave a value of 0.8 m.y.).
122
of
The magmatic chamber, of great dimensions, could be centred at

the swelling structures along the belt of thermal anomaly which
stretches
from
Abra
de
Napa
to
Fuente
Towa,
and
which
is
characterized by springs and thermal manifestations.
As far as the geothermal model is concerned, distinct reservoir

units and covers cannot be clearly individuated. The outcropping
volcanites present locally a fair degree of permeability, which

becomes high at times, both of primary origin (pyroclastics and
volcanic
breccias)
and
of
secondary
origin
(fissures).
The
lacustrine terrains and volcanic sediments, whenever present, act
as
an
impermeable
cover.
Nevertheless,
the
same
outcropping
volcanites reveal quite a variable degree of permeability and, in
many cases, none at all as a result of self sealing because of

hydrothermal alteration processes.
3. Classification of water samples
The
classification
of waters
was
carried
out by
means
of
correlation diagrams based on main chemical costituents. In the

classic formulation of the Piper diagram all samples are found in
the
quadrant
of
the
alkaline-chlorides
alkaline-earth
ones.
In
sulphate
order
to
ones
and
obtain
in
the
better
discrimination, we have preferred to use two modified diagrams, as
in
figs.
2 and
3, which
consider Cl
and
S04
respectively
as
separate anions. The two diagrams differ only in the distribution

of the points in the two upper quadrants.
Apart from Ell, a spring emerging west of the salar, cold
waters are situated
between ten and a few hundred metres above
the level of the salar. The maximum temperature of these samples

is 14 C and the T.D.S. is less than 1000 mg/1. As shown in fig. 3
and in table 1, most of these have a high sulphate content and

sometimes acid pH.
123
Cl-
S04
100
100
n
QJ
4(D
Ht-
100
HC03-
+ S04-
F i g . 2 - P i p e r d i a g r a m w i t h Cl as s e p a r a t e d am on.
100
HC03- + Cl-
F i g . 3 - P i p e r diagram w i t h s u l p h a t e as s e p a r a t e d anion
These characteristics are uncommon in freshwaters, but can be
explained
locally
hydrothermal
by
the
activity.
This
presence,
in
activity
the
led
to
past,
the
of
intense
formation
of
large, intensely altered zones and to numerous sulphur deposits

which culminate in the Mina Conception. During circulation, the
air-saturated
shallow
waters
encounter
these
formations
and
sulphur is transformed by oxidation into sulphuric acid and then

to sulphate.
All these surface samples belong to Group A, subdivided into

subgroups
Al
and
quadrant of fig.
A2
respectively
located
in
the
NW
and
NE
3. E5 (t = 22C, T.D.S. = 980 mg/1) , a surface
water slightly contaminated by thermal fluid, falls just below the
NE quadrant.
The other water points, which make up Group B, are located in
the quadrant of alkaline-chloride waters. Normally these waters

are associated with a deep origin, but the chemical composition of
many of these, in the Empexa valley, may be explained with the

leakage
of evaporitic deposits.
These deposits derive
from
the
progressive receding of the Empexa salar, as shown by the numerous
concretions
located
of
calcium
and
few kilometres away
magnesium
sulphates
and
carbonates
from the present edge defining
its
past extension.
In fig.3 the position of the fluids originating from theoretic

isochemical leaching of three brine samples of the salar (SE 135,
SE 140 and SE 141)
sampled in 1976 for a mining study
[2],
close to the warmest thermal fluids.
The
points
distribution
in
fig.
3 allows
only
dilution
process of the B group samples with Al or A2 freshwaters without
discriminating
in
any
way
between
thermal
springs
and
high
salinity hypothermal or cold waters.
125
is
The A-B section of the fig. 2 Piper diagram vs. T.D.S., as
shown in fig.
4, although confirming a dilution process does not
supply further information.
Fig.4 - Correlation diagram between T.D.S. and the A-B section

in the Piper diagram of Fig.2.
This
suggests
that,
in most
manifestations,
deep
and
sub-
superficial circulations are widely interconnected. Fluids rising
from the geothermal reservoir interact with the superficial saline

deposits and the original internal ratio of the major costituents
changes. So it is very difficult not only a reliable individuation
of
the
original
deep
composition,
geothemometric evaluations, but also

extension of the circuit.
126
which
is
necessary
an estimate
for
any
of the actual
The
Na/K ratio contributes greatly to the solution of these
problems. The points distribution in fig. 5 shows two trends;

samples E6, 7, 8, 11, 20, 21, 22, 23, 24 and WE5 fall on line A
(Na/K = 50), while samples E13, 14, 15, 16, 17, 19, 26, 28, 29,
WE1, WE4 and WEC fall on line B (Na/K = 16.7). This last one is
very close to the average Na/K ratio of the three brine samples of
the salar SE135, SE140 and SE141 (= 15.5). The rest of the B group
samples fall in the area between the two lines A and B.
30
Slit-
Na = 3700.0
Na = 2610
17
20
x O
O
Lu
10
00
100
200
300
400
500
NA(MEQ/L)
Fig.5 - K vs. Na diagram.
127
&/
/''
.-- "
^
o o
29
/'
o"
' '
Qj<
18
O
20
Na= 21p S
#
0
/
o
^ ""
' /
i
,- " "
o --
,, - "o
23 /
0/
^
0/
SV^ n
P
- " ^
I
20
40
60
80
1C)0
12!0
NA(MEQ/L)
Fig.Bb - K vs. Na diagram.
As regards the water points of the first trend (line A): E6, 7
and 8 (Rio Quebrada Calorno), are located very close together in
proximity
of
the
Cerro Wichu Kkollu.
They
have
temperatures
of
30, 35 and 15C; T.D.S. are around 10000 mg/1 for the first two
and 5000 mg/1 in the last. The Ell sample is a cold spring which
emerges from the westernmost edge of the salar with T.D.S. of 5000
mg/1. E20, 21, 22, and fuentes Towa (23, 24, 25) are a group of
very interesting springs located in the Estancia Towa area, while
the WE5 test hole is situated roughly 2 km west of the fuentes
Towa. The temperatures of these 6 springs range from 22"C for E21,
to 87 for E24, for the test hole, at a depth around 150 m,
was
registered a temperature of 115C. The T.D.S., around 4000 mg/1 in

E23,
24, 25 and WE5,
increases considerably (15000 - 32000 mg/1)
in E20, 21, and 22 situated between 3 and 5 km north of fuentes

Towa.
128
The main chemical differences among these samples regard the

percentages of sulphate and of earth alkaline contents. These are
higher
in the
water
points E6,
halved in E20, 21, and 22; for
7, and
8, but
are
the hottest samples
and WE5) , the sulphates percentage is the same as
previous
water
points,
but
the
concentration
practically
(fuentes Towa
in the three
of
the
earth
alkalines practically disappears.

Among the samples falling on line B: E13,
are
located
in
restricted
area
14, 15, 16, and 17
little
north
of
Mina
Conception. Their temperatures range between 14 and 75C, while

the T.D.S. varies between 4000 mg/1 and 32000. Spring E16,
which
emerged at 75C at the salar edge with a 23000 mg/1 T.D.S., was
covered in 1986 by the dump of Mina Conception; its pH (1.7) was

extremely
low
compared
to
the
S04
content
(50
mg/1)
and
the
concentration of Cl (in meq/1) was considerably higher than the

sum of Na and K. Very little is known of the E17 sample (17C and
35000 mg/1), collected not far from the preceding one,
maintains
the characteristics, except for temperature. The three
samples E13,
14, and 15, which emerge 2-3 km north-west of E16,
have a temperature of 34 C,
a maximum T.D.S. of 5400 mg/1,
always exceeding 1000 mg/1 and

to
the
of which
sum
of
Na
and
K.
E19
SO4
Cl content stechiometrically equal

(14C,
3000
mg/1)
located
near
Estancia Towa, because of its moderate acidity and Cl in excess of
the sum of Na and K is similar to E16 and 17, although has a much
higher percentage of SO4. The E26, 28 and 29 samples (temperatures
between 10 and
35C, T.D.S. between
1100
and 2200 mg/1), are
situated on the south eastern edge of the area; their chemism is

identical and characterized, once again, by an excess of chlorides
compared to the sum of Na and K, apart from the higher content of
SiO2 in E29 (the warmest of these springs, although less saline) .
129
The other samples, E9, 12, 18, and WE2, located in areas rather
distant
from
one
another,
fall
in the diagram
of
fig. 5
in an
intermediate position between the two lines A and B.
Finally, in fig. 6 and 6b, sum
of Na and K vs. Cl, the samples
are well discriminated and may be distinguished thus:

- a
cluster
of
points
constitued
by
Fuentes
Towa
and
the
test holes WE2 and WE5, defined as subgroup Bl;

- samples falling on line A (subgroup B2);
- samples
falling
characterized
by
on
line
an
excess
(subgroup
of
the sum of Na and K, including
B3),
chlorides
as
all
regards
the three representative
brines of the Empexa salar.
500
x/"
31 Jj
Na =36950^
.
. -iu ,
Na = 56400^
â'Na = 5360
.400
O
Lu
/-'
0
^,"X
300
20
s'
'
-P*"
O 200
UJ
/;6X
100
'V
X*
^'
^ I
1 1 !
1 1 l
1C )0
2C 0
1 !
1 1 I
1 1 I
3C10
4C 0
CL(MEQ/L)
Fig.6 - Na + K vs. Cl diagram.
130
1 1 1 I
1 [
1 [
5C 0
1 1 1
1 1 1
6C0
120
X
X
X
O x
X
X
o^
0x^
O
LJ
X
X
^f'
y/
<
i^
80
SUBGROUP
E 1
x
X
X
X
X
X
1 1 1 M
^"
-^
r?> ' -
^
""
X
X
X
X
Ox'
11
x
X
/o
X
<f
3-
v^
X
""
', 0 ^ /
O
by 40
X
X
i' csi?v
>
/!2
\,_
'
ig
XO
ox
28 X
^
:ex
,
X
1 1 1 1
1 1 1 M
1 1 1 1
2D
1 1 M
1 ! 1 1 1
4D
1 1 1 1 1 1 1 1 1
6D
1 1 I II
I I I I I I I I I
1 ! 1 1
80
1C 0
I 1 I I I ! I
12 0
-0
14
CL(MEQ/L)
F i g . 6 b - Na + K vs.
It
Cl d i a g r a m .
is supposed, therefore, that the composition of
all the
water points which are situated along the latter line is greatly
influenced by leakage of evaporitic salt deposits, a process which

has certainly modified the original ratios between the different
constituents
even
in
the
warmest
fluids.
An
additional
confirmation of this hypothesis is represented by the ratio Cl/Br

(mg/1) ; this, in the samples E23, 24, is slightly over 700,
not
very far from the typical one for formation waters, whereas for
the others it varies between 3000 - 4000, values which distinguish
statistically
waters
that
principal
variations
which
original
composition
decrease
of
the
ratio
in
interact
with
the
occur
this
case
the
in
reservoir,
Na/K and
the
are
increase
evaporites.
as
the
of
regards
The
the
considerable
the
original
concentration of Ca and Mg.

131
Even the
samples with a higher temperature which belong
to
subgroup B2 present modifications, although lower than those of

subgroup B3. These are a result of the last phase of circulation:
in effect, while the ratio Na/K remains similar to that of Fuentes

Towa and of WE5,
the concentrations of earth-alkalines
and the
ratio Cl/Br increase considerably.
Finally, the samples of subgroup Bl, for lack of any surface
contamination, can be considered the most representative

deep fluid; its
possible modifications
of the
depend only on processes
of riequilibration during its uplift to the surface.
4. Geothermometric Considerations
Fig. 7 and 8 show the Na, K, Mg triangular diagram according to

Giggenbach [3]. The difference between the two figures consists of
the different scales used for the Na, K, and Mg concentrations. In

the
latter
fluids
case,
this
thermically
permits
more
clearer
degraded
visualization
and/or
more
of
mixed
the
with
freshwaters.
In Fig.
7 the E23 and 24 (Fuentes Towa) samples are situated
slightly above the "full eguilibrium" curve, at an estimated deep

temperature
of
about
170 "C.
The
shift
is probably
due
to
the
boiling and degassing phenomena which occur during the upflow with
subsequent precipitations of Ca and Mg. The E25, WE5, E20, 21, and
22
samples,
f reshwaters
fall
on
(right
a line
corner) .
which
This
joins
is
in
Fuentes Towa
accordance
to
the
with
an
enrichment process in earth-alkaline components at constant Na/K.

Fig.
8 shows a second trend, which joins points E16,
17, WE4,
WEG and E28. This first two as a proof of the leakage process of
evaporitic
deposits
discussed
in
the
previous
paragraph,
are
located in proximity of the points representing the brines of the

Empexa salar; we may, however, think that they could, originally,
132
OQ No/1000
20
K/100
40
%
60
80
Mg
100
MG O.5
Fig. 7 - N a , K , V M g t r i a n g u l r d i a g r a m .
, Na/400
V
40
K/10
Mg
MgfO.5
Fig.8 - Na, K, ViMg triangulr diagram.
133
be found in a higher position from which they moved away because
of
Na/K ratio
decrease
(evaporite
phenomena of the E16 and 17 samples

WE4,
contamination).
Dilution
could originate points E28,
and WEG.
The temperatures that can be calculated from SiO2 [4], assuming
the equilibration of chalcedony as the most probable, on the basis

of values calculated with ionic geothermometers,
and 24
resulted for E23
175 and 186C respectively.
Therefore, the results obtained using the most common solute

geothermometers are
in accordance among them,
geothermometer Na/Li
(also the
empiric
[5] gives values of 175 and 180C). This
lead us to assume that the maximum temperature in the reservoir
does not exceed 180C.
4.1 Examination of the State of Equilibrium

By using the activities of aqueous chemical species computed
for homogeneous equilibria at temperatures ranging
from
150 to
20CTC, it is possible to compute the degree of under- or supersaturation of the aqueous components with different mineralogical
phases.
This can be expressed for any mineral in terms of log AP/K.
AP/K refers to the activity product of the species concerned in a

given solute chemical
equilibrium compared with the equilibrium
constant K for that hydrolysis reaction at a prefixed temperature.
This ratio is greater than zero for supersaturated minerals and

less than zero for the undersaturated ones. These log AP/K values
are plotted vs. a proper temperature range (based for example on
geothermometers
results) ;
the
paths
of
convergence
of
the
resulting curves to the zero value establish the possible mineral

assemblages of the reservoir and enable the identification of the
fluids
equilibration
temperature
by
analyses and some proper constraints.
134
using
only
their
chemical
The E24 spring can be considered the most representative fluid

of
the
Empexa
deep
reservoir,
but
pH,
calcium
and
magnesium
content at the sampling point are the result of riequilibration at

shallow levels after degassing; this process explains the thick
travertine deposition characterizing all the hot springs around

the
Fuentes Towa
area.
The
only
simple
and
reasonable
way
to
compute the possible concentration of these components in the deep
fluid
is based on. the constraint of
calcite equilibration at
180C.
Fig. 9 shows the log AP/K values for the E24 spring, corrected
composition are plotted vs. temperatures ranging between 150" and

200 C. The
fluid
is well
equilibrated
with
both
series
of
minerals that are typical components of volcanic rocks present in

the Empexa area and the phases deriving from their hydrothermal
alteration at a temperature of around
175C. This confirms the
geothermometers values.
^:
Q_
cn
o
-1.0 -
-2.0 -
3.0
i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i i
Temperature C
F i g . 9 - Log AP/K vs. T diagram.
135
Another interesting aspect to be pointed out is the calcium

concentration, computed according to this method, in the reservoir
condition (23.4 rog/1); this is very close to the 28.1 mg/1 found
in the gradient test hole WE5 during production.

3.4 Remarks on the isotopic data
Before
this
survey
manifestations and cold
no
isotopic
analyses
of
thermal
springs had ever been performed
in the
Empexa area. The results of the 1986 sampling are shown in table
1, the relative 618O vs. <5D diagram in fig. 10. With the exception
of samples E21 (stagnant pool) and FE (condensed steam of the Mina
Conception fumarole), no fluid exists that significantly deviates

from the meteoric line; in other words no appreciable exchanges of
18
O between fluids and host rocks are observed. As the hypothesis
of chemical
equilibration at depth
is
strengthened by the
low
tritium values of the waters, the lack of isotopic shift can be
explained only in terms of the low temperature in the reservoir.
~>u
ACT^6'
^^ -^ -^
CN
\
-
/<
^'
,-"
/^
<\,'
130-16
3)"'
0
I I 1 I I 1I I I
-15
-14
-13
-12
180
-11
IN H20 (%o)
Fig.10 - oD vs. 0180 diagram.
136
-10
-9
This
confirms
the
geothermometers
computable
sulphate
for
and
estimated
and
the
the
values
according
AP/K logs.
exchange
reaction
for
E23
water
the
The
of
sample
to
159 C
n o
-LOO
the
solute
temperature
between
also
agrees
dissolved
with
the
previous results.
5) Conclusions
The general situation in the Rio Empexa valley, on the basis of

the information available and of this geochemical
survey, can be
summarized as follows:
a) - Three
water
groups
with
well
identified
chemical
characteristics exist.
The first is a surface one constituted of cold meteoric waters
emerging at a higher level than the salar, with low salinity and
mainly of an earth-alkaline sulphate type.
The second of subsurface character, includes cold and thermal
springs spread over the whole Empexa area, with salinity ranging
from medium to high values. The chemistry, due to the leakage of
evaporitic deposits, is mainly alkaline-earth-alkaline chloride;

the chloride content is higher than the sum of Na and K.
The third, representative of a deep circulation, consists of

the Fuentes Towa and others hot
springs
located
very
close to
these. In this zone favorable structural patterns for the uprising

of thermal
fluids are present. The
chemistry
is mainly
sodium
chloride with the exception of the most peripherical springs that

can leach evaporitic deposits; the salinity and the temperature at
depth should not exceed 4000 mg/1 and 180C.
b) - There is a general absence of leakage anomalies and a very
limited presence of free gases. These, with the exception of the

Mina Conception fumarole, are completely lacking in H2S and have
an extremely low content of H2. These conditions make most of the
137
gas
geothermometers
practically
useless;
with
the
use
of
the
formulation based on carbon monoxide the calculated temperature is

approximately 100"C higher than that obtained by considering the
liquid.
Despite the
fact that
the thermal
information of the gases
normally refers to the deepest part of a geothermal system and

that notable differences can sometimes be found in the calculated
temperatures based on equilibria involving different phases, the

gas results in this area are unreliable.
c) - In no sample was observed an appreciable isotope shift.

On the basis of all this, the conclusions that may be drawn for
the Empexa area, at least from a geochemical point of view, are
not very promising. In theory, higher temperature fluids could be

present in deeper levels than ones in which the waters of E23 and
24 type circulate. With these premises, a geoelectric survey could
be of use for the evaluation of subsequent developments.
References
[1] APPROVECHAMIENTO
SUDOESTE
DE
BOLIVIANO
LOS
RECURSOS
- Areas de Salr
GEOTERMICOS
DEL
d 1 Empexa y Laguna
Colorada - Aquater 1979.

[2] ERICKSEN,
G.E.
&
VINE,
T.D. (1976)
Preliminary
re-
port on the lithium rich brines at Salr de Uyuni and

nearby salars in southwestern Bolivia.
[3] GIGGENBACH,
ria.
W.F. (1980)
Derivation
Geothermal
solute
equilib-
of Na - K - Mg - a geoindicators.
GEOCHIMICA ET COSMOCHIMIC ACTA, 52, 2749-2765.
[4] FOURNIER,
expanded
R.O.
silica
&
POTTER,
quartz
R.W. (1982)
geothermometer.
RESEARCH COUNCIL BULLETIN, V. 11, 3 - 9 .
138
revised
and
GEOTHERMAL
[5] FOULLIAC,
ratio
C.
in
&
water
MICHARD,
applied
G.
to
the
(1981)
Sodium-lithium
geothermometer
of
geo-
thermal waters. GEOTHERMICS 10, 55 - 70.

[6] REED,
M.
mineral
cation
& SPYCHER,
equilibria
to
dilution.
N.
in
(1984)
hydrothermal
geothermometry
GEOCHIMICA
- Calculation
ET
and
waters
studies
COSMOCHIMICA
of
ACTA,
of pH
with
appli-
boiling
48,
and
and
1479 -
1492.
139
GEOCHEMICAL REPORT ON THE SAJAMA

GEOTHERMAL AREA, BOLIVIA
G. SCANDIFFIO
Ente Nazionale per 1'Energia Elettrica,
Pisa, Italy
J. RODRIGUEZ
Universidad Mayor de San Simon,
Cochabamba, Bolivia
Resumen-Abstract
INFORME GEOQUIMICO SOBRE LA ZONA GEOTERMICA DE SAJAMA, BOLIVIA.

La zona geotrmica de Sa jama, al noroeste de Bolivia, esta muy cerca de
la frontera con Chile y a unos 60 km de distancia de la frontera con el Peru.
La actividad volcnica, durante el Terciario, se relacionaba con dos sistemas principales de fallas, formados durante la fase orognica del periodo,
con tendencias N-S y E-0. Mas tarde se desarrollo un vulcanisrao cuaternario

relacionado con sistemas NO-SE y NE-SO.
Este ultimo vulcanismo se caracteri-
zaba por volcanes compuestos que producian lavas y rocas piroclsticas, que
cubren ahora las ignimbritas terciarias.
Las actividades trmicas mas importantes, que se manifiestan en un fluido profundo que llega a la superficie tras su evaporacin, se producen junto
al rio Junthuma, a una altura de 4 400 m sobre el nivel del mar, y se relacionan directamente con el sistema NO-SE. Se dan otros casos a 7 km al este y
200 m mas abajo, con menos salinidad, que pueden considerarse como flujo de
salida lateral del mismo sistema. Este flujo latral parece estar diluido con
agua meteorica que tiene una composicion isotpica mas negativa que las aguas
trmicas junto al rio Junthuma.
Segn geotermometros ionicos, la temperatura del depsito es de entre 230
y 250C; los datos isotpicos apoyan estos valores.
Solo se han recogido muestras de gas en depsitos alimentados por fluido
residual (tras su evaporacin); estas muestras carecen de oligoelementos, por

lo que no pueden utilizarse como geotermometros y no son representativas del
estado del depsito.
141
GEOCHEMICAL REPORT ON THE SAJAMA GEOTHERMAL AREA, BOLIVIA.
The geothermal area of Sajama, Northwestern Bolivia, occurs

very close to the border with Chile and about 60 km away from
the border with Peru.

During Tertiary the volcanic activity was related to two
main fault systems, formed
period,
with
volcanism
This
N-S
developed
latter
and
during the orogenig phase of the
E-W
trends.
Later
on
quaternary
in relation to NW-SE and NE-SW systems.
volcanism
was
characterized
by
stratovolcanoes
producing lavas and pyroclastic rocks, that are now overlying

the tertiary ignimbrites.
The most important thermal manifestations, representing a

deep fluid coming at the surface after flashing, occur near Rio
Junthuma at an elevation of 4400 m a.s.l. and are directly
related to the NW-SE system.
200 m
downward
other
Seven kilometers
occurrences
are
eastward
found,
with
and
lower
salinity, that can be regarded as a lateral outflow of the same

system.
This
lateral
outflow
seems
diluted
with
a meteoric
water having an isotopic composition more negative than the

thermal waters near Rio Junthuma have.
Reservoir temperature, according to ionic geothermometers,
is between 230 and 250C; isotopic data support these values.
Only gas samples from occurrences
(after
flashing) have been
collected,
fed by residual fluid

they
trace components and so cannot be used
are
of
as geothermometers,
being not representative of reservoir conditions.
142
depleted
1). Geologic outline
In the year
carried
out
1977
by
a geological reconnaissance study was
Geotecneco
[1],
the
results
of
which
are
summarized in this chapter.

The
Sajama
area
consists
of
Tertiary
and
Quaternary
terrains of volcanic origin. It is characterized by numerous

strato-volcanoes producing lavas and pyroclastites which have
grown
over
an
older
ignimbritic
cover
with
vast
lateral
extension. The most recent volcanic activity occurs west of Rio

Sajama, along the border between Bolivia and Chile where the
volcanoes Huallatani (Chile), Parinacota, Pomerape, Kakepe and
Condoriri volcanoes are present.
1.1 Stratigraphy
The
most
ancient
stratigraphie
unit
is
an
ignimbritic
sequence of unknown thickness. The upper part, with a maximum

thickness of some tens of meters, is composed of intensely
fractured ignimbrites. The lower levels consists, instead, of
tuffs
intercalations with variable, but often very
permeability.
The
base
of
the
ignimbritic
body
reduced
is
not
outcropping. It probably rests in stratigraphie unconformity on

the sedimentary sequence of Corocoro. The latter occurs in
other
places
in
the
region
with
thick
prevalently muddy, Tertiary continental
succession
of
sediments containing
arenaceous horizons, conglomerate and tuff levels.

Above
the
oldest
ignimbritic
unit,
volcanic
units
of
various age and composition, which refer to distinct centres of

emission, are
found. These do not
form
uniform
covers. In
143
chronological order they are:
- Andesitic porphyritic lavas of Nevado Sajama.

They are probably of Pleistocene age as proven by the
intense development of forms of glacial erosion associated to
morainic deposits and traces of fossil fumarole activity.
- Intermediate andesitic lavas, partly vesicular, of the
Cerro Quisi Quisini.
Acid
porphyrites
of
Cerro
Condoriri,
Nevado
Kakepe
Junthuta, and Nevado Payachata.

In the most pronounced
incoherent deposits with
have
accumulated,
depressions of the
fine and
composed
of
Sa jama basin
intermediate granulometry
tuffs
and
ash
materials
intercalated with muddy levels. The origin of these deposits is

attributed to episodes such as mud flows (Lahars), ash flow and
explosive activities (ash fall - pomices) connected to the most

recent volcanic activity. These terrains have been abundantly
eroded.
1. 2 Tectonics
The
area
principal
is characterized by tensional
structural
elements
have
structures.
conditioned
both
The
the
volcanism and the hydrologie surface structure.

Two principal fractures systems may be distinguished. The
first, and seemingly older system, with N-S/E-W direction on

which
the
positioned
Rio
Kasilla
themselves.
and
tracts
Traces
of
of
the
this
Rio
Sajama
system
can
have
be
individuated on the Nevado Sajama.

The second, more recent system with NW-SE/NE-SW direction,
has
influenced
conditioning the
144
to
larger
extent
the
present
morphology
alignment and the development of the most
recent eruptive centres. The Rio Junthuma has
its location
along an element of this system.
1.3 Volcanism and geothermal implications

On the basis of stratigraphie data, a possible sequence of
volcanic events is the following:
- first
phase
probably
along the
emission
of
with
intense
fissure
eruptive
oldest structural N-S/E-W
viscous
acid
products
which
activity,
systems, with
form
the
basal
ignimbrites.
- There
follows a phase
in which the eruptive activity
becomes less frequent, it is concentrated along limited sectors

of
the
fractures
system,
forming
central
volcanoes.
The
products emitted are andsites with a porphyritic texture. To

this phase belongs the formation of the Sajama Volcano but the
same materials make
up
the
lower
parts of
other volcanic
structures in this zone.

- Volcanic activity moves west as time passes with central
effusive, and more rapid and tranquil eruptions of intermediate
andesitic lavas (Cerro Quisi Quisini).
- There
follows
the
most
recent
phase
of
partially
explosive nature, with the emission of great quantities of

porphirytic acid material. This is composed of rhyolites and
rhyodacites with phenocrystals of plagioclase, pyroxene, and
biotite (normative quartz > 20%) .
The centres of this activity are:
Cerro Condoriri, Nevado
Kakepe Junthuta, Nevado Payachata and Huallatani. Among these,

the most recent seem to be the Huallatani volcano, still in
fumarole activity, and the Payachata, which has two eruptive
145
centres; the Cerro Parinacota, and the Cerro Pomerape which

shows
evident
collapse
structures
and
has
solfataric
activity. The Nevado Condoriri and Nevado Kakepe are older and
without present manifestations, even though the latter volcano
still shows thermal anomalies (hydrothermal manifestations).
- After the deposition of acid porphyrites comes a period
of mud flows with formation of lahar-type deposits in the most

depressed zones of the Sajama basin. These deposits are,
at
present, highly eroded, and are mostly along the Rio Junthuma.
- On top of the lahars there are deposits of ash flow,
partly consolidated and containing also organic material. The
summit of these deposits is transformed into paleosoil. This

would indicate a period of lacking eruptive activity during
which vegetation developed.
- The paleosoil is covered by a level of 30 - 40 cm of
uniform
thickness,
of piroclastic
products, mostly
ash
and
pumice of acid composition with sedimentary lithic intercalated

fragments. This level records a particularly violent explosive
event,
perhaps
phreato-magmatic,
during
which
materials
belonging to deep stratigraphie levels have been torn from the
walls of the pipe (Corocoro formation?). This episode could be
attributed to the Cerro Parinacota or Pomerape or even to the

most recent Huallatani, despite this being the furthest away
from the deposits.
- Above the pumices occur again levels of fine and medium

ash flow material which form the present soil.
From
indications
geothermal
of
point
of
volcanologie
view
nature
there
in
are
favour
numerous
of
the
hypothesis that today there exists a not very deep magmatic

146
body in the process of cooling. Among these there are: active

fumarole and solfataric activity of some volcanoes; the recent
age of the last volcanites emitted; their evolutive trend from

andsites to rhyolites with femic phenocrystals as witness of a
acid
differentiation
process
caused
by
fractional
crystallization in a quiescent stage; the overall volume of the

youngest differentiated volcanites suggesting the presence of
magmatic chambers with considerable possible storage and long

cooling periods.
As
regards
the
hydrogeologic
model,
the
relict
lahars
deposits, together with the ashes, form an impermeable cover

sufficiently continuous and extensive in the lowest parts of
the basin. The outcropping volcanites at the highest altitudes

along the slopes of the volcanoes have quite variable degree of
permeability.
In
theory,
these
are
permeable
because
of
fracturing and could provide an important recharge area, but

thermal fossil manifestations in all the zone must be noted as
evidences of self-sealing processes connected with
a previous
rather intense activity. This makes the permeability of the

volcanites very discontinuous with rapid horizontal variations
and the development of independent (closed?) circuits, as shown
by the existence of cold and warm springs a few meters away

from each other. The identification of the reservoir is also a
problem. This should develop under the strato-volcanoes in the
basal ignimbrites, the permeability of which
is ascertained
only for the first tens of meters. The volume of the entire
ignimbritic body does not seem sufficient to form a reservoir;

therefore, if this reservoir exists, it should continues at
depth
in
knowledge
the
of
pre-volcanic
this
substratum.
substratum,
apart
We
from
have
the
no
direct
sedimentary
147
intercalation in the pumices, deriving from the fragments torn
by
the explosions. One hypothesis is that this substratum
consists of the continental terrigenous succession of Corocoro

but the presence of this group under the Sajama area is not
certain. Furthermore the Corocoro group presents a considerable
variation in composition and, therefore, in permeability (clay
members,
arenaceous
conglomerates,
etc.).
As
result
of
intense tectonic deformation, the members of the sequence are

not always mantained. Therefore, even if the existence of the
Corocoro Group in the Sajama area were ascertained, this would
not necessarily constitute a permeable reservoir.
2). Sample collection and field determinations

The Sajama geothermal area is located
in the north-west
part of Bolivia, very closed to the boundary line with Chile

and about 60 Km away from the border with Peru. The area, with
an
average
elevation
of
4400
m.
a.s.l.,
shows
an
uneven
morphology; the most important manifestations are localized in

a small valley along Rio Junthuma.
Two more springs of lower flowrate occur at a level of
approximately 4200 m a.s.l., located some 7 Km east of the Rio
Junthuma ones. The sample location map is shown in fig. 1
The survey in this area was carried out over a period of
seven days from the 5ht to the llth of June 1988. A total of 15
samples of hot and cold springs were taken, 3 of both free
total and condensate gases. Unfortunately more than 50% of gas
samplers were damaged during the freight to Italy.

Water
aliquots
148
samples
for
were
analyses
collected
of
major
generally
and
trace
in
separate
constituents,
}f<\f
^'f^â^V V
TM60 QUEMAOO
HUALL/iTANI
= Cold waters
Q = Hot waters
Fig. I - Location map of Sajama area samples.

149
monomeric aluminum
silica, stable
isotopes
(180
and D) and
tritium.
Temperature,
pH,
conductivity
and
alcalinity
were
determined in the field. Major and trace chemical costituents

were
analyzed
in
ENEL
laboratory
in
Italy;
isotopes were
analyzed in IAEA and DSIR laboratories.
3). General outline of the Rio Junthuma manifestations
In
this
area
manifestations:
(fig.
the
2)
active
occur
ones
several
active
(more than
fifty),
and
fossil
showing
temperatures ranging between 50 C and over 85 C (that is the

boiling
point
distributed
for
this
for a length
altitude
"
4400
a.s.l.),
of two kilometers. Their
are
location
range between some centimeters to a few tenths of meters from

Rio Junthuma. In some springs occurs appreciable gas and the
total hot water flow rate can be estimated around 45 1/s; fig.
2 shows how manifestations are located
separated
zones.
The
first
one,
in two structurally
northward,
provides
more
occurrences at a temperature close to boiling than the southern

one does. This latter one, however, besides showing a slightly
higher
conductivity
for
the
most
presents mud pools and at least two
important
water
points,
fumaroles. Sampling of
these manifestations was impossible because of the dangerous

access to them.
150
1.10000
Fig. 2 - Location map of the thermal manifestations

of the Rio Junthuma .
151
4). Water chemistry
4.1. Classification of the water samples

The analytical results of the fluids sampled during the
survey are reported in tab. 1 (waters) and 2 (gases).
The classification of the samples was carried out by means
of cartesian diagrams and correlations existing between some
chemical components.
The classic Piper diagram is shown in fig. 3. The latter is

divided
into
four
quadrants
and
samples
are
generally
distributed as follows. In the first NW are found the earthalkaline-bicarbonate
waters,
generally
linked
to
shallow
circulation; in the second SW the alkaline-bicarbonate ones; in

the
third
SE
considered
of
alkaline-chloride
deep
origin;
waters
in the
fourth,
occur,
NE,
normally
the
earth-
alkaline-sulphate ones.
Among the samples of the Sajama area only SA16 and 16B
occurring
before
the
Rio
Junthuma
hot
springs
start,
are
located in the NW quadrant; both are low salinity cold waters

with an anomalous SiO2 (75.5 mg/1), the first one is a stream,
the latter is the Rio Junthuma itself. Samples SA41 and SA42
fall in the NE quadrant; SA41 is a streamwater, SA42
(31C,
T.D.S. around 500 mg/1), a spring located 30 Km to the north of
the
main
manifestation
composition
can be
area,
considered
on
as
the
a
base
of
freshwater
its
chemical
conductively
heated. The SiO2 and SO4 content, respectively 120 mg/1 and 226
mg/1,
is higher than for the others freshwaters. Regarding
water points located in the SE quadrant: SA40, collected near
SA42, is a low salinity hypothermal spring with a noticeable

sulphate content; SA37 (29C, T.D.S. 1427 mg/1), is another Rio
152
TABLE 1 - Lab. analytical results for water samples.
OODE
Tf
pHf
Condf
Alkf
mS/cm meq/l
Hg
Na
mg/l mg/l mg/l
Cl
S04
H3S03
NH4
mg/l
ipg/l
mg/l
Si02
mg/l mg/l mg/l
H2S
mg/l
Li
Rb
Br
mg/l
mg/l
mg/l
Fe
Sr
Ba
mg/l
mg/l
mg/l
mg/l
mg/l
2.50
2.20
2.20
1.80
0.14
0.15
2.10
2.20
2.50
0.130
0.120
0.100
0.100
0.005
2.40
0.120
0.050
AIT
SA1
84.5
7.30
6170 4.06
18.5 2.00
1250.0
127.0 1790.0
339.0
192.0198.0
0.660
1.9
6.70
1.10
5.70
1.90
0.033
0.06
SA11
68.9
6.19
5830
3.18
12.8 0 . 2 0
1420.0
144.0 1950.0
372.0
240.0 214.0
0.780
0.0
7.20
1.30
5.90
2.10
0.022
0.00
SAU
71.7
87.8
12.0
9.8
6.30
6350
3.11
7.43
6590
3.30
25.0
6.45
516
1.40
14.4 8.00
9.9
3.1
1.6
15.0
6.31
168
1.56
14.6 8.20
9.8
3.4
1.7
14.9
SA13
SA16
SA16B
7.4
0 . 2 4 1380.0
138.0 1950.0
3.20 1180.0
217.0
1.100
0.0
7.40
1.30
5.80
2.20
0.250
0.21
184.0
213.0
0.560
0.8
5.90
1.10
4.60
1.80
0.000
0.00
78.8
0.5
0.4
78.4
0.000
0.0
0.01
0.00
0.00
0.25
0.000
0.00
0.000
1.3
0.01
0.00
0.00
0.25
0.044
0.16
371.0 236.0
118.0 1630.0
313.0
0.006
6080
8.9
0.48 1340.0
123.0 1870.0
358.0
207.0
208.0
0.410
0.0
7.00
1.20
5.20
2.00
0.000
0.15
SA21
51.5
53.3
6160
7.9
0.07 1430.0
129.0 1930.0
374.0
243.0
216.0
0.400
0.0
7.20
1.20
5.90
2.10
0.047
0.02
SA35
86.5
5240
4 3 . 4 7.60 1140.0
115.0 1560.0
294.0
201.0 175.0
0.390
0.8
3.00
1.10
4.50
0.000
SA36
79.0
5670
28.7
197.0
214.0
0.480
6.70
1.20
5.10
1.90
1.80
0.000
0.00
0.01
S A3 7
29.1
2240
18.9 6.50
4 6 . 5 591.0 124.0 119.064.7
0.140
0.0
2.20
0.39
1.70
0.81
0.000
0.45
SA38
39.3
2270
43.5
47.9
155.0
0.290
0.6
2.20
0.30
1.40
0.43
0.000
0.03
0.91
0.90
SA39
45.2
1670
27.1
30.5
319.0 163.0 148.0
0.310
0.8
1.50
0.23
0.86
0.31
0.000
0.00
0.61
0.005
SA40
19.3
193
74
0.8
. 1 0.000
0.0
0.09
0.00
0.00
0.30
0.000
0.00
0.20
0.004
SA18
SA41
S A4 2
OODE
82
Date
28.30
pHl
1290.0
442.0
439.0
127.0 1740.0
56.0
17.10 300.0
14.8
270
12.3
31.0
2.80
476.0
49.0
6.90 31.8 3.5
16.7 9.00 20.3 4.6
6.3
0.4
2 6 . 4 13.2
Condl
A l k l Ralkl
mS/cm meq/l meq/l
188.0
2.8
68.8 18.00
340.0
62.0
65.3 64.4
226.0
120.0
0.02
0.00
0.00
0.44
0.023
0.01
0.17
0.020
0.3
0.000
0.0
0.01
0.06
0.00
0.17
0.036
0.04
0.50
0.006
06/06/88
06/07/88
SA13
06/06/88
SAH
06/07/88
4.00 3.80 4 . 4 0 0.00 1.90 0.00 0.00

0.700.00
3948
6.35 3.16 2.96 4.70 0.00 2.30 0.01 0.00 0.00
0.80 4372
7.21
5 . 4 0 3.24 3.04 3.90 0.00 2.10 0.00 0.00
0.70 3692
0.00
1.00 4331
6.90 6.47
3.16 3.00 4.80 0 . 0 0 2.30 0.00 0.00 0.00
SA16
06/07/88
6.32 0.18 1.34
SA 168
06/11/88
6.31
SA18
06/08/88
6.87 6.29 2.92 2.76
SA21
06/08/88
7.02 6.25 2.84
A. S. L 018_H20
0/00
D_H20 H3_H20 018. .504 S34_S04

o/oo
T.U.
7.33 5 . 8 5
4380
-13.99 107.9
7.21
4410
-12.73 -108.6
4410
-14.14 -110.8
4410
-12.68 -107.0
0.00
134
4430
-16.52 120.9'
2.7
0.00
0.00 1.20 0.00
2.68 4.80 0.00 1.20
5.68
5.48 3.90
0.00
4430
-16.54 -118.0
4400
-12.83 -105.6
0.000.700.00
4346
4410
-12.56 -105.6
2.3
0.1
1.1
0.50
0.003565
0.004415
-14.00 -110.2
0.6
0.00
0.50
0.14
3964
0.00 4425
-13.74 -110.2
0.7
0.68 0.00
0.00
0.30
0.00 4370
1427
-15.63 -115.6
1.8
1450
4290
-16.60 -123.1
1.0
0.00
1021
4290
-16.92 -123.3
0.6
0.6
SA35
06/08/88
7.36 5.21
06/08/88
7.18
0 . 0 0 1.90
SA37
06/08/88
6.76 2.31
SA38
06/09/88
7.05 2.35
6.84 6.74 1.80 0.00 0.45 0.00 0.00 0.00

0.30
SA39
06/09/88
7.24 0.28
4.82
5.67 4.18 4 . 0 2 4.10 0.00

2.40 2.40 1.30
2.10
0.00
0.00
4.72 0.95 0.00 0.34 0.00
1.12
0.00
SA40
06/09/88
6.60 0.30 1.12
SA41
06/10/88
6.56
SA42
06/13/88
7.13 0.63 1.38 1.38 0.00 0.00 0.00 0.00 0.00 0.00
0.14 0.92
0.8
139
SA36
0.14 0.00 0.00 0.00 0.00
0.92 0.86 0 . 0 0 0.00
0.00
0.00 202
0.00
0/00
0/00
0.9
0.000.6U
0.00<,144
0.17 1.38 1.38 0.00 0.00 0.00 0.00 0.00 0.00

4.70
0.020
0.0
SA11
0.00 0.00
0.130
0.000
SA1
0.00
0.110
1.4
1
As Alm
Cs
Zn
Pb
Sb
TDS
mg/l mg/l mg/l mg/l mg/l mg/l
mg/l mg/l
1.34 0.00
0.100
4400
-17.65 -126.7
0.00
196
4400
16.92 -123.3
1.5
476
4410
-17.26 -125.4
0.6
6 .00
11..50
-2 .00
12..20
3 .90
11. 30
TABLE 2
Sajama gas sample analysis (vol, 7)

CODE
C02
H2S
H2
CH4
N2
SA14A
99.78
0.0
0.0
0.007
0.0
SA-36
99.52
0.0
0.0
0.011
0.47
Cl-
-t- SQ4
CO (ppmV)
11.20
9.65
100
1_____ 1 1 1 i i i i '
+SA42
+BA16B
+ SA41
- 0)
-f
+ SA40
-f
(D
(D
Z .
+ SA37
+$44( 3
_.....,.. ! . .
3*
. -J J ..._....!.-. . . . . . .
100
HC03- + COS
Fig.3 - Piper diagram for Sajama area water samples.
Junthuma
sample
taken
little
downstream
occurring manifestation; SA38 and SA39
from
the
are the two
last
thermal
springs located ~7 km eastward of the main springs area. These

show temperatures of 39.5C and 45.2C with T.D.S. of 1450 and
"1000 mg/1 respectively. All the other water points, collected

along
the
Rio
Junthuma,
51.5C and 87.8C and T.D.S

154
have
temperatures
ranging
between
between 3700 mg/1 and 4400 mg/1.
In fig.4 the Piper diagram was plotted with chloride as a

separated
anion:
straight line.
0
all
samples
appear
well
correlated
on
100
Cl-
4.SA41
.. Ql
+
+SA40
3:
IQ
ro
100
HC03- + 504
Fig.4 - Piper diagram with Cl
as separated anion.
In fig,5 the correlation between total salinity, expressed
in meq/1,
and an A-B section of the previous diagram confirms
a dilution process of the deep hot water with a local ground
water.
Only SA38 and SA39 slightly shift from the dilution trend.
This is mainly due to a percentual increase in alkalinity and
sulphates. As later on explained, considering the isotopic data
these springs are characterized by dilution with a ground water
that is not the same interacting with the thermal occurrences
along Rio Junthuma.
155
-14
Fig.
5 - Gorrelation diagram between TDS and A-B section

in the Piper diagram with Cl
as separated anion
Besides this difference SA38 and 39 can be related to the
same deep thermal inflow that feeds the main system. In fact
considering
the
representative
points
of
all
the
thermal
springs in the study area in the triangular diagram correlating
Li, Rb and Cs [fig.6], they result quite close.
Concluding
their
location
7 km
to
the
East
and
their
altitude, "200 m below the Rio Junthuma springs, make of SA38
and 39 a likely lateral outflow of the same system.

156
' l1} T
I I l i l l | l i l l l l l l l
100
80
20
60
Rb * 4 (mg/!)
Fig.6 - Li, Rb, Cs triangular diagram,
4.2. Geothermometry
The temperature of the deep
fluid
on the basis of the
triangular Na, K, Mg diagram [2] (fig.7) should run not below

230C. The mixing process of this deep water with different
percentages
of
freshwater
is
highlighted
by
perfectly
straight lining up of the water points until the bottom-right

corner of the diagram (shallow waters representative zone).
157
Na/1000
V
100
MgtO.5
Fig.7 - Na, K, \/Mg triangulr diagram.
Again
the
plotting
of
10*CMg/(10*CMg+CCa)
vs.
10*CK/(10*CK+CNa) [2] (fig. 8) supports this dilution with the

only difference that the extrapolation of the line, connecting
the
samples
equilibrium
representative
curve
at
the
points,
up
different
to
the
temperatures
theoretic
gives
reservoir fluid at 250C of temperature.

In fig. 9 [3] are shown the log AP/K values for SA21 spring
composition vs.
temperatures ranging
between
150
and
260C
(with the only constraint of the calcite equilibration at the

different temperatures). The curves for a series of volcanic
158
10 Mg
10 K
o.o
l l l l f l l l J
l i l ! l l l l l
l l l l l l l L l
l l l l l l l l l
l I l i i l I l
Fig.8 - 10K / (10K + Na) vs. lOMg / (lOMg + Ca) diagram.
Sample SA21
Added Carbon (o solution

133.8 mmol/Kg (at 240C)
l l l l l l l l l | l l Ml l l l l | l l l l l l l l l | l l l l l l l l l | l l l l l l l l l | l l l l l l l l l | l l l l Ml l l | l l l l l l l l l |
'100
120
140
160
180
200
220
240
260
Temperature C
F i g . 9 - Log AP/K values vs. t e m p e r a t u r e -
159
rock components, and the phases derived from their hydrothermal

alteration, converge at a temperature around 240C. The curves
match
at
value
of
log
AP/K below
zero,
this
could
be
explained by a poor computation of theoretic pH values due to a
lack of the pH value in the field. In the same way can be

explained the apparent equilibration of fresh minerals at a
lesser temperature of the altered ones.
For this reason it is been assumed as the equilibration
temperature value the one correspondig to the lines crossing

point instead of the conventional log AP/K = 0.
As far as concerning the SiO2 geothermometer
interesting to examine fig.
[4] may be
10, here SiO2 is plotted against
1000/TK.
Amorphous
Silica
to(N
o:
cn
Eo
"^LOT'
(N
o :
c/)gj
o.
inO--T-T
1.50
i i i ir t i | i i r i i IT i ijiiiiiiiii[iiiifi
2.00
2.50
3
.
0
03.50
1000/T
Fig.10 - Si02 concentration vs. 1000/T0 K.
160
4.00
Many representative points fall along the solubility curve

of
amorphous
silica,
this
agrees
with
the
presence
of
ignimbritic layers at depth and with an equilibration process

at the temperature of outflow. Because of it, the Si02 content
cannot be
used to estimate the temperature at depth.
4.3. Remarks on the isotopic data

No
isotopic
analyses
of
thermal
manifestations
or
cold
waters present in this area had ever been performed before,

besides in the course of this survey only very few cold springs
were found; so the relative results presented in tab. 1 are
only
enough
to
draw
tentative
meteoric
model
of
the
circulation patterns.
The
positive
highest
springs
chloride
content
SAH,
SA14,
and the
SAIS
most
and
isotopically
SA21,
despite
their
temperatures are not the highest in the Rio Junthuma area, have
been considered as residual waters originated from a deep fluid
single step boiled from a 260C reservoir temperature to 85C.
As
the
(diagram
representative
5180
vs.
SD)
points
are
of
these
slightly
springs
scattered,
in
to
fig.
11
reduce
possible errors to a minimum, the boiled water composition (BW)

has been computed extrapolating to zero the tritium content in
the three diagrams of fig. 12, 13 and 14, respectively 3H vs.
S18O, 3H vs. 6D and 3H vs. Cl.
The values obtained in such a way: 518O -12.65, <SD 105.1 and Cl 1950 mg/1 are comparable to those resulting
averaging the analytical results for SA14, 18 and 21. On the
base of the single step flash the 260C deep water composition
(DW) should be: 518O = -14.64, SD = -116.6 and Cl = 1290 mg/1.
161
-95
105
O
C\J
X
-1 15
-125
1354-7
-18
-16
-15
180
-14
-12
IN H20(%o)
Fig.11 - > D vs. 180 d i a g r a m .
o. u 16
2 5 -
,.*-)
/I5\s
o 2.0
C\l
-_
1.5
-E
x
3
o\
n:
\
Q
\_/
n:
38
1.0 -E
40
-1?3.0
1 l
1 1 l
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1
1 1 1 1 1 1 1 1 1
\^
1 1 1 1 1 1 1 1 1
1 I
1 1 1 1 1 1
-17.0 -16.0 -15.0 -14.0 -13.0 -12
180
IN H20(%o)
Fig.12 - Tritium content vs.
162
35
o /o o
0
5' _~
*' *
0.0 -
;a
,42
21
180 diagram.
3.0
2.5
,16B
O 2.0
(N
X
-0e
1.5 T
O:
1.0
oQ
i;
0.5
0.0
-130
O1
-125 -120
-115
- 1 -105
10
-100
D IN H20(%o)
Fig.13 - Tritium content vs. o D diagram.
3.0
2.5 -E
H
O 2.0
CN
n:
1.5
-e-
1.0
o o
,3
31
0.5
0.0
400
800
12001600
2000
CI (mg/l)
Fig.14 - Tritium content vs. Cl diagram.
163
The resulting oxigen shift from the GMWL is around 2 delta

units of 180 and the recharge water should have an isotopic
composition similar to that of Rio Junthuma.
Considering now samples SA1, 13, 35 and 36 they both for
salinity
and
tritium
content,
look
like
dilution
with
percentages between 15% and 35% of local groundwater.

This process is supported by their location on the diagrams
in fig. 12, 13 and 14.
In
the
c518O
vs.
SD diagram
of
fig. (11) they
occur
in
intermediate position with respect to lines A and B. The first

one,
A, represents the
dilution
line
along which
fall
all
possible mixture between the local groundwater (SA16B) and the

undiluted single step boiled deep water BW. Curve B shows in
turn the theorical isotopic composition of the residual waters
originated, according a single step flash, from the possible

mixtures
between
local
groundwater
and
deep
water
ranging
temperatures between 85C and 260C.

The first hypothesis (superficial mixing) is automatically
excluded because SA1, 13, 35 and 36 have temperatures always
close to or even higher than boiling temperatures, despite the

evident
dilution
(chloride
and
tritium
content).
Also
the
second hypothesys (mixing at the depth) can be excluded, the

location points of these springs in fig. 11 could be explained
only by low contributes of local groundwater that again do not
fit the analyzed chlorides and tritium.
The SD vs. Cl diagram
(fig. 15), shows that such mixtures
arise at a subsuperficial level. The representative points of

SA1,
SA13, SA35 and SA36 are well below the curve B (theorical
location
of
residual
waters
originating
from
diluited
deep
fluid) and can be explained on the basis of a boiling process

164
for the undiluted deep water up to about 120C, and afterwards

a mixing with the local groundwater (SA16B). This fit properly
both the analytical chlorides and tritium contents.
Finally considering the location of samples SA38 and 39 in
the diagrams 518O vs. 5D (fig. 11) and SD vs. Cl (fig. 15) is
evident:
1) The groundwater that acts as superficial end member for
the mixing has an isotopic composition more negative than the
one interacting with the Rio Junthuma springs; the tritium

content very close to
0 entails long circulation time peculiar
to regional patterns. The more positive values for samples SA16

and SA16B can be better explained with daily cicling process of
freezing and melting than with a lower infiltration level.
2) The deep component again seems to be an actual reservoir
fluid more than a residual water. This confirms the hypothesis

of a lateral outflow.
-95
-135
1000
1500
2000
CI (mg/l)
Fig.15 - oD vs. Cl d i a g r a m .
165
4.4. Extimation of the Rio Junthuma springs total flowrate

Given the
particular morphology
in which manifestations
along Rio Junthuma lies, it is possible to compute the total

deep water flowrate. As measured water flow rate at points Ql
and Q2 (fig.2) are respectively
106 1/s and 150 1/s, the deep
water contribution should be 44 1/s (~30%).

The chlorides and tritium contents of BW, SA16B and SA37
agree closely with this value.
5). Gases
The only two
available gas analyses
(tab.
2) belong to
springs which are fed by a deep fluid that underwent a boiling

process during its raise.
Such gases, besides being not representative any more of
the
deep
condition,
are
therefore
depleted
of
the
trace
components.
In order to estimate a geothermometry or, in any case, to
have an idea of the original reservoir composition it should be
advisable to sample gases from mud pools or fumaroles fed by
the steam produced with the boiling process.
References
[1] APPROVECHAMIENTO
SUDOESTE
DE
BOLIVIANO
LOS
RECURSOS
Areas
de
GEOTERMICOS
Salr
d'Empexa
DEL
Laguna Colorada - Aquater 1979.

[2] GIGGENBACH, W.F.
ria.
Derivation
(1980) - Geothermal solute equilib-
of Na - K - Mg - a geoindicators.
GEOCHIMICA ET COSMOCHIMICA ACTA, 52, 2749-2765.
166
[3] REED, M. & SPYCHER, N. (1984) - Calculation of pH and

mineral
equilibria
in
hydrothermal
waters
with
application to geothermometry and studies of boiling

and dilution. GEOCHIMICA ET COSMOCHIMICA CTA. 48,
1479
- 1492.
[4] FOURNIER, R.O. & POTTER, R.W. (1982) - A revised and
expanded
silica
quartz
geothermometer.
GEOTHERMAL
RESEARCH COUNCIL BULLETIN. V. 11, 3 - 9 .
167
GEOCHEMICAL AND ISOTOPIC EXPLORATION OF THE

GEOTHERMAL AREA OF PAIPA, CORDILLERA ORIENTAL,
COLOMBIA
R BERTRAMI*1, A. CAMACHO**, L. DE STEFANIS***,
T. MEDINA**, G.M. ZUPPI***
* Ente Nazionale per 1'Energia Elettrica,

Pisa, Italy
**IAN,
Bogota, Colombia
***Dipartimento di Scienze della Terra,

Universit di Torino,
Turin, Italy
Resumen-Abstract
EXPLORACION GEOQUIMICA EISOTOPICA DE LA ZONA GEOTERMICA DE PAIPA, CORDILLERA
ORIENTAL, COLOMBIA.
La explotacion de la zona geotrmica de Paipa (150 km al N de Bogota) se

realize durante el priode de 1987-1989, obtenindose los siguientes resulta-
dos y conclusiones principales:

I II -
Las aguas geotrmicas tienen una facis de cloruro-sulfato sdico.

El componente gaseoso principal es CO , aunque tambin estn prsentes CH , H S y N .
Ill -
La composicin isotpica estable del agua muestra efectos importantes
de evaporacin y de separacin del
vapor.
El fraccionamiento
isotpico indica una temperatura entre 200 y 230 C.
IV -
La presencia de componentes que indican prdida de vapor geotrmico,

taies
como
NH,
NH. , , H
H yy HBO,
H B0, sugiere
sugiere 1tambin
4
que
existe
un
depsito profundo de agua a alta temperatura.

V -
Todos los geotermmetros quimicos senalan una temperatura del depsito de 220C o mas.
El modelo de la zona geotrmica que se saca de los datos geoquimicos e

isotpicos indica que existe, al menos en la parte sur, un protnetedor poten-
cial geotrmico.
1
Present address: ENEL Pietrafitta, Perugia, Italy.
169
GEOCHEMICAL AND ISOTOPIC EXPLORATION OF THE GEOTHERMAL AREA OF PAIPA, CORDILLERA ORIENTAL, COLOMBIA.
In the period 1987-89 the geochemical and isotopic

exploitation of the Paipa geothermal area (150 km N of Bogota)
was carried out with the
following main results and
conclusions :
I
- The geothermal waters have a sodium

facis
chloride-sulphate
II - The main gas component is C02, but also CH4, H2S and
N2 are present
III - The stable isotope composition of water shows important
evaporation and steam separation effects. The isotopic
fractionation indicates a temperature between 200 and
230 C
IV
- The occurrence of components indicating loss of

geothermal steam, as NH4, H2 and H3BO3 also suggest the
exsistence of a high temperature water reservoir at depth
- All chemical geothermometers indicate a

temperature equal to or higher than 220 C
reservoir
A model for the geothermal area, derived from geochemical

and isotopic data, indicates a promising geothermal potential,
at least in the southern part.
Introduction
The Paipa geothermal district, located 150 km north of

Bogota and 250 km east of Nevado del Ruiz volcano (Fig.l),
belongs to the Altopiano Cundi-bayacense in the Cordillera
Oriental; its geological setting, typical of this region,
consists of a Mesozoic-Cenozoic substrate, generally acting
as a geothermal reservoir, overlying a Precambrian and
Paleozoic metamorphic basement (Fig.2). The Cretaceous-Miocene
sediments are formed by shales alternated by quartzitic
sandstones, mudstones and dolostones. Levels of evaporites
(Upper Cretaceous) and coal (Eocene) are present (1,2).
170
Figure 1
Geographical location of Paipa geothermal district.

The area belongs to the Altopiano Cundi-bayacense in
the Cordillera Oriental.
The volcanic rocks, intruded in previous sediments, are

composed of an extensive sequence of riolitic and porphiritic
lava flows and pyroclastic deposits. The Upper Pliocene to
Pleistocene sediments are an assemblage of coarse grained
volcanogenic rocks derived from Cuerpo Volcanico de Oolitas
and Pan de Azucar (1,2).
The Paipa geothermal field is strictly connected to the
Colombian Andes tectonics, which strike the north-south
parallel to the Ecuador-Colombia trench. The geothermal field,
in fact, is located in the central axis of the Tunja
sinclinorium and is limited to the east side by the NNE-SSW
El Salitre fault (1,2,3).
171
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Figure 2
Geological setting of the Paipa area.

tip: Cretaceous-Eocene sediments (shales alterned with
quartzitic sandstones, mudstones and dolostones).
dotted:
Upper
Pliocene-Pleistocene
sediments
(coarse-grained volcanogenic rocks).
dark: volcanic rocks (riolitic and porphiritic lavas)
gray: alluvial sediments
dash: lake Sochatoga
lines: main faults
172
The main aim of the present study is the evaluation of

the chemical and isotopic characteristics of water and gas
samples collected by Colombian members of IAN and IAEA
experts, in order to define the relations between the
different types of water in this area as well as the probable
distribution of temperature at depth.
2 Field and analytical methods
Ground-based field work was carried out in July 1987 and

in August 1989 at all the hot discharges and steaming grounds
present in the area. Samples of cold waters were collected
at the same time from streams and springs adjacent to the
thermal discharges. The hot water points (> 50C) of this
area received attention during reconnaissance studies of the
geothermal energy potential of Colombia since the early 1980s
(4,5); therefore, detailed sketches or models for the Paipa
geothermal system are available. Altogether 19 water samples
were
collected
for
chemical
and
isotopic
analyses.
Temperature, Eh, pH and conductivity were measured in situ
using portable meters. All samples were filtered through
Millipore membrane filters.
The major dissolved constituents were determined at
Institute de Asuntos Nucleares (IAN), at ENEL laboratory
(Lardarello) and at Dipartimento di Scienze della Terra ( DST
- Torino) by atomic absorption spectrometry (cations), by ion
chromatography (anions) and by titration (alkalinity) using
standard methods. Moreover, some analyses of anions (HC03-,
SO4=, S=, PO4=, N03-) have been performed in the field using
a portable spectrometer.
The gas samples from steam vents as well as from

discharges were collected in evacuated vessels previously
filled with 500 ml of 4N NaOH; the gases were analysed in
ENEL laboratory by a combination of wet chemical and gas
Chromatographie methods. The non absorbed gases were analysed
by chromatography.
Isotopes of water molecule were analysed in the IAEA
laboratory, while Sulphur-34 and Oxygen-18 of dissolved
173
sulphates precipitated with BaCl2 carried out at the Paris-Sud

University.
The results are reported
table 3 (isotope).
in tables 1-2 (chemistry) and
3 Chemical composition of water discharges
3.1 Major elements

On the basis of a preliminary survey of the analytical
data given in table 1 and reported in figure 3, the major
part of water can be classified as acid-sulphate-chloride,
as defined by Giggenbach (6). The chemical composition
appears to be rather homogeneous and only cations can mark
the differences between the cold and hot waters. High
temperature
waters
are
mainly
characterized
by
the
significant presence of Na-K, whereas waters from a partial
or total superficial origin show a variable Ca-Mg component.
Moreover, the temperature of hot discharges ranging
between 30 and 75C does not present a regular areal
distribution, as could be suggested by the groundwater flow
inside the Paipa district. On the other hand the Ca and
Mg content increases from Rio Salitre-La Playa (P08 ) to
Banos Termales (P01-P03, P05, P20) following the water
movement, irrespective of temperature.
As shown in figure 4, it is correct to consider P08
the closest sample to the chemical end-member of the Paipa
waters, even if it indicates an intermediate temperature

(50C).
The
second
pole is formed
by environmental
temperature waters that flow in the shallow aquifers and
are characterized by a neutral chloride chemistry. In this
case, the chemical content is mainly controlled by the
hydrolysis of volcanic porphyrites as indicated by samples
collected in the hydrographie network (Q.Honda) or by the
solubility of the Cretaceous-Eocene deposits (Mina de
Carbon).
However
all
the
samples
do
not
contain
bicarbonates. A gradual intermixing between two groups
appears.
174
tab. 1
Chemical data of water samples - L indicates laboratory analysis;
F, field analysis. Elements are
expressed in p.p.m.
Sample Year
P-01
P-02
P-03
P-04
P-05
P-06
P-07
P-08
P-09
P-11
P-13
P-18
P-20
P-22
OH
MC
87
89
87
89
87
89
87
89
87
89
89
TF
C
525
506
525
51 8
CondF
US/cm
725
740
21 5
20 1
732
720
19 7
59500
41000
3630
4130
87
459
87
89
87
56 5
56 3
380
24 8
242
87
89
89
89
89
89
89
89
51 2
720
166
128
185
pH F
33500
35500
24200
72
48300
1018
140
152
38300
40900
6300
20
5670
tab. 2
Sample
P-01
P-02
P-03
P-06
P-07
P-13
P-13a
P-20
Eh F
ALK F
CondL
40000
39000
6 7 105
43
68
25
ES
98
40
68
68 -312
41
20
69
58
105
44 335
64
-42
72
76
-30 265
45
150 O B
6 4 -91
6 8 -232
43
4 7 147
37
70
59
225
62
59 1 8
73
68
78
75
3 1
8
29
-32
0
236
33000
40000
Ca++
Mg++
66
134
90
23
16
15
16
15
16
72
4200
21000
65
24700
95
20000
44000
49500
77
47
4000
41500
144
80
129
83
21
16
36
30
3
33
65
51900
158
42
40
65
05
pH L
22
15
49
52
13
12
64
76
70
11
1
76
73
450
Na+
K+
HCQ3
L
56
45
48
14600 2300
11200 1200
13300 3650
10500 1200
42
12500 2900 50
11000 1200
43
34
963
159 23
77 35
5
720
29
13
9115 2375
12
592 26 9
5300
140
14
3 09
26
46
7813 1000
32 17708 1593
50
5 13000 1200
45
58
06
1
130
52
187
07
23
17
15
11000
10200
1500
1100
950
155
05
300
2
52
04
6
66
1 5
6
44
40
45
Cl5800
5400
5700
5400
5800
5300
438
164
3698
2700
43
3270
7430
4800
53
20
27
56
5300
5200
725
5
3
S04 = H2S Si02 NH4 + U+
19700
18200
18400
19200
18200
18400
1435
1520
10100
6900
23
10318
23814
16250
236
19
15
812
19000
18500
750
1
4500
48
47
72
56
35
42
60
43
5
85
82
14
1 4
Fe Sr++ Ba-H- AI tot
088
04 26
094
1
90 05
075
1
80 04
70
83
32
48
! 6 28
61
02 04
049
44
2
03 07
05
035
100
03 04
48
08
43
40
135
1 5 11 6
1 6
1 5
118
04
1 3
03
08
55
22
18
19
24
33
25 007
14
03
42
16
1 6 102
46 185
07
46
16
02
14
29
16
33
03
10 003
28
15 0 11
02
12 004
05
17
24
10
29 0 13
03 008
03
03 03
80 03
75 05
10 09
1
2
1 5 550
25
42
33
02
05
15
05
09
37
03
08
021
33
29
326
16
33
87
89
87
89
87
89
87
89
87
87
89
89
89
02+ Ar
H2
88
0.06
0.009
0.05
-
0.001
0.009
0.006
CH4
N2
0.23
1.4
0.05
3.29
0.05
7.35
0.06
1.43
0.1
0.77
0.07
0.11
0.12
11.8
0.33
21.81
0.3
0.32
1 01
16 86
0.37
0.77
0.02
0.78
0.01
0.06
0.29
4.37
0.06
0.61
0.06
0.79
0.03
1.66
1 03
2 16
C02
98.3
84.14
99.6
70
99.6
98.11
98.6
77.5
99.5
97.6
98.79
97
13.94
H2S
0.021
Ha
ppm
10.3
08
190
C2H6
ppm
2.3
CO
ppm
4.7
2.16
0.82
0.63
38
15
5.8
33
2.69
n.d.
:
0.003
65 11 5
1 6
18
25
09
77
1 7
02
33
07
1 2
0.027
0.055
0.012
21
23
Chemical data of gas samples. Analyses are expressed in per cent,

Year
Br- N03- P04 =
17
06
53 252
99
F-
53
10
58 468
34
0.717
tab.
Isotopic data of water samples, referred to international

standards.
Sample
Year
P-01
87
89
87
89
87
89
87
89
87
89
89
87
87
89
87
87
89
89
89
89
89
89
P-02
P-03
P-04
P-05
P-06
P-07
P-08
P-09
P-11
P-18
P-20
P-22
Q.H.
M.C.
5 D
%. SMOW
-68.0
-67.2
-67.0
-72.0
-68.4
-63.2
-67.4
-72.6
-67.4
-68.0
5 180
%. SMOW
-6.55
-6.61
-6.68
-6.89
-7.05
-7.32
-9.47
-9.67
-8
-7.91
-15.01
-8.44
-6.54
-6.08
-8.69
-9.97
-9.99
-6.72
-6.9
-8.73
-9.25
-9.57
T
T.U.
5 34S
(S04)
8.90
0.30.2
5 180
(S04)
4.0
0.0+0.2
0.3+0.2
10.20
0.4+0.2
8.00
2.0+0.2
3.7+0.3
9.50
11.00
0.40.2
10.00
0.3+0.2
0.010.2
0.0+0.2
9.10
9.70
10.30
7.60
6.4
11.5
7.2
17.0
6.0
4.9
5.1
13.5
15.0
100
100
100
CI
Figure 3
176
Relative HCO3, Cl, SO4 contents (mg/kg) of waters

collected in 1989 and listed in table 1. The major
part
of
waters
can
be
classified
as
acid-sulphate-chloride.
8\ 100
O/
Figure 4
Particular of relative Na+K, Mg, Ca contents. Only

cations can mark the differences between surface and
deep waters. Sample P08 could be considered rather
close to the chemical end member of Paipa deep waters.
The S:C1 ratios are smaller than those of the magmatic

discharges in the Nevado del Ruiz volcano (7-10) which
supports the assumption that the chemistry of these waters
is due to the partial absorption of deep gases (9, 10).
Although the water temperature is higher than 30 C,

thermal spring discharges show a low content of dissolved
silica. This could be explained either by an aquifer matrix
relatively depleted in quartz and silicates, or by waters
heated without reaching complete chemical equilibrium. This
second process needs slow reactional kinetics (11, 12)
which could be favoured by the presence, in the volcanic
rocks, of quartz phenocristals (1-3). The undersaturation
with respect to quartz no longer appears in the equilibrium
177
diagrams (Fig.5) of aqueous phases at a temperature of

60C. Therefore, as at this temperature, which corresponds
to the mean temperature of all the Paipa thermal springs,
waters are always saturated with respect to quartz, it is

correct to consider that in rising up, the fluids could
be thermically equilibrated with external conditions. The
new equilibrium allows precipitation of exceeding SiO2, as
indicated by the presence of hydrothermal calcedony in the

sedimentary formations.
16.0
1 2.0
m
01
80
QUARTZ
SATURATION
4.0
OH
AMORPHOUS
SILICA
SATURATION
MC
0.0
-6.0
-4.0
-ao
Figure 5 Equilibrium diagram of acqueous phase at 60C. The

fluids are equilibrated with external conditions: this
allows precipitation of excess SiO2 as indicated by
the presence of hydrothermal calcedony
in the
sedimentary formations.
178
At the same time, figure 6 showss the different stages

of maturity reached by waters during dynamic hydrothermal
alteration. The most important alteration process consists
of attack by acids formed through absorption of deep gases
into groundwaters and leads to rock destruction (6, 11,
12). In the Paipa geothermal district, separation of the
C02 rich vapour phase and its absorption into water generate
an environment of increasing acid alteration. However, when
the volume of waters reacting with gases is small (P08),
or when the exchange reaction time between the water and
the gases is long (Pll), the continuous gas flow permits
the waters to reach equilibrium with C02, leading to a
rapid increase in their reactivity. Besides, when the gas
volume is smaller than that of water (P18) or when the
exchange reaction time is short (QH), the amount of
dissolved CO2 is reduced, decreasing the reactivity of the
water towards the aquifer matrix. The principal processes
Na
1JOO
so
/
/
/
/
220/
/
/shallow
f i
/Z00
/
waters
/
/
11 \
60*
50
QH
100
Figure
Relative Na,
K, Mg, content
of
thern
Isotherms calculated according to Giggenbach equations

(6) are given together with the full equilibrium
curves.
179
affecting geothermal fluids during their further rise to

the surface are summarized in figure 7, where dissolved
C02 is reported with respect to discharge temperature.
Dissolved CC>2 shows the same order of magnitude in hot as
in cold waters. Therefore, waters do not precipitate the
travertine deposits in all the geothermal district, as
could be suggested by the high partial pressure. In the
case of Mina de Carbon and of water point P06 (steam
heated pool), superficial oxidation of H2S provides a source
of acidity and an excellent environment for intense rock
leaching. The waters thus show a high content of dissolved
sulphate.
o-
08
MC
o
u
-111
0!
<0
-2-
0
3
18
0
4
-3
0
20
J2L
30
10
Figure 7
50
70
Dissolved C2 as fonction of discharge temperatures.
3.2 Trace elements

The most significant trace elements in Paipa waters,
halogens (F and Br), B and Li, could complete interpretation
of the water origin and circulation. By including analytical
data obtained during a comprehensive study of Nevado del
Ruiz gases (7, 9, 10, 13), the relative Cl, Br and F
180
contents are compared in (Fig. 8). The most striking feature

of this plot is the pronounced mixing line between the
Nevado del Ruiz gases and magma and marine evaporites (14).
The volcanic pole is formed by samples P06 and Pll, whereas
P04 represents the evaporitic pole. The thermal water
samples appear to be partially enriched in F and Cl,
confirming the attack of strong acids (HC1 and HF), formed
through the absorption of magmatic gases, on the aquifer
matrix. The destruction of evaporitic layers follows a
selective evolution, thus enriching thermal waters in the
dissolved chlorides. However, agreement of Br:Cl and F:C1
ratios is not merely a coincidence. Other "markers"
dissolved in the waters, such as B and Li, plotted in
Nevado
del
Ruiz
V
100
Figure 8
Br
Relative Cl, Br, F contents plot. The most striking

feature is the pronounced mixing line between magmatic
and evaporitic points.
181
figure
9 confirm
the double
origin of
fluids.
The most
striking feature of this plot is the pronounced mixing

line described by cold groundwater collected inside the
geothermal area and trending towards the Li pole. Similarly
B:C1 and SO4:C1 ratios suggest that acid waters are mixtures
in the depth of water from an acid-sulphate-chloride
reservoir, with various proportions of shallow groundwaters.
The principal source of sulphate and halogens may be done

by
high-temperature
deep
gases
interacting
with
the
sedimentary deposits that cover the reservoir.
CI/100
100
gases
from
Nevado
del
Rui z
marine
evaporites
100
Figure 9
182
Relative Cl, Li, B contents plot. The double origin

of fluids is confirmed. The diagram emphasizes the
mixing at various proportions of waters from an
acid-sulphate-chloride
reservoir
and
a
shallow
aquifer.
Li
marine
evaporites
Nevado del Rui

magma
Paipa t h e r m a l
waters
Nevado
del
Ruiz
gases
100
50B
Figure 10
Relative Cl, B, SO* contents plot. The principal
source of suphate and halogens may be the high
temperature
deep
gases
interacting
with
the
sedimentary deposits.
However the lack of any intermediate water suggests

the existence of two separate circulation systems: a deep
one,
concerning water rock interaction and involving
sedimentary rocks of Cretaceous-Eocene age, and a shallow
one,
where cold waters interact with volcanic rocks or
adsorb deep gases of steam vents.
4 Gases chemistry
The areal distribution of gas discharges shows the absence

of steam vents in the southern sector of the Paipa area
inside the Cuerpo Volcanico de Olitas. Moreover, a preliminary
analyses of gas chemistry
(Tab.2) indicates that the
183
discharged
gases are mainly
formed
by C02,
followed
by
N2,
and show a rather constant chemical content. Because of the

comparatively
high
discharge
temperatures,
the
relative
proportions of more soluble (H2S) to less soluble (H2, N2 and

CH4 ) gases in the free gas phase sampled are likely to be
similar
to
those
found
in the deep
fluid,
thus permitting
the evaluation of the equilibrium temperatures.

The
O2+Ar
affecting
content
is
samples
during
gases
seems
atmospheric
normally
lower
collection.
fairly
than
The
small
the
error
contribution
and
is
of
strictly
controlled by hydrogeological conditions; in fact, in 1989,

collection took place after an heavy wet period and surface
cold waters significantly diluted deep fluids, as pointed out
by
the
high
discharges
N2
content.
may
be
However
two
distinguished
major
groups
(Fig.11).
The
of
gas
samples
collected
in the Rio Salitre sector indicate a high H2 and
saturated
hydrocarbons
observed
high
in
all
temperature
relatively
short
comparatively
content.
discharges
of
of
The
presence
this
sector
interaction
with
residence time of
lower
of
suggest
deep
In
matrix
the rising
temperature.
H2 and
very
and
fluids
addition,
CH4
a
at a
samples
collected in the northern sector show the presence of volatile

sulphur compounds. The H2S system is controlled by the redox
conditions
during
the
upward
movement
of
fluids;
in
this
case, a short residence time of gases in a likely oxydizing
environment near the surface and a short interaction of the

fluids with areated groundwaters is suggested. Moreover, He
contents are relatively higher than in the Rio Salitre sector,
indicating
a longer residence time of fluids in the depth.
In other words, the reservoir cap must be more important and

show
lower
permeability
in
Paipa
than
in
the
southern
sector, where the holocene aquifer, although probably having

a higher storage capacity, does not show a very significant
thickness.
Thus,
the
chemistry
of
the
gases
collected
in
the
geothermal district provides additional information about the

mineralogical
matrix
of
the
deep
reservoir,
about
the
fracturation intensity of the upper system and the hydraulic

conductivity of the cap.
184
CO./100
100
Figure
11
CO 2/
N2,
CH4
relative
contents
plot.
Full
and
empty
circles
indicate
respectively
gas samples
collected during 1987 and 1989. Two major groups of
gas discharges may be distinguished: samples collected
in Rio Salitre district (P06, P07 and P13 ) and in
Banos Termales (P01, P02, P03 ).
The spatial
distribution of
relative proportions of
gases probably
reflects
the
magmatic gases interacting with the
shallow groundwater layer overlying the carapace. The small

amount of liquid stored in the Rio Salitre area only provides
a low buffer capacity with respect to chemical variation.
185
Isotopic
composition
5.1 Water molecule
of waters
isotopes
The isotopic composition of water samples is given in

table 3 and the results for Deuterium and Oxygen-18 are
reported in figure 12. The best fit for sample data points
is a line described by the equation
62// = (1.440.20)6180-(S7.80.8)
intercepting
Local
Meteoric
Line
at
62 H = 74.0
and
18
& O = -10.5. Using the correlation linking 18O of local

precipitation to altitude, as reported by Torres et al.
(15), an "isotopic altitude of recharge" of 2700 m is
obtained. This altitude is in agreement with the mean
elevation of Cordillera Oriental in the Paipa district.
-40.
-60-
EXCHANGE
WITH
C02
(=50%)
5 D = ( 1.44 0.20) 6180 - (57.78 1 0.7?)
-80^RECHARGE
-100.
-1 5
-10
, 18_
0 0
Figure 12
Deuterium versus Oxygen-18. Sample P06 that does
not fall on the evaporation line as all the other
samples is interpreted as a continuous isotopic
exchange
( of about
50% ) between
O of
local
precipitations and deep CO2.
186
The slight slope of the 6 2 H-6 18 o correlation line could

be explained by the isotopic enrichment for steam heating
and non-equilibrium evaporation of deep waters at a
temperature higher than 220C. The waters have the same
hydrogeological origin, as indicated by the good correlation
coefficient (r? = 0.95). A similar conclusion could be
drawn from figure 13 where 5 L8 O is reported in relation to
chloride content :
I8 O = 0.75[CZ"]- 1CT3- 10.1
Moreover, the upward movement of fluid is accompanied

by boiling and phase separation, and secondarly by mixing
with cold waters. Nevertheless the lack of observed steam
points in the district allows for neither quantification
of the steam production nor the measurement the isotopic
composition of the separated water phase. Considering the
water collected in P08 as very close to the end-member of
deep fluids, and assuming a cooling process as boiling and
-4
-6
-8
18
-\
~3
O= (0.75CI ) 10-10.1
-10
-12
-14
CI
-1
mg I
-16
2000
Figure 13
4000
Oxygen-18 versus chloride content.
187
multistage steam loss, the vapor isotopic composition should
be
618O
-15.2 for
and
o2//.
-82.5 for
The
liquid-vapor
separation strongly partitions dissolved salts, increasing
in our case to about 1.2 times the chloride concentration

in the Paipa thermal waters.
The cooling processes are recognizible in the central
sector of Paipa district, where mainly gaseous vents are

present, not only because of the major role on steam loss
played
by
proximity
because
Rio
fault
but
to the hydrogeological
of
Moreover,
Salitre
superficial
in
the
also
recharge
groundwater
northern
because
area
of
the
areas and
thus
movement
the
mixing
absence.
with
cold
groundwaters takes place.

However, sample P06 does not follow the scheme described
above. This sample was collected
in a small pool in the
Rio Salitre sector. The pool is filled with surface waters

in relation to the meteorological and hydrogeological
cycles. Sample P06 could be interpreted either as a
continuos
isotopic
exchange
between
ISQ
of
summer
18
precipitations (6 0~-9%.) and CO2 or as Deuterium enrichment
of
an
hypothetical
residual
vapour
phase
in
the
whole
geothermal system.
The first hypothesis is in agreement with the C02
discharged in the pool; the gas volume is larger than that
of the water. Taking in account a mean isotopic composition
of
18
in
C02
equal
to
-14
%.
(16)
and
f ractionation
factor of 42.5 %. valid for a temperature of 15 C (mean

yearly
temperature),
it
is
correct
to
consider
precipitations isotopically depleted of 5.8 %. and exchanged

for 50%.
Due
to
the
lack
of vapour
steam
in
the
area,
as
previously mentioned, it is not possible to take in account

the second hypothesis. Moreover, the Hydrogen exchange
kinetic seems faster than the required and, at the same
time, the reactional temperature needed (more than 300)
is not in agreement with that evaluated in Paipa geothermal
district.
188
Tritium activity in thermal and cold waters is always

lower than in Bogota precipitations (15, 17) during the
same period. The Tritium low level indicates a non
significant component of present precipitation, defining in
this way a mean residence time higher than 50 years. Only
P06 shows a Tritium content close to that of actual
precipitations, confirming the hypothesis of an isotopic
exchange betweeen meteoric waters and C02 steam vents.
5.2
Isotopes in dissolved sulphates
In table 3 the isotopic composition of stable isotopes

in dissolved sulphates is reported. The 534S values of
thermal waters are consistent with a mixing between an
evaporitic mineral source and a deep sulphide; but M.C.
sample appears to be quite enriched in the heavy isotope
if the oxidation from a secondary sulphide is considered
(Fig. 14).
18
Cretaceous
evaporites
14
10
,22
O
"
O 20
is
MC
Figure 14
Sulphur-34 versus sulphate-chloride weight ratio.
189
In fact the isotopic composition of Sulphur with a

magmatic origin ranges between 0%. and + 2%. vs. C.D. (11,
12) and the 634s of Cretaceous evaporites, like those present
in the subvolcanic stratigraphy, ranges between +15%. and
+ 18%. vs. C.D. (17).
Dissolved sulphate formed by the oxidation of subsurface

sulphides preserves the original isotopic signal; in this
way the solid sulphide pole in the Paipa aquifer matrix
should have a 634s of about +8%. (M.C. sample). This
composition should be considered as a result of the
absorption of volatile Sulphur compounds inside carbon
levels of the Guadua formation, which forms the cap of
the geothermal reservoir.
In
points
of its
as a
a 634s vs. 6 18 O diagram (Fig. 15) all representative

of thermal waters fall on a straight line. Because
slope (about 1.5), this line could be considered
reduction line. It cannot be considered as a
+ 20
o
to
+ 15
22
+ 10
MC
+ 5
+10
+ 15
18
0 O
(so4)
Q/
xoo
Figure 15 Sulphur-34 versus Oxygen-18 of dissolved sulphates.

Star indicates isotopic composition of Cretaceous
evaporites. All thermal waters fall on a straight
line with a slope of about 1.5, that could be
considered as a reduction line. Samples at low
temperature (P04, P06, P22, M.C.) do not achieve
isotopic equilibrium during subsurface oxydation.
190
precipitation line of gypsum and anhydrite since the thermal

water always remains undersaturated with respect to these
minerals. Thus, this line is interpreted as a mixing line
where the end-members have to be identified in the
Cretaceous sulphates and the geothermal gases. During
subsurface oxydation, the isotopic equilibrium between
molecular Oxygen and water is not achieved for low
temperature samples. On the basis of classical equilibrium
equations (18, 19), the percentage of molecular Oxygen
ranges between 90 and 100%. Nevertheless it is possible
that the C02 Oxygen participates to the sulphide oxydation.
Sample M.C. indicates that the oxydation takes place
instantaneously at an environmental temperature and a low
pH. Under such conditions the equilibration time for
isotopic exchange reaction is a few hours.
The other water samples indicate reactional conditions
close to the equilibrium and a participation of water
Oxygen of more than 50%. In this way the reaction half-life
ranges between 50 ( P08 ) and 300 years ( P01 ). The time
herewith obtained is in agreement with water age calculated
by Tritium content, confirming once more that the aquifer
where all isotopic exchanges take place is confined and
has a low permeability.
Similar conclusions can be drawn from figure 16, where
the 180 content of dissolved sulphates is plotted versus
that of corresponding waters. The isotherms representing
the mean fractionation factors for isO exchange between
sulphate and water are determined according to Lloyd (18)
and Mizutani & Rafter (20) equations. The plot of thermal
waters
indicates
a
close
approach
to
equilibrium
temperatures, similar to those evaluated by the means of
water isotopic enrichment in Deuterium and Oxygen-18.
Moreover, cold waters oxidizing close to surface conditions
with molecular Oxygen indicate temperatures generally lower
than those measured at the discharges.
191
-5
Figure 16
Oxygen-18 in dissolved sulphates versus Oxygen-18
in corresponding waters. The isotherm are determinated
according to Lloyd (18) and Mizutani & Rafter (20)
equations.
6 A model for the Paipa hydrothermal system
The use of classical geothermometers Na-K

(21), Na-K-Ca-Mg
(22)
and CO (23) defines a reservoir temperature close to
200 C (tab.4). As expected, the same geothermometers applied
to cold water indicate an equilibrium temperature similar to
the one measured at the discharge. Only TNK2 gives for cold
groundwaters of Cuerpo Volcanico (Pli), a temperature in
disagreement with the one measured, because of Na excess in
volcanic rocks.
tab.
Reservoir temperatures defined by classical geothermometers
Sample
P-01
P-02
P-03
P-04
P-05
P-06
P-08
P-11
P-13
P-18
P-20
P-22
Q.H.
M.C.
192
TQA
100
95
95
40
100
80
90
100
TNK
200
210
205
200
210
75
190
230
TNKCM
240
245
240
140
240
55
265
50
T C02
-
105
80
95
95
55
50
-
200
195
200
300
210
220
220
60
40
40
T CO
250
230
240
175-200
T 18 0
170
130
65
115
10
150
50
160
150
55
45
Silica geothermometer, as previously shown, indicates a

lower temperature than the one
obtained
with the other
geothermometers. Thus, the Si02 content of thermal waters
does not reflect the fluid-rock equilibrium reached in the
reservoir and underevaluates dissolution temperature. By the
use of Triangular diagram (6), evaluation of analytical Na,
K, Mg contents allow the definition of deep equilibration
temperatures and the effects of water mixings (Fig.6).
The position of all data shows either a trend towards
the partial equilibrium or a complete immaturity. Only water
sample P08 reaches full equilibrium at a temperature of about
250 C. Because of the faster rate of equilibration in the
system K-Mg with respect to K-Na, a difference of about 40C
can be evaluated between conditions in the shallower levels
(K-Mg) and those in the depth (K-Na) for the Paipa thermal
waters. Gas geothermometers are affected by surface or
subsurface oxidation of H2S, CH4 and other non-absorbed gases.
Moreover, mixing with cold waters leads to an incorrect
evaluation of the last equilibrium temperature. Nevetheless
for sample P13 collected in a steam vent, temperatures
obtained with gas geothermometers must be compared with those
evaluated by dissolved geothermometers in the close area
(P08); in this sector of Paipa geothermal district, the deep
temperatures are always higher than 200C as indicated by CO
geothermometer ( 23 ).
The
water
maturity
index
(6)
is
always
above
2.0;
therefore it is correct to evaluate the CO2 fugacity in the

geothermal system using K, Mg, Ca relative contents. All
thermal waters are aligned and trend towards sample P08,

confirming once more, that it could be considered like, or
very close to, deep end-member
(Fig.17).
For the Paipa geothermal system a fugacity of 100 bars

could be taken into account. Considering a water column in
equilibrium with such a pression in an open system, a depth
of about 1000 meters must be evaluated.
All thermal waters have a constant value of mole ratios

n CO2/n H20 for vapour phase (about 5 ), indicating homogeneous
conditions inside the system. Starting with equation 30 of
193
40
60
100
200
/ \
t(c)
KC
5 _
-1
_ 100
L (Km)
Figure 17 Evaluation of CO2 fugacities in Paipa area by using

K, Mg, Ca contents in discharge waters according to
Giggenbach equations ( 6 ).
Giggenbach ( 6), water fugacity of about 20 bars could be

obtained, indicating a reservoir temperature higher than
210C.
Thermal waters are in equilibrium with minerals forming

the sedimentary cap (tab.5). Using the heat and mass balance
equation, the composition of waters before separation were
recalculated. In this case at a temperature of 220C, waters

reach,
or
are close to, equilibrium with
respect
to
hydrothermal or metamorphic minerals.
The influence of deep uprising fluids is higher in Banos
Termales (northern sector) than in La Playa (southern sector),
as
indicated
by the presence of discharges at high
temperatures.
194
tab. 5
Sample
P-Q1
P-02
P-03
P-04
P-5
P-06
P-08
P-11
P-18
P-20
(Ji
Saturation index with respect to some sedimentary and metamorphic minerals.

Anhyd.
-0.59
-0.618
-0.51
-1.769
-1.073
-3.6
-1.391
-3.199
-0.662
-0.589
Laum.
-3.245
-6.15
-1.193
-20.843
0.589
-
Low Alb.
-1.161
-2.69
-0.58
-9.741
0.723
-
Microcl.
-0.16
-1.68
K Mica
-3.167
-7.08
-3.009
-4.468
-
0.26
-2.009
-2.044
-24.318
1.883
-
-11.347
-1.07
-
-8.86
1.7
-
Analc.
Calced.
0.24
0.18
-0.02
-0.26
0
0.25
0.04
0.43
0.19
-0.04
Prehn.
-8.421
-11.5
-3.449
-30.027
-3.677
-
Calc.
-1.91
-2.086
-1.439
-3.744
-1.272
-6.5
-4.449
-2.34
-1.579
-1.651
Quartz
0.632
0.566
0.298
0.298
0.313
0.75
0.407
0.916
0.579
0.287
Moreover, the southern sector, being closer to the aquifer

recharge area, is characterized by the presence of diffuse
steam vents for the local hydrostatic conditions and sediments
hydraulic conductivity. The low upward movement of gases, as
indicated by the low fracturation intensity of pelitic
formations and the depth of resevoirs as previously defined
could force the uprising gases, mainly the more reactive
ones, to equilibrate with the new thermal and geochemical
conditions.
This model is valid for the sectors where volcanic rocks

are covered by a significant thickness of sediments. When
volcanic rocks outcrop (Cuerpo Volcanico de Oolitas and Cuerpo
Volcanico Pan de Azucar) steaming grounds and thermal
discharges are completely absent.
The temperature difference between fully equilibrated
waters (P08 at 250C) and partially equilibrated waters
(P01-P03 at 220C) allows the evaluation of chemical and
isotopic composition of the deep end-member:
a2!!
= -65.5;
6180 = -5.80;
Cl-
= 5720
The potential source for high chloride content may include

the
dissolution
of
evaporites
within
the
subvolcanic
stratigraphy, incorporated into fluids.
7 Conclusions
The above geothermal model was constructed for the Paipa

district assuming uniform permeability conditions of the
sedimentary cap; therefore, it is likely to indicate only
the potential distribution of fluids inside the system.
The actual model is governed by the scarce knowledge
about the local stratigraphy and the presence and rate of
faults and fissures. Because of these geological problems,
exploratory drilling in Paipa and La Playa sould be seriously
considered.
196
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N.W. (1990)
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R.M. (1968)
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Y.,
RAFTER,
T.A.
(1969)
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BERTRAMI,
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199
ISOTOPIC COMPOSITION AND ORIGIN OF THERMAL AND

NON-THERMAL WATERS FROM THE MIRAVALLES
GEOTHERMAL FIELD, COSTA RICA
W.F. GIGGENBACH
Division of Chemistry,
Department of Scientific and Industrial Research,
Petone, New Zealand
R. CORRALES, L. VACA
Institute Costarricense de Electricidad,
San Jos, Costa Rica
Resumen-Abstract
COMPOSICION ISOTOPICA Y ORIGEN DE LAS AGUAS TERMALES Y NO TERMALES DEL YACIMIENTO GEOTERMICO DE MIRAVALLES, COSTA RICA.
Si se va del norte al sur a lo largo del yacimiento geotrmico de Hiravalles, en Costa Rica, se comprueba que los contenidos de deuterio y de oxigeno 18 de las aguas en movimiento que reprsentai! sistemas freticos locales,
disminuyen
un
25 /oo
distancia de solo 40 km.
un
3 /oo
respectivamente
lo
largo
de
uiia
Las aguas fluviales con flujos de il 000 kg/s, que
transportan la mayor parte de las aguas de escorrentia de la zona, tienen composiciones isotpicas parecidas a las del agua fretica del norte, lo que sugiere que los vientos del norte hacen que la mayor parte de la precipitacin
se produzca en la ladera norte de la cordillera.
El contenido de deuterio de
los caudales de agua de pozo geotrmico y cloruro natural se corresponde con

el de las corrientes del norte, lo que indica que se produce un proceso de
realimentacin a partir de las aguas freticas del norte cuya cantidad es prdominante.
Las aguas termales con mayor contenido de cloruro se enriquecen
con oxigeno 18, lo que posiblemente se debe a que se produce un intercambio
isotpico con la roca.
Sin embargo, a la vista de los recientes hallazgos en
sistemas hidrotrmicos situados a lo largo de plaas con limites convergentes,

se considra como mas probable que el enriquecimiento con oxigeno 18 se deba a
la mezcla del 15 al 20% con un agua "andesitica" cuyo contenido en deuterio es
o
-20 /oo
+10 /oo
en
oxigeno 18.
La
absorcin
de
esta
agua
andesi-
tica, que se desprende en forma de vapor de las masas profundas de magma en

proceso de enfriamiento y cristalizacin, conduce inicialmente a la formacion
de aguas cidas cloruro-sulfatadas.
La llegada de estas aguas a un pozo geo-
trmico tras el proceso de profundizaeion sugiere que la conversion de aguas

cloruro-sulfatadas inmaduras en aguas de cloruradas neutras maduras se produce
en nivels compart!vamente poco profundos.
201
ISOTOPIC COMPOSITION AND ORIGIN OF THERMAL AND NON-THERMAL WATERS FROM THE
MIRAVALLES GEOTHERMAL FIELD, COSTA RICA.
Progressing from the n o r t h e r n to the s o u t h e r n

extent of the M i r a v a l l e s G e o t h e r m a l F i e l d , Costa Rica, the
d e u t e r i u m and oxygen-18 contents of stream waters,
representing local groundvaters, decrease by 25/oo and 3/oo

r e s p e c t i v e l y over a distance of only 40 km. R i v e r waters with
flows >1000 kg/s, carrying most of the d r a i n a g e f r o m the area,
have isotopic c o m p o s i t i o n s close to those of n o r t h e r n groundwater suggesting that most of the p r e c i p i t a t i o n , c a r r i e d by
n o r t h e r l y winds, falls to the n o r t h of the C o r d i l l e r a . The
d e u t e r i u m content of g e o t h e r m a l w e l l and n a t u r a l c h l o r i d e
water d i s c h a r g e s agrees w i t h that of northern streams,
p o i n t i n g t o recharge from t h e q u a n t i t a t i v e l y p r e d o m i n a t i n g ,
northern g r o u n d w a t e r . The h i g h e r c h l o r i d e t h e r m a l waters are
e n r i c h e d in oxygen-18 p o s s i b l y due to i s o t o p i c exchange w i t h
rock. In v i e w of recent f i n d i n g s on hydrothermal systems
located along convergent plate boundaries, however, the
e n r i c h m e n t in oxygen-18 is c o n s i d e r e d more l i k e l y to be due to
the a d m i x t u r e of 15 to 20% of an "andesitic" water w i t h a
d e u t e r i u m content of -20/oo and oxygen-18 of +10/o. A b s o r p t i o n
of this andesitic water, released as vapor from cooling and
c r y s t a l l i s i n g magma bodies at depth, leads i n i t i a l l y to the
formation of acid sulfate-chloride waters. Incursion of such
waters into a geothermal well a f t e r d e e p e n i n g suggests that
the conversion of immature sulfate-chloride to m a t u r e neutral
c h l o r i d e waters takes place at c o m p a r a t i v e l y shallow levels.
INTRODUCTION
The Miravallec Geothermal Field, Costa Rica, lies some 125 km

to the NE of the capital San Jos. Following an i n i t i a l
assessment in 19G3 by United Nations experts, more detailed
geochemical investigations into its potential for electric
power production began in 1975 (Gardner and Corrales, 1977).
These studies suggested that a suitable geothermal reservoir
with temperatures of around 240C underlies the study area.
Three wells were d r i l l e d from 1979 to 1980, all proving
productive. Until 1990 a further five wells were completed
202
comprising a total electric power production potential of

about 40 MW e .
The present investigation was carried out within the framework
of the IAEA Coordinated Research Program on the Application of
Isotopic and Chemical Techniques to Geothermal Exploration in
Latin America. Most of the stream and river samples were
collected by S Arnorsson and R Corrales during a mission of
the former in September 1985. The isotopic analyses of the
waters were carried out at the IAEA laboratories in Vienna,
the geochemical data for thermal waters used here are those
reported by Giggenbach and Corrales (1993).
The major aim of this study was the application of isotopic
techniques to obtain information on possible source components
making up the thermal discharges and on the d i s t r i b u t i o n and
movement of the waters within the Miravalles geothermal
system.
THE ISOTOPIC COMPOSITION OF THERMAL AND NON-THERMAL WATERS
The isotopic composition of samples of thermal and non-thermal

waters collected from the Miravalles Geothermal Field are
given in Table 1. For non-thermal waters estimated flow rates
are shown, they are uêd to distinguish rivers (R), w i t h flows
fclOOO kg/s, from streams (Q). For thermal waters, discharge
temperatures, in C, and c h l o r i d e contents, in mg/kg, are

g i v e n . On the basis of a n a l y t i c a l data reported by Giggenbach
and Corrales (1991), thermal waters are also classified in
terms of their major anion into chloride (c), bicarbonate (b)

and sulfate (s) waters. The well discharge compositions are
weighted means of separated water and steam samples and,
therefore, represent total discharge compositions. They also
represent averages of the compositions reported by Giggenbach
and Corrales (1991). The samples are arranged with regard to
their geographic distribution from north to south, sample
locations are shown in Fig. 1.
203
TABLE 1
The isotopic composition of river (R), stream (Q), thermal
spring and geothermal well (P) discharges over the Miravalles

Geothermal Field, from north to south, together with estimated
flows, in kg/s and temperatures and chloride contents, In
mg/kg, for thermal waters. Thermal waters are classified in
terms of their major anion: c- chloride, b- bicarbonate, ssulfate.
Location
flow
02H
( C )
type
( /oo )
10000
Guacalito
La Chepa
3000
San Isidro
1000
Los Angeles
Las Huacas
Frijoles
Los Chiles
Q
Q
R
Higueron
QC
Q de la Chepa
Q
LT
Raudales
La Torre
32
LQ
18
Los Quesos
Stream N of GB
GB
Guayabal, pool
70
Guayabal, river
El Carmen
Q
36
20
PH-36, well 140m
67
Herrumbre
QG
Gaveteros, stream
20
34
PH-34, well 280m

Guayabo River
115
a18o
("/o)
Cl
(mg/kg)
-
-26 .5
-4. 74
-4. 89
-26 . 3
-4 .92
6000
-25 .0
-4. 88
1500
50
10
-27 . 7
-4 .70
-27 .2
-4 .90
-26 .5
-4 .84
2000
b
-28 .5
-4. 98
-27 .9
-5. 04
500
-30 .3
-5. 35
s
b
-29 .9
-5. 20
12
-40 .6
-6. 52
150
s
s
-35 .5
-5. 86
-24 . 5
-4. 43
660
-38 .1
-6. 44
80
-37 .6
-6. 30
-24 .0
-4. 52
701
350
-37 .9
-6. 08
s
b
-38 .1
-6. 50
-34 .9
-5. 10
-34 .1
-5. 48
-28 .9
-3. 48
2570
-29 . 1
-2 .86
3090
-34 .8
-29 .0
89
2370
P10
PMG-10
c
c
c
c
-3. 00
2830
Pll
PMG-11
-31 . 3
-3. 23
2630
-38 .0
-45 .9
-6. 40
-7. 08
52
-40 .7
-30 .2
-6 .72
-5. 42
Pl
PMG-1
245
P2
deep
PMG-2
220
P5
wells PMG-5
240
El Gomes
La Fortuna
Peje
Cuipi lapa
Las Palmas
Arena
30
10
Blanco
Benaon
S Bernardo Arriba
50
EG
Q
BN
BB
SB
BJ
Q
RO
PP
Q
Q
R
204
temp .
Salitral Bagaces
S Bernardo Abajo
Estanque
Rio Blanco
37
70
300
3000
-49 .2
-41 .7
-38 .2
-7. 52
-6. 68
96
_ ^
50
46
b
b
-48 .9
-7. 46
-48 .8
-7. 12
155
72
50
c
b
10
-34 .9
-3. 92
2560
-48 .3
-7. 43
112
-7 .51
-52 .9
-50 .8
-7 .59
81
37
45
-44 .0
-6. 68
60
-53 .7
-7 .53 -
Villa Vieja
70
-52 .2
-7. 22
Rio Tenor io
30000
-39 .2
-5. 76
Punto de Palo
Rio Bagaces
25
rvers
streams
Chloride waters
bicarbonate w.
sulfate waters
Fig. l- Sketch map of Miravalles Geothermal Field showing

sample locations for thermal and non-thermal waters
The isotopic compositions of the waters listed in Table 1 are

plotted in Fig.2. Both river and stream samples follow a trend
close to that indicated by the global meteoric water line, but
somewhat shifted to higher deuterium, or lower oxygen-18,
values suggesting that the formation of groundwaters over this
area may be governed by a "local meteoric water line" with a
somewhat steeper slope of 9. Most of the thermal waters, with
the clear exception of the chloride waters, follow a similar
trend suggesting that they are largely derived from local
groundwaters.
205
62H
Woo)
-30-
-40
-50
-7
Fig.
-4
-6
6'80(%o)
-3
2- Plot of <3 2 H versus 0 *8 0 for thermal and non-thermal
water discharges over the M i r a v a l l e s Geothermal Field

For symbols see Fig.
1 and Table 1.
Comparison of the isotopic composition of all these waters

with their geographic position shows that there is a
pronounced decrease in heavier isotopes on going from north to
south, a trend most clearly reflected in the composition of
streams. Rivers can be assumed to represent the weighted- mean
of groundwaters over a much larger catchment area (Fritz,
1981). The compositions of river waters, close to those of
northern groundwaters, suggest that they are recharged largely
from the northern part of the M i r a v a l l e s area and that most of
the r e g i o n a l p r e c i p i t a t i o n falls over the northern, "Atlantic"
parts of the study area, carried there by predominantly
northerly winds (Vialc et al.,
1986).
The chloride waters, as discharged from deep wells and at
Salitral Bagaces (SB), are "shifted" to higher oxygen-18

contents. The shift of thermal waters to higher oxygen-18
contents is generally ascribed to isotopic exchange of the
thermal waters w i t h rock d u r i n g t h e i r r i s e to the surface
206
(Craig, 1963). Accepting this process to be active at

Miravalles, the deuterium content of the most shifted water
(P2) would point to recharge from northern groundwaters. The
pattern exhibited by individual wells and the discharge from
Salitral Bagaces points to subsequent m i x i n g of a deep parent
water with southern groundwater.
The waters most enriched in deuterium of the area are

represented by the acid sulfate-chloride waters discharged
from a spring at Guayabal (GB) and a nearby shallow well PH-36
(36). None of the groundwaters is isotopically heavy enough to
qualify as the recharge water suggesting these waters contain
an as yet undefined component even more enriched even more
1 Q
enriched in deuterium. A slight " 0-shift" is also indicated
for the other shallow well PH-34 (34). The water discharged
there, however, is a very d i l u t e bicarbonate water.
The large variability in the isotopic composition of
groundwaters renders the Miravalles area especially suitable
to investigate recharge processes and the origin of possible
source components of the geothermal discharges. In order to be
able to establish the isotopi<~ identity of the various groups
of waters more clearly, variations in deuterium and oxygen-18
contents as a function of geographical position are
investigated in more detail.
ISOTOPIC COMPOSITIONS AS A FUNCTION OF GEOGRAPHIC POSITION
Variations in deuterium contents of waters discharged over the

Miravalles Geothermal Field are shown in Fig. 3. For the nonthermal waters, two groups are distinguished: r i v e r c w i t h
estimated flows fclOOO kg/s, and streams with lower flow rates.
This distinction allows probable differences in the size of
the respective catchment areas to be taken into account. Small
streams are more likely to represent local groundwaters while

the waters of rivers usually contain contributions from much
more distant groundwaters. Generally river waters are
isotopically depleted as compared to smaller tributaries
because of the presence or predominance of isotopically
207
-50-
(km)
30
Fig. 3- Deuterium contents of waters discharged over the
Miravalles Geothermal Field from north to south.

Reference point for distances is summit of Miravalles
volcano. For symbols see F i g . 1 and Table 1.
depleted, higher altitude p r e c i p i t a t i o n (Fritz, 1981;

Giggenbach et al., 1983).
Over the Miravalles area the pattern is reversed, river waters
being isotopically considerably enriched as compared to most

of the streams. Also, in contrast to the generally observed
depletion in heavier isotopes of groundwaters with increasing
a l t i t u d e , waters of the Miravalles area become isotopically

enriched on moving north from the coast u p h i l l to the
Cordillera. The most likely explanation for such behavior is
based on the assumption that the isotopic composition of these

groundwaters is governed by a "continental" effect rather than
an "altitude" effect (Eriksson, 1983). In this case
atmospheric moisture moving predominantly from north to south

(Viale et al., 1986) would lose its heavier isotopes on
approaching the Cordillera leaving isotopically more and more

depleted moisture to fall on the areas to the south.
208
Both stream and river waters follow distinct trend lines, the
deuterium content of the streams together with that of most of
the bicarbonate springs decreasing much more rapidly on going
from north to south than the river samples. The close
correspondence in the composition of streams and bicarbonate
springs suggests that the latter are essentially derived from
infiltrating local groundwater. The preservation of high

d e u t e r i u m contents in river waters collected far to the south
of the C o r d i l l e r a , e.g. Rio Tenorio, indicates that the
composition of river waters all over the study area is d o m i -
nated by groundwaters forming over the northern parts of the

Miravalles area, from essentially "Atlantic" p r e c i p i t a t i o n .
The chloride waters have deuterium contents corresponding to
those of the northern groundwaters. In the case of Salitral
Bagaces, the waters would have travelled a horizontal distance

of some 25 km without losing their isotopic i d e n t i t y . Such
long horirontal travel paths for thermal waters are not very
common, but have been identified isotopically e.g. for the El
Tatio geothermal system in Chile (Giggenbach, 1978). As

a;ready pointed out, the deuterium content of the acid
sulfate-chloride waters from the Guayabal area (GB and 36) are
higher than those of any other thermal or non-thermal water.
The only water likely to be affected by an isotopic "altitude"
effect is that discharged at Los Quesos (LQ). Its comparative
isotopic depletion is probably due to admixture of higher
altitude precipitation falling on the h i g h e r slopes of
Miravalles volcano.
The overall pattern is repeated with the oxygen-18 contents as
shown in Fig. 4, except that chloride waters are much more
enriched than any of the other waters. Again, the two acid
sulfate-chloride waters (GB and 34) are isotopically heavier
than any of the potential recharge waters. Further insight
into the relative importance of the various source components
making up the thermal waters may be obtained by taking into
account variations in one of the chemical components of the
1p
waters, e.g. by comparing
0 and Cl contents of the thermal
waters, as done in Fig.5.
209
-4-
6180
("/oc )
-5-
-6-
-7-
1O
Fig.
10
2O
(km)
4 - Oxygen-18 c o n t e n t o f w a t e r s d i s c h a r g e d over t h e
Miravalles Geothermal Field from north to south.
0
Fig.
1000
2000
300O CI (mg/kg)
5 - P l o t o f oxygen-18 v e r s u s c h l o r i d e c o n t e n t f o r t h e r m a l
waters f r o m the Miravalles Geothermal Field.
210
The correlation between chloride and oxygen-18 contents can be

fully explained in terms of intermixture of three endmember
1 P
n
components: northern groundwater with
0 of -4.8 /oo.
southern groundwater with 180 of -7.5/oo/ both low in
chloride, and a deep, high chloride, "parent" water with 3300
mg/kg of Cl and a 180-content of -2.5/oo All the stream, river
and bicarbonate waters can be assumed to be derived from
groundwaters present over the M i r a v a l l e s area. Geothermal well
and the Salitral Bagaces discharges are likely to o r i g i n a t e
from a common parent water and to be diluted to varying
degrees by southern precipation.
The position of the data points for the two acid sulfatechloride waters from the Guayabal area would also agree with
derivation from this common deep Cl water, but through
d i l u t i o n w i t h northern p r e c i p i t a t i o n . Because of the large
d i f f e r e n c e in the degree of m a t u r a t i o n (Giggenbach, 1988)
between the Guayabal and deep well waters, however, it appears
unlikely that they are derived from the same deep source
components or have been generated under similar conditions.
The Guayabal waters are likely to have formed at much
shallower levels. The simple pattern of Fig. 5, corresponding
to dilution of a common deep chloride component to form both
the well and Guayabal waters, is likely to be only be
accidental .
SOURCE COMPONENTS OF THERMAL WATERS
Based on an allegedly generally observed close correspondence

in the deuterium contents of thermal waters and local
groundwater, Craig (1963) concluded that geothermal waters
have a predominantly local meteoric origin, with contributions
from any common "magmatic" component being too small to be
detected. The frequently observed enrichment in oxygen-18 for
higher temperature waters was ascribed to an 1 R 0-shift caused
by isotopic exchange between the waters and rock generally
enriched in oxygen-18.
By use of a large set of isotopic data for a wide range of

geothermal systems along convergent plate boundaries
211
(Giggenbach, unpublished results), however, it becomes

apparent that deuterium contents of thermal and local
groundwaters generally do not agree. Deuterium contents of
most higher temperature geothermal discharges appear to be
affected by an a d d i t i o n a l , d i s t i n c t shift to heavier values,
the m a g n i t u d e of this apparent "deuterium shift" increasing
w i t h decreasing d e u t e r i u m content of the local groundwater.
By p l o t t i n g the isotopic compositions of pairs of geothermal
and local groundwaters for a number of such "andesitic"
systems, Giggenbach (1991) concluded that much of the

-i P
o
d e v i a t i o n s in both
0 and ^H of thermal waters from those of
local groundwater may as well be explained in terms of mixing
between local groundwater and a quite well defined, common
endmember water with a deuterium content close to -20/oo and an

oxygen-18 content of + 10/oo.
The isotopic composition of this water coincides with that of
a large number of fumarolic condenstes from andesitic
volcanoes e.g. in Kamchatka (Taran et al., 1989) and Japan
(Sakai and Matsubaya, 1977) and many other such centers. At
present the origin of this "andesitic" water is still quite
uncertain, but is likely to represent modified seawater,
subducted together with marine sediments (Taran et al., 1989).
"Magmalic" waters from other tectonic environments, such as
hot spots and r i f t s and r i d g e s along d i v e r g e n t plate
b o u n d a r i e s , may well be q u i t e different and similar to that of
the frequently invoked "juvenile" water w i t h a H content of
about -SO 0 /oc
A c c e p t i n g a d m i x t u r e of "andesitic" water to be the m a i n cause
of isotopic enrichment of the M i r a v a l l e s Cl waters, p o s s i b l e

rel a t i o n s h i p s among the v a r i o u s source components may be
discussed by use of F i g . 6. Both the acid s u l f a t e - c h l o r i d e
waters i s s u i n g at Guayabal and the neutral c h l o r i d e vaters
discharged from the wells are assumed to have formed through

absorption of "andesitic" vapors into the northern
groundwater, quantitatively predominating over the Miravalles

area. In the case of neutral chloride waters, this process is
thought to lead to the formation of an i n i t i a l l y acid parent
212
water with a <32H of -25 /ooand 0180 of -2.0 /oo. Subsequent

water-rock interaction and dilution with now southern
groundwater gives rise to the formation of the range of
neutral chloride waters as encountered in the wells.
The very fact that no a d d i t i o n a l oxygen-18 shift is rbserved
for the Salitral Bagaces waters, even rafter having travelled
for another 10 to 15 km, suggests that isotopic exchange with
rock, under "geothermal" conditions, may be a process
affecting the isotopic composition of thermal waters only
little.
The presence of comparatively immature waters within the
Miravalles geothermal system is indicated by the incursion of
an acid sulfate water into well PGM-2 after deepening from
1200 m to 2000 m in 1984 (Giggenbach and Corrales, 1992). The
similarly acid, high sulfate waters of Guayabal, however, are
more likely to have formed at more shallow levels, through
absorption of volcanic gases higher up within the Miravalles
volcanic system.
F i g . f> contains contour l i n e s corresponding to the fraction x a
of andesitic vapor absorbed to form a geothermal discharge, if
the above model is correct. Values of x a may also be obtained

from
*a = '"g - <V/(fla ~ <V
Where the subscripts a, g and m refer to the respective
andesitic, geothermal and meteoric waters. Inserting values of

-2 %o for <5180g/ -4.8/oo for <3180m and +10/oo for fl 1 ?> a/
the fraction of andesitic vapor contributing to the formation
of the hypothetical geothermal parent water becomes 0.39 or

19%. Subsequent d i l u t i o n by southern groundwaters reduces this
proportion to about 15%.
For the Guayabal waters a value of xa of 2.5% is obtained.

Their S/Cl mol-ratio of 1.5 is close to that of many volcanic
vapor discharges (Giggenbach et al., 1990) suggesting that
both Cl and SO^ in these waters are derived through direct
absorption of volcanic vapors rising within the system.
213
-6CH
-5
Fig. 6- Plot of H versus 00
18,
&'O(/oo)
10
illustrating possible
formation of Miravalles thermal waters through

absorption of "andesitic" vapors into groundwater.
Contours x a correspond to fraction of andesitic vapor
absorbed.
Assuming all the Cl present in the well discharges, 3000

mg/kg, to have been introduced with the magmatic vapor, its Cl
content would have to be about 20 000 mg/kg or 2* b.w.. This

value is somewhat above the range of 0.4 to 1.8% b.w. usually
observed for HC1 contents in high temperature vapor discharges
from active volcanoes (Giggenbach et al., 1990), but of the

same order. While not providing conclusive proof as to the
cause of the "oxygen-18" shift observed for the Miravalles

chloride waters, the above findings may s t i l l be used to
derive a hydrological model of the Miravalles geothermal
system compatible with geochemical evidence.
GEOCHEMICAL MODEL OF MIRAVALLES GEOTHERMAL SYSTEM
A geochemical model describing the origin and distribution of

the various fluid components w i t h i n the Miravalles geothermal
system, compatible w i t h the isotopic composition of the water
discharges, is shown in Fig. 7. The procedures used in its

construction follow closely those described for the Nevado del
214
bicarbonate w
chloride waters
sulfate-chloride w
cooling magma
(km)
0
Fig.
10
15
(km)
7- Cross-section through Miravalles geothermal system
along line N - S of Fig.

1 showing distribution of
fluids compatible with geochemical evidence. Upper
numbers in boxes are deuterium ratios, lower numbers
oxygen-18 values of respective waters.
R u i z volcanic-magmatic-hydrothermal system (Giggenbach et al.,

1990). P e r m e a b i l i t i e s dre assumed to be isotropir and u n i f o r m ,
the model, therefore, describes only the potential
distribution of the fluids underground. Actual fluid movement
is governed by the generally unknown distribution of faults,

fissures and permeable strata.
The overall direction of fluid movement is assumed to be
dominated by the influx of the quantitatively most important
groundwater component, that forming from precipitation falling
to the north of the Cordillera. Vapors released from cooling
and crystallising bodies of magma at depth are absorbed into
this deeply percolating groundwater forming initially quite
acid, sulfate rich waters. Ongoing water-rock interaction
leads to the gradual conversion of these early primitive
waters to neutral chloride waters (Giggenbach, 1988). Because
of the general direction of groundwater flow from north to
south, the halo of neutral chloride waters is
likely to be deflected to the south where it mixes to varying
degrees with minor proportions of groundwater there.
215
Over the northern, "upstream" parts of the rising thermal

plume, and w i t h i n the Miravalles volcanic structure, residence
times of the fluids are probably too short to permit
conversion of the acid sulfate-chloride to neutral chloride
waters and they are able to reach the surface at Guayabal
(GB). Interaction of these immature waters with rock at

shallow levels, especially after dilution, may give rise to
quite neutral bicarbonate-sulfate waters as discharged e.g. at
Los Quesos 'LQ),
El Gomes (EG)
and from well PH-34 (34).
The tongue of neutral c h l o r i d e waters is obviously able to

travel underground for a distance of some 10 km m a i n t a i n i n g
its i s o t o p i c and c h e m i c a l i d e n t i t y . M a r g i n a l layers of this
water, still containing dissolved CC>2, interact f u r t h e r with

rock l e a d i n g to the f o r m a t i o n of the b i c a r b o n a t e - c h l o r i d e
waters as discharged, again in d i l u t e d form, from springs at
San Bernardo (BB,
BJ) and Rio Blanco (RO).
The appearance of
acid sulfate-chlor i de waters in the easternmost w e l l PGM-2,
a f t e r d e e p e n i n g from 1200
to 2000 m in 1984,
suggests that
immature water reach shallow levels over t h i s part of the
field.
On the basis of the above model, the optimum siting of wells
will have to take into account several conflicting tendencies:

d r i l l i n g close to the center of thermal upflow enhances the
l i k e l i h o o d of encountering higher temperatures, but also that
of incursion of acid waters. Drilling farther "downstream"

reduces the risk of a c i d i f i c a t i o n but also lowers discharge
enthalpies or temperatures and with them increases the risk of
calcite deposition (Vaca et al.,
1989).
ACKNOWLEDGMENTS
The present i n v e s t i g a t i o n was carried out w i t h i n the framework
of the IAEA Coordinated Research Program on the "Application

of Isotopic and Chemical Techniques to Geothermal Exploration
in Latin America" (COS/8/002) with financial support from the

Government of Italy.
216
REFERENCES
Craig H, 1963: The isotopic geochemistry of water and carbon

in geothermal areas. In Nuclear Geology on Geothermal
Areas, CNR Pisa, 17-53.
Eriksson E, 1983: Stable isotopes and t r i t i u m in p r e c i p i tation. In Guidebook on Nuclear Techniques in Hydrology.
IAEA Techn. Report 91: 19-33.
Fritz P, 1981: River waters. In Stable Isotope Hydrology Deuterium and Oxygen-18 in the Water Cycle. IAEA Techn.
Report 210: 177-201.
Gardner M C and R Corrales S, 1977: Geochemical investigations

of the Guanacaste Geothermal Project, Costa Rica.
Geothermal Resources Council, Trans., 1: 101-102.

Giggenbach W F, 1978: The isotopic composition of waters from
the El Tatio geothermal field, Northern Chile. Geochim.
Cosmochim. Acta: 42, 979-988.
Giggenbach W F, 1988: Geothermal solute equilibria. Derivation
of Na-K-Mg-Ca geoindicators. Geochim. Cosmochim. Acta,
52: 2749-2765.
Giggenbach W F, 1991: What is the real cause of the oxygen-18
shift of waters from geothermal areas along convergent

plate boundaries? Geotherm. Resources Council, Trans.,
Reno .
Giggenbach W F, Gonfiantini R, Jangi B L and Truesdell A H,
1983: Isotopic and chemical composition of Parbati Valley
geothermal discharges, North-West Himalaya, India.
Geothermics, 12: 199-222.
217
Giggenbach W F, N Garcia P, A Londono C, L R o d r i g u e z V, N

Rojas G and M L Calvache V, 1990: The chemistry of
f u m a r o l i c vapor and thermal-spring discharges from the
Nevado del Ruiz volcanic-magmatic-hydrotherma1 system,
Colombia. J Volcanol. Geotherm. Res.,
42: 13-39.
Giggenbach W F and R Corrales S, 1991: The i s o t o p i c and

chemical composition of water and steam discharges from
volcanic-magmatic-hydrotherma1 systems of the Guanacaste

Geothermal Province, Costa R i c a . Appl. Geochem., (in
press ) .
Sakai H and Matsubaya 0, 1977: Stable isotopic studies of

Japanese geothermal systems. Geothermics, 5: 97-124.
Taran Y A, Pokrovsky B G and Esikov A D, 1989: Deuterium and
oxygen-18 in fumarolic steam and amphiboles from some

Kamtchatka volcanoes, "andesitic" waters. Dokl. Akad.
Nauk. USSR, 304:
440-443.
Vaca L, Alvarado A and Corrales R, 1989: Calcite deposition at

M i r a v a l l e s Geothermal Field, Costa Rica. Geothermics, 18:
305-312.
Viale P, Corrales R, M a n i e r i A, Mayra C and Vaca L, 1986:
Mineral alteration and fluid characteristics of

Miravalles Geothermal Field - Costa Rica. Extended
Abstr . , Fifth Int. Symp. Water-Rock Interaction,
Reykjavik, Iceland, p. 667-670.
218
MODELO GEOTRMICO PRELIMINAR DE REAS VOLCNICAS

DEL ECUADOR, A PARTIR DE ESTUDIOS QUMICOS E
ISOTPICOS DE MANIFESTACIONES TERMALES
E. ALMEIDA, G. S ANDO VAL
Instituto Ecuatoriano de Electrificacin,

Quito, Ecuador
C. PANICHI, P. NOTO, L. BELLUCCI
Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Resumen-Abstract
MODELO GEOTRMICO PRELIMINAR DE REAS VOLCNICAS DEL ECUADOR, A PARTIR DE
ESTUDIOS QUMICOS E ISOTPICOS DE MANIFESTACIONES TERMALES.
fi partir de 1986 se mostrearon y anaii:aron las aguas y gases de ocho reas geotraicas, para establecer
su composicin quiica e isotpica, En Chachisbiro y Cuicocha, se observan enriqueciaientos de hasta el 5X.
en {) y SOS, en Beuteno. La evaporacin de una hipottica agua geotersica profunda, desde 2WC hasta la
teaperatura en superfice, puede ser responsable de las variaciones isotpicas observadas en Chachisbiro,
Por otra parte, en Cuicocha, un proceso de sezcla entre agua subterrnea caliente y agua fresca de una
laguna es responsable de los valores observados. En otras reas, la coiposicin isotpica de las aguas
trsales corresponde escencialsente a aguas aetencas que caen a diferentes altitudes, desde 2500 nasta
4200 a sobre el nivel del sar. Las relaciones Na/K indican teiperaturas del reservono de aproxiaadasente
EW, 210 y EOfl'C, para aguas cloruradas que eiergen en las reas geoterncas de Chacbibiro, Cuenca y
p
apaliacta respectivasente. En la caldera de Chalupas, los datos no peralten hacer ninguna hiptesis
razonable sobre la existencia de jn acdfero profundo de alta teiperatura. Muestras procedentes del -olean
Tungurahua son de aguas sulfatadas-acidas, que tienen una coiposicin isotpica concordante con aguas
calentadas por gases a teiperaturas de 200'C aproxisadanente. En el rea de Chiiborazo, la reducida
cantidad de suestras disponibles no peralten dar ninguna inforaacin acerca de sus caractersticas
trsales. En Tufi5o, las aguas provienen de aculferos superficiales aodificados por gases calientes, cuyos
geotersfisetros dan teaperaturas de SSO'C.
PRELIMINARY GEOTHERMAL MODEL OF VOLCANIC REAS IN ECUADOR BASED ON CHEMICAL

AND ISOTOPIC INVESTIGATION OF THERMAL INDICATORS.
Since 1986, the waters and gases of eight geothermal reas have been
sampled and analysed to establish their chemical and isotopic composition. In
Chachimbiro and Cuicocha ^0 enrichment up to 5% and deuterium enrichment up
to 20% have been observed. The isotopic variations seen in Chachimbiro could
be explained by hypothetical deep geothermal water with a temperature range
from 240C to surface temperature. The vales observed in Cuicocha, on the
other hand, are due to mixing of hot groundwater with fresh lagoon water. In
other reas, the isotopic composition of the thermal waters basically
corresponds to that of meteoric water falling from various altitudes ranging
from 2500 to 4200 m above sea level. The Na/K ratios indicate reservoir
temperatures for the chloride waters emerging in the Chachimbiro, Cuenca and
Papaliacta geothermal reas of approximately 240C, 210QC and 200C,
respectively. From the data on the Chalupas caldera it is impossible to
construct any reasonable theory regarding the presence of a deep,
high-temperature aquifer. Tungurahua volcano samples consist of sulphuric
219
acid water with an isotopic composition similar to waters evaporating at about

200C. The number of samples from the Chimborazo rea was too low to justify
any assumptions about the thermal characteristics of the water. The waters in
Tufio orignate in surface aquifers modified by hot gases registering 230C
on the geothermometers.
INTRODUCCIN
En el marco del Programa de Exploracin de los Recursos Geotrmicos de la

Repblica del Ecuador, ejecutado por INECEL, se han efectuado estudios
geocientificos exploratorios en las reas de Tufiflo, Chachimbiro, Cuicocha,
Papallacta, Chalupas, Tungurahua, Chimborazo y Cuenca, a fin de determinar
las posibilidades de utilizacin del recurso geotrmico en la generacin
elctrica.
Parte
importante de
estos
estudios,
constituyen
las
investigaciones geoqumicas e isotpicas llevadas a cabo con el apoyo de la
Organizacin Internacional de Energa Atmica (OIEA), a travs del Contrato
de Investigacin 3991/IG, suscrito con INECEL. Los resultados finales de
estas investigaciones se resumen en este documento.
SITUACIN GEOLGICA REGIONAL
El margen continental activo del Ecuador es caracterizado por la subduccin

de la placa Nazca, que transporta a la Cordillera de Carnegie creada por el
paso de la Nazca sobre el punto caliente Galpagos. La subduccin de Nazca
y Carnegie es muy importante en la evolucin de la Cordillera de los Andes,

particularmente de su volcanismo. El Ecuador continental se divide en tres
regiones: Llanura costanera (Costa), Cordillera de los Andes (Sierra) y
Cuenca superior amaznica (Oriente).
La Costa esta1 formada por la parte emergida de
constituido por basaltos tolelticos cretcicos
ocenica C13 y sedimentos volcanoclsticos que
pertenecientes a cuencas terciarias y cuaternarias
un prisma acrecionado,
que representan corteza
yacen bajo sedimentos
(Figura 1).
La Sierra tiene en su mitad septentrional dos cordilleras paralelas, la

Occidental y la Real, separadas por un valle angosto conocido como
Depresin Interandina. La mitad meridional, es una cordillera de menor
altura y sin un valle central. La Occidental es formada por rocas
volcnicas bsicas e intermedias de edad cretcica, emplazadas en un
ambiente submarino (arco volcnico ocenico), y cubiertas de sedimentos
pelgicos. La Real es un cinturn metamrfico barrowiano, cuyos protolitos
son sedimentos de plataforma y pendiente

Cretcico y Terciario inferior CE],
continental metamrfizados en el
El Oriente forma parte de la cuenca amaznica; tiene un basamento

precmbrico sobre el cual se encuentran potentes depsitos sedimentarios
marinos de plataforma continental, sedimentos lacustres y detrticos
continentales.
los terrenos volcnicos continentales se extienden a lo largo de la Sierra,
con un ancho promedio de 80 km. La actividad terciaria fue importante en
toda la cordillera, en tanto que la cuaternaria esta' restringida a la
mitad septentrional, donde se localizan casi todas las reas geotrmicas
estudiadas (Figura 1).
220
80
79
78
SIMBOL06IA
CUENCA SEDIMENTARIA CUATERNARIA DE LA COSTA
VOLCNICO CUATERNARIO Y
TERCIARIO DE LOS ANDES
BASAMENTO TOLEITICO; SEDIMENTOS MESOZOICOS Y TERCIARIOS DE LA COSTA

JJ
ARCO VOLCNICO MESOZOICO DE

LOS ANDES
CUENCA AMAZNICA .MESOZOICO HASTA CUATERNARIO
BASAMENTO METAMORFICO WLEOZCHCO DE LOS ANDES
FIGURA I.
REA GEOTRMICA
ESQUEMA GEOLGICO DEL ECUADOR
El volcanismo
durante el Cuaternario es muy
importante; han sido
identificados aproximadamente EOO centros de emisin C33 y muchos de ellos
presentan una evolucin magmtica muy desarrollada. Los volcanes ms
voluminosos y activos se caracterizan por una compleja alternancia de lavas
bsicas e
intermedias, domos
cidos y productos
piroclstcos de
composiciones dacticas y riollticas. El volcanismo en la parte meridional
de la Sierra es fundamentalmente terciario C4-, 53 y ha sido poco estudiado.
3
ASPECTOS QUMICOS E ISOTPICOS
3.1
TUFINO
Se encuentra en la frontera entre Ecuador y Colombia; los volcanes Chiles y

Cerro Negro se
sitan en su interior. La cmara
magmtica que alimento' a
este complejo volcnico constituye la fuente de calor [6, 73

geotrmico estudiado.
La mayora
de las aguas analizadas tienen
del sistema
temperaturas comprendidas entre
los 32 y 5EC, su composicin qumica e isotpica esta1 resumida en la

Tabla I. El 75% de las muestras son bicarbonticas; el 12,57. son sulfatadas
y corresponden a los manantiales ms salinos y calientes, representando la
interaccin de aguas superficiales con gases volcnicos CB3. Las restantes
muestras son cloruradas y magnsicas, que se ubican a varios kilmetros de
distancia del rea de inters. En la Figura E estn las relaciones entre
el 'I) y el Deuteno, donde se aprecia que tanto las aguas termales como las
fras se encuentran sobre la recta meterica y no se ve un enriquecimiento
del '13, lo que no permite evidenciar fenmenos de intercambio agua-roca, de
particular inters.
221
- 70
+ T< 30 C
QT>30C
-110
-14
-15
-13
B 0(% 0 . V - S M O W )
FIGURA Z. D I A G R A M A
-12
DE VARIACIN **0/0 DE TU FINO
El anlisis
de los datos permite concluir que todas las manifestaciones

termales de Tufflo, incluso las ms calientes, pertenecen a un acuifero
superficial alimentado por
aguas metericas de circulacin bastante
restringida, segn lo indica el contenido de tritio. Estas aguas han sido
modificadas qumica y trmicamente por el aporte de gases calientes de
origen magmtico (1!C del orden de +2,7*/,. hasta +5,6*/.. PDB) C8] y,
probablemente mnimas cantidades de vapor.
El nico indicio geoqumico sobre la posible existencia de un sistema

geotrmica de alta entalpia es constituido por la notoria presencia de gas,
cuyos geotermmetros dan temperaturas del orden de los 230 C.
3.2
CHACHIMBIRO
Se encuentra en un segmento de la Cordillera Occidental, que tiene

una
gran concentracin de aparatos volcnicas y un volcanismo persiste desde el
Plioceno. La caracterstica bsica, desde el punto de vista de la fuente de
calor, es que los centros eruptivos del complejo volcnico de Chachimbiro
han sido alimentadas por varias cmaras magmticas evolucionadas C9].
El reservorio estarla localizado en rocas volcnicas a profundidades
variables entre los 10OO y EOOOm. Evidencias para su existencia estn dadas
por: Zonas de alteracin hidrotermal; Fuentes termales, y; Emanaciones de
gases. Las aguas termales son Cloruradas con temperaturas de ^"C, caudales
de 70 1/min, salinidad de 7000mg/l. El contenido de 5iOB varia entre 180 y

EOOppm; adems, tienen una gran cantidad de gas disuelto, fundamentalmente
COE CIO].
La Figura 3 presenta las relaciones entre el "D y el Deuterio; alli' se
evidencian dos grupos de aguas: Aguas fras de circulacin somera, con la
misma composicin isotpica de las aguas metericas, y; Aguas termales que
se desvian fuertemente de la recta de las precipitaciones.
222
-40
-50 -
>D- 86 0+ 10
-60 -
-70 -
>
o
SINGLE STAGE
STEAM LOSS
-80 -
-90 A (AGUA PROFUNDA ORIGINAL . T= 240 C; Cl =1 5 g / Kg )
-100-
B (AGUA PROFUNDA RESIDUAL : T = 60 C; CI = 2.4g/Kg)
- 110-14
AGUAS CLORURADAS
AGUAS BICARBONATADAS
T
-12
-10
S' o
-8
3 ,V.
-6
-4
SMOW)
FIGURA 3. DIAGRAMA DE VARIACIN 5 * 0 / 8 0 DE CHACHIMBIRO
Las aguas termales muestran una evidente evolucin qumica, desde aguas
bcarbonatadas hasta aguas cloruradas, en donde el 'ti se incrementa de -11
a -6%.; los slidos disueltos tambin se incrementan conforme aumentan los
istopos pesados en solucin, sugiriendo un mecanismo de enriquecimiento de
solutos, debido a
una evaporacin del agua meterica
original en
condiciones termales anmalas, o tambin, por procesos de mezcla de aguas
termales salinas con aguas fras.
La evaporacin del agua desde una temperatura
relativamente alta
(p.e.
2^0C), hasta condiciones superficiales (cerca de 60C), ocasiona un
incremento del " en aproximadamente 2,8%. y, un enriquecimiento del cloro
hasta el 30% de los valores originales. Para el caso de Chachimbiro,
solamente este proceso no explica como, partiendo de aguas metericas que
inicialmente tienen contenidos de "O y cloro ms bajos que -10%. y lOOmg/kg
respectivamente, se observe que el "D alcanza un desplazamiento del 57.. y
el
contenido de cloro llegue a 2250mg/kg.
Una explicacin puede
encontrarse considerando, adicionalmente, otro proceso en el cual las aguas
metericas que circulan por rocas ms oxigenadas del reservorio profundo,
si la temperatura es ms alta que EOOC Cll, 123, incrementan su contenido
de "O en aproximadamente el 3%., por intercambio con la roca. Estos dos
procesos estn esquemticamente indicados en la Figura 3, donde, partiendo
de un agua meterica se llega a un agua geotrmica "A" que experimenta un
proceso de evaporacin en profundidad (single stage steam loss), hasta
alcanzar un valor composicional como el de "B". Esta agua residual se
mezcla con aguas subterrneas someras para dar el conjunto de aguas que se
encuentran sobre la linea de mezcla.
En la Figura ^ se indican las variaciones del "O con la altura de
emergencia, en las aguas de Chachimbiro y Cuicocha. Para Chachimbiro, es
evidente la existencia de dos diferentes grupos: El primero, son aguas
subterrneas someras de circulacin restringuida, por cuanto las reas de
infiltracin estn muy prximas a la zona de emergencia; El segundo grupo
223
4000
a n
= O 18 %o
LAGUNA DE
CUICOCHA
3000 -
< 2000
D CHACHIMBIRO
O CUICOCHA
r
- 14
-12
-10
-8
-6
6 "o (%0 , v SMOW)

FIGURA 4. DIAGRAMA DE VARIACIN <J18 O/ALTITUD DE CHACHIMBIRO Y CUICOCHA
D CHACHIMBIRO
O
CUICOCHA
2000
1000
3000
Cl(ppm)
FIGURAS. DIAGRAMA DE VARIACIN C I / B DE CHACHIMBIRO Y CUICOCHA
224
400
B ( AGUA ORIGINAL PROFUNDA
240 C }
O CHACHIMBIRO
O CUICOCHA
50
2000
1000
3000
Cl ( p p m )
FIGURA 6.
DIAGRAMA DE VARIACIN C L / S I O E DE CHACHIMBIRO Y CUICOCHA
(muestras que se desvian a la derecha de la recta), refleja procesos de

mezcla puestos en evidencia en la Figura 3, asi 1 como, en las Figuras 5 y
6, donde los contenidos de boro y slice son confrontados con el cloro.
En el diagrama Cl/SiOe existe una correlacin positiva entre las aguas

termales y fras de tipo bicarbonatado, con las cloruradas, que se desvian
hacia la derecha de la recta de dilucin, porque tienen altos contenidos de
cloro con respecto al slice. Por el contrario, en el diagrama Cl/B, todas
las muestras presentan una correlacin lineal. Esta discrepancia puede ser
explicada tomando en cuenta que tanto el boro como el cloro son parmetros
"conservadores", y, la solubilidad del slice vara con el enfriamiento de
las aguas termales emergentes C13]. Esto implica que, aparte de la mezcla,
el enfriamiento tambin puede considerarse en las aguas cloruradas que
emergen a la superficie. La simultnea existencia de los dos mecanismos,
explica las composiciones presentadas en las Figuras 5 y 6, donde es
interesante notar que las lineas de mezcla definen un componente profundo
similar al obtenido del modelo isotpico presentado en la Figura 3.
3.3
CUICOCHA
Incluye
los
volcanes Cotacachi
y
Cuicocha cuyas
caractersticas
vulcanolgicas permiten inferir una importante fuente de calor. El Cuicocha
tuvo un
estilo eruptivo
explosivo C5,
lf, 15]
emitiendo flujos
piroclsticos daciticos [16]. La actividad se
inicio' en el limite
Pleistoceno-Holoceno, durante la cual se formo' una caldera, hace 3100 arios
[173. El Cotacachi es un estratovolcn andesltico de edad pleistocnica al
cual se asocian varios domos daciticos de edades holocnicas.
Las aguas que afloran en el sector son Bicarbonatadas, con temperaturas de

45C, notndose que
hacia las cercanas de la caldera
existe un
significativo aumento en el contenido de cloruros CIO].
225
De la relacin "/Deuterio (Figura 7) se desprende que el desplazamiento es

consecuencia de la mezcla entre el agua de la laguna de Cuicocha y las
aguas termales de los alrededores. La linea de mezcla corta a la de las
aguas metericas en la abscisa -1S'., que puede representar el contenido de
I!
D en las aguas de alimentacin de la laguna. La pendiente de esta linea es
igual a 4,8 que es concordante con con una evaporacin superficial a baja
temperatura C18].
Si este es el caso, un enriquecimiento del 67,. en el "t)
ocurre en las aguas del lago hasta alcanzar condiciones estacionarias. Sin
embargo, este fuerte enriquecimiento no esta' acompasado de un sensible
incremento en la salinidad total de las aguas evaporadas. En efecto, las
aguas del lago presentan un muy bajo contenido de sal (^20 ^Siemens), donde
el ion dominante es el bicarbonato. Esto sugiere que las aguas metericas
que lo alimentan, son escencialmente constituidas por nieve fundida, la
cual esta' presente en el vecina volcn Cotacachi. En realidad, la mezcla
del agua de la laguna con las aguas termales ocasionara1 una desigual
dilucin de las soluciones termales, porque acurre solamente a lo largo de
fracturas y fallas. Por esta causa, las dos muestras ubicadas en la linea
de mezcla (Figura 7) contienen cada una el 70 y el 30'/, del agua del lago y,
los slidos disueltos totales son de 3800 y 500mg/kg respectivamente,
sugiriendo con esto, que estas dos aguas termales representan
dos
reservorios distintos.
En la Figura 4, se aprecia a un grupo de aguas que se desplaza a la

izquierda de la recta, esto se interpreta como aculferos con larga
circulacin, parque las reas de alimentacin estn a alturas mucho ms
elevadas. Particularmente el
lago de Cuicocha, ubicado a mayor
altura que
las fuentes termales.
-40
-50-
LAGUNA DE
CUICOCHA
-60 -
LINEA DE MEZCLA
-70-
-80-
-90-
-100-
-110
-14
-IZ
-10
-8
-6
I 8 0 (% 0 , V - S M O W )
FIGURA 7.
226
DIAGRAMA DE VARIACIN <5~'8 O/ f D DE CUICOCHA
-4
3.4
PAPALLACTA
Esta rea tiene manantiales de composicin clorurada sdica con un

importante componente sulfato calcico, una elevada salinidad C193 y
temperaturas de 66C. Estas aguas afloran en una zona de fallamiento, en el
contacto entre el basamento metamrfico de la Cordillera y el volcnico
terciario. Una compleja
situacin tectnica y volcnica,
dificulta
establecer hiptesis sobre el origen de la fuente de calor, a nivel de
reconocimiento.
Si bien los datos disponibles son pocos, lo que condiciona fuertemente la
interpretacin, desde el punto de vista trmico la situacin parece
interesante.
La Figura 8
presenta la relacin "D/Deuterio de las tres
vertientes muestreadas; una de ellas esta' enriquecida en "D con respecto

a las otras dos, que se ubican en la linea de las aguas metericas. Por lo
tanto, suponemos que un posible mecanismo de intercambio con las rocas pudo
tener
lugar; adems,
las
relacin "D/altura indican
caractersticas geomorfo lgicas
que esta
agua tiene una
del rea
zona de
y la
alimentacin
600m ms elevada que las otras dos. Todo esto, permite asumir que esta agua
experimento' condiciones de alta temperatura en profundidad, lo que parece
confirmarse
adelante.
al
aplicar
los
geotermmetros
qumicos
reportados,
ms
-70
-75-
-80
-65-90
INTERCAMBIO CON LA ROCA ?
O- 86 0+10
tn
-95
-100
TIPO DE AGUA
HCO3
SO4
EB
CI
PAPALLACTA
-105-
TUNGURAHUA
CHWBORAZO
-12.5
-12
-10.5
- 10
.V-SMOW)
FIGURA 8. DIAGRAMA DE VARIACIN cfÔ/ 6 D DE LAS REAS DE PAPALLACTA

TUNGURAHUA Y CHIMBORAZO
3.5
CHALUPAS
14)k<n, formada por el colapso del

emiti' por lo menos 100 km
posteriormente, el volcanismo
cbicos CEO] de materiales riollticos C163;
se reactivo' en el interior de la caldera. Las particulares caractersticas
Se
trata
de
una
caldera
estratovolcn Chalupas,
(16
luego de
que ste
227
del sistema de
alimentacin magmatica de
este complejo
volcnico, activo
desde hace un milln de aftos, son buenas evidencias de la existencia de una

fuente de calor.
En la Figura 9, las muestras relativas al rea de Chalupas, caen sobre la

recta de las aguas metencas en un amplio intervalo de composicin. Esto
permite suponer la existencia de una fuerte circulacin superficial sin
encontrarse condiciones anmalas de temperatura, esto confirma el modelo

geovulcanolgico de INECEL CEO] en el cual se indica que la caldera esta'
rellenada por materiales impermeables (piroclstos y sedimentos lagunares)
que constituyen un efectivo sello al sistema geotrmico. Las variaciones en
el contenido isotpico corresponden a diversas cotas de infiltracin,
situadas entre los 3500 y 4c?00m de altura.
-7O
-75-
-80
o
2
o
oS
o
AGUAS BICARBO NATA DAS
(J)
FIGURAS
3.6
A G U A S SULFATADAS
DIAGRAMA DE VARIACIN s'80/,5 D EN CHALUPAS
TUNGURAHUA
En
los flancos
del activo
volcn Tungurahua,
existen abundantes
manifestaciones de aguas bicarbonatadas acidas y sulfatadas, con temperaturas hasta de 53C [21]. Tres muestras fueron analizadas (EUI-42, 43 y M de
la Tabla I), la correlacin entre el "D y el Deuterio es una recta de
pendiente +1,8 (Figura 8)
sugirindonos que las aguas pudieron ser
sometidas
procesos de
evaporacin-condensacin
una temperatura
de
aproximadamente EOOC C18].

La EUI-^4 es agua subterrnea local que durante su descenso por el interior
del cono, interacciona con gases volcnicos calientes (S0e , I-JS y C0, ),
dando como resultado un fuerte incremento de HC03 y SQ en la solucin y, un
simultneo incremento de la
temperatura del liquido hasta alcanzar
probablemente los 200C. Bajo estas condiciones, se produce la evaporacin
parcial de la solucin, formndose vapor que se condensa en la parte alta
del volcn,
228
originando un aculfero
termal con una
composicin qumica
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3
m
t~
2
a~.
s^
^*J
t3 v~~
t*H
S 2
> 5
S 3
8^
231
isotpica similar a la de la muestra EUI-42. Por otra parte, las aguas

residuales de la evaporacin circulan hacia la base del cono, originando
aguas termales similares a la muestra EUI-*f3, que tiene
al sulfato como
ion dominante en la solucin, y presenta adems, un alta concentracin de
los istopos pesadas.
3.7
CHIMBORAZQ
Es el
estratovolcn ms alto del Ecuador, su actividad se inicio' en el

Pleistoceno
y fue
prcticamente
continua hasta
el
Holoceno. La
interpretacin petrolgica de los productos emitidos en sus tres etapas
evolutivas, sugiere la presencia de una cmara magmtica en donde el magma
basltico-andestico de las etapas iniciales, evoluciono' hasta un producto
final de composicin dacltica- noltica C16. Durante su evolucin, el
magma transfiri' calor provocando una anomala trmica, cuya primera
evidencia en superficie son fuentes termales con temperaturas de 46C.
La nica muestra que ha sido analizada puede ser considerada como agua
subterrnea cuyo origen esta' en los deshielos del Volcn Chimborazo, a
alturas superiores a los 4500m.
La desviacin que se observa en la Figura
B, respecto a la recta de las aguas metericas no encuentra, en este
momento, una explicacin satisfactoria debido a la falta de otros datos
anal iticos.
3.8
CUENCA
Esta rea es conocida por la existencia de fuentes termales con una

elevadlsima salinidad, alta conductividad y caudales del orden de los EO
1/s CIO, 193. Estas aguas
tienen las mayores temperaturas (73,3C)
registradas en el pas y, precipitan travertinos que son explotados como
roca ornamental. Esta zona termal se encuentra en una cuenca sedimentaria
cretcica y los materiales volcnicos ms prximos son de edad terciaria.
Las manifestaciones aflorantes son de dos clases: Aguas cloruradas

con
temperaturas mayores que 48C, concentradas en un rea de aproximadamente
un kilmetro cuadrado y que son aprovechadas como balnearios (Baos de
Cuenca), y; Aguas bicarbonatadas
fras (17 a 2C), diseminadas en una
zona relativamente amplia, varios kilmetros alrededor de los balnearios.
En esta zona marginal existe un manantial fro de tipo clorurado que tiene
el menor contenido de "D y una elevada salinidad (TDS - 8,g/kg).
Las aguas termales tienen una zona de alimentacin situada aproximadamente
a una elevacin de 3EOOm, esto es, 500m sobre la altura de los balnearios.
En el rea de Baftos se muestrearon 11 vertientes
cuya temperatura de
emergencia varia entre 48 y 73,3C. No obstante tal diferencia trmica, la
composicin isotpica de los diversos manantiales es muy homognea (Figuras
10 y 11), situndose sobre o muy prximos a la linea de las precipitaciones; al mismo tiempo, el contenido de ion cloruro se mantiene constante.
Todo esto permite suponer que el agua profunda alcanzo' condiciones de
equilibrio qumico con las rocas de un reservarlo somero, en el tope de la
potente cuenca sedimentaria.
232
o
2
tf)
"o
AGUAS BICARBONATADAS
AGUAS
CLORURADAS
AGUAS
FRAS
-90
-11.5
-13
FIGURA
-IV.^
,,Q
00
(%o,V- SMOW)
10. DIAGRAMA DE VARI ACIN &18,O / D EN CUENCA
80
80
o
70
70
o
o
IX)
ce
60
60
$
ce
50
50
4O
40
30
-12
30
-II
-10500
<5'80 (%0 V-SMOW)
La
1000
1500
CI(mg/Kg)
FIGURA II. DIAGRAMA DE VARIACIN 6'%

EN CUENCA
ce
ui
a
Y Cl CON LA TEMPERATURA
EVALUACIONES GEOTERMOMETRICAS
Figura IB
presenta
un diagrama
triangular
donde se
relacionan
las
concentraciones relativas de K, Na y Mg en todas las aguas analizadas. Este

diagrama ha sido
modificado de un original propuesto por
Giggenbach CE23,
con el fin de ampliar el rea correspondiente a la esquina del magnesio, en

la cual generalmente estn localizadas las aguas inmaduras. Muchas de las
233
Na/5
200
CHACHIMBIRO
CUICOCHA
CHALUPAS
CUENCA
CHIMBORAZO
PAPALLACTA
TUNGURAHUA
\T Mg
FIGURA 12. CONCENTRACIONES RELATIVAS N o . K , M g ( m f l / k g ) DE
TODAS LAS AGUAS ESTUDIADAS
muestras de agua caen entre las dos lineas que describen la temperatura
K/Mg en el rango de 40 a 60C, indicando con esto que este par inico es
incapaz de reflejar las condiciones termales profundas. Por otra parte, la
relacin Na/K parece ms til para evaluar las temperaturas profundas, pero
esta1 restringuida a pocas muestras. Realmente, la Figura 1E indica que
muchas de las muestras tienen temperaturas Na/K mas altas que E50C pero,
no parecen ser reales si se toma en cuenta las caractersticas isotpicas
ya discutidas.
Solamente pocas muestras de Chachimbiro, Papallacta, Chimborazo y Cuenca

parecen admitir la aplicacin del geotermmetro Na/K, ellas son aguas
cloruradas y parecen ser maduras o parcialmente equilibradas con rocas de
los
acuiferos
(segn la
definicin
dada
por Giggenbach
CEED).
Consecuentemente, temperaturas de E*tO, EOO, 100 y EOO'C pueden ser
obtenidas, respectivamente, en las reas indicadas.
En cuanto se refiere a Tufiflo, las manifestaciones termales, incluso las
ms calientes, son aguas superficiales modificadas por el aporte de gases
calientes, no existiendo una evidencia segura de la contribucin de un
componente liquida
profundo. La
evaluacin de la
termalidad, por
consiguiente, es posible nicamente con ayuda de la geotermometria de
gases. Las temperaturas obtenidas de esta manera, dan un mximo de EEO a
E30C CE3,
CONCLUSIONES
Los indicadores qumicos e isotpicos presentados, ratifican el inters

geotrmico de las reas
de Tufiflo, Chachimbiro y Cuenca.
Adems,
constituyen
argumentos
positivos que
justifican la
iniciacin de
234
investigaciones geocientlficas detalladas en Papallacta y Chimborazo. Con

respecto a Chalupas, los mtodos qumicos e isotpicos no han sido de mucha
utilidad, debido a las caractersticas de las aguas muestreadas.
AGRADECIMIENTOS
Los autores agradecen a INECEL y al IIRG por las facilidades para elaborar
el presente trabajo, elaborado en el marco del "Programa Coordinado de
Investigaciones para Amrica Latina, sobre la Aplicacin de Tcnicas
Geoqumicas e Isotpicas en la Exploracin Geotrmica", financiado por el
Gobierno de Italia. Especial reconocimiento a la OIEA y, particularmente,
al Dr. Roberto Gonfiantini quien brindo' su total apoyo a las gestiones
tcnicas del Contrato de Investigacin 3991/IG mediante el cual se
realizaron las investigaciones de las reas ecuatorianas.
REFERENCIAS
[13
FEININGER, T. "La Geologa Histrica del Cretcico y Palegeneo de la

Costa Ecuatoriana" Politcnica, Monografa de Geologa. Vol. V, No.
2, (1980) 7-45 p.
C23
FEININGER, T. "El Basamento Metamrfico del Ecuador" Politcnica,

Monografa de Geologa 3, Vol. VIII, No. 2, (1983) 37-48p.
[33
ALMEIDA, E. "El Riesgo Volcnico en el Ecuador Continental" Memorias

Segundas
Jornadas
Nacionales de
Geologa, Minas
y Petrleo.
Universidad Central del Ecuador, (1988), 57-60 p.
[43
HALL, M.,
CALLE,
J.
"Control
Eventos Tectnico-Magmticos
Geocronolgico
del Ecuador"
de
los Principales
Politcnica, Monografa de
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[53
C63
BARBERI, F., COLTELLI, M., FERRARA, G., INNOCENTI, F., NAVARRO, M.,
SANTACROCE, R. "Plio-Quaternary Volcanism in Ecuador" Geol. Magm. 135
(1), (1988), 1-14 p.
NAVARRO, J.,
ALMEIDA, E., AVALA,
Ecuador y, en Particular, del
J. "Geovolcanologla
del Norte
del
rea de Tufiflo" OLADE-INECEL, Inf. Int.
(1982), 98 p.
[73
GEOTRMICA ITALIANA. "Aprovechamiento de los Recursos Geotrmicos de

la Zona de Tufiflo, Ecuador Septentrional, Informe Geovulcanolgico"
OLADE-INECEL, Inf. Int., Quito. (1982), 110 p.
[8]
ENEL, Unita' Nazionale Geotrmica, "Indagine Isotpica nella Regione

di Tuf iflo-Cerro Negro, Repubblica dell'Ecuador, Sintesi dei Dati
Raccolti ed Interpretazione Preliminare" IAEA-INECEL, Pisa, Diciembre
1986.
[93
ALMEIDA, E. "Alternativas
Repblica del Ecuador"
(1990), 49 p.
C103
para el Desarrollo Geotermoelctrico en
Inf. Int. INECEL, Proyecto Geotrmico.
SANDOVAL, G. "Investigacin
Geoqumica e
Isotpica en
la
Quito,
la Regin
de
Cuenca-Chalupas-Chachimbiro en la Repblica del Ecuador, Sntesis de

Datos Obtenidos e Interpretacin Preliminar" INECEL-OIEA, Inf. Int.,
Quito, (1988), 8 p.
235
Cll]
PANICHI, C., GONFIANTINI, R. "Geothermal Waters" n: Stable Isatape

Hydrology: Deuterium and Oxigen-18 in the Water Cycle. IAEA, Tecncal
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[123
GIGGENBACH, W., GDNFIANTINI, R., PANICHI, C. "Geothermal Systems" n:

Guidebook on Nuclear Technques n Hydrology. IAEA, Tecnical Reports
No. 91, Vienna, (1983).
[13]
TRUESDELL,
A., FOURNIER,
R.
"Procedures
for Estimating
the
Temperature of Hot Water Component n a Mixed Water Usng a Plot of
Dissolved Silca Versus Entalphy" J. Res., U. S. Geol. Survey, V. 5,
(1977), p. 49.
[14] HALL, M.
"El Volcanismo en el Ecuador" Inst.
Historia. I.G.M., Quito, (1977), 120 p.
Pan. Geografa e
[15]
CALVACHE,
M., BARREIRO, J., ORTIZ, S. , CORONEL, V., CREUSOT, A.,

GONZLEZ, V., JARAMILLO, S. "Estudio Geovulcanolgico del rea de
Cuicocha-Cotacachi" Informe Final del Primer Curso Latinoamericano de
Geovulcanologla Aplicada a la Exploracin Geotrmica, Quito, OLADE,
(1983), 50 p.
[16]
COLTELLI, M. "II Vulcanismo del le Ande Ecuadoriane" Tesis, Corso di

l.aurea in Scenze Geologiche, Unversita* Degli Stud di Pisa,
(1984).
[17]
von HILLEBRANDT,
Ch.
"Estudio Geovulcanolgco
del Complejo
Volcnico Cuicocha-Cotacachi
y sus
Aplicaciones, Provincia
de
Imbabura" Tesis, Escuela Politcnica Nacional, Quito. (1989).
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TRUESDELL, A., NATHENSON, M. "The Effects of Subsurface Boilng and

Dluton on the Isotopic Compositon of Yellowstone Thermal Waters"
J. Geoph. Res. V. 82, No. 26, (1977), p. 3694.
[19]
AQUATER.
"Proyecto de Investigacin Geotrmica de la Repblica del
Ecuador, Estudio de Reconocimiento" Informe preparado para OLADE e
INECEL, San Lorenzo n Campo, Italia, (1980).
[20]
INECEL. "Estudio de Exploracin de los Recursos Geotrmicos en

Chalupas, Primera Fase Prefactibi1idad". Informe interno preparado
por el Proyecto Geotrmico, (1983).
[213
INECEL. "Estudio Geolgico de las Fuentes Termales de Palctahua,

Provincia de Chimborazo". Informe interno preparado por el Proyecto
Geotrmico, (19B4).
[22] GIGGENBACH, R.
"Geothermal
Solute
Equilibria.
Derivation
of
Na-K-Mg-Ca Geoindicators". Geochm. Cosmochim. Acta, 52: 2749-2765.
[23] AQUATER.
Estudio
(1987).
"Proyecto Geotrmico Binacional Tufiflo-Chiles-Cerro Negro,

de Factibi1idad" Informe interno preparado para OLADE.
[24] BARBERI, F., PATELLA,

D., SCANDIFFIO, G. "Proyecto
Geotrmico
Binacional Tuf iflo-Ch les-Cerro Negro, Informe de la Reunin Final de
la Junta Asesora" Informe interno preparado para OLADE. (1988).
236
AVANCE DE LAS PRUEBAS DE RADIOTRAZADO EN EL CAMPO

GEOTRMICO DE AHUACHAFAN, EL SALVADOR
W.J. McCABE
Instituto of Nuclear Sciences,
Petone, Nueva Zelandia

E. MAYEN, P. HERNNDEZ
Centro de Investigaciones Geotrmicas,
San Salvador, El Salvador
Resumen-Abstract
AVANCE DE LAS PRUEBAS DE RADIOTRAZADO EN EL CAMPO GEOTRMICO DE AHUACHAFAN,

EL SALVADOR.
Con el fin de encontrar las rutas hidrolgicas de las aguas geotrmicas y localizar tanto reas productoras, como reas idneas para realizar el proceso de reinyeccin de las aguas
residuales, cinco pruebas con el trazador radioactivo 1-131, se han realizado en el Campo Geo_
trmico de Ahuachapn (S.O. de la Repblica), desde diciembre de 1987 a marzo de 1990. En la
primera experiencia, el trazador fue inyectado en el pozo AH-5 y nicamente fue detectado en
el pozo AH-1; en la segunda prueba, fue inyectado en el AH-2, no logrndose obtener respuesta radioactiva, la tercera inyeccin fue realizada en el AH-29, obtenindose respuesta en el
AH-1 y escasamente en los pozos AH-20 y AH-22. Todas las pruebas anteriormente mencionadas
fueron llevadas a cabo a reinyeccin esttica, con agua residual proveniente del AH-1. Posteriormente se hizo una cuarta inyeccin, en el mismo AH-29 a reinyeccin constante por tres
meses, y se obtuvo respuesta significativa en los pozos AH-1, AH-5, AH-20 y AH-22. Una quinta
prueba fue iniciada inyectando el 1-131 en el pozo AH-2, a reinyeccin constante con agua del
AH-1 por 3 meses pero problemas con el detector de centelleos lquido, obligaron a suspenderla a 10 das de inicio.
En todas las pruebas fueron recolectadas muestras de aguas de la mayora de pozos del
campo, tanto aguas residuales en superficie, como muestras a profundidad.
Las muestras fueron llevadas al laboratorio y procesadas qumicamente por mtodo gravimtrico, separando el compuesto radioactivo en forma de ioduro de plata y cuyo rendimiento
fue comparado con un segundo anlisis usando el mtodo del electrodo especfico para iodo.
Posteriormente se realiz el conteo del iodo radioactivo por el mtodo instrumental de centelleo lquido.
PROGRESS IN RADIOTRACER TESTS IN THE AHUACHAFAN GEOTHERMAL REA, EL

SALVADOR.
Five tests were carried out with the radioactive tracer 131j ^n the
Ahuachapn geothermal rea, in the SW of the country, over the period
December 1987 to March 1990, to lcate the hydrological courses of geothermal
waters and to find both productive reas and reas suitable for residual water
reinjection. In the first experitnent, the tracer was injected into the AH-5
well and detected only in the AH-1 well. In the second test, the tracer was
injected into AH-2, but no radioactive response was obtained anywhere. The
third injection was into AH-29 and a response was obtained in AH-1, with a
slight response detected in the AH-20 and AH-22 wells. All the above tests
were carried out with static reinjection of residual water from AH-1. A
fourth injection was subsequently made, also into AH-29, using constant
reinjection over a period of three months, and this gave a significant
response in the AH-1, AH-5, AH-20 and AH-22 wells. A fifth test was
started. 131j was ô be injected into the AH-2 well with constant
reinjection of AH-1 water for three months, but problems with the liquid
scintillation detector forced the test to be abandoned after ten days.
237
In all the tests, samples of both residual surface water, and deep
water were collected from most of the wells in the rea.
The samples were taken to the laboratory and subjected to gravimetric
cheroical processing. The radioactive constituent was separated out in the
form of silver iodide and the yield compared to a second analysis using the
iodine-specific electrode method. Afterwards, a count was made of the
radioactive iodine using a liquid scintillation detector.
INTRODUCCIN
El Campo Geotrmico de Ahuachapn, El Salvador, es un campo "lquido dominan
te", con temperaturas mxima de 240C, y que inici operaciones en 1975, con
una unidad de 30 MWe. En 1976 y 1980 fueron instaladas dos unidades ms (30 y
35 MWe respectivamente) para un total de 95 MWe. Posee 14 pozos productores

(600 - 1200 mts) de un total de 32 perforados, con presiones de separacin de
6-7 Kg/cm2 (150-160C) y porcentaje promedio de vapor de 20% en peso. El agua
residual ha sido eliminada por dos ntodos: Por reinyeccin al reservorio a
presin de separacin (suspendida temporalmente desde 1982) y por descarga superficial por gravedad al Ocano Pacfico a travs de un canal de concreto de
80 Km de longitud.
Diversos estudios han sido realizados desde su inicio, con el fin de optimizar la explotacin del yacimiento y prolongar la vida til del mismo. Estudios recientes (1) han revelado la conveniencia de expansin a la zona Sur del
campo y de la reinyeccin de las aguas residuales como acciones a corto y mediano plazo, que mantengan y amplen la explotacin del recurso. Como parte de
lo anterior, y con la colaboracin del Organismo Internacional de Energa Atmica (OIEA) , se han implantado experimentos de radiotrazado y estudios de istopos ambientales en el rea, desde 1986. El 1-131 ha sido el elemento radioactivo escogido como trazador en los experimentos realizados al presente, en base a experiencias exitosas en otros campos geotrmicos y en pruebas de corta
duracin, ya que su tiempo de vida media es de 8 das. (2, 3)
PRIMERA PRUEBA RADIOTRAZADO
Con el objetivo de corroborar una prueba previa llevada a cabo en 1971

con tritio antes de iniciada la explotacin del campo, y de chequear el sistema de tratamiento de muestras y anlisis en el laboratorio de istopos inesta
bles del Centro de Investigaciones Geotrmicas de CEL, el 11 de diciembre 1987
se ejecuta la primera inyeccin de material radioactivo, 1-131, con una concentracin de 0.8 curies (31 GBq); este fue introducido en el pozo AH-5 con
un volumen de agua residual de 140 m^ proveniente del pozo AH-1. (Ver Figura
1). La recuperacin radioactiva obtenida en el pozo AH-1 fue ms del 25% en
los 76 das monitoreados, obtuvo su mxima concentracin a los 20 das de inyectado y comenz a detectarse a los dos das de iniciada la prueba. Fueron
significativas las recuperaciones detectadas en los pozos AH-20 y AH-26. No
se detecto en ninguno de los dems pozos en el campo. El sistema de inyeccin
del trazador es mostrado en la Figura 2.
Comparando con los resultados obtenidos de la prueba en 1971, an cuando
en esta oportunidad fue recuperado en un 10% y detectada una concentracin pico a los 3 das, parece ser que es consistente con la prueba actual, teniendo
en cuentra las diferentes condiciones del campo antes y despus de su explotacin. En la Figura 3 se muestran las dos curvas, donde se puede apreciar dos
concentraciones pico o trayectorias de llegada en la prueba reciente y alguna
posibilidad de una tercera alrededor del da 50. La prueba con tritio dio una
similar dimensin de la trayectoria del flujo, pero no dio una resolucin suficiente para mostrar una segunda trayectoria.
Aparentemente existe un flujo preferencial entre el pozo AH-5 y el AH-1
con una velocidad de 100 m/da y aproximadamente un tercio del agua desde la
vecindad del AH-5 es descargada al AH-1. Esta buena conexin podra estar asociada a una falla o contacto plano; ya que el AH-1 es uno de los pozos mas pro
fundos en la parte principal del campo, esto sugiere una paralelismo con otros
238
312
SIMBOLOGIA
|> POZO SEOT. PERFORADOS
^ POZO SEOT. PROYECTADOS
XFALLA GEOLGICA
5
FUMAROLAS
310
O
25O
5OO______lOOOmr
ESCALA I 25,000
309
411
412
413
414
FIG. 1. Pozos profundos campo geotrmico de Ahuachapn.
SEPARADOR CICLNICO
POZO REINYECTOR AH-I

SILENCIADOR
I I
CANALETA
Vlvula cuten
2 Vlvulas dr quridad
3 Vlvula at gurldorj
4 Vlvula d* compuerta 000 PSIG

5 Vlvula d* tgurldad
Mi ManlMtra iKttma Inyiccltfn
MMane'mitro dtl cobtial
na d mny*ccla<<
LP'Lmvo d* purga
LBPiLl'nto O* Bypaii
Wi,Wg.-Caudal n poto AH-I.AM-5

Hu-Entolpi'o dtl agua
FIG. 2. Esquema del sistema de inyeccin del trazador, pozo AH-5.
239
t
O
Q
<
NI
Ah-1
1987
Ah-1
1971
O
O
2000 -
gj
o
z
CC
1500 M
o ,-
u O
a: T-
1000
1 T
o
fl
(
U.
500 -
O l*
80
DAS
DESPUS
DE
INYECCIN
FIG 3 Prueba de radiotrazado en el pozo AH-5, Ahuachapn
campos como Wairakei N.Z., en donde se ha demostrado, despus de muchas prue-
bas con trazadores, que agua ligeramente enfriada (160-200C), entrando al cam
po desde arriba a la zona principal de produccin a travs de fallas, se mueve a gran velocidad a nivel de zona de contacto con el basamento. Este movimiento podra ser ayudado por fallas abiertas que coincidan con ese plano, logrndose de esa forma que slo los pozos que penetran a la formacin del basamento sean detectados, no as los pozos menos profundos cercanos al pozo inyector, en donde el trazador es descargado hasta que ha sido mezclado con el cuerpo de agua varios das mas tarde. Probablemente la segunda curva del AH-1 po-
dra representar el trazador mezclado en el reservorio.

SEGUNDA PRUEBA RADIOTRAZADO
Con el ob]eto de comprobar la influencia del sistema de reinyeccin utilizado en el campo de 1975 a 1982, se realiz una segunda inyeccin (9/Jul/88)
en el pozo AH-2 con una concentracin de 0.6 curies (21 GBq) y 216
mts^
de
agua residual proveniente del AH-1; fueron monitoreados por 56 das todos los
pozos del campo, tanto muestras a profundidad como en superficie. A pesar de

la profundidad del AH-2 {1200 m) , comparable con alguno de los pozos cercanos
como el AH-29 (1200 m) y el AH-1 {1205 m), no se obtuvo ninguna seal radioactiva en estos, ni en los restantes con respecto al rumbo tomado por el agua den-
tro del reservorio, por lo que probablemente, se haya encausado hacia un reservorio mas profundo. Debido a lo anterior, esta prueba puede considerarse positiva, y si en la prueba programada a reinyeccin constante se obtiene similar
respuesta, podra considerarse una zona idnea de reinyeccin al reservorio
geotrmico.
TERCERA PRUEBA RADIOTRAZADO
Esta prueba se realiz en el pozo AH-29 el da 12 de marzo de 1989, con el

objeto de corroborar tambin el grado de incidencia de la reinyeccin en el
campo, ya que desde 1975 hasta 1982 se mantuvo la reinyeccin de agua residual
en el AH-29, producindose cambios termodinmicos en pozos adyacente
240
al mismo,
lo que llevo a suspenderla. En esta oportunidad se inyectaron 2.0 curies (72.6

GBq) de 1-131 con 738 mts3 de agua residual del pozo AH-1, monitorendose el
campo por 45 das y obtenindose seal radioactiva solamente en el AH-1y someramente significativa en el pozo AH-20 y AH-22. Las Figuras 4 y 5 ilustran a
diferente escala (normal y semilog), los resultados de esta prueba.
0.0
10
20
DAS
DESPUS
30
DE
INYECCIN
FIG. 4. Prueba de radiotrazado en el pozo AH-29, Abril de 1989.
'
'
. i
"o
POZO N.-
100.0. o o
10.0
00
<
"*l"1>
AH-22
*-* *>KI i
:
A
i
1
r /i\
/
tf ^'1\
rir~~
4
tj- 1^1
\I
/
. . . . . . . . I . .. '
^-*^
/ ^
"*%--:
-o'V"
v*- 0
i
2
1 1
a <i
^
ce
o
z
AH-I
1.0
<
o'
/ J
I "
0.1
10
20
DAS DESPUS
zo
40
5l
DE INYECCIN
FIG. 5. Prueba de radiotrazado en el pozo AH-29, Abril de 1989.
241
CUARTA PRUEBA RADIOTRAZADO
Esta inyeccin del 1-131 se llev a cabo el 29 de junio de 1989 en el mismo pozo que se utiliz para la tercera prueba (AH-29), solamente que se realiz a reinyeccin constante con un flujo de agua de 49 Kg/seg durante el pero-
do del monitoreo, el cual tuvo una duracin de 67 das. En esta oportunidad se

introdujo una concentracin de 1.7 curies (62 GBq) y fue detectado en 4 pozos,
los cuales en orden de aparicin fueron: El AH-5 (apto en esta oportunidad para
monitorearlo) y el AH-20 se comenzaron a detectar al primer da y
los pozos
AH-1 y AH-22 al cuarto da, variando solamente en la concentracin o fraccin

de radioactividad detectada, de acuerdo a la cercana desde el pozo inyector
al pozo monitoreado. Debido a acciones operativas propias del campo, los pozos
AH-5 y AH-22 fueron monitoreados slo por 30 das. Las Figuras 6 y 7 ilustran,
a diferente escala (normal y semilog), los resultados de esta prueba.
500
IM
"b
POZO
4OO
oo
N":
AH-I
AH-5
Q
o
300
&&
AH-20
AH-22
z
200
r5
./
100
oou -'
10
20
30
+0
50
60
70
DAS DESPUS DE INYECCIN

FIG. 6. Prueba de radiotrazado en el pozo AH-29, Junio de 1989.
1000
o
X
TJ
Z
O
o
<
ce
o
U)
h-
o
o
10
20
DAS
30
DESPUS
4-0
DE
50
60
INYECCIN
FIG. 7. Prueba de radiotrazado en el pozo AH-29, Junio de 1989.
242
70
QUINTA PRUEBA RADIOTRAZADO
Esta correspondi al mismo esquema que la segunda, slo que a reinyeccin

constante del pozo AH-1 (38 Kg/seg) y tuvo que ser suspendida a los 10 das de
iniciado por desperfectos del equipo contador de centelleos liquido, utilizado

para detectar el radiotrazador. La concentracin del 1-131 inyectado el 7 de
marzo de 1990 fue de 2.0 curies (72.6 GBq) y en una muestra a profundidad del
pozo AH-29 colectada al tercer da de la prueba, indic ya la presencia del
1-131 en ese punto.
PROTECCIN RADIOLGICA DURANTE LOS EXPERIMENTOS
El procedimiento para inyectar el trazador es simple y sencillo. Esta diseado de tal forma se obtenga una mnima dosis de radiacin al operador. Transferir el frasco con el 1-131 del contenedor al sistema de inyeccin toma normalmente de 10 a 20 segundos. Con una cantidad de 2 curies (74 GBq) de 1-131
(valor tpico utilizado) resultar en una dosis equivalente efectiva menor de
3 mrem (0.03 mSv), la cual es mucho menor que la dosis ambiental anual de 200
mrem (2 mSv).
Para todas las pruebas, se realizan las siguientes medidas de seguridad rja
diolgica:
a)
El sistema de inyeccin es chequeado visualmente a condicin de la prueba

antes de realizarse para detectar fugas y defectos en vlvulas y accesorios .
b)
Material plstico es colocado debajo del sistema de inyeccin.
c)
El personal encargado del experimento se protege completamente con gabachas y accesorios de caucho y plstico.
d)
El frasco con el elemento radioactivo es manejado con largas pinzas especiales, y colocado internamente en una vlvula de compuerta, recubierta de
plomo, en el sistema de inyeccin.
e)
Las dosis de radiacin se miden y registran adecuadamente durante la inyeccin del radiotrazador.
f)
Se construye una fosa de 1 mt. de profundidad cercana al sistema de inyeccin, como prevencin y desecho del material descartable utilizado.
SEPARACIN DE IODO DE LAS AGUAS GEOTERMALES PARA EL CONTEO RADIOACTIVO
La siguiente tcnica gravimtrica es utilizada para recuperar el iodo sin

precipitacin de slice o cloruros: El sulfhdrico es oxidado con permanganato
de potasio acidificado, sulfito es adicionado para reducir el iodato a ioduro,
y cido fluorhdrico es agregado para complejar y prevenir la precipitacin de
la slice. Esta solucin se filtra a travs de una membrana. Posteriormente se

adiciona nitrato de plata para precipitacin de los cloruros. Debido a la rea,
tiva solubilidad de los haluros de plata, el iodo es cuantitativamente precip_i
tado, mientras slo se forma una pequea cantidad de cloruro de plata. Esta solucin es filtrada nuevamente a travs de una membrana previamente tarada y los
cloruros de plata fijados, son removidos con amonaco diluido.
DETERMINACIN DEL IODURO EN AGUAS GEOTERMALES CON ELECTRODO DE ION ESPECIFICO
El electrodo para ioduro es sensitivo al sulfhdrico y tambin a los bromuros, pero en menor capacidad. Por lo tanto, es necesario oxidar el sulfhdrico de las aguas geotermales antes de la determinacin de ioduro. Los bromu-
ros no pueden ser usados como agentes oxidantes sin introducir un apreciable
"blanco reactivo". El permanganato de potasio alcalino oxida el sulfhdrico a
sulfato pero el ioduro existente es tambin oxidado a iodato. El iodato tiene
que ser entonces reducido a ioduro nuevamente con la adicin de cido y sulfito de sodio.
Para evitar problemas con el electrodo, es aconsejable mantenerlos fuera
de la solucin mientras hay un excedente de agente oxidante y ninguna formacin de ioduro.
243
CONTEO DE CENTELLEO LIQUIDO DEL IODO SEPARADO DE LAS AGUAS GEOTERMALES
Es la tcnica mas sensitiva para la deteccin y cuantificacin de radioactividad. Es aplicable a todas las formas de medicin de emisiones con desint
gracin nuclear (Alfa, Beta, etc.). La tcnica analtica esta definida por la
incorporacin de un elemento radioactivo distribuido uniformemente en un medio
lquido capaz de convertir la energa cintica de las emisiones nucleares en

emisiones de fotones. El elemento radioactivo colocado en un frasco con la so_
lucin centellante, encerrado en la oscuridad, permite que la intensidad del
fotn sea observado en la regin ultravioleta del espectro de energa electro_
magntica. Esta seal es ampliada y detectada despus de procesos que crean
un pulso elctrico representativo de los fotones. El registro de cada pulso
durante el tiempo de medicin, provee una indicacin del nmero de eventos centellantes que ocurren en ese tiempo.
CONCLUSIONES
Los resultados obtenidos al presente en Ahuachapn, han demostrado la utilidad de esta tcnica de avance, como una herramienta extremadamente poderosa
que conlleva a poseer un conocimiento hidrolgico de las condiciones de operc
cin de los campos geotrmicos, en un tiempo relativamente corto, lo que ayu-
da a planificar estrategias inmediatas de explotacin-reinyeccin del recurso.
REFERENCIAS
(1)
Aunzo, Z.P., Bodavarsson, G.S., Laky, C., Lippman, M.J., Steingrimsson,

B., Truesdell, A.H., and Witherspoon, P.A., 1989. The Ahuachapn Geothermal Field, El Salvador: Reservoir Analysis, Lawrence Berkeley Laboratory, Report LBL-26612, U.S.A.
(2)
(3)
McCabe, W.J., 1990. Artificial Tracers in Geothermal Hydrology. Institute

of Nuclear Sciences, Department Science and Industrial Research, New
Zealand.
McCabe, W.J., Barry, B.J., Manning, M.R., 1983. Radioactive Tracers in
Geothermal Underground Water Flow Studies. Geothermics, Vol. 12, No.2/3,

pp 83-110.
244
ISOTOPIC AND CHEMICAL COMPOSITION OF

WATER AND GAS DISCHARGES FROM THE
ZUNIL GEOTHERMAL SYSTEM, GUATEMALA
W.F. GIGGENBACH
Divisin of Chemistry,
Petone, New Zealand
D. PAI AGUA DE GUDIEL, A.R. ROLDAN MANZO
Instituto Nacional de Electrificacin,
Guatemala City, Guatemala
Resumen-Abstract
LA COMPOSICIN ISOTPICA Y QUMICA DE LOS CAUDALES DE AGUA Y GAS PROCEDENTES

DEL SISTEMA GEOTRMICO DE ZUNIL, GUATEMALA.
Las diferencias en la composicin qumica e isotpica de los caudales de

agua y vapor sugieren que el sistema geotrmico de Zunil es un tpico sistema
volcnico magmtico-hidrotrmico estrechamente relacionado con el complejo
volcnico de Cerro Zunil - Domo El Azufral que se encuentra al SE de la zona
trmica principal. Los vapores magmticos originales llegan a la superficie
del depsito de azufre de Azfrales con mnimas alteraciones. Su interaccin
con aguas subterrneas locales en niveles comparativamente poco profundos origina la formacin de aguas acidas sulfatadas que se descargan sobre las laderas de la estructura volcnica. El movimiento de
das hacia el N y el O conduce a su neutralizacin
ladas con CO , con predominio de Cl, tal como
profundos. La proporcin del agua originalmente
aguas primitivas ms profuny conversin en aguas aciduse encuentran en los pozos

magmtica en las aguas pro-
fundas con Cl es de ~20%. La posterior interaccin agua-roca transforma la

mayor parte del CO en disolucin en HCO , y las aguas bicarbonatadas resultantes se descargan a travs de manantiales situados a lo largo del ro Smala.
Los vapores que se desprenden de las aguas profundas calientes sirven
de alimento a fumarolas y depsitos vapocalentados. A medida que disminuye la

distancia con las zonas ascendentes principales de los fluidos trmicos relacionados con el complejo de Cerro Zunil, puede esperarse que aumenten las temperaturas profundas del agua. Al mismo tiempo, sin embargo, existe un peligro
creciente de que lleguen a los pozos fluidos cidos y oxidantes inmaduros de
origen magmtico.
245
ISOTOPIC AND CHEMICAL COMPOSITION OF WATER AND GAS DISCHARGES FROM THE ZUNIL
GEOTHERMAL SYSTEM, GUATEMALA.
Variations in the chemical and isotopic composition of water and steam

discharges suggest that the Zunil Geothermal System is a typical volcanic magmatic-
hydrothermal system closely associated with the Cerro Zunil - Domo El Azufral
volcanic complex to the SE of the main thermal area. The originally magmatic vapors
reach the surface least altered at the Azufrales sulfur deposit. Their interaction with
local groundwater at comparatively shallow levels gives rise to the formation of acid
sulfate waters discharged over the flanks of the volcanic structure. Movement of
deeper primitive waters to the N and W leads to their neutralisation and conversion
to C2 charged, predominantly Cl waters as encountered in the deep wells. The

proportion of originally magmatic water in the deep Cl waters is --20%. Further
water-rock interaction converts most of the dissolved CC>2 to H>3, the resulting
bicarbonate waters are discharged from springs along the Samal River. Vapors
released from the deep hot waters feed fumaroles and steam-heated pools. Deep
water temperatures can be expected to increase with decreasing distance to the major
upflow zones of thermal fluids associated with the Cerro Zunil complex. At the same
time, however, there is increasing danger of the incursion into wells of immature acid
and oxidising fluids of magmatic origin.
INTRODUCTION
The Zunil Geothermal Field lies some 200 km west of Guatemala City. On the basis
r\
of geoscientific surveys in 1973 and 1977, a 4 krrr area was cosen for the drilling of
six deep exploration wells during 1980 to 1981 to a maximum depth of 1310 m, the
highest temperature encountered was 288C. According to these early investigations,

the heat source of the field was thought to lie to the west of the Samal River
(Caicedo and Palma, 1990). Initial production testing indicated rapid pressure
drawdown due to restricted permeabilities (Bethancourt and Dominco, 1982). In a
246
recent series of papers, Adams et al. (1990a) evaluate the geochemistry and
hydrology of the Zunil Field and agree that a plume of high temperature water
originates in the western part of the existing well field to travel south and east and to
mix with shallow steam-heated water there; Adams et al. (19905) describe another set
of hydrogeochemical investigations and suggest that the reservoir at Zunil is
geochemically inhomogeneous and that the recharge to the field comes primarily from
the north and east. Menzies et al. (1990) report the results of an integrated well test
program and conclude that steam output from the presently drilled wells could sustain
a 15 MW power station, however, additional wells would have to be drilled to
maintain production. Foley et al. (1990) discuss the geology and geophysics of the
Zunil geothermal system and suggest that fluid production is controlled by the
intersection of NW and NE trending faults.
The present investigation was carried out within the framework of the IAEA
Coordinated Research Program on the Application of Isotopic and Chemical

Techniques to Geothermal Exploration in Latin America. The major aim of this study
is the development of an internally consistent hydrological model of the system
possibly useful in the selection of more favorable drilling targets. The model is based
largely on the isotopic and chemical composition of water and steam discharges.
CHEMICAL COMPOSITION OF WATERS

The chemical composition of samples from well and spring discharges collected during
the present investigation are given in Table 1. The results agree closely with those
reported by INDE (1978) for earlier much more extensive surveys. The three well
samples were taken from the weirbox, but are corrected for steam loss and therefore
represent total discharge compositions. Sample locations are shown in Fig. 1. AR is
the composition of a solution resulting from the "dissolution" of 10 g of average
crustal rock in 1 kg of water. For all neutral to alkaline waters Al contents were < .05
247
Table 1.- The chemical composition of well and spring discharges from the Zunil
Geothermal Field, in mg/kg.
pH
Li
Na
Rb
Cs
Mg
Ca
H(:O3
SiO2 SO4
Cl rf.
wells, weirbox samples

Z3 8.1 8.70
933 231.0
2.33 2 .02 .012 15 40.0
51 951 31 1810 a
Z6 8.4 8.10 1028212.0
1.89 2 .01 .040 11 45.0 157 889 61 1700 a
ZU
7.8 6.31
1092 101.0 0.55 2.26 .070 30 50.8
41 580 105 1740 a
Chloride springs
cl 9.0 2.70
545
51.1
C2
33.9
0.39
1 .35
0.2
7.4
10.0
12.2
18.6
37.2
36.6
0.02
0.02
0.03
0.05
0.07
0.07
0.08
.003
.012
.027
.037
.030
.022
.025
11.6
8.3
6.05
788
Bicarbonate waters
Bl 9.2 0.13
79
B2 7.0 0.18
65
B3 7.0 0.28
166
B4 8.4 0.37
199
B5 7.8 0.56
286
B6 8.7 0.56
372
B7 8.7 0.57
258
B8 6.1 0.91
157
sulfate water
SI 2.1 0.12
S2
S3
3.1
2.1
S4
2.0
0.08
0.05
0.07
surface waters
Rl 7.0 <.01
R2 7.1 <.01
R3 6.1 <.01
43
80
89
27.3
19.0
134
14.5
7.7
30.9
32.3
9
8
16
4.4
3.3
5.9
0.09
0.04
0.04
0.11
0.23
0.3
5.4
5.9
18.1
36.2
40.5
7
48
26.2
34.2
96
32
22
11
0.7
1.3
2.8
3.4
79
140
160
132
64
22
259
138
161
194
196
103
129
210
194
17
25
42
4.7
4.7
4.6
2.5
340
463
491
501
503
0.2
<.l
1.8
1.7
AI
7
42
59
39
41
45.2
43
.019 30.8 18
.009
.009
.004
.010
18.9 76
45.0104
14.6 43
28.3 72
200 193
146 235
242
117
292 633
209 1600
287 2060
728
1236
c
a
31
57
101
114
a
b
b
a
a
a
a
b
180
163
168
71
15
10
7
8
b
b
a
15
15
20
b
b
b
HCO3
0.01 .002
c.Ol < .01
0.01 < .01
5.6
3.8
3.6
9
8
7
0.3
<.l
0.2
solution of average crustal rock (10 g/kg of water)

AR
0.30
240 210.0
1.50 0 .04 230.0 420 0.12
a.- DSIR
C.- INDE (1984)
b.- pH, HCO3, SO4, Cl by INDE
d.- Taylor (1964)
248
404 210
396 115
74
69
38
28
52
22
56
18
NW
chloride wate
bicarbonate w.
sulfate waters
fumaroles
proposed drill sites
Fig. l - Sketch map of Zunil Geothermal Field showing positions of collection points
for water and steam samples, the inferred flow of deep fluids (arrows) and the
suggested position of drillsites.
mg/kg. An initial classification of the waters, on the basis of relative Cl, SO^ and
HCC>3 contents is carried out in Fig. 2. The samples belong to three distinct groups:
The first group consists of chloride waters discharged from the three wells (Z3, Z6,
Zll), the only natural high chloride spring Z-20 (Cl), and an abandoned exploration
well, ZP-6 (C2),
The second group covers all the neutral bicarbonate springs along Rio Samal (Bl to
B8) and also includes the much less mineralised waters of rivers entering (RI, R2)
and leaving the thermal area.
249
neutralised
deep
/water
HCO:
Fig. 2 - Relative Cl, 804 and HCO-j contents of waters from the Zunil Geothermal
System.
The third group is made up of acid, high sulfate waters. Samples SI and S2 represent
boiling, evidently steam-heated pools. Waters S3 and S4, discharged from over the
slopes of Dome El Azufral, have considerably higher sulfate contents, but are well
below boiling.
There appears to be very little mixing among the three groups of waters. Cl and C2
are to a minor degree affected by possible admixture of a high sulfate water. The
waters from the central group of bicarbonate springs, B3 to B7, form a tight
cluster,those farther to the north, Bl and B2, show deviations to higher and lower
804 contents respectively. The trend described by these data points may be
interpreted in terms of mixing of sulfate waters with a hypothetical bicarbonatechloride water possibly resulting from direct partial or complete conversion of the
CC2 in the deep Cl waters to HCO3.

250
B8 at the southern end of the thermal area has lower Cl contents. Together with the
other HCOj springs it may delineate another trend corresponding to mixing of deep
Cl waters, as represented by the wells, with a low Cl, sulfate-bicarbonate water

possibly formed through underground absorption of CC^ rich vapors into local
groundwater. The composition of the river waters, R2 and R3, is likely to reflect
admixture of minor proportions of HCO^ waters. The existence of three distinct
groups of waters is likely to reflect three distinct environments of water-rock
interaction and three distinct degrees of attainment of water-rock equilibrium.
The interaction of fluids within hydrothermal systems with close volcanic-magmatic

associations can be evaluated in terms of two endmember processes: initial rock
dissolution adding cationic components in proportions close to those in the original

rock, and eventual rock equilibration with minerals thermodynamically stable over the
major water-rock equilibration zones within the system (Giggenbach, 1988). An initial
evaluation of the Zunil waters in terms of these processes is carried out in Fig. 3 on
the basis of relative Na, K, Mg and Ca contents. The two deep well discharges (Z3,
Z6) plot close to the rock equilibrium line at temperatures close to those measured,
the more shallow well Zll at a correspondingly lower temperature. The water
discharged from the abandoned exploration well reflects water-rock equilibrium at

considerably lower temperatures, ~18(to
that from the only natural high C] spring C1
the effects of admixture of the more shallow bicarbonate waters. Extrapolation onto
the full equilibrium line suggests a temperature close to that of Zll.
Assuming relative Na, K contents of the HCOj springs to reflect those of deeper
equilibration, temperatures of 220 to 240C are indicated. Their highly increased Mg
contents point to extensive interaction with rock at lower temperatures (Giggenbach,
1988). The data points for both river waters and acid sulfate springs approach the
composition expected for rock dissolution. Again all three groups are well separated
suggesting distinctly different formation conditions.
251
10 Mg
l
R 3 rivers
0-8
S3
HCO3 - waters
rock
acid J dissolution
waters
0-6-
10K
Na
0-4 -
0-2-
wa terrock
equilibrium
0-2
0-4
0-6
0-8
a
Fig. 3 - Plot of 10cMg/(10cMg + cCa) versus 10cK/(10cK + cNa) (in mg/kg) for
water discharges from the Zunil geothermal Field.
Other techniques to evaluate water-rock equilibration temperatures are based on
dissolved silica and relative K, Mg contents. Corresponding temperatures may be

obtained by use of the relationships (Giggenbach, 1988)
and
ts = (1000/(4.55 - log csi02)) - 273
(1)
tkm = (44107(14 - log(c^/cMg)) - 273
(2)
where the temperatures t are in C and Cj are the concentrations of SiO2, K and Mg
in mg/kg. In Fig. 4 a line is shown for ts = t^m. For the three well discharges, both
temperatures are very similar, again close to those measured suggesting attainment of
full equilibrium among the waters and a mineral assemblage containing Na and K
feldspars, chlorite, a CaA^-silicate and chalcedony.
252
50
tfcn, (C)
150
100
200
250
300
-300
2.!
2.0-
1.5-
50
Fig. 4 - Evaluation of silica, ts, and K-Mg,
Lkm
tj^, temperatures .
The two surface samples of Cl waters, Cl and C2, plot above this line possibly
indicating equilibration with a more soluble polymorph of silica or quenching of
higher chalcedony equilibration temperatures, 240C. The differences between ts and
tfcm are
even more
pronounced in the case of the HCC3 and 804 waters. Their data
points plot close to the line representing the most soluble silica polymorph,
amorphous silica. In this case, equilibration temperatures for both silica and K-Mg
are
close to those measured in the surface pools (70).
Many of the solution components depicted in Figs 2 and 3, such as HCO^, 804, Mg
and Ca, are greatly affected by shallow processes. In order to obtain information on
deeper processes and to establish possible genetic links among the various types of
waters, relationships among the more "conservative" constituents such as Cl, B, Li, Rb
and Cs are investigated in Figs. 5 and 6. Relative Cl, B and Li contents confirm the
253
Cl/10
.01
02
03
.05
B/CI
.10
1O Ll
Fig. 5 - Relative Cl, B and Li contents of water dischatges from the Zunil Geothermal Field.
Li/10
Rb/4
Cs
Fig. 6 - Relative Li, Rb and Cs contents in waters from the Zunil Geothermal Field.
254
close relationship between Cl and HCO waters as already proposed by Bethancourt

and Dominco (1982) an the basis of B/C1 ratios. The two groups of sulfate waters
occupy distinct positions. The low B content of the two obviously steam heated pools
SI and S2 is likely to reflect the low B content of the comparatively low temperature
steam injected. The position of the acid waters S3 and S4 suggests interaction with a
much more B enriched, probably much higher temperature vapor at greater depth.
There is no obvious genetic relationship between the 804 and the Cl-HCO^ waters.
The overall pattern is confirmed by reative Li, Rb and Cs contents shown in Fig. 6.
Again, 804 waters occupy positions approaching that of dissolved rock suggesting
much of their solute contents to be derived from straightforward rock dissolution. The
Cl, HCC>3 waters desribe a trend corresponding to removal of Cs from the deep Cl
waters at close to constant Li/Rb ratios. The most likely process giving rise to this
pattern is incorporation of Cs into secondary zeolites at lower temperatures (Goguel,

1983). The degree of Cs removal, therefore, may reflect variations in the distance
travelled by the waters. Accepting this explanation, Waters B3 and B4 have travelled
the shortest distance or are closest to the major flow path of the thermal waters, Bl
and B8 are likely to represent waters having moved farthest or having resided
underground longest.
According to this evaluation, the natural upflow of thermal waters is centered on the
area represented by springs B3 and B4, with the waters approachig the valley floor
either from the NW or SE, but probably not from the SW or NE. Relative Cl, B, Li,
Rb and Cs contents of the Zunil waters point to the existence of a common parent
water for both Cl and HCO waters. Information on the origin of this deep water may
possibly be obtained from their isotopic compositions.
255
ISOTOPIC COMPOSITION OF WATERS AND STEAM

The isotopic composition together with sampling dates and temperatures, tritium and
Cl and S4 contents of the samples listed in Table 1 are given in Table 2. The
isotopic composition of steam discharges, together with the 6^S and mole fraction of
F^S are given in Table 4. Isotopic relationships among the samples are best discussed
on the basis of Figs. 7A and B.

Table 2.- Isotopic compositions (%o) and tritium (TU), Cl and 804 contents (mg/kg) of
well and spring discharges from the Zunil Geothermal Field.
INDE
date
temp.
wells (total discharge)

Z3 ZCQ-3
09 .85 260
Z6 ZCQ-6
09 .85 280
Zll Z-ll
08 .87 250
5 180
62H
-8 .74
-8 .36
-7 .25
Cl
-79 .3
-75 .9
-70 .1
1.3
1.3
1140
1070
992
20
38
60
a
a
b
1.1
700
202
115
c
b
31
64
22
103
129
210
194
193
235
b
a
a
b
b
b
b
a
SO4
ref
chloride springs
Cl
C2
Z-20
ZP-6
01 .80
11 .88
93
-8 .20
93
-7 .22
-74 .2
40
-11 .89
-85 .2
50
-10 .38
-10 .75
-11 .39
-11 .30
-11 .89
-11 .54
-11 .05
-77 .0
1.2
57
-79 .7
0.0
101
4
180
-7 .25
-70 .6
-67 .4
-75 .8
-80 .7
15
10
7
8
-84 .7
-85 .7
-85 .4
-55 .3
15
15
20
-
56
1236
bicarbonate waters
Bl
B2
B3
B4
B5
B6
B7
B8
Z-23
Z-29
Z-4
Z-9
Z-17
Z-10
Z-13
Z-15
08 .87
06 .86
06 .86
07 .87
07 .87
07 .87
07 .87
06 .86
sulfate waters
SI ZF-38
06 .86
S2 Z-36
06 .86
S3 Z-19
08 .87
S4 Z-31
08 .87
surface waters
Rl ZR-1A
06 .86
R2 ZR-2A
06 .86
R3 ZR-16
06 .86
R4 rain
06 .86
a.- IAEA
256
b.- DSIR
63
62
70
67
87
64
91
90
56
74
18
16
18
-
-7 .58
-9 .38
-10 .02
-11 .64
-12 .23
-12 .22
-8 .47
1.1
-77 .5
-83 .3
-84 .1
-84 .7
-82 .4
1.1
0.3
3.2
4.8
163
168
71
633
a
a
1600
2060
117
18
-
a
a
a
c.- Fournier and Hanshaw (1981)
-60-
-80-
&2H
-80-
-100'
-14
-12
-10
S180(%0)
-8
Fig. 7 - The isotopic composition of waters (A) and steam condenstes (B) from the
Zunil Geothermal Field. In Fig. 7A a line is shown representing the
composition of residual waters after single step steam separation at a given

temperature, in Fig. 7B the compositional area of steam having separated
from the deep chloride, DW, or the more shallow bicarbonate (SW) waters
or their mixtures.
Data points for the HCO^ waters plot close to the meteoric water line suggesting that
they are largely made up of local groundwater. By assuming the river waters to be
most representative of this local groundwater, its composition is represented by point

LG. Most of the bicarbonale waters, however, are isotopically considerably "heavier"
possibly pointing to the existence of a distinct type of shallow thermal water, its
isotopic composition, SW, is taken to correspond to the mean of all bicarbonate
waters.
257
The two deep well discharges, Z3 and Z6, show increased 18O contents. Such 18Oshifts are generally explained in terms of water-rock isotope exchange (Craig, 1963).
Recent findings on water and vapor discharges from hydrothermal and volcanic
systems along convergent plate boundaries, however, suggested that much of this
"oxygen shift" may be due to admixture of a so-called "andesitic" water with 6180 Qc
f\
+ 102%o and 6ZH of -2010%o . In this case their should also be some "deuterium
shift". Comparing the isotopic compositions of the two deep well discharges and that
of the range of possible groundwaters as represented by the bicarbonate springs and
the river waters, there appears to be indeed a ^H enrichment in the well discharges.
The isotopic composition of the deep Cl water, DW, is assumed to correspond to the
mean of the two well waters. Before discussing possible admixture of a magmatic
water further, an attempt is made to interpret the isotopic composition of the
remainder of the samples.
Again the two groups of acid sulfate waters occupy distinct positions. The two steam-
heated pools, SI and S2, show clearly the effects of isotopic enrichment due to surface
evaporation (Giggenbach and Stewart, 1982). The much higher 804 contents of S3
and S4 are not accompanied by higher isotopic enrichment suggesting that they are
probaby formed through absorption of S-rich vapors undergound. The composition of

the two lower temperature Cl waters, C2 and Z11, would be in agreement with
possible isotopic enrichment due to vapor loss as indicated by the line marked "steam
separation".
The isotopic composition of fumarolic vapors and the effects of vapor separation
processes are discussed by use of Fig. 7B. Two of the fumaroles were re-sampled
about one year apart, their isotopic compositions are quite different. For both Paxmux
(PX) and Fumarola Negra (FN), the 1988 samples appear to be isotopically conside-
rably depleted compared to the 1987 samples. All five data points including that of
the fumarolic area of Las Fresas to the west, however, fit into an area delineated by
258
the theoretical composition of vapors possibly produced from the deep Cl water, DW,
or the shallow water (SW), representing the HCO^ waters, or their mixtures. The
vapor at Las Fresas is most likely separated from the deep Cl water at a temperature
of around 200 C. The compositions of the 1987 samples from Paxmux and Fumarola
Negra suggest derivation from an intermediate water, between DW and SW, the 1988
samples from SW only at quite low temperatures of about 140C. The shift in isotopic
composition for these two vents from 1987 to 1988 may reflect differences in rainfall
giving rise to differences in the underground distribution and temperatures of the feed
waters.
The isotopic compositions of the vapor from the "dry" well ZCQ-5 (Z5) and from the
Azufrales area on Domo El Azufral (Fig. 1), are close to that of D W and therefore
show also both an 1O and ^H shift. The similar isotopic compositions of the Azufral
vapor and of the well discharges suggests that they are derived from a common, high
temperature parent water and that the body of this parent water extends from the
main drilling area, to the west of Samal River, to well underneath Domo el Azufral.
According to Fig. 7A, the isotopic composition of samples Zll and C2 may be
explained in terms of isotopic enrichment due to underground vapor loss. A check as
to the validity of this conclusion can be made by use of Fig. 8 taking into account
variations in Cl contents with those in the isotopic composition of the waters. The Cl
content of the deep water is again assumed to be that of the mean of the total
}
discharge compositions of the two deep wells of 1100 mg/kg. In the case of ZH
contents, the position of sample C2 corresponds to that of the residual water after
steam separation from DW at temperatures close to 210C. The increased ^H content
at a reduced Cl content of sample Zll suggests that its composition is due to a
process other than simple steam loss from DW.

This conclusion is supported by the position of data points in Fig. 8B. None of the
more shallow Cl waters lies along the line representing steam separation from DW.
259
-60-
4OO
80O
120O
Cl (mg/kg)
Fig. 8 - Deuterium and oxygen-18 contents versus Cl contents. Lines indicatind th

effects of dilution and steam loss on deep water DW are shown.
1S
All three show considerable enrichment in 10
O at Cl contents too low to be
compatible with simple single step underground steam separation. Their compositions
are likely to reflect, in addition to steam separation, the effects of surface evaporation
or mixing with shallow waters, other than local groundwater LG, but resembling SI
and S2. A similar mixing process is likely to be responsible for the variability in the
isotopic composition of the bicarbonate waters.

As pointed out above, the increased 1O and ^H contents of the deep well waters
with respect to the isotopic composition of local groundwater LG, may be explained in
18
therms of the admixture of a magmatic, in this case "andesitic" vapor with 610O of
260
around +10%o and 52H of about -20%o (Giggenbach, 1991). The derivation of the Zunil
waters from an "andesitic" water is evaluated by use of Fig. 9. Again assuming the
composition of local groundwater to be represented by LG, any admixture of an
"andesitic" water is described in terms of three lines representing the likely range of
compositions. The data point for DW falls within the expected range, as do those for
Zll and C2, and even those of the highly immature sulfate waters S3 and S4. The
isotopic compositions of all these waters would therefore be compatible with
formation through absorption of an andesitic vapor into local groundwater.
Fig. 9 also contains lines representing the possible fractions xa of andesitic water
involved in the formation of a thermal water. They may also be calculated by use of
the relationship
- 6m)
where the subscripts refer to the isotopic composition of the andesitic water (a), of
the thermal discharge sampled (d) and of the local meteoric water (m). For DW a
value of close to 0.2 is obtained implying that 20% of the water is of andesitic,
62H
-5O-
-100-
-10
-5
&18O Woo)
10
Fig. 9 - Derivation of Zunil geothermal waters through mixing of local groundwater,
LG, with "andesitic" water.

261
magmatic origin (Giggenbach, 1991). Assuming all the Cl to have been introduced
with the andesitic vapor, its Cl content is 1100/0.2 = 5500 mg/kg or 0.55% by weight.
ISOTOPIC COMPOSITION OF SULFUR SPECIES

The isotopic composition of sulfur species present in geothermal discharges can be
expected to provide additional information on the origin of the fluids and on the
conditions over the deeper parts of the system. The
S contents of H^S in steam
samples are given in Table 3, the s and *O contents in dissolved sulfate in Table
4. Possible correlations are discussed by use of Fig. 10.
Table 3.- Isotopic composition (in %o) and mol-fraction (Xj_j in pmol/mol) and 6-^S
(in %o) of H2 in steam condenstes from the Zunil Geothermal Field.
25
C2
ZCQ-5
LF
Las Fresas
Paxmux
PX
PX
FN
FN
AZ
AZ
ZP-6
it
Fum. Negra
n
Azuf rales
"
date
09 .85
11 .88
08 .87
08 .87
11 .88
08 .87
11 .88
08 .87
11 .88
170
93
94
93
93
94
93
91
81
6180H2O 62HH 0
2
H2S
634SR
2S
-8.66
-
-75 .0
-
90
28
-1. 6
-11 .5
-12 .3
-83 .6
257
-0. 8
-82 .9
260
-0.4
-14 .0
-12 .9
273
-5. 1
-14 .1
-
-94 .2
-94 .0
-97 .4
-
178
196
802
+ 0.1
-1. 8
-9 .1
-83 .7
-0. 1
1143
""" J.
Table 4.- Sulfur-34 and oxygen-18 content of dissolved SO^ together with oxygen-18
content (%o) and 804 and Cl contents (mg/kg) of associated waters.
date
ST
C
Zll
B4
B5
B6
B7
S3
S4
262
08.87
07.87
07.87
07.87
07.87
08.87
08.87
144
62
70
67
87
56
74
so4
ci
(mg/kg)
60
129
210
194
193
1600
2060
992
4
180
163
168
7
8
634S
6180
H2S
S04
SO4
H2O
+3.6
+15.8
+ 4.3
-7.3
+7.6
+8.6
+9.7
+8.9
+0.9
+0.7
-11.4
+4.4 -11.3
+6.1 -11.9
+5.9 -11.5
+ 13.0
-9.4
+9.5 -10.0
+4.0
<518o S0
-10
518oHO(/o,)
-5
-5
Fig. 10 - Oxygen-18 contents in dissolved sulfate and waters (A) and sulfur-34
contents in dissolved sulfate and I^S (B) of Zunil geothermal fluid
discharges.
The isotherms shown in Fig. 10A are based on the temperature dependent
fractionation of 1O between water and sulfate as determined by Lloyd (1968) and
Mizutani and Rafter (1969) according to

A
S04-H20 * looolnaS04-H20 = (3 65 S00^2) - 4-9
(4)
where T is in K. For the two acid waters, S3 and S4, attainment of equilibrium is
indicated at temperatures close to those measured, a process greatly facilitated

by the low pH of the waters. The trend observed for the bicarbonate springs suggests
an increase in 1"O equilibration temperatures from just below 100 for the two
southern samples, B6 and B7, to 110 to 120C for the two more northern samples, B4
and B5. This minor trend may reflect an actual difference in equilibrium
temperatures, but also differences in the residence time of the waters underground.
263
For the shallow well Zll a temperature of 155 is suggested if the total discharge
1O content is used, 180 if that of the separated water is used. Both are, for
unknown reasons, below that measured of 250 (Table 2). Residence times of the
waters within the Zunil geothermal system are obviously long enough to allow 1O in
sulfate to adjust to quite low temperatures.
A much "slower" process is 34S exchange between SO4 and H2S. Accepting the
isotopic composition of H2S within much of the Zunil system to be close to the range
of about -2 to 0%o, as observed for the fumarole discharges, apparent equilibration
temperatures may be evaluated by use of
A
S04-H2S ~ 100lnS04-H2S = (6 04 0 0 ^) + 2-16
(4)
as reported by Robinson (1973).

Both the two acid sulfate waters were collected from springs on the slopes of Domo
El Azufral. The most closely related discharge of H2S is likely to be that from the
Azufral fumaroles. Their 6 S values are within the range observed for the other
vapor condenstes. By use of a value of -l%o for H2S, exceedingly high temperatures of
>1000C are obtained for S3 and S4. The very low isotopic fractionation suggests that
formation of sulfate from a sulfur containing vapor proceeded under conditions
preventing attainment of equilibrium even for these acid waters. Such conditions are
likely to prevail over parts of the system were the originally magmatic, or "andesitic",
vapors first interact with groundwater. These vapors would contain much of their
sulfur in the form of SO2. In this case the acid sulfate waters form through
disproportionation of SO2 according to
4 SO2 + 4 H2O = 3 H2SO4 + H2S
(5)
If the H2S and H2SO4 are separated shortly after their formation, the s content of
the sulfate may still reflect that of the original magmatic gas of around 0 to + l%o.
264
Sulfur-34 equilibration temperatures for the bicarbonate waters are also unrealistically
high, the shift to higher ^S values, however, would point to some equilibration.
The composition of sample Zll suggests reasonable equilibration temperatures of
350 if a value of -l%o is accepted for the l^S, 500 if equilibrium with coexisting Ir^S
(+3.6%o, Table 4) is assumed. Both temperatures are very high but may reflect the
occurrence of such temperatures deeper within the Zunil hydrothermal system.
The 34s content of 804 in the two acid waters S3 and S4 points to their formation
under conditions preventing even minor re-equilibration with I^S. Such conditions
are likely to occur if the zones of conversion of magmatic to hydrothermal fluids lie at
shallow levels. The isotopic compositions of sulfur species in fluids from the Zunil
geothermal field, therefore, strongly suggest that initial interaction of magmatic vapors
with groundwater takes place within Domo el Azufral structure. On moving away
from these zones the initially highly immature waters are converted to neutral chloride
waters as encountered in deep wells and lateron to more dilute bicarbonate waters
discharged from surface springs.
CHEMICAL COMPOSITION OF VAPOR DISCHARGES

The chemical compositions of steam samples from the Zunil Geothermal Field are
given in Table 5 together with typical analyses from other fields in Guatemala for
comparison. The samples were collected and analysed by use of procedures described
by Giggenbach and Goguel (1989). For the 1987 samples from Paxmux and Fumarola
Negra (Table 3) only data for the gases absorbed into the alkaline condensate are
given.
An initial assessment of the possible origin of the gases is carried out in Fig. 11 on the
basis of relative N2, He and Ar contents. The samples from Zunil, representing a
wide variety of steam discharges from wells (Z3, Z5, Z6, Zll) and fumaroles (LF, PX,
FN, AZ) still cover quite a limited range halfway between the composition of
265
K)
Os
Table 5.- Composition of vapor discharcjes fr om the Zunil Geotherma 1 Fiela, in ^mol /mol .
Os
wells
260
Z3
280
Z5
280
Z6
Zll 250
fumaroles
ys
.30
1.0
.34
.43
1.0
C2
93
94
LF
1.0
93
PX
1.0
94
PX
1.0
1.0
94
FN
93
1.0
FN
91
AZ
1.0
81
1.0
AZ
San Marcos
SM
93
1.0
Tecuamburro
TA
95
1.0
Amatitln
LC
95
Moyuta
MC
97
H2
co2
H2S
NH3
He
Ne
H2
Ar
CH4
997
997
997
996
700
200
200
900
2192
2691
2682
2994
67
90
56
43
5.2
4.0
5.1
3.1
.0060
.0059
.0056
.0040
.00018
.00014
.00039
.00040
13.10
12.30
11.90
12.31
0.14
0.08
0.25
0.28
<.2
<.2
<.3
<.3
23
11
36
46
0.58
0.39
0.67
1.02
998
995
990
989
996
994
994
992
710
800
800
120
200
500
200
505
1230
3797
8942
10215
3620
5120
4843
6165
28
257
260
273
178
196
802
1143
6.5
1.3
0.3
<.l
0.3
<.l
0.3
0.6
.0061
.0206
-
.00051
.00118
-
1.31
40.65
-
0.30
0.76
-
33
101
0.44
2.77
-
.0534
-
.00330
-
3.60
-
2.94
-
0.6
<.2
<.9
-
389
20.00
-
.0248
.0296
.0353
.00121
.00116
.00053
35.40
0.46
0.38
1.10
0.70
0.60
0.8
<.3
<.9
139
151
186
6.98
0.46
0.98
1150 83
0.6
.0051
998 700
.00013
956 000
36740
5764
0.7
.1280 .01230
1.0
944 900
54300
110
7.7
.3700
.00055
1.0
994 400
5387
44
<.l
.0235
.00039
0.35
0.44
0.90
6.60
14.30 0.11
6.90
0.45
<.l
60
<.4 1480
606
<.6
0.20
3.52
19.3
162
0.05
N2/100
air
air saturated
water
10He
Fig. 11 - Relative N2, He and Ar contents in gases from the Zunil Geothermal System.
meteoric gases (air, air saturated water) and "andesitic" gases as defined on the basis
of a large number of volcanic gases from around the world (Giggenbach, unpublished
results). The similarity in relative N, He and Ar contents supports a common origin

of the gases within the Zunil system. The compositions of the gases from the San
Marcos (SM), Tecuamburro (TA) and Moyuta (MC) geothermal fields follow this
trend, typical of geothermal systems along convergent plate boundaries, that from
Amatitlan (LA) shows a somewhat increased He content.
Relative contents of the three quantitatively most important constituents of
geothermal vapors, Ô, CC>2 and ^S are shown in Fig. 12. Except for Paxmux,
data points for the Zunil field lie along a line indicating large variations in ^S
contents at close to constant CC>2 contents of about 0.3 mol-%. Well discharges and
C2, SM and MC show the lowest ^S content, the two low altitude fumaroles FN and
PX occupy intermediate positions, the highest relative ^S content is found for the
267
H2O/100
0-1
"/CO
30H2S
5
CO2 /H 2 S
Fig. 12 - Relative HÔ, CC^ and H2S contents in vapor discharges from Zunil.
sulfur depositing vent at Azufrales. The high I-^S content there corresponds to that of
similar S-depositing vents at Tecuamburro (TA). The repeat samples from Zunil
occupy very similar positions suggesting no major changes in the chemistry of these
gases over the period from August 1987 to November 1988.
The major causes of variations in CC^/I^S ratios of geothermal steam discharges are
differences in the solubility of the two gases, I-^S being three times as soluble as CC>2
(Giggenbach, 1980). Vapors boiling off from a deep liquid phase, therefore, are
initially enriched in CC^, the residual solution becoming enriched in IH^S. The wells
then are likely to tap little degassed water having travelled deeply without much
opportunity to lose gas. The fumaroles discharge vapors from probably more shallow
bodies of already degassed water. The validity of this assumption may be checked by
including a gas with an even higher solubilty contrast, such as

268
Because of its very low solubility, CH^ contents can be expected to be highest in
"early" vapors, very low in vapors from already degassed bodies of water. Relative
CH4, CC>2 and I^S contents are plotted in Fig. 13 together with lines representing
the composition of vapors and residual fluids formed on removal of the fraction of
steam, y, at 150 and 300C from a an original deep water with a composition close
that of the wells Z3, Z6 and Zll. The theoretical lines were calculated for closed
system, single step steam separation. The effects of temperature on the relative
position of the "early" and "late" steam separation lines are obviously quite small.
Separation of even very minor fractions of vapor, however, leads to marked shifts in
relative gas contents, especially at lower temperatures. Contrary to the findings
suggested by Fig. 12, PX and FN appear to represent very "early" vapor carrying much
of the little soluble CH^ while the vapor from Z5 is possibly derived from a body of
5000CH4
250
300
MC
350'
400'
30
20
\
10
10
30HoS
5
C0 2 /H 2 S
Fig. 13 - Relative CH^ CC>2 and H^S contents of Zunil vapor discharges. Lines are
shown illustrating the effects of vapor separation from the deep water DW, as
a function of y, the fraction of steam removed, in %, at 150 and 300C.
269
water having lost a few percent of vapor. The composition of vapors from the
Azufrales fumarole may indicate derivation from an extensively degassed deep water.
The above evaluation, of course, assumes that all the vapor samples are derived from
a common body of deep water with a uniform composition. There are however a
series of other processes which could have affected relative CH^ CC>2 and ^S
contents. One of the most obvious is re-equilibration of CH4/C2 ratios in response
to variations in temperature. Variations in this ratio are indicated in Fig. 13 in terms
of isotherms calculated by use of

tMC = (46257(10.4 + log(xCH4/xCo2))) -273
(6)
where tjyjc is the temperature for equilibrium of CH4 and CO2 with crustal rock
(Giggenbach and Goguel, 1989). According to this interpretation, the two gases in the
three wells (Z3, Z6 and Zll) and in C2 equilibrated at about 340. The apparently
higher temperature derived for Z5 is probably due to some earlier underground steam
loss, while the temperatures of 360 to 380 for the steam discharged from vents on
top of Domo El Azufral (AZ) may be indeed those in deeper zones. The lower
temperatures of 270 to 300 indicated for PX, FN and LF may reflect equilibration in
more shallow, cooler zones of the system.
Additional gas phase equilibration temperatures may be obtained by use of recently

derived relationships (Giggenbach and Goguel, 1989)
lo
g(xH2/xAr)
-014t - 2-5
(7)
and
log(xco /XAT) = 0.0277t - 7.53 + 2048/(t + 273)
(8)
where Xj are again the mole fractions as given in Table 5 and t is the temperature in
C. In Fig. 14 a line is shown representing equilibrium for both H2 and CC>2 in a

single liquid and a single vapor phase. Tie lines represent equilibrium mixtures of
liquid and fluid.

270
equilibrium vapor
-HA
HA=
1 '
0-
-1-
L CA =log(x c02 /x Ar )
5 . 6L
CA
Fig. 14 - Evaluation of temperatures of H2 and CC>2 equilibration with rock. Lines are
shown for attainment of equilibrium of the gases dissolved in a single liquid
and in a single vapor phase.
All the data points for the wells and for some of the steam vents (LF, FN) plot close
to the full equilibrium line at temperatures between 250 and 300C. For the more
outlying vapor discharges (C2, PX), H2-Ar temperatures are below CO2-Ar
temperatures possibly reflecting the different rates of equilibration of the two gases
with H2 being considerably "faster" than CO2 (Giggenbach, 1987). Apparent H2/Ar
and CO2/Ar temperatures for the fumaroles are lower than those of the deep wells
suggesting long residence times at lower temperatures, in agreement with CH4/CO2
temperatures (Fig. 13).
Table 6 gives the hydrocarbon contents xj of the Guatemalan thermal vapor
discharges. The mole fractions given may be converted to total discharge mol-fractions
Xj, in nmol/mol, according to

X
i = vs XCH4 xi
(9)
where ys and XCH are the steam fractions and CH4 contents given in Table 5.
271
Table 6.- Hydrocarbon contents of geothermal gases in Guatemala, in mmol/mol of
the hydrocarbon fraction.

met
ete
eta
pre
pra
ibu
nbu ipa
npa ben
toi
ebe
pmx o-x
Z3
Z5
969
980
4.0
1.4
8.8
4.6
1.4
0.4
1.5
0.8
0.2
0.3
1.2
0.8
0.8
1.0
1.5
1.2
3.9
4.0
1.5
0.9
0.9
0.7
1.0
0.9
0.8
0.7
Z6
978
1.1
8.5
0.8
1.2
0.4
0.7
3.7
0.5
0.3
0.4
0.4
Zll
535
<.5
42
135
219
57
C2
349
1.1
7.2
<.5
1.5
<.5
<.5
<.5
<.5
6.5
70
225
215
59
LF
988
<.3
2.7
0.4
<.3
<.3
<.3
<.3
<.3
1.3
0.5
1.4
2.5
0.8
PX
FN
AZ
993 .02 4.3 .01 1.0

990 < . 0 2 4.1 < . 0 2 0.9
970 <.5 3.1 <.5 <.5
0.2
0.2
<.5
0.2
.25
<.5
.05
.06
<.5
.05
.14
<.5
1.0
2.1
2.0
.08
.40
1.7
.03
.78
7.8
.07
.93
11
.02
.31
3.9
AZ
841
17
42
55
17
1.5
4.2
2.7
2.5
90
108
5.2
<.5
0.7
0.2
<.5
0.6
<.5
<. 5
<.5
<.5
<.5
3.8
<1
<.5
<.5
<.5
<.5
<.5
3.1
0.5
3.2
0.7
1.1
<.8
<.8
1.3
2.5
0.4
0.3
<.2
<.2
<.2
<.2
4.8
39
LC
940 <.5 3 0 . 8 <.5
Moyuta
7.6
0.9
1.9
0.5
0.5 13.6
1.4
1.8
1.3
<.5
<.5 3 8 . 3
7.9
9.3
16
San Marcos
SM
950
1.5
1.4
Tecuamburro
TA
707
2.9
36
Amatitlan
MC
910
3.2
met: methane
ete: ethene
eta: ethane
5.6
<.5
2.1
pre: propene
pra: propane
ibu: i-butane
0.7
<.5
1.2
4.0
nbu: n-butane
ben: benzene
pmx: p+m-xylene
ipa: i-pentane toi: toluene
o-x: o-xylene
npa: n-pentane ebe: ethyl benzene
Hydrocarbons in geothermal vapor discharges are largely derived from the

decomposition of sedimentary organic material subjected to increased, up to magmatic
temperatures. The presence of unsaturated and aromatic hydrocarbons in the Zunil

well discharges points to the existence of very high temperatures (<500C) of
interaction with sedimentary material (Giggenbach, unpubl. results).
Because of their higher solubility in water, aromatic hydrocarbons tend to accumulate

in residual waters, again allowing the differentiation between "early" and "late" vapors.
The very low contents of aromatic hydrocarbons in PX and FN, and possibly LF,
agrees with their position in the "early" vapor part of Fig. 13. Similar low contents in
the deep wells, Z3, Z5, Z6, would also classify them as "early" vapors. The extremely
272
high contents of aromatic hydrocarbons in the more shallow Cl water discharges Zll
and C2 can only be explained in terms of possible enrichment from percolating vapors
without affecting much relative CH^ >2 and IH^S contents. The comparatively high
contents in samples from Azufral, AZ, agrees with their possible "late" nature as
already indicated by Fig. 13. Generally speaking, the hydrocarbon contents of all the
Guatemalan vapors are those expected for geothermal systems closely associated with
volcanic-magmatic systems.
The chemistry of gases associated with fluid discharges fom the Zunil Geothermal
Field suggests an essentially magmatic, or more specific "andesitic" origin. Gas
equilibration temperatures are close to those measured in the wells or higher pointing
to the possible presence of higher temperature zones within the system.
GEOCHEMICAL MODEL OF THE ZUNIL GEOTHERMAL SYSTEM

The evolution of fluids with close volcanic-magmatic associations generally proceeds
along the sequence magmatic vapor - acid chloride - msulfate waters - neutral
chloride water - bicarbonate water. Accepting this general pattern also for Zunil, both
chemical and isotope evidence clearly show that the first step, the conversion of
magmatic vapors to acid waters occurs within the andesitic structures of Domo El
Azufral and Cerro Zunil, to the SW of the discharge area. The next step, the
conversion of the initial acid waters takes place during further movement of the
waters to the north and west.
The driving force behind the upward movement of thermal waters is the buoyancy
caused by the density difference between hot thermal and surrounding groundwater.
The level to which the waters are able to rise is determined by the static groundwater
level. In the case of Zunil it is likely to be defined by the level od the Samal river.
Any water rising within the El Azufral - Cerro Zunil Complex will spread out to reach
the surface at the nearest hydrological low, the bed of the Samal River. Steam may
273
boil off from the spreading tongues of hot water as they approach the surface to
reach the surface as fumaroles or steaming ground. Vapors generally rise close to
verticallty thus marking the epicenters of deeper boiling zones.
Relative HCG^/Cl ratios of the bicarbonate waters correspond closely to CC^/Cl

ratios in the waters supplying the deep wells. The HCC>3 waters, representing most of
the natural thermal water discharge from the Zunil Geothermal Field, then are most
likely to have formed through virtually quantitative conversion of CC>2 to HCO by
interaction with rock preceding or following about tenfold dilution with groundwater
The incresased sulfate content of these waters may be due to admixture of some of
the immature acid sulfate waters (S3, S4) at shallow levels or incomplete "maturation"
of the more primitive, deep parent water.

The extent of the deep body of high temperature waters can be expected to be
delineated by the occurrence of hot springs and vapor discharges. To the NW the
limit of the field is likely to be marked by the Los Vahos vapor discharges, to the N
by the Almolongo bicarbonate springs. The inferred flow paths of the waters
compatible with isotopic and chemical evidence is marked in Fig. 1 by arrows, the
likely distribution of the waters underground is shown in Fig. 15.

The model was constructed by assuming uniform and isotropic permeability conditions
underground and therefore is likely to represent only the potential distributuion of
fluids within the system. The actual distribution is largely governed by generally
unknown geological factors such as the nature and distribution of igneous and
sedimentary rocks and the presence and rate of formation of faults and fissures
facilitating fluid movement. Isotherms were drawn by assuming conductive heat
transfer and a thermal gradient of 50/km outside the actual geothermal system. The
hydrothermal system is assumed to be associated with a body of cooling magma

beneath the El Azufral - Cerro Zunil complex. On the basis of models drived for the
White Island (Giggenbach, 1987) and Nevado del Ruiz (Giggenbach et al., 1990)
274
NW
C CANDLARIA
LLANO DEL FINAL
LosVohos
chloride waters
liquid+vapor
sulfate waters
-2-
10 (km)
-=
Fig. 15 - Cross-section through the Zunil geothermal system along line N W - SE of

Fig. 1. The distribution of fluids is that indicated by the geochemistry of the
fluids discharged.
volcanoes, the magmatic system is assumed to be surrounded by an extensive twophase, vapor-brine envelope. It provides the environment for initial conversion of
magmatic fluids to acid brines. Over the upper slopes of Domo El Azufral, the vapors
released from deeper primitive waters reach the surface leading to the formation of
extensive patches of steaming ground, the deposition of elemental sulfur and the
formation of the acid sulfate waters S3 and S4. At greater distance, continuing
intertaction with rock leads to the neutralisation of the acid waters, removal of most
of the magmatic sulfur in the form of alteration minerals such as sulfates (alunite,
anhydrite) and sulfides (pyrite). Much of the neutral Cl water appears to remain
stored underground. A small fraction was discharged naturally from spring Z-20 (Cl)
or is discharged in diluted form from the bicarbonate springs.
According to Fig. 15, the major upflow zones of thermal waters lie to the east of
Samal River. Because of permeability problems encountered over the present

production area to the west, exploratory drilling to the east should be considered
275
seriously. The choice of drillsite is largely a function of accessibility and depth to the
production zones. Another limiting factor which has to be taken into account when
drilling close to Domo El Azufral, is the possible ingression of immature, acid

waters both at shallow and deep levels. The potential for such ingression is likely to
increase with decreasing distance to the Azufral Dome. The position of drillsites
representing possibly the best compromise are indicated in Fig. 1.
ACKNOWLEDGMENT
The present investigation was carried out within the framework of the IAEA
Coordinated Research Program on the "Application of Isotopic and Chemical

Techniques to Geothermal Exploration in Latin America" (GUA/8/009-2) with
financial support from the Government of Italy.
REFERENCES
Adams M C, Mink L L, Moore J N, White L D and Caicedo A, 1990a: Geochemistry
and hydrology of the Zunil Geothermal System, Guatemala. Geoth. Res.
Council, Trans., 14, 837 - 844.
Adams A, Goff F, Trujillo P E, Counce D, Medina V, Archuleta J and Dennis B,

1990b: Hydrogeochemical investigatios in support of well logging operations
at the Zunil Geothermal Field, Guatemala. Geoth. Res. Council, Trans., 14,
829 - 835.
Bethancourt H R and Dominco E, 1982: Characteristics of the Zunil Geothermal

Field (Western Guatemala). Geoth. Res. Council, Trans., 6, 241 - 244.
Caicedo A and Palma J, 1990: Present status and development of the geothermal
resources of Guatemala. Geoth. Res. Council, Trans., JA, 97 - 105.

276
Craig H, 1963: The isotopic geochemistry of water and carbon in geothermal areas.
In: Nuclear Geology on Geothermal Areas, CNR, Pisa, 17 - 53.
Foley D, Moore J N, Lutz S J, Palma J C, Ross H P, Tobias E and Tripp A C, 1990:

Geology and geophysics of the Zunil Geothermal System, Guatemala. Geoth.
Res. Council, Trans., 14, 1405 - 1412.
Fournier R O, Hanshaw B B and Urrutia J F, 1982: Oxygen and hydrogen isotopes in

thermal waters at Zunil, Guatemala. Geoth. Res. Council, Trans., 6, 89 - 91.
Giggenbach W F, 1980: Geothermal gas equilibria. Geochim. Cosmochim. Acta, 44,

2021 - 2032.
Giggenbach W F, 1987: Redox processes governing the chemistry of fumarolic gas

discharges from White Island, New Zealand. Appl. Geochem., 2, 143 - 161.
Giggenbach W F, 1988: Geothermal solute equilibria. Derivation of Na-K-Mg-Ca

geoindicators. Geochim. Cosmochim. Acta, 52, 2749 - 2765.
Giggenbach W F, 1991: Isotopic shifts in waters from geothermal and volcanic systems
along convergent plate boundaries and the origin of "andesitic" water. Earth
Planet. Sei. Let.,
Giggenbach W F and Goguel R K, 1989: Collection and analysis of geothermal and
volcanic water and gas discharges. DSIR Chemistry Report CD 2401, pp 82.
Giggenbach W F and Stewart M K, 1982: Processes controlling the isotopic
composition of steam and water discharges from steam vents and steam
-heated pools in geothermal areas. Geothermics, 11, 71 - 80.
277
Giggenbach W F, Garcia N, Londono A, Rodriguez V, Rojas G and Calvache M,

1990: The chemistry of fumarolic vapor and thermal spring discharges, from
the Nevado del Ruiz volcanic-magmatic-hydrothermal system. J Volcanol.
Geotherm. Res., 42, 13 - 39.
Goguel R L, 1983: The rare alkalies in hydrothermal alteration at Wairakei and

Broadlands geothermal fields, New Zealand. Geochim. Cosmochim. Acta, 47,
429 - 437.
INDE, 1978: Proyecto Zunil, Informe Geoquimico, pp. 65.
Lloyd R M, 1968: Oxygen isotope behaviour in the sulfate-water system. J. Geophys.

Res., 73, 6099-6110.
Menzies A J, Granados E E, Sanyal S K, Mink L L, Merida L and Caicedo A, 1990:
An integrated test program for the definition of a high temperature

geothermal reservoir: a case study from the Zunil Geothermal Field,
Guatemala. Geoth. Res. Council, Trans., 14, 1233 - 1239.
Mizutani Y and Rafter A T, 1969: Oxygen isotopic composition of sulfates. NZ J.

Science, 12, 54 - 59.
Robinson B W, 1973: Sulphate - water and I-^S isotope geothermometry in New
Zealand geothermal systems. 4th Int. Conf. Geochronol. and Isotope

Geochem.. USGS Open File Report, 78-710, 354 - 356.
Taylor S R, 1964: Abundance of chemical elements in the continental crust, a new
table. Geochim. Cosmochim. Acta, 28, 1273 - 1285.
278
INVESTIGACIONES GEOQUMICAS REALIZADAS EN

LOS CAMPOS GEOTRMICOS DE ZUNIL Y AMATITLAN,
GUATEMALA
A.R. ROLDAN MANZO
Unidad de Desarrollo Geotrmico,
Instituto Nacional de Electrificacin,
Ciudad de Guatemala, Guatemala
Resumen-Abstract
INVESTIGACIONES GEOQUMICAS REALIZADAS EN LOS CAMPOS GEOTRMICOS DE ZUNIL Y
AMATITLAN, GUATEMALA.
Los estudios geotrmicos en Guatemala se iniciaron en 1971 en el

campo geotrmico de Moyuta. En 1981 OLADE realiz un estudio
regional determinando trece zonas de inters geotrmico.
Zunil y
Amatitln, analizados en este estudio, fueron clasificados dentro

del grupo A o de prioridad uno.
Las aguas de Zunil se clasifican segn tres tipos: cloruro-sdicas,

neutras o bicarbonatadas y acidas. Anlisis de gases indican origen
meteorice y magmtico, con recarga local, y la existencia de dos
acuferos diferentes.
Anlisis
isotpicos evidencian origen
profundo y un tiempo de residencia para el agua de aproximadamente
200 aos.
Geotermmetros de aguas, gases e istopos proporcionan
temperaturas entre 180 y 400C.
Por medio de prospecciones de
mercurio y radn se identificaron zonas de alta permeabilidad.

Las
aguas
de
Amatitln
se
clasifican
segn
dos
cloruro-sdicas y bicarbonticas.
Anlisis isotpicos
grupos:
sugieren
origen profundo y un tiempo de residencia mayor de 100 aos.

Anlisis de gases indican origen magmtico. Geotermmetros de
cationes proporcionan temperaturas de 240 a 245C, mientras que las
temperaturas de equilibrio para gases van de 220 a 300C. Estudio
de
radn
evidencia
anomalas
con
orientacin
NO-SE
las
cuales
indican un rasgo estructural profundo.
GEOCHEMICAL INVESTIGATIONS IN ZUNIL AND

GUATEMALA.
AMATITLAN GEOTHERMAL FELOS
Geothermic studies in Guatemala began in 1971 in the Moyta

geothermal field. In 1981 OLADE realized a regional study, finding
13 reas as geothermal prospects. Zunil and Amatitln, object of

this study, were classified in group A (priority one).
The Zunil waters are classified in three groups: sodium-chloride,
bicarbonate or neutral and acid.
Gas analysis shows magmatic and
meteoric origin with local recharge and two different reservoirs.

Isotopic analysis yields deep origin and a residence time of
aproximately 200 years. Water, gas and isotopic geothermometers
279
yield temperatures between 180C

surveys show high permeable zones.
and 400C.
Mercury
and
Radon
The Amatitlan waters are classified in two groups: sodium-chloride

and bicarbonate. Isotopic analysis suggests deep origin and a
residence time greater than 100 years. Gas analysis yields magmatic
origin. Cation geothermometers yield temperatures from 240C to
245C and gas equilibrium temperatures ranging from 220 to 300C.
Radon surveys show anomalies NW-SE oriented which could correspond
to a deeper subvolcanic structure.
1.
INTRODUCCION
Dentro
de
la
bsqueda
de
fuentes
alternas
de
energia
para
contrarrestar los elevados precios del petroleo, en Guatemala, se

iniciaron las investigaciones geotrmicas en el ano de 1971 a traves
del Proyecto Minero de las Naciones Unidas conjuntamente con la
Direccion General de Mineria e Hidrocarburos. Posteriormente, el
Institute Nacional de Electrificacin (INDE) ha sido el responsable
de la investigacin geotrmica en el pais; los primeros estudios se
efectuaron en el rea de Moyuta, de 1971 a 1976. En el rea de
Zunil, las investigaciones se iniciaron en 1973, con la colaboracin
de Japan International Cooperation Agency, llegando a concluir en

1976 que Zunil es un rea de alto potencial para el desarrollo de la
energia geotrmica (JICA, 1977).
En 1981 OLADE efectu un estudio rgional en el rea limitada al
norte por la falla del Motagua, al sur por la costa del Pacifico, al
oeste por la frontera con Mexico y al este por la frontera con El
Salvador. Como resultado de este estudio se definieron trece zonas
de inters geotrmico clasificadas en trs diferentes grupos. Los
campos de Zunil y Amatitln, objeto de este estudio,
fueron
clasificados dentro del grupo A o de prioridad uno. (Figura 1).
2.
CAMPO GEOTERMICO DE ZUNIL
El campo geotrmico de Zunil esta situado al oeste de la ciudad de

Guatemala a aproximadamente 218 km por carretera asfaltada, a una
280
00
FIG. 1. Localization de los campos geotrmicos de Zunil y Amatitln.
altura de 2000 ra.s.n.m.
La temperatura ambiente vara entre 15 y
20C, la precipitacin promedio anual es de 2000 mm, mientras que la

evapotranspiracin es de 750 mm por ao.
El campo ha sido dividido en dos reas: Zunil 1, donde se instalar
una planta generadora de 15 MW y Zunil 2 donde actualmente se
efectan estudios de prefactibilidad. (Figura 2).
NW
O AGUAS CLORUROSODICAS
O AGUAS BICARBONATADAS
O AGUAS SULFATADAS
O FUMAROLAS
FIG. 2 Locahzacin de muestras seleccionadas en el

campo geotrmico de Zunil y delimitacin de las reas
de Zunil 1 y Zunil 2.
2.1
GEOLOGA
Zunil se encuentra localizado en el borde sur de la depresin de
Quezaltenango, considerada una caldera de edad terciaria precedida

por un volcanismo efusivo del tipo andestico dactico.
Se trata
de un graben de unos 3 kms de ancho con direccin noreste-suroeste
formado por un sistema de fallas a lo largo del cual se localizan
los domos Cerro Candelaria, Cerro Quemado y el Volcn Zunil.
El basamento es de naturaleza grantica y granodiortica de edad
cretcica, sobreyaciendo discordantemente un fuerte espesor de lavas
andesticas y piroxnicas de edad terciaria, tobas y brechas

tobceas, tobas riolticas, tobas soldadas, lahares, flujos
riodacticos y flujos baslticos con espesor entre 800 y 1000 m.
(Figura 3).
282
COMPLEJO DOMICO DEL CERRO

QUEMADO
RIODACITAS DOMO LA PEDRERA.
GRABEN DE ZU L
COMPLEJO OE ROCAS
VOLCNICAS TERCIARIAS
ANDESITAS DOMO EL AZUFRAL. P5RH ROCAS METAMORFICAS,
ROCAS PIROCLASTICAS RECINTES.
RTCpn COMPLEJO ROCAS VOLCANIIS&ICAS TERCIARIAS.
ANDESITAS Y LAVAS DEL DOMO

CERRO QUEMADO.
ROCAS INTRUSIVAS.
PTP,LAVAS RECENTES
HDEL DOMO ZUNIL.
FIG. 3. Geologa del rea geotrmica de Zunil (Tobas, 1977).
2.2
GEOQUMICA DE FLUIDOS
Como producto de las primeras investigaciones, se localizaron 70

manantiales los cuales fueron qumicamente analizados y 20 de ellos
son analizados mensualmente hasta la fecha. Seis pozos productores

han
sido
analizados.
perforados
desde
1980 y
sus
fluidos
qumicamente
Las aguas de Zunil se clasifican en tres tipos (Tabla 1
y Figura 4) cloruro-sdicas (con alto contenido de Na y Cl )

neutras o bicarbonatadas (con alto contenido de HCO ) y acidas
(con alto contenido de SE~) (Giggenbach 1988, Bethancourt 1978,
JICA 1977).
Se considera que las aguas del tipo cido provienen del
calentamiento de las aguas superficiales por vapor de origen

profundo, rico en sulfates y que las aguas bicarbonatadas son el
producto de aguas superficiales calentadas por conduccin, mientras
que las aguas cloruro sdicas tienen un origen profundo.
283
T A B L A
COMPOSICIOH QUMICA DE FOJOS 1I HARAHTIALES DEL CAMPO GEOTEBMICO DE 20NIL (ig/kg)
(Giggenbach 1988)
INDE o.
pH
HCO, SiOj
S04
Cl
re
951
889
580
31
0.51
51
157
41
61
105
1810
1700
1740
A
A
96
404
210
728
(.05
3.4
4.7
4.7
4.6
2.5
0.09
<.05
(.05
(.05
(.05
(.05
(.05
79
140
259
340
463
491
501
503
160
132
138
161
194
196
200
146
64
22
103
129
210
194
193
235
31
57
101
114
180
163
168
71
A
B
B
A
A
A
B
9
8
7
0.3
(0.1
0.2
0.08
0.06
4.40
74
69
38
28
52
22
15
15
20
B
B
B
76
104
43
72
0.2
(0.1
1.8
1.7
6.70
42.0
59.0
39.0
15
10
7
8
B
8
A
A
Li
Ka
Bb
Cs
Ca
8.70
8.10
6.31
933
1028
1092
231.0
212.0
101.0
2.33
1.89
0.55
2.02
2.01
2.36
.012
.040
.070
15
11
30
40.0
45.0
50.8
545
51.1
0.3
26.2
0.02
0.02
0.03
0.05
0.07
0.07
0.08
0.09
.003
.012
.027
.037
.030
.022
.025
.019
11.6
5.4
5.9
18.1
36.2
40.5
45.2
30.8
22
11
17
25
42
41
43
18
0.7
1.3
2.8
0.01
.002
(.01 (.002
0.01 <.002
5.6
3.8
3.6
Al
Pozos (vertedero)
K3
CQ-3
92 8.1
2CQ-6
92 8.4
-1I 144 7.8
(UDantiales cloruro sdicos

Cl
J - 2 0 89
9.0
2.70
Aguas bicarbonatadas
0.13
0.18
0.28
0.37
0.56
0.56
0.57
0.91
79
65
166
199
286
372
258
157
(.01
(.01
(.01
9
8
16
4.4
3.3
SI
S2
S3
S4
ZP-38
91 2.1 0.12
2 - 3 6 90 3.1 0.06
Z-19
56 2.10.05
2-31
74 2.00.07
43
80
89
134
14.5
7.7
30.9
32.3
0.04
0.04
0.11
0.23
.009
.009
.004
.010
18.9
45.0
14.6
28.3
AR
Soca proiedio
3.00 2400
2100
15.0
.500
2300 4200
Bl
B2
1-23 40
2 - 2 9 50
9.2
7.0
B3
Z-4
63
7.0
B4
B5
S-9
62
!-17 70
8.4
7.8
B6
B7
2-10 67
M3
87
8.7
8.7
B8
2 - 1 5 64
6.1
7.4
10.0
12.2
18.6
37.2
36.6
27.3
19.0
Aguas s u p e r f i c i a l e s
El
82
IB-1A
ZE-2A
18
16
7.0
7.1
B3
IB-16
18
6.1
5.9
56
18
Aguas sulfatadas
Befereccias:
A.
DS1R
B.
C.
pB, flCOj, SO,, Cl

INDE
284
INDE
242 117
292 633
209 1600
287 2060
-
AGUA PROFUNDA
NEUTRALIZADA
COMPLETAMENTE
lADA
HC03
FIG. 4. Diagrama CI-HCO3-S04 para las aguas de Zunil

(Giggenbach, 1988).
Varias
zonas de fumarolizacin activa se
localizan en el campo
geotrmico de Zunil y son denominadas: Fumarola Grande o Zona del
Geiser, Fumarola Negra, Fumarolas de Paxmux, Los Vahos, Alteracin

Hidrotermal La Cascada y Fumarolas de las Fresas (Tobas 1971,
Figura 2).
Alteracin hidrotermal se observa en las reas
adyacentes a las fumarolas, donde la roca original se ha
transformado produciendo minerales arcillosos y oxidaciones
ferromagnesianas,
se
observa
especialmente
caolinizacin
y
silicificacin; depsitos de azufre nativo se encuentran en al rea
de Las Fresas, mientras que en la Fumarola Negra se ha localizado
mercurio.
Anlisis
de
gases
muestran
un
bajo
condensables
(0.85%
aproximadamente)
contenido
principalmente
de
gases
CO*
no
H i S.
Las concentraciones relativas de nitrgeno, helio y argn indican

origen tanto meteorice como magmtico indicando la existencia de dos
acuferos diferentes (Figura 5 y Tabla 2). Esta tesis fue propuesta
inicialmente por OLADE (1982) considerando que existe un acufero
superficial producto de la dilucin de aguas provenientes de un
acufero profundo con elevada temperatura.
285
TABLi
CONPOSICIO DEL VAPOR DEL CAKPO GEOTRMICO DE IDIIL
(liol/iol o ppi por voluien!
(Giggenbach 1988)
HDE Do. C
!3
26
!5
111
LF
PI
P
AZ
2CQ-3 138 0. 30
ICO.-6 123 0. 34
- 1.00
2CQ-5
2-11
144 0. 43
FRESAS
94 1.00
PAIMD
93 1.00
F.IEGEA 94 1.00
AiDFRAL 91 1.00
IKDE Do.
3 2CQ-3
26 2CQ-6
25 2CQ-5
211 Z-ll
LF
PI
PN
AI
Is
He
.00018
.00039
.00014
.00040
FRESAS .00118
PAIHO
F. NEGRA
A20FRAL .00116
C02 H2S B,
997700 2192
997200 2682
997200
996900
995800
990800
996200
994200
2691
2994
3797
8942
3620
4843
Bj
Ar
13 .10
11 .90
12 .30
40 .65
40 .65
0 .46
0. 14
0. 25
0. 08
0.28
0. 76
Oj
0.2
0.3
0.2
0.3
0.2
0. 70 0.3
He
67 5 .2 0.0060
56 5 .1 0.0056
90 4.0 0.0059
43 3 .1 0.0040
257
260
178
802
1 .3 0.0206
0.3
0 .3
0 .3 0.0296
CH,
23 0.58
36 0 .67
11 0.39
46 1.02
101 2 .77
151 0.46
-4.88
-4.92
-4.91
-4.91
-4. 39
-
-6. 33
AIRE SATURADO CON

AGUA SUBTERRNEA
OH*
FIG. 5. Diagrama N2-Ar-He para los gases de Zunil

(Giggenbach, 1988).
286
Anlisis isotpicos fueron efectuados inicialmente para determinar

el origen de la recarga en el campo de Zunil (Fournier y Hanshaw
1981) concluyendo que la recarga es de origen local. Anlisis
posteriores (Giggenbach 1986) confirman la tesis de Fournier y
Hanshaw, y en base a los mismos, Giggenbach propone una hidrologa
tentativa del campo geotrmico de Zunil, la cual se muestra en la

Figura 6. Un modelo diferente fue desarrollado por West Jec (1990)
en base a los estudios de prefactibilidad efectuados en el rea de
Zunil 2 (Ver figura 7). Los resultados isotpicos muestran un
enriquecimiento de 18O entre 2.2 y 5%o (Giggenbach 1988, Cordn y
Marida & M K Ferguson 1990), lo cual evidencia un origen profundo
luego de un equilibrio agua-roca; asi mismo puede observarse la
existencia de aguas calentadas por vapor (Tabla 3 y Figura 8). El
tiempo de residencia ha sido calculado en base al contenido de
tritio (1.3 Unidades de Tritio en promedio) utilizando la ecuacin
de Pearson y Truesdell en aproximadamente 200 aos (Cordn y Marida
& M K Ferguson 1990.
2.3
GEOTERMOMETRIA
Diversos geotermmetros han sido aplicados en el campo geotrmico de

Zunil los cuales revelan temperaturas dentro del rango de 180a
400C. Utilizando los geotermmetros de cationes, se considera la
existencia de dos acuferos (OLADE 1982) como fuera mencionado en el
prrafo 2.2; uno profundo a temperatura de aproximadamente 260C, y
otro ms superficial, producto de la dilucin del primero, a una
temperatura de 210C. Estas temperaturas han sido confirmadas en

los pozos exploratorios y se sugiere que el acufero puede presentar
mayor
potencial
a mayor profundidad.
Geotermmetros
de gases
aplicados a muestras provenientes de los pozos (Giggenbach 1986)

confirman la existencia de altas temperaturas en profundidad
(superiores a 200C),zlas cuales se han obtenido adems aplicando
geotermmetros isotpicos, (West-Jec 1990) y cuyos resultados
aparecen en la Tabla 4. Los valores ms altos se obtienen con los
istopos de carbono,
cuyos valores
corresponden a niveles muy
profundos, revelando que la temperatura se incrementa dentro del

basamento.
287
NW
C CANDELARIA
LLANO UL. PIAL
chlondewcters
haud-t vapor
sul'ate waters
lO(k-n)
Hidrologa tentativa del sistema geotrmico de Zunil, compatible con la

composicin qumica e isotpica de los fluidos descargados (Giggenbach,
1988)
chlonde waters
J bicarbonate
sulfate wate
^/ fumoroles
proposed dnlls
3 km
Trayectorias de flujo de las aguas propuestas por W.F. Giggenbach (1988)
FIG. 6. Modelo hidrogeoqumico del campo geotrmico de Zunil

propuesto por Giggenbach (1988).
288
NO
Altura (m)
Volcan
Cerro Quemado
Altura
Azufrles
Fuentes Gaoramos
3,000 -,
SE
(m s.n.m)
Volca'n de Zunll
- 3.000
- 2,000
- 1,000
otro)~400C
Qiniolltnongo-Conll(7)T
pora Loa Sim<ji t Zunll-l

Almolonga y Funiorola Ntgro-Grond
Flujo de fluidos
subterrneos
>
Fluo de agua frfa
Flujo de vopor
Flujo de ogua callente
~~~
Flujo de aguo calentado poi
profunda del tipo Cl
SO
Altura
Aguas Amargas
3.000 Agua caliente

del tipo SO,
rFumarolo Grande del tipo Cl

I
Fumarola Negro
Zona de mezcla \
Agua callente
del tipo HCO,
2,000
1,000
Agua co'ivnh
d*l tipo Cl C-HCOj)

Ara d* recarga
paro lot >litmo

d lo Fumarolo Noro y
rumorlo Crond*
~*
Coi mogmaHco (C02
y olrot)
Flujo de fluidos
subterrneos
:
Flujo de aguo fna
Flujo de aguo callente
profunda del upo Cl
- -* :
:
Flujo de vapor
Flujo de agua
calentada por vapor
FIG. 7. Modelo hidrogeoqumico del campo geotrmico de Zunil

propuesto por WEST-JEC (1990).
289
TABLA
COMPOSICIOH ISOTPICA I COHTEHIDO TOTAL DE Cl 1 SO, DE

POSOS HASAIIT1ALBS DEL CAHPO GEOTRMICO DE SOSU
(mg/Kg)
(Giggeabacb 1988)
ISDE 8o. 1,
"0
0/00
0/00
fi
Cl
S04 REP
o/oo ig/kg ig/kg
Pozos
CC-3 0.63 92
JCQ-6 0.63 92
1
N2
K3
-11
0.5?144
-8.74 -79. 3 1.3 1140 20 A

-8. 36 -75. 9 1.3 1070 38 A
-7.25 -70. 1 992 60 B
Manantiales cloruro sdicos

Cl
-20
93
-8.20
1.1
700 202 C
-90
Aguas bicarbo Datadas
J-23
-29
-4
-9
-17
-10
-13
-15
Bl
B2
B3
B4
B5
B6
B7
B8
40
50
63
62
70
67
87
64
-11. 59
-10. 38
-10. 75
-11. 39
-11 30
-li 89
-11 54
-11.05
-85. 2
-77. 0
-79. 7
-77. 5
-83. 3
-84. 1
-84. 7
-82. 4
1.1
1.2
0.0
31 64 B
57 22 A
101 103 A
4 129 B
1.1
0.3
180
163
165
71
210
194
193
233
56
18
-
A
A
117
633
1600
2060
3.2
B
B
B
A
-12
FIG. 8. Relacin de deuterio-oxgeno 18 (A) y

sulfato-oxi'geno 18 (B) para las aguas de Zunil
(Giggenbach, 1988).
Aguas superficiales
Bl
R2
R3
R-1A
R4
LLOVA
!R-2A
ZR-16
TA BLA
18
16
18
-
-11.64
-12.23
-12 22
- 8 .47
-84 7
-85 7
-85.4
-55.3 4.8
15
15
20
91
90
56
74
- 7 .25
- 7 .58
- 9 .38
-10 .02
-70.6
-67.4
-75.8
-80.7
15
10
7
8
TEMPERATURAS GEOQUMICAS BR C BASADAS

ES ISTOPOS Y GASES (HjS-Bj-CH.-COj)
EN EL REA DE ORIL. (NEST JEC 1990)
Aguas sulfatadas
SI
S2
S3
S4
ZP-38
Z-36
H9
-31
290
Azfrales
8.- DSIR
c.-
Pournier and Baaba* 119811
CARBOR OIIGHO
HIDROGEHO GASES
CO 2-C8 HjO-CO, Bj-CB4;HjO-B2
B
B
ZCQ-3
Referencias:
A.- IAEA
LOCALIZACIOS
Puentes Georginas
Chuitziquin
Puentes Gergicas
Los Vahos
Los Vahos
Azufralito
Las Presas
Puiarola Segra
Panui
383
320
344
339
378
272(304)
174
14311451
282
140(157)
...
208
358
288
399
364
267
263
125(205)
164(206)
157(186) 163
138
175 329
249
227
...
291
...
146
188
249
334
248
2.4
PROSPECCIONES DE MERCURIO Y RADON
Tanto el mercurio como el radn estn relacionados con procesos de

actividad
geotermal
profunda
(Tobas
1987,
Koga
1989)
prospeccin de los mismos es ampliamente utilizada para determinar

zonas de ascenso de fluidos hidrotermales al localizar fallas y
fracturas activas (Gutierres y Lpez 1983, West Jec 1990).
La primera prospeccin de mercurio en el rea de Zunil fue efectuada
en muestras de agua y arcillas por Japan International Cooperation
Agency (1973), encontrando valores altos de mercurio (33 a 690 ppm)
principalmente en el rea de la Fumarola Negra. Se reportan adems

valores relativamente altos en la zona de Fuentes Georginas. En el
rea de Zunil 1, el consultor Cordn y Marida & MK Ferguson (1989)
efectu un estudio de mercurio en suelos, analizando 47 muestras a
66 cm de profundidad. Los valores encontrados varan de 55 ppb a
3.42% con los valores ms altos entre los pozos ZCQ3, ZCQ5 y ZCQ6,
incluyendo reas de fumarolizacin activa; adems, la distribucin
de los valores altos de mercurio indica la existencia de fallas
permeables con orientacin NE y NO. (Ver Figura 9). Finalmente,
00o
SSO
LOCALIZACION DE MUESTRAS CON CONCENTRACIONES DE MERCURIO EN PARTES POR BILLN,

EXCEPTO CUANDO SE INDICA.
^~-^
FALLA MODIFICADA, DE FOLEY (1,989)', DISCONTINUA DONDE SE I N F I E R E ,
00
POZO PRODUCTIVO.
FIG. 9. Isoconcentraciones de Hg en el rea de Zunil 1 (Cordn y Mrida, 1990).
291
la
N>
\O
K>
Ceri(o El Galpago
i
i
Las Majadas
~, v
abor Pa|omaiuyup~\\
^=g^^
^\
Tuncenlro Fuenles Georgmas
La Estancia
de la Cruz
x 2700m
FIG.
10. Anomalas de mercurio y radn en el campo geotrmico de Zunil (WEST-JEC, 1990)
como parte del estudio de prefactibilidad del rea de Zunil 2, la

firma consultora West Jec realiz prospecciones de mercurio y radn,
habindose analizado mercurio en suelo, mercurio en el aire del
suelo y radn, torn y radn total en el aire del suelo. Los
resultados indican que las anomalas de mercurio estn orientadas en
direccin ESE-ONO y que las mismas coinciden con las anomalas de
radn y con una zona de baja resistividad determinada por el estudio
CSMAT.
Las
zonas
anmalas
encontradas
en
este
estudio
pueden
observarse en la Figura 10.
3.
CAMPO GEOTRMICO DE AMATITLAN
El campo geotrmico de Amatitln se localiza aproximadamente a unos

28 kms al sur de la ciudad de Guatemala dentro de los municipios
Amatitln, San Vicente Pacaya y Villa Canales (Figura 1).
Las
alturas dentro del rea varan de 1,188 m.s.n.m. (nivel del lago del
mismo nombre) hasta mayores de 1,800 m.s.n.m. (Laguna de Calderas).
El lago Amatitln recibe el agua proveniente de la cuenca del ro
Villalobos y descarga hacia el Pacfico por medio del ro
Michatoya. La temperatura media anual es de 22C, se tiene una
precipitacin promedio
potencial de 800 mm.
3.1
de
1,400 mm
una
evapotranspiracin
GEOLOGA
Geolgicamente, Amatitln se ubica en el extremo sur del graben de
Guatemala dentro de una caldera de origen cuaternario antiguo, donde

actualmente se encuentra el lago del mismo nombre.
El rea
geotrmica se localiza en la parte norte del complejo dmico del
Pacaya, la cual est limitada al oeste por la falla de Mixco, al
este por la falla de Santa Catarina Pinula y al norte por la falla
de Amatitln. Un sistema de fallas con orientacin norte-sur
formado por las fallas Mal Paso, Laguna Seca, Los Humitos y otras
menores atraviesa el campo.
Estratigrficamente la zona tiene lavas
andesticas, andesitas baslticas,
lahares y lavas intermedias del
293
perodo
terciario;
dmicas
dacticas
piroclsticos
del
sobreyacen
y
ellas
riodacticas,
perodo
lavas
lavas
cuaternario.
andesticas,
bsicas
El
del
basamento,
rocas
Pacaya
cretcico
superior y de naturaleza grantica, se encuentra discordantemente

bajo las vulcanitas terciarias.
Los domos El Limn y La Mariposa,
ubicados al suroeste del lago, son del tipo riodactico y sugieren

la formacin de cmaras magmticas como probable fuente de calor del
campo geotrmico.
En el extremo sur de la caldera se encuentra el
volcn Pacaya, actualmente en actividad, el cual est formado por
basaltos diferenciados. Cercano al Pacaya hacia el noreste, se

localiza el Cerro Grande de composicin andestico-dactica. (Tobas
1987, Figuras 11 y 12).
DEPRESIN VOLCANO-TECTNICA
DE
COTA
Im 3 n m )
2500
AMATITLAN
Crro C h i n o
Fallo de
2000
AmotitlOfl
I50O
1000
500
Kg(?>
O
Tv o Kg ( basamento grantico)
-500
-1000
15 Kms
DISTANCIA
LEYENDA
Qc
oo | Aluvin y Cokivlo'n
Lovat basltico de I
Qb
Qr-d
Qp
M volcan de P o c o y a
a.
Sedlmnto lacustres
estratificado*
F u m a r e la
Qc
Conglomerado arenoso
(paleo- aluvldn)
Manantial c a l i e n t e
ft111 > ' I Lavas micas nodaclticas
I ' "j f doclticas
Ta
f < < i Productos plroclo'sticos (pmez,
Tv
IIyI*vl
I ****!
6ron
I* * ' bloques de lava, paleosuelos )

!.. I Lavas andejtlcoi del
l.'.'.'.'l velcon ancestral
I] Lava* t e r c i a r l a s andeeltlcos
r c | a r 'o volcnico Indlferenclado
"> g r a n o d l o r l t b , c o l l z a s (? )
FIG. 11. Geologa del rea geotrmica de Amatitln seccin norte-sur (Tobas, 1987).
294
COTA
( m a. n m }
NW
SOUTHWESTERN
EL
L I M N ANO MARIPOSA DOMES
--7^r---rr-6"~-Ji^2
*o o o o -Jsp oVo o o
O S-D
OF
AM-3
O O- OÔ O ^- O
POZO EXPLORATORIO DE
DIMETRO REDUCIDO
600
E x p l o r o * o r y well of mol
dlameter.
(Basament* Rock
Rocas bsales (Basaments Rock)
<Qs
y terrazas aluviales
Qa
Qr-d P(l7l I Roca* domicas (Rlodacitas y d e c i t a )
I Domic rocks( Rhyodoclte and docite)

T*~>=1 Pom de rlodoclto y d o c i t o
l> * 1 Dcil and r h y o d o c l t e pumlce
Q I* *,
I 1 S e d i m e n t o s lacustres
AMATITLAN
I-'-^l L a c u s t n a n sediments
I Aluvin and diluvial t e r r e c e s
Qp
SKm
DISTANCIA
LEYENDA
Qc
|o o o Conglomerado a r e n o s o
I I Sondy conglomrate
SECCIN G E O L G I C A
Lavas andesltlca* terciarlas

T e r t l a r y andesite*
To
volcnica* cuaternarias
I Quoternary v o l c a n t e r o c k
(andesite)
Inst N a c i o n a l de Electrificado^
Unidad de Desarrollo Geotrmico
NW-SE
|v v y] Volcnico terciario Indif erenciado

I * * I T e r t i a r y volcanlc undlferenclated
Isotemperatura C
Isotemperature
-80-
FIG. 12. Geologa del rea geotrmica de Amatitln seccin noroeste-sureste (Tobas, 1987).
3.2
La
GEOQUMICA DE FLUIDOS
primera
localizacin
muestreo
de
manantiales
en
el
rea
geotrmica de Amatitln se efectu en 1977, luego se seleccionaron
los
manantiales
considerados
representativos
estos
se
han
muestreado sistemticamente hasta la fecha (Figura 13). En base a

su composicin qumica los manantiales han sido clasificados en dos
categoras; (ELC 1989, Giggenbach 1986, Tobas 1987, Figura 14)
aguas cloruro sdicas localizadas a la orilla sur del lago Amatitln
con valores hasta de 1450 ppm de Cl y temperaturas mayores de

90C y aguas bicarbonticas alrededor del domo El Limn y a lo largo
del valle del ro Michatoya, con temperaturas entre 40 y 70C, y
contenido de HCO de 750 ppm. El manantial AM-8, con la ms

alta concentracin de cloruros, se considera representativo de aguas
termales
de
origen profundo.
Al
resto
de manantiales
se
les
295
Ciudad dt Guottmala a 23 Km
voLcan dt Pacaya
4 km
FIG. 13. Localizacin de manantiales seleccionados en

el rea geotrmica de Amatitln (Giggenbach, 1986).
cu
INOE
IOSO.
HCOj
FIG. 14. Diagrama de CI-HCO3-S04 para las aguas de Amatitln

(Giggenbach, 1986).
clasifica como derivados de este por dilucin con aguas

superficiales. OLADE (1982) considera que los dos grupos de aguas
provienen de acuferos diferentes; el grupo clorurado sdico con una
temperatura en profundidad de aproximadamente 200C y el grupo
bicarbontico, mas superficial, con temperatura aproximada de 100C.
296
Supone adems, la existencia de un acufero ms caliente a mayor

profundidad el cual es mencionado tambin por ELC (1989) quienes
consideran que el fluido original puede llegar a 300C.
Anlisis isotpicos efectuados en manantiales seleccionados del rea
sugieren una simple relacin entre las aguas clorurado sdicas,

bicarbonatadas y superficiales, de tal manera que todos los
manantiales corresponden a mezclas de agua de origen profundo con
agua superficial (Giggenbach 1986, ELC 1989, Tabla 5 y figuras 15 y
16). El enriquecimiento en el contenido de 18O (aproximadamente
1.8% ) indica una considerable interaccin agua-roca a temperaturas
mayores de 300C. Por otro lado, si se considera el agua del lago
como
representante
del
contenido
actual
de
tritio,
las
aguas
cloruro-sdicas tienen ms de 100 aos.

reas fumarolizadas se localizan desde la orilla sur del lago hasta
Laguna Calderas.
Bsicamente son reas calientes formadas por
material areno-arcilloso de color gris claro a blanco, provenientes
de alteracin de piroclsticos o lavas neutras a acidas. Han sido
clasificadas en tres sistemas (Tobas 1987); uno alrededor del
T iB LA
COMPOSICIN ISOTPICA DE AGOAS DEL CAMPO

GBOTBRHICO DE AKATITtA iCigseabach 19861
INDE do.
AK-1
AN-7
AH-8
AM-19
AH-24
A-32
AH-44
AH-57
AH-67
AH-69
AH-7
AL-2
AL-4
re. < 0 0/00

l
72
97
91
50
64
65
84
57
20
50
20
22
25
-8.68
-6.44
-6.22
-8.88
-8.88
-8.49
-6.63
-7.26
-9.36
-7.07
-7.86
-1.61
-2.92
3B o/oo JE (T.O.) Cl-dg/kg)

-61.2
-54.6
-53.3
-64.2
-64.0
-60.2
-52.9
-57.5
-62.9
-49.4
-52.5
-19.2
-26.4
0.0
0.6
0.9
0.0
0.4
0.4
0.5
1.6
1.8
13.2
11.4
9.4
3.9
166
1250
1420
158
105
306
1160
235
2
245
5
5
101
297
Dilucin con aguo

ubt*rrano " jovn
CL(mg/Kg)
I9OO
FIG. 15. Relaciones tritio-cloruros, deuterio-cloruros

y oxgeno 18-cloruros para las aguas de Amatitln
(Giggenbach, 1986).
Precipitacin d
bala altitud
FIG. 16. Relacin deuterio-oxgeno 18 para las aguas de Amatitln

(Giggenbach, 1986).
298
crter de Los Humitos, otro en los domos El Limn y La Mariposa y un

tercero en el extremo sur-oeste del lago. Dos muestras de gases
fueron analizadas por Giggenbach (1986); una cercana al lago
Amatitln (ALA) y la otra cercana a la Laguna Calderas (ALC) Tabla
6). El contenido de gases para ambas es muy diferente; 0.9 mmol/mol
para el Lago Amatitln y 55.1 mmol/mol para la Laguna Calderas.
Se
considera que el bajo contenido de gases en la muestra de Amatitln

es debido a una alta desgasificacin del agua. La composicin
relativa de los gases helio, nitrgeno y argn en ambas muestas
sugiere un origen magmtico comn con una dilucin por nitrgeno y
argn provenientes de aguas superficiales (Figura 17). Por otro
lado, el contenido relativo de hidrocarburos confirma este origen
magmtico (Figura 18, Tabla 6).
3.3
GEOTERMOMETRIA
Geotermmetros de slice presentan valores de aproximadamente 200C

tanto para las aguas bicarbonatadas como para las aguas clorurado
sdicas. Geotermmetros de cationes por su parte, indican valores
de 240 a 245C.
El uso del diagrama sodio-potasio-magnesio
(Giggenbach 1986) revela que las nicas muestras que han alcanzado
equilibrio agua-roca en profundidad son aquellas con valores altos
de cloruros, intersectando la lnea de equilibrio a una temperatura

aproximada de 230C
(Figura
19). Por otro
lado
temperaturas de
equilibrio de gases presentan valores de 220 a 300C (ELC 1989,

Giggenbach 1986).
En base a los resultados obtenidos, Giggenbach
propone un modelo hidrogeoqumico el cual se presenta en la Figura

20.
299
AIRE
AIRE SATURADO CON

AGUA SUBTERRNEA
10 He
FIG. 17. Diagrama nitrgeno-argn-helio para

los gases de Amatitln (Giggenbach, 1986).
ETANO/IO
PROPAKO
BENCENO
FIG. 18. Diagrama etano-benceno-propano para

los gases de Amatitln (Giggenbach, 1986).
300
TABLA
COMPOSICIOS QDIHICA DE GASES DEL CAHPO
GEOTRMICO DE AHATITLAK (ppt)
(Giggenbach 1986)
TC
C02
55.1 986
0.9 961
95
95
AlC
ALA
Ar
02
ALC .02 1.0

ALA .40 1.2
ALC
IB,
2.0
4.5
CH4
0.14
5.17
11 0.35
25 3.42
be
-2.8
-6.7
pra
ibu
(.5
7.6
0.1
0.9 (.5
ebe
1-1
p-z
o-i
tol
.0068 .00001
.0061
.00073
"ClCOjl
pre
ALA
Be
0.1
nbu
ete
940
(.5 30.8
U 0.4
opa
1.9 0.5 0.5

U U
ALC
1.4
1.8
1.3
0.6
0.6
ALA
0.8
0.9
0.6
0.3
0.3
let:
ete:
eta:
pre:
letano
eteno
eta no
propeoc
.05
let
998
ipa
.26
pe
eta
benz
13.6
0.7
be: buteno
tol: tolueno
nbu: n-butano ebe: etilbenceno
ipa: isopentano i: nleno
npa: n-pentano ALC: Laguna de Calderas
pra: propano
pe: penteno
ibu: isobutano benz: benceno
ALA: Lago de Aiatitln
301
FIG. 19. Diagrama sodio-magnesio-potasio para

los aguas de Amatitln (Giggenbach, 1986).
FIG. 20. Modelo hidrogeoqutmico propuesto por Giggenbach

para al rea geotrmica de Amatitln (Giggenbach, 1986).
3.4
PROSPECCIN DE RADON
Con el objeto de detectar fallas y fracturas tectnicamente activas,
en 1985 se procedi a efectuar una prospeccin de radn en el campo

geotrmico de Amatitln, cubriendo un rea aproximada de 100
kilmetros cuadrados, mediante el sistema de cpsulas con pelculas
detectoras. Ciento dos cpsulas se colocaron cada 500 1000 m en
302
c
o
* i
i!
o
I!
5 1
f f
"
i 5
8 E
iT
u.
2
Q
S
o
ro
<D
a
o
o
o
O)
C3)
O
Q.
E
(O
"55
o
<3
1
O
o
ro
o
oj
303
ocho lneas con direccin NO-SE, separadas 1 km cada una. El tiempo

de exposicin fue de treinta das y posteriormente se efectu el
anlisis calculando el nmero de trazas por centmetro cuadrado y
2
por hora (T/cm -hr) .
Se considera que la emisin de radn hacia
la superficie se efecta a travs del sistema de fallas norte-sur.

El anlisis de los resultados evidencia tres anomalas en el rango
2
de 20 a 40 T/cm -hr, entre el domo El Limn y la falla Los

Humitos. Una cuarta anomala se localiza superficialmente asociada
a la falla de Mixco (Figura 21). Las tres anomalas presentan una
alineacin
NO-SE,
desplazadas
ligeramente
hacia
el
sur
de
las
manifestaciones geotermales; el eje de alineacin puede corresponder

con un
rasgo
estructural profundo subvolcnico
relacionado
directamente con el reservorio geotrmico principal (Tobas 1987).
REFERENCIAS
Bethancourt,
Hugo
R.
1978.
Proyecto
Zunil.
Estudio
de
Factibilidad Preliminar. Informe de Factibilidad Preliminar.

Instituto Nacional de Electrificacin. Guatemala.
Cordn
Mrida
&
MK
Ferguson
Geotermoelctrica de 15 MW.
Company.
1990. Planta
Proyecto Zunil I, Quezaltenango.
Estudios Geocientficos No. 1. Informe final.

ELC Electroconsult. 1982. Primera Unidad Geotrmica. Campo de
Zunil, Quezaltenango.
Milano, Italia.
Informe
de
Factibilidad
Preliminar.
ELC Electroconsult. 1989. rea Geotrmica de Amatitln. Estudio
de
Prefactibilidad.
Informe
de
Geoqumica
de
los
Fluidos.
Milano, Italia.
Fournier, Robert & Hanshaw, Bruce B. 1981. Oxygen and Hydrogen

Isotopes in Thermal Waters at Zunil, Guatemala, report
submitted to the Instituto
Guatemala.
304
Nacional de Electrificacin (INDE).
Giggenbach,
Werner
F.
1986.
The
Isotopic
and
Chemical
Composition of Water and Steam Discharges from the Lago de

Amatitln, San Marcos and Zunil Geothermal Fields, Guatemala.
Chemistry Divisin, DSIR. Private Bag. Petone, New Zealand.
Giggenbach, Werner F. 1988. Isotopic and Chemical Composition

of Discharges from Zunil, Tecuamburro and Moyuta Geothermal
Fields, Guatemala. IAEA Report. Chemistry Divisin, DSIR.
Private Bag. Petone, New Zealand.
Goff, Fraser., Adams, Andrew., Meeker, Kimberley., Truesdell,
Alfred., Roldan Manzo, Alfredo Rene., Janik, Cathy. 1989.
Hydrogeochemical Exploration of Tecuamburro Volcano Regin,
Guatemala.
Gutirrez L.C.A. y Lpez, Arturo. 1983. Concentraciones
superficiales de Radn en el Campo de Los Azufres, Mich.
Informe 32-83. Comisin Federal de Electricidad. Mxico,
Japan
International
Cooperation
Agency.
1977.
Republic
of
Guatemala. Report on Geothermal Power Development Project.

OLDE. 1982. Estudio de Reconocimiento
Geotrmicos de Guatemala. Informe Final.
de
los
Recursos
Roldan Manzo, Alfredo Rene. 1989. An Outline
of Geothermal
Development
in
in
Guatemala.
Report
presented
the
20th
International Group Training Course on Geothermal Energy, held

at Kyushu University, Japan.
Tobas, Edgar. 1977. Proyecto Zunil. Estudio de Factibilidad
Preliminar.
Informe Preliminar Geolgico y Vulcanolgico.
Instituto Nacional de Electrificacin (INDE). Guatemala.
Tobas, Edgar. 1987. Proyecto Geotrmico Amatitln. Estudio de
Prefactibilidad. Instituto Nacional de Electrificacin (INDE).

Guatemala.
305
CARACTERSTICAS GEOQUMICAS E ISOTPICAS DE

LOS FLUIDOS PRODUCIDOS POR LOS POZOS DE
LOS HUMEROS, PUEBLA, MXICO
E. TELLO HINOJOS A
Gerencia de Proyectos Geotermoelctricos,

Comisin Federal de Electricidad,
Morelia, Mxico
Resumen-Abstract
CARACTERSTICAS GEOQUMICAS E ISOTPICAS DE LOS FLUIDOS PRODUCIDOS POR LOS
POZOS DE LOS HUMEROS, PUEBLA, MXICO.
Los anlisis qumicos e isotpicos de los fluidos producidos

por
los
pozos
del
campo
geotrmico
de
Los
Humeros,Puebla.,fueron estudiados con el objeto de conocer la
qumica del yacimiento y los procesos que ocurren en l. De
acuerdo con las caractersticas qumicas de los fluidos se
encontr que la salmuera producida por los pozos productores
es una agua de b a j a salinidad,cuyo carcter geoqumico es
variable y depende del tipo de pozo y la zona donde produzca.
Los pozos ms someros presentaron un carcter bicarbonatadosdico. Mientras que los pozos ms profundos presentan un tipo
geoqumico clorurado-sdico.Tambin se encontr que de acuerdo
con los datos de exceso de vapor el pozo Hl produce en una
zona de lquido dominante, mientras que el resto de los pozos
producen en una zona de dos fases. Debido a lo anterior para
el pozo Hl la composicin qumica en la descarga total es
igual que a condiciones de yacimiento, para el resto de los
pozos no se puede decir lo mismo. Ya que, son pozos que
presentan un exceso de vapor alto, y la composicin a descarga
total no es la misma que a condiciones de yacimiento cuando se
presentan estas caractersticas.
De acuerdo con su composicin isotpica los p o z o s de
Humeros presentan un corrimiento de oxgeno-18 caracterstico
de fluidos de origen geotrmico que se han equilibrado con la
roca a altas temperaturas. Los manantiales aledaos al campo
en su mayora se ubican en la linea meterica. La muestra
proveniente de Alchichica presenta una composicin isotpica
tpica de una agua que ha sido m o d i f i c a d a por procesos de
evaporacin a temperatura ambiente.
GEOCHEMICAL AND ISOTOPIC CHARACTERISTICS OF THE FLUIDS GENERATED IN LOS

HUMEROS WELLS, PUEBLA, MXICO.
Chemical and isotopic analyses of the fluids produced by wells in the

geothermal rea of Los Humeros, Puebla, were carried out to establish the
chemical composition of the field and the processes taking place in it.
The
chemical characteristics of the fluids showed that the brine produced by the
wells is a low-saline water, whose geochemical character vares according to
well type and production zone. Shallower wells produced sodium bicarbonatetype water, whereas the deeper wells exhibited a sodium chloride geochemical
307
type. It was also found, according to vapour excess data, that the Hl well is
in a zone where liquid is dominant, while the remaining wells are in a
dual-phase zone. As a result, the chemical composition of the Hl well total
discharge is the same as that of the field as a whole, whereas that statement
cannot be made for the other wells. Thus there are wells which produce a high
vapour excess, and the total discharge composition is accordingly not the same
as for the field as a whole.
The isotopa composition of the Humeros wells shows an ^0 shift
which is characteristic of fluids of geothermal origin that have reached
equilibrium with the rock at high temperatures. The springs adjoining the
rea are mostly located on the meteoric line. The Alchichica sample has an
isotopic composition typical of a water which has been modified by evaporation
processes at ambient temperature.
1.
INTRODUCCIN
El presente t r a b a j o fue realizado dentro del marco del

programa de investigaciones sobre la aplicacin de tcnicas
isotpicas y geoqumicas en la exploracin geotrmica en
Amrica Latina.
El campo geotrmico de Los Humeros, Puebla se encuentra
ubicado en la porcin Centro-Oriente del Estado de Puebla, en
lmites con la porcin Centro-Occidente del Estado de Veracruz
a 53 Km al noroeste de la ciudad de Jalapa,Ver.
El o b j e t o del presente estudio es r e a l i z a r una
caracterizacin geoqumica e isotpica de los fluidos producidos por los pozos de Los Humeros. Adems de incluir manantiales localizados en la periferia del campo, con el fin de ver
si existe alguna interaccin de estos con fluidos geotrmicos.
Para la realizacin de este trabajo se seleccionaron los
datos qumicos de los pozos que hasta el momento han sido
m u e s t r e a d o s . Por t a n t o , a q u se c o n t e m p l a r o n los datos
qumicos de pozos que se perforaron hasta diciembre de 1989.
32 pozos han sido perforados a partir de 1981 a 1990 de

los cuales 22 son productores, 4 estn contemplados como
inyectores, 4 f u e r o n f a l l i d o s y 2 estn en c a l e n t a m i e n t o
(Figura 1).
2.
COMPOSICIN QUMICA DEL AGUA SEPARADA DE LOS POZOS Y

DE MANANTIALES
AGUA
Con el fin de caracterizar el tipo de agua que producen

los pozos se utiliz la grfica 2, la cual relaciona el contenido relativo en peso de SO4, Cl, y HCO3 ( Giggenbach, W . , 1 9 8 9
).
L o s pozos H 6 , H 7 , H 9 , H 1 0 ,
H l l , H 1 2 , H13, H17, H 2 0 , H 2 3 ,
H24, H 2 7 , H 2 8 , H 3 0 , H32 Y H33 presentan un carcter cloruradosdico. Este tipo geoqumico es caracterstico de agua proveniente de un yacimiento geotrmico . Normalmente en un yacimi-
ento geotrmico el equilibrio agua-roca se lleva a cabo a

profundidad y a altas temperaturas. Ahora bien, el agua de los
pozos H 6 , H10,
308
H l l , H12,H 2 3 , H 2 4 , H 2 7 , H 2 8 , H 3 0 , H32 y H33
2I80C
)500
661500
663500
665 500
2180000
I
H-21
ffi
H-22
' H-9
2178000
# "
V '
H-16
^ H-32
2178000
8*-
H-29
H-20
H-8
217*000
H-27
H-5
H-25
- 2176000
y?'* ^î^""1-"'
A? H-26 _W H~s
v
T ^<
*
'",-<
C
^c,^ ^
2174000
2174000
2172000
2172000
2170000
FIGURA IrLOCALIZACION DE LOS POZOS DE HUMEROS, PUE.
caen en la zona de aguas equilibradas con la roca. En la tabla

1 estn referidos los resultados del anlisis qumico del agua
separada de los pozos que la producen.
Los pozos Hl, H16 y H18 presentan un carcter geoqumico
bicarbonatado-sdico. Estas caractersticas son adquiridas
debido a que estn produciendo en la parte ms somera del

yacimiento. Esta parte del yacimiento corresponde o se comporta como una zona de condensacin ( Figura 2 ).
309
TABLA 1.- COMPOSICION OU/MICA DEL AGUA SEPARADA DE LOS POZOS DE LOS HUMEROS.PUEBLA.
LA CONCENTRACION DE LOS SOLUTOS ESTA DADA EN mg/1 Y LA CONDUCTIVIDAD
ELECTRICA ESTA ENjmhos/cm. LA ENTALPIA TOTAL ESTA EN kJ Ikg.
No
DE
FECHA
POZO
H-1
H-6
H-7
H-8
H-9
H-10
H-11
H-1 2
H-1 3
H-1 5
H-1 6
H-17
H-1 8
H-20
H-23
H-24
H-27
H-28
H-30
H-31
H-32
H-33
121089
121089
191089
121089
261089
190789
111089
121089
121089
70689
131089
131089
131089
60989
210189
180589
130489
180789
140389
121089
131089
261089
ENTALPIA
DE
MEZCLA
1385
2378
2587
2168
2662
2662
2636
2596
1671
2115
2498
2662
1747
2628
2064
2491
2260
1731
2662
2489
2637
2662
PH
C.B.
8.2
7.9
6.6
8.0
6.8
6.0
4.8
7.1
8.1
5.2
8.9
7.6
8.0
7.3
7.6
7.6
7.4
8.4
5.3
7.7
5.7
7.2
1200 282. 0
1025 227.0
750 147.0
1150 282.0
775 170.0
1010 141.9
3500 203.0
440 180.0
1650 350.0
550 120.0
2100 586.0
635 112.0
1645 123.0
525
93.0
1060 146.0
1500 285.0
1075
75.0
2400 533.4
1925 112.0
455 112.0
1275 107.0
900 180.0
A/a
Mg
Si02
Cl
46.0
41.0
22.0
46.0
26.0
19.1
27.0
32.0
66.0
15.0
32.0
19.0
23.0
16.0
10.0
46.0
6.0
28.1
14.4
21.0
21.0
27.0
1.78
0.80
0.05
0.05
0.04
0.07
0.02
0.02
0.40
0.04
0.07
0.07
0.05
0.03
0.04
0.02
0.06
0.11
0.07
0.01
0.08
0.05
0.18
0.04
911
1142
885
988
940
99.6
252.7
76.9
96.8
79.4
265.1
982.7
133.4
393.1
9.8
99.3
158.8
112.3
79.5
193.6
324.6
252.5
556.0
498.4
14.4
2.20
2.20
0.76
1.80
7.10
0.50
4.00
1.20
0.90
0.84
0.92
1.20
6.00
1.50
1.70
0.60
0.80
1.00
5.30
1.70
NOTA: C.E. CONDUCTIVIDAD ELECTRIC A

LOS ANALISIS FUERON REALIZADOS POR CFE
909
1023
949
502
551
519
229
441
163
406
152
970
914
911
329.9
178.0
SO4
HC03
110.8 207.5
39.8
1.7
34.3
73.2
100.3
99.6
82.0
4.0
12.4
80.5
28.2
33.3
1.7
49.3
87.7
71.5
131.9
10.0
142.0 463.8
41.5
75.3
42.8 396.6
19.4
70.6
2.4
107.7
58.2
27.3
10.3
21.0
110.4
31.8
13.9 259.6
26.3
0.6
9.5
15.8
33.2
5.7
B
247
253
2410
503
2648
5331
1716
1743
267
142
220
184
118
469
73
422
187
227
5963
1192
1628
1495
Li
0.85
0.75
0.30
0.57
0.76
0.34
0.83
0.58
1.37
0.40
0.85
0.40
0.37
0.31
0.20
0.90
0.10
1.54
0.23
0.42
0.24
0.40
FIGURA 2..
CONTENIDO RELATIVO DE CI.S04

Y
HCOi EN PESO (mg/Kg). LA
RAZON HCOi/CI ESTA EN RAZON

PO ZO S
PESO.
MANANTIALES
OK)
0-25
% CI
HCO/CI
1.0
4-0
HCOi
SO 4
60____% HCO____80
Cuando los pozos estn produciendo en una zona de

condensacin normalmente se detectan bajas concentraciones de
cloruros. Sin embargo, se detectan altos contenidos de bicarbonatos y sulfatos. Esto se debe a que el vapor que transporta
consigo CO2 y H2S condensa en el acufero (zona de
condensacin). Bajo estas condiciones la reaccin con la roca
produce soluciones bicarbonatadas-sulfatadas con pH cido y/o
alcalino.
El pozo H15 presenta un carcter sulfatado-cido, el cual
tambin es adquirido cuando el pozo est produciendo en la
parte ms somera del yacimiento, la cual corresponde a una
zona de condensacin. Esto hace que al interaccionar el H2S de
origen geotrmico con el agua de la zona de condensacin parte
del H2S, es disuelto en la fase lquida enriquecindose sta
en sulfatos. Como se puede ver en la figura 2 el pozo H15 cae
en la zona indicativa de aguas calentadas por vapor. Esto solo
puede ocurrir en la parte ms somera de un yacimiento
geotrmico o bien en manantiales superficiales. Debido a lo
anterior se puede decir que tambin este pozo produce en una
zona de condensacin.
Con respecto a los manantiales aledaos al campo, los

cuales estn referidos en la tabla 2, en su mayora son del
tipo bicarbonatadosdico. Este carcter geoqumico sugiere
que se trata de aguas de reciente infiltracin que han interaccionado con roca de origen volcnico a bajas temperaturas
(Figura 2). Cabe mencionar que solo el agua proveniente de

Arteziano (M7) presenta un carcter clorurado-sdico
caracterstico de agua de origen geotrmico ( Figura 2).
Los geotermmetros de solutos inicos tales como Na/K
(Ellis and Manon, 1964) y de Na-K-Ca ( Fournier and Truesdell,
1973) son una poderosa herramienta para evaluar las condiciones profundas de sistemas geotrmicos. Normalmente el
problema que se presenta en la utilizacin de estos
geotermmetros es el que se deriva del uso indebido a muestras
que no se les puede aplicar. Una seleccin o depuracin inicial para determinar si es aplicable uno de estos
geotermmetros est basado en el valor del pH y los contenidos
relativos de Cl, SO4 y HCO3 ( Figura 2 ).
Recientemente ( Giggenbach, W. 1986 y Ginggenbach, W.
1988 ) desarroll una tcnica que da una indicacin automtica
sobre la aplicabilidad de geoindicadores de solutos inicos.
Esta basada esencialmente en la dependencia de la temperatura
de las dos siguientes reacciones:
K-Feldespato + Na = Na-Feldespato + K
( 1 )
2.8 K-Feldespato +1.6 H20 + Mg =

0.8 K-Mica +0.2 Clorita +5.4 Slice + 2 K
312
(2 )
TABLA 2- COMPOSICIN QUMICA E ISOTPICA DEL AGUA DE MANANTIALES Y NORIAS DE LOS HUMEROS.PUE.
LA CONCENTRACIN DE LOS SOLUTOS ESTA DADA EN mg/l Y LA CONDUCTIVIDAD ELCTRICA ESTA
EN/ffnhos/cm.
No
FECHA
NOMBRE
DEL
PH
C.E. TIPO
Na
Ca
Mg
S02
Cl
17.0
0.9
0.7
1.5
1.0
1.3
0.9
19.3
78.4
5.6
8.3
45.0
23.0
37.7
23.0
47.5
40.2
1.3
2.7
2.0
2.7
4.0
13.4
32.8
2364
622.0
0.0
28.0
23.0
23.0
30.5
32.8
52.3
13.4
42.6
45.0
49.6
22.2
25.2
4.1
15.2
11.1
4.8
8.2
2.7
8.2
1.3
5.5
70.5
S04
HC03
DEUTERIO
OXI-18
TRITIO
MANANTIAL
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
24
U)
270188
HUICHOTITA
4.5 90 J
ATOLUCA
300188
7.0 70
20188
MIXQUIAPAN
7.5 105
10288
CHACHAR
8.1 135
SOTLA
270188
7.6 120
270188
HUIZILPOPOCA
7.6 91
250188
ARTEZIANO
9.0 13100
250188
S.N. PIZARRO
8.5 5150
260188 TEXCALPITZAHUAC 8.1 340
250188
BARRIENTOS
8.5 350
250188
8.3 400
SANTIAGUITO
250188
SAN ROQUE
7.8 134
260188
8.2 540
HUIZILTEPEC
260188
GONZAGA
8.7 400
290188
7.4 134
TZOCUILA
260188
MATLAHUACALA
8.2 540
290188
TEMOXIZA
7.6 106
30288
MAZAPA
7.3 137
30288
7.6
EL TESORO
1000
290188
CHIGNAUTLA
7.5 145
10288
S.J. XIUTETELCO 7.5 108
30288
6.6 95
ZOATZINGO
280188
7.1 55
TRES OCOTES
M
M
M
M
M
N
N
N
P
N
P
N
N
M
M
M
M
M
M
M
M
M
M
5.0
3.6
5.0
4.3
6.6
1.7
1.4
8.6
3.2
5.6
3.2
6.6
3160 300.0
833.0
95.0
30.4
1.4
27.0
5.3
39.6
3.9
2.1
42.0
17.6
4.6
47.6
6.0
8.3
7.0
9.6
83.0
14.0
9.0
6.0
4.3
4.2
4.2
2.5
1.7
2.5
9.2
1.4
1.0
3.2
2.5
12.0
9.2
19.5
7.1
5.6
26.9
15.6
21.8
20.2
32.4
18.8
28.0
25.0
7.0
76.0
20.0
17.0
38.0
11.6
11.9
4.0
3.4
12.2
8.7
3.3
1.1
1.7
2.8
1.0
2.2
27.6
1.1
1.4
1.0
0.5
46.5
37.5
4.1
4.1
5.5
2.7
4.1
2.7
0.0
0.0
0.0
0.0
8.9
3.9
1974
899.0
5.8
8.8
18.3
7.8
2.8
9.4
2.9
34.8
0.0
0.0
3.5
0.0
0.0
0.8
0.0
31.5
0.00
24.2
0.00
46.1
0.00
29.1
0.00
9.7
0.00
24.2
0.00
1379 37.80
3.34
1128
0.08
128.6
114.1
0.17
179.0
0.08
0.04
182.0
152.9
0.00
0.00
0.0
36.4
0.00
223.3
0.00
0.00
38.8
53.4
0.08
1.27
371.4
0.00
50.9
29.1
0.00
0.00
24.3
0.00
16.9
-68.5
-64.8
-67.1
-72.2
-82.6
-80.4
-48.4
-75.5
-74.2
-71.4
-70.8
-72.2
-86.4
-88.4
-57.1
-75.1
-68.3
-68.5
-77.3
-68.2
-71.4
-53.3
-67.9
-10.6
-9.8
-10.2
-11.0
-12.0
-12.1
-5.3
-10.2
-11.0
-10.5
-10.3
-10.8
-12.3
-11.0
-8.8
-11.1
-10.6
-10.6
-11.2
-10.6
-10.1
-8.6
-10.2
9.7
8.3
0.7
8.4
11.7
3.5
0.8
4.0
2.6
( confinacin Tabla 2 ~ pgina 2 de 2)
NOMBRE
No
25
26
27
28
29
30
31
32
33
34
35
36
37
FECHA
20288
20288
20288
10288
20288
10288
280188
280188
260188
260188
270188
270188
11287
NOTA :
DEL
MANANTIAL
COATLAMINGO
EL RANCHO
EL ATRIO
LA BARRANCA
AHUACATLAN
LA PASADA
LA CUEVA
ACUACO
HUITZILAPAN
XALTIPANAPA
CALZACATENO
SIETE AGUAS
ALCHICHICA
PH
C.E.
TIPO
7.3
6.7
6.9
7.7
76
107
M
M
N
M
M
M
180
100
77
65
70
7.7
7.1
7.8
8.2 200
8.1 164
8.1 740
7.7 65
7.6 58
Na
M
P
5.0
4.6
4.6
6.0
4.6
3.6
4.6
7.6
N
N
M
M
9.0
73.0
4.6
4.0
Ca
2.5
2.5
4.8
7.3
12.5
7.0
6.7
4.3
12.5
21.4
9.6
69.3
3.0
2.9
6.0
2.1
3.2
2.5
2.5
2.1
3.5
15.0
2.8
2.1
Mg
0.7
1.5
1.7
1.4
0.9
0.6
1.0
1.5
1.9
4.4
0.5
0.4
SiO2
Cl
SO4
HCO3
31.5
43.7
82.5
0.00
34.4
17.9
0.0
31.3
19.2
31.3
58.7
40.4
31.3
20.7
0.0
4.1
2.7
2.7
2.7
1.3
3.5
4.1
4.1
1.3
0.0
0.0
0.0
46.5
43.5
25.2
31.3
19.2
2.8
0.4
0.0
0.1
1.0
28.3
0.0
2.8
38.8
31.5
16.9
28.7
71.9
62.2
0.0
76.7
24.0
0.00
0.10
0.08
0.08
0.00
0.00
0.00
0.08
0.00
0.00
0.08
DEUTERIO
-67.5
-52.7
-62.0
-66.8
-45.9
-53.7
-65.5
-73.2
-75.0
-66.3
-66.3
-65.5
-12.3
(M) MANANTIAL, (N) NORIA, (P) POZO ARTEZIANO, (C. E.) CONDUCTIVIDAD ELCTRICA
EL MUESTREO PARA ANLISIS ISOTPICO FUE REALIZADO DE OCTUBRE A DICIEMBRE DE 1987

EL ANLISIS QUMICO FUE REALIZADO POR CFE. DEUTERIO YOXIGENO-18 LO ANALIZO EL HE Y EL TRITIO
FUE ANALIZADO EN EL LABORATORIO DEL OIEA EN VIENA.
OXI-18
-10.5
-7.9
-9.6
-10.3
-8.1
-8.6
-9.8
-10.9
-10.6
-10.1
-10.3
-10.3
0.7
TRITIO
4.2
2.5
2.5
Ambas reacciones involucran minerales en equilibrio total

que se espera obtener despus de la recristalizacin
isoqulmica de una roca de la corteza de composicin promedio,
bajo condiciones de inters geotrmico. La reaccin (2)
responde ms rpido y entonces se obtiene la ltima
temperatura de reequilibracin dando generalmente temperaturas
bajas. Combinando los dos subsistemas, se obtiene un mtodo
que permite obtener el grado de equilibrio agua-roca, y
determinar si es factible aplicar los dems geotermmetros. En
la figura 3 est graficado el contenido relativo de Na, K y Mg
para el agua de los pozos y manantiales de Humeros,Puebla. Los
anlisis de agua de los pozos, se sitan en la zona de
equilibrio parcial, a excepcin del H16 que est en equilibrio
a una temperatura de 200C. El pozo H28 el cual se localiza
ms arriba de la linea terica indica que este pozo presenta
prdida de vapor e incremento del contenido absoluto del
soluto (Giggenbach, W. 1989).
Las aguas que corresponden a manantiales estn todas

desplazadas hacia la esquina del Mg. Esto indica que se trata
de aguas de reciente infiltracin bicarbonatadas-sdicas que
se han equilibrado con roca de origen volcnico a temperaturas
inferiores a 100C. Solamente la muestra proveniente de Arteziano (M7) se ubica en la zona de equilibrio parcial con una
temperatura del geotermmetro K/Mg de 156C.
3. EVOLUCIN DE LA COMPOSICIN QUMICA DEL AGUA DEL YACIMIENTO
Un muestreo sistemtico de los fluidos producidos por los

pozos de Los Humeros se ha llevado a cabo por CFE desde 1982 a
la fecha. Para conocer la historia de los solutos en el yacimiento se seleccion a los pozos Hl, H6, H8 y H13 los cuales
producen una mezcla vapor-agua.
En las figuras 4 y 5 esta graficado el contenido de cloruros a descarga total y a condiciones de yacimiento contra
tiempo para los pozos Hl, H6, H8 y H13 desde su inicio hasta
diciembre de 1989. Para el caso del pozo Hl (Figura 4), se
puede observar que tanto a descarga total como a condiciones
de yacimiento los cloruros han permanecido constantes con
respecto al tiempo.
Para el pozo H6 (Figura 4) , se observa que la
concentracin de cloruros tanto en la descarga total como a
condiciones de yacimiento tambin ha permanecido constante con
respecto al tiempo.Para el pozo H8 se puede decir que al
principio se detectaron los valores mayores de cloruros en el
yacimiento y en la descarga total. Sin embargo, a partir de
1986 a la fecha el comportamiento a sido asinttico.El H13 que
es otro de los pozos que producen una mezcla vapor-agua, la
composicin qumica a descarga total y a condiciones de yacimiento se ha incrementado con respecto al tiempo. Esto se debe
a que este pozo estuvo
produciendo en la
zona de
condensacin y ahora produce en la zona de dos fases de ah
que los cloruros se incrementen con respecto al tiempo.
315
FIGURA 3 -
K/IOO
CONTENIDO RELATIVO DE Na, K Y Mg

EN PESO ( m g / K g )
No/1000
A
POZOS
MANANTIALES
Lo* Mumros
H-l
110
100
90
80
70
f*
60
**
50
40
30
20
Cl de Y o c m .
10
Cl en la M e z c l a
1i
84
82
86
90
88
TIEMPO (AMOS)
300
280 -
H-6
260240 220 -
200-
180 -
140 120 -
100-
.
* n D
80-
6040 20 -
086
Cl.de Y a c i m
.+ +* ^
+ Cl en la Mezcla
t
87
88
i
89
90
TIEMPO (AROS )
Figura 4. Cloruros contra tiempo
317
Los Humeros
zuu 190 -
H-8
180 170 160 -
150 140 *"N
130 | 120 V-
'
3u
110 -
100 -
90 -
80 70 -
2k
60 -
50 -
40 -
Dn
*+
*t-
20 -
-H-
"*"++
gana130 ntftijf1
30 -
CL, Cpn'"1 n
10 0-
85
,
87
TIEMPO
, ----
r89
-- i
(AOS)
280 -
H-13
260 240 -
220 -
200 -
180 -
160 -
^.
Jf*B
^
140 -
V)
__
120 -
100 -
+^
80 -
60 -
40 -
Cl de Y a c i m .
20 -
C 1 en la M e z c l a
"
88.5
88.7 88.9
89.1
TIEMPO (AOS)
Figura 5. Cloruros contra tiempo
318
89.3
89.5
89
4. COMPORTAMIENTO DINMICO DEL YACIMIENTO
La composicin qumica del agua de los pozos puede cambiare Estas variaciones se pueden deber a reducciones en la
presin de yacimiento bien a fenmenos de mezcla, dilucin,
evaporacin, condensacin, desgasificacin etc.
Por varios aos los pozos productores de Los Humeros han

sido muestreados para observar los cambios ocurridos en su
composicin qumica. Adems la variacin en las temperaturas
del agua profunda durante la produccin puede ser monitoreada
por medio de geotermmetros qumicos.En las figuras 6 y 7 est
graficada la temperatura de los geotermmetros de slice y
Na/K para los pozos Hl, H6, H8, y H13 con respecto al tiempo.
Se puede observar en estas figuras que los dos geotermmetros
concuerdan muy razonablemente y adems han permanecido constantes con respecto al tiempo para estos pozos.
La solubilidad de la slice y la razn de Na/K al variar
la temperatura pueden ser usados para determinar que mecanismo
es el que causa cambios en la composicin qumica. Por ejemplo, cuando la temperatura disminuye a causa de una ebullicin
rpida o a la influencia de agua fra puede no afectar inmediatamente la razn Na/K. Sin embargo, una mezcla de dos aguas
previamente equilibradas a diferentes temperaturas podra
afectar ambas razones SiOo y Na/K (Ellis, A. J. and
Manon,W.A.J., 1977).
En las figuras 8 y 9 se ilustran los cambios que ocurren
en la concentracin de cloruros y la temperatura de la slice
para el pozo Hl durante el periodo 1982-1988. Adems en estas
figuras se incluye un patrn de lineas las cuales cada una
indica un proceso diferente el cual puede ocurrir en el yacimiento. Por tanto, se puede decir que para el pozo Hl los
cambios son regulares y variables y se observa que estos
cambios estn dominados por una serie de procesos complejos de
ebullicin, evaporacin, condensacin, dilucin y en el periodo de 1986 a 1988 predominan los procesos de prdida y ganancia de vapor. Para el pozo H6 los procesos que predominan
durante el tiempo de observacin, que comprende de 1986 a 1988
fueron: condensacin de vapor, ebullicin, ganancia y prdida
conductiva,dilucin por aguas fras y aguas a 150C ( Figura
10 ). En el caso de del pozo H8 se sigui el mismo procedimiento encontrndose que los cambios en la concentracin de
cloruros de yacimiento y temperaturas de slice han sido
grandes los cuales han ido hacindose menos variables con
respecto al tiempo. Los procesos predominantes son:
condensacin de vapor, dilucin por aguas a 150C, ebullicin,
evaporacin, ganancia y prdida conductiva.
5. EXCESO DE VAPOR Y COMPOSICIN EN LA DESCARGA TOTAL Y A
CONDICIONES DE YACIMIENTO
Si la entalpia de descarga de los pozos excede la de un

lquido saturado a la temperatura de reservorio, se considera
que existe un exceso de vapor. Las entalpias de descarga de
los pozos del campo geotrmico de Los Humeros varan de 1385 a
2662 kJ/kg. Una alta entalpia de descarga refleja dos fases
319
Los Humeros
H-i
400 -
n
+
300 -
n
200 -
100 -
82
84
86
88
90
TIEMPO (AOS)
500
H-6
400 -
300 -
a.
200 -
100 D
Nal K
T S0
-\iir
86
87
68
ir~
89
TIEMPO (AROS)
figura 6. Geotermmetros contra tiempo
320
90
Los Humeros
500
H-8
4OO -
2
%
300 -
nn
200-
100 -
i
85
r~
87
89
TIEMPO (ANOS)
500
H-13
400 -
300 -
200 -
100 D
T NalK
T S02
i
88.4
88.6 88.8
i
89
89.2 89.4 89.6 89.8 90
TIEMPO (AROS)
Figura 7. Geotermmetros contra tiempo
321
u)
NJ
P E R I O D 0 2 4 - I O - 8 3 o 16-10-84
P E R I O D O 16-10-840 12-08-85
EVAPORACIN
EVAPORACIN
0(
""""!lg Conductivo
90
90
Ptrdldo Conductiva
Oononcla C o n d u c t i v o
Cond * f t * o c t on
Cond*n$aclon
80
80
12
CT
0>
E
J
70
c/j
co
CE
ce
_j
70
D
cu
o
14
CE
O
-J
O
60
50 -
60
50
40
260
10
40
270
280
290
GEOTERMOME""RO DE S L I C E (C )
FIGURA
300
260
270
280
290
GEOTERMOMETRO D E S I L I C E ( C )
8 .- CAMBIOS EN LA C O N C E N T R A C I N DE C L O R U R O S Y T E M P E R A T U R A DE S L I C E CON
R E S P E C T O AL TIEMPO P A R A EL POZO H - l .
300
PERIODO 12-08-85 a 13-10-86

EVAPORACIN
100
100-
90-
Perdida Conducta
lando Conductiva
P E R I O D O 13-10-86 o 1 9 - 0 7 - 8 8
90
<?. *
Condtniaclon
80
80
o>
z
UJ
UJ
70
V)
co
ce
CE
ce
o
_i
Z)
ce
3
o
60
50
40 _
260
60
50
40
270
280
290
GCOTERMOMETRO D E S L I C E ( C )
K)
3S-
70
FIGURA
300
260
270
280
290
GEOTERMOMETRO DE SLICE ( C )
9 . - C A M B I O S E N L A CONCENTRACIN DE CLORUROS Y T E M P E R A T U R A DE S L I C E CON

RESPECTO AL TIEMPO PARA EL P O Z O H-l
300
3/0
PERIODO 11-07-86 a 1 9 - 0 7 - 8 8
150 -
140 -
130 -
LJ
o:
3
oc
o
_J
o
100 -
270
280
290
300
310
3 2O
GEOTERMOMETRO D E S L I C E ( C )
FIGURA
1 0 . - C A M B I O S EN LA CONCENTRACIN DE C L O R U R O S Y
T E M P E R A T U R A DE S L I C E CON RESPECTO A L T I E M P O
P A R A EL POZO H-6
(vapor y agua) en el yacimiento y su separacin parcial en el

acufero antes de entrar al pozo. En la tabla 1 est referida
la entalpia de mezcla de los pozos de Los Humeros. Si se
observa en la tabla 1 la entalpia de descarga del pozo Hl
corresponde a la de un liquido saturado a la temperatura de
reservorio; por consecuencia el exceso de vapor a condiciones
de yacimiento es pequeo. Esto sugiere que el yacimiento
penetrado por el pozo Hl es de liquido dominante ( Tello,H.E.,
1984a).
Para el resto de los pozos la entalpia de mezcla es mucho
mayor que la entalpia de un liquido saturado a la temperatura
de yacimiento, cuando esto se presenta se debe a que a condiciones de yacimiento en forma natural existe una fraccin de
vapor coexistiendo con la fase liquida.
324
Una de las causas del exceso de vapor o entalpia de los

pozos es que las fases de vapor y agua no son transmitidas a
travs de la formacin en el reservorio con igual facilidad
porque las dos fases tienen diferentes permeabilidades
relativas. Es tambin concebible que el exceso de vapor se
deba a la evaporacin de agua por conduccin de calor
proveniente de la roca del reservorio, ya que la cada de
presin causada por la extraccin del fluido por los pozos
productores origina el enfriamiento ( por ebullicin )de este
fluido y por esta razn hay flujo de calor conductivo de la
roca a ese fluido. Sin embargo, hay dificultades involucradas
en la evaluacin qumica del agua del reservorio, basada sobre
datos de exceso de vapor de los pozos. Si el reservorio
contiene solamente agua, entonces es fcil relacionar la
composicin de las muestras a superficie con las condiciones
de reservorio. En el caso contrario, si el fluido en el pozo
es un fluido de dos fases con exceso de vapor, no es posible
relacionar la composicin qumica del fluido en la superficie
con las condiciones de reservorio, sin hacer algunas
suposiciones fundamentales. Por tanto, para este estudio la
composicin qumica del agua en Los Humeros fue evaluada
suponiendo dos posibles causas del exceso de vapor de los
pozos: a) transferencia de calor conductivo de la roca b)
efectos de permeabilidad relativa para el flujo de ambas fases
vapor y agua. Se consider que ambos procesos ocurren en forma
excluyente. El primer caso supone que la transferencia de
calor involucra evaporacin de agua desgasificada (ya
hervida), de tal forma que se aade vapor libre de gas al
vapor formado con anterioridad. Este modelo supone que la
descarga total representa una sola fase lquida en el
yacimiento (Pozo Hl). En el segundo caso, se supone que el
exceso de vapor es debido a los efectos de permeabilidad
relativa para las fases agua-vapor. Aqu, los clculos de las
concentraciones del agua en el yacimiento supone dos fases en
el reservorio, lo cual ocurre en los pozos H6, H8 y H13. Es
importante mencionar que para los pozos H9, H10, Hll, H12,
H16, H17, H18, H19, H20, H23, H27, H28, H29, H30, H31,
H33 el mtodo de exceso de entalpia no es posible aplicarlo

para hacer alguna correccin de los solutos en el yacimiento
debido a que algunos pozos producen poca agua, y la poca que
producen es difcil muestrearla, o bien presentan entalpias
que corresponden a las de un vapor saturado. Por tanto, si se
aplicara este mtodo de correccin de la composicin qumica
del agua basados en los datos de entalpia se tendran datos
errneos para estos pozos.
6. COMPOSICIN A DESCARGA TOTAL Y EN EL YACIMIENTO
Dependiendo de la presin ejercida en la descarga, las

concentraciones de varios solutos varan en las fases individuales agua-vapor; mientras que la concentracin en la
descarga total permanece constante para condiciones de
yacimiento constantes. Los componentes son distribuidos entre
las fases de acuerdo con la fraccin de vapor, la cual es una
funcin de la presin.
325
Para la concentracin de solutos de los fluidos evaporados

a presin atmosfrica se corrigieren a descarga total usando
la siguiente ecuacin:
Ao = Aa(l - Xv)
(3 )
donde Ao es la concentracin a descarga total del componente

A, Aa es la concentracin a presin atmosfrica del componente
A, y Xv es la fraccin de vapor, la cual se calcula de acuerdo
con,
Xv = Ho - Ha / Hv - Ha
(4 )
donde Ho es la entalpia de mezcla y Ha y Hv son la entalpia de

lquido y vapor a la temperatura de saturacin respectivamente, que en el caso de los Humeros es de 91C.
Es importante determinar las concentraciones a condiciones
de yacimiento, ya que es posible detectar variaciones en la
composicin del fluido del reservorio. Estas concentraciones

pueden ser calculadas por medio de la siguiente expresin,
Ay = Ao / ( 1 - Xv )
(5 )
donde Ay es la concentracin a condiciones de yacimiento del

componente A, Ao es la concentracin del componente A en la
descarga total y Xv es la fraccin de vapor, la cual se calcu-
la de acuerdo con,
Xv = Ho - Ha / Ha - Hv
(6 )
donde Ho es la entalpia de mezcla y Ha y Hv son las entalpias

del lquido y vapor a la temperatura del yacimiento.
En las figuras 4 y 5 estn representados los cloruros de
yacimiento y en la descarga total contra el tiempo para los

pozos Hl, H6, H8, y H13. Se puede ver en estas figuras que
solamente las concentraciones del Hl concuerdan muy razonablemente tanto a descarga total como a condiciones de yacimiento.
Ahora bien, el hecho de que se agrupe el contenido de cloruros
en la descarga total como a condiciones de yacimiento significa que el pozo est produciendo en una zona de lquido dominante (Tello,H. E. 1984 a). Por lo tanto, cuando esto ocurre
la composicin qumica a condiciones de yacimiento es igual a

la descarga total. Para el pozo H6 la composicin qumica en
la descarga total no es la misma que a condiciones de yacimiento. Esto indica que est produciendo en una zona de dos
fases ( Figura 4 ).
Para los pozos H8 y H13 nuevamente se presenta la
separacin entre ambos valores, lo que indica que tambin
estos pozos producen en una zona de dos fases ( Figura 5 ).
Para el resto de los pozos como se mencion en prrafos

anteriores no es posible aplicar este mtodo para corregir la
concentracin de los solutos a descarga total y a condiciones
de yacimiento. En la tabla 4 est referida la composicin
qumica a descarga total y a condiciones de yacimiento de los
pozos Hl, H6, H8 y H13.
326
TABLA 3.- COMPOSICIN QUMICA DE LOS GASES DE LOS POZOS DE LOS HUMEROS .PUEBLA.
EL CONTENIDO DE LOS GASES ESTA DADO EN % PESO. LA ENTALPIA ESTA DADA
kJ/kg Y PRESIN DE CABEZAL ESTA DADA EN (MPA)
FECHA
121089
121089
191089
121089
261089
190789
111089
121089
121089
70689
131089
131089
131089
060989
H-23 210189
H-24
180589
H-27
130489
H-28
180789
H-29
131089
H-30
140389
H-31
121089
H-32
131089
H-33
171089
POZO
H-1
H-6
H-7
H-8
H-9
H-10
H-11
H-12
H-1 3
H-15
H-16
H-17
H-18
H-20
ENTALPIA TEMPSEP
1385
126
5.69
3.51
2378
133
2587
137
2.27
177
2168
5.61
1.39
2662
128
2662
1.43
125
2636
133
2.78
2596
275
7.39
1671
144
3.43
2116
136
2.89
1.94
2498
241
2662
134
3.02
2530
105
36.5
2.38
2628
143
2064
5.17
160
2491
124
6.42
2260
4.67
143
1731
1.43
129
2662
7.67
2662
137
2.49
2489
112
2.56
2637
113
1.50
2662
188
1.39
xg
COZ
98.27
91.87
93.64
96.73
84.96
91.43
94.84
94.36
93.60
84.86
89.27
95.49
95.66
91.77
90.30
96.48
91.29
80.06
88.45
88.82
89.92
91.59
85.40
H2S
0.92
6.26
5.59
2.37
10.52
5.77
3.81
3.76
4.61
11.26
8.60
3.11
1.73
6.13
NH3
0.64
0.71
0.20
0.39
1.74
1.15
0.76
0.49
0.49
0.37
0.45
0.73
0.22
7.99
0.64
0.19
1.58
5.10
12.49
9.08
6.40
7.33
7.10
12.10
0.33
0.41
2.37
0.28
0.17
0.66
0.21
1.21
HELIO
0.0001
0.0000
0.0000
0.0000
0.0008
0.0000
0.0000
0.0000
0.0000
0.0022
0.0000
0.0000
0.0000
0.0000
0.0005
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0003
H2
0.0006
0.0061
0.0309
0.0240
0. 1650
0.0574
0.0270
0.0620
0.0590
0.1440
0.0810
0.0270
0.0990
0.0709
0.1140
0.0754
0. 1450
0.2090
0.1110
0.2600
0.1040
0.0550
0.0946
TEMPSEP.- TEMPERATURA DE SEPARACIN EN ( C)

GGDP.-GEOTERMOMETRO DE GASES DE D'AMORE Y PANICHI EN ( C )
UJ
K)
-J
LOS ANLISIS FUERON REALIZADOS POR CFE
Ar
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
N2
0.154
0.546
0.504
0.466
1.430
1.570
0.431
1.240
1.030
3.180
0.795
0.333
0.186
0.486
1.060
0.650
3.030
4.840
1.990
2.990
0.623
0.994
0.827
CH4
0.009
0.546
0.025
0.013
1.170
0.001
0.129
0.800
0.217
0.180
0.800
0.249
2.100
0.916
0.322
0.879
0.018
0.033
0.084
2.050
1.360
0.036
0.820
GGDP
155
269
277
269
301
319
244
246
264
310
300
249
239
257
287
238
286
282
305
289
268
285
280
TABLA 4.- COMPOSICIN QUMICA DEL AGUA SEPARADA A DESCARGA

TOTAL YA CONDICIONES DE YACIMIENTO. LA ENTALPIA
ESTA DADA ENkJ/kgYLA CONCENTRACIN EN mg /1.
CONCENTRACIN EN LA DESCARGA TOTAL

Mg
POZO FECHA ENTALPIA Na
K
Ca
Si02
B
Cl
H-1
1.0
121089
158
26
56 138
1385
0.03
510
H-6
28
0.1
0.006
142
121089 2378
5
31 32
0.02
H-8
121089 2168
61
10
0.5
214
21 109
H-1 3 121089 1671
152
29
2.0
0.03
412
171 116
POZO
H-1
H-6
H-8
H-1 3
TNa/K
263
273
263
278
CONCENTRACIN A CONDICIONES DE YACIMIENTO

SO2
K
Ca
Mg
Cl
B
TNa/K
1.0
0.03
596
30
65
161
263
0.4
0.02
552
122
20
122
273
0.04
26
1.0
562
55
286
263
2.0
0.04
577
162
40
239
278
FECHA ENTALPIA
Na
182
121089 1385
121089 2378
110
121089 2168
160
121089 1671
213
TNa/K.- GEOTERMOMETRO DE SODIO / POTASIO ( C )
7.
EQUILIBRIO QUMICO DEL YACIMIENTO Y GEOTERMOMETRIA DE FASE

LIQUIDA
Se ha demostrado que el estudio del equilibrio

soluto/mineral es de gran ayuda para hacer una evaluacin
completa de un sistema geotrmico. Esto est basado en el
hecho de que la qumica de los fluidos est primeramente
gobernada por la solubilidad de los minerales, lo cual es
importante para poder entender los factores termodinmicos que
afectan el equilibrio. Por ejemplo el uso de geotermmetros
qumicos, y la prediccin de la tendencia de la depositacin e
incrustacin de los minerales depende grandemente del estado
de saturacin que se haya logrado entre el fluido y la roca.
Debido a la gran importancia que esto representa para el mejor
entendimiento del estado termodinmico del yacimiento. Se han
realizado estudios con este enfoque desde 1986 los cuales
fueron
realizados por
( Tello,
H.
E.
1986 ) ,
(Tello,H.E.,1987), ( Tello,H.E.,1989ab). Ahora bien, sabiendo
el estado de equilibrio agua-roca sirve entre otras cosas para
predecir las tendencias de depositacin de los minerales. Es
sabido que las especies qumicas son controladas por la solubilidad de los minerales y que el estado de saturacin es
altamente dependiente de los procesos fsicos que puedan
ocurrir durante el transporte del fluido del reservorio a la
superficie Estudios sobre la cintica de interaccin aguaroca, ebullicin,desgasificacin,enfriamiento y dilucin con
fluidos ms fros han demostrado que estos son los principales
procesos los cuales causan que algunos minerales se desvien de
su estado de saturacin original ( Arnorsson et al.,1982b).
Por ejemplo se ha visto que una ebullicin con una mxima

desgasificacin produce un fluido supersaturado con respecto a
la calcita, y de una progresiva ebullicin y enfriamiento a
temperatura ms bajas se obtienen fluidos saturados en slice
amorfa. Es por tanto, deseable para la propia interpretacin
de los datos qumicos, que cada factor sea tomado en cuenta.
328
8. ESTADO DE SATURACIN DEL FLUIDO PROFUNDO RESPECTO A

MINERALES SELECTOS
En las figuras 11 se muestra el estado de saturacin del

agua a profundidad respecto a la calcita, anhidrita y cuarzo,
a la temperatura medida en la zona principal de produccin.
Los valores de solubilidad para cada uno fueron calculados
a partir de los datos termodinmicos de Helgeson (1969), y
las actividades de las especies se calcularon a partir de los
datos analticos, usando un programa de computadora desarrollado por Arnorrsson et al (1982 a). El estado de saturacin de
cada mineral es expresado como:
LOG K anhidrita = a Ca * a S04
(7)
LOG K calcita
= a Ca * a CO3
(8)
LOG K cuarzo
= a H4SiO4
(9)
En la figura llb puede observarse que los pozos Hl, H6,

H7, H8, Hll, H12, H20 y H23 estn sobresaturados con respecto
a la calcita. El pozo H9 est insaturado con respecto a la
lnea de equilibrio. Cabe mencionar que las aguas geotrmicas
a profundidad se equilibran con la calcita. Sin embargo, la
sobresaturacin con respecto a la calcita que presentan la
casi totalidad de los pozos que producen agua, se debe a
procesos de ebullicin que ocurren alrededor de la zona
productora de estos pozos. Por tanto, esas aguas profundas
parecen supersaturarse y este mineral tiende a precipitar.
Con respecto a la anhidrita se puede decir que los pozos

Hl, H8, y H12 estn en equilibrio ( Figura lia ). El H7 y H6
tienden al equilibrio, mientras que el Hl, H20, y H23 estn
sobresaturados con respecto a la anhidrita. El pozo H9 presenta una gran insaturacin con respecto a la anhidrita.
Con respecto al cuarzo (Figura lia) los posos Hl, H6, H8,
tienden al equilibrio aunque presentan una pequea
insaturacin con respecto a lnea de equilibrio. El resto de
los pozos estn insaturados con respecto al cuarzo. Ahora
bien, puede concluirse que la variacin en la composicin
qumica de los pozos que producen agua se debe a procesos que
ocurren en forma normal en un sistema geotrmico y que la
variacin en la produccin se debe a la depositacin de los
solutos debido a los cambios en la concentracin y temperatura
que originan dichos procesos. La depositacin e incrustacin
de algunos minerales depende de su estado de saturacin. Cabe
mencionar que la depositacin de algn mineral de alteracin,
como regla general ocurre en aguas sobresaturadas. Con base en
lo anterior y despus de observar el estado de saturacin de
los pozos con respecto a minerales selectos, puede decirse que
los pozos Hl, H6, H7, H8, Hll, H20 y H23 pueden presentar
problemas por depositacin de carbonato de calcio, debido a
que estn sobresaturados con respecto a la calcita o El H9 es
probable que no presente depositacin de este mineral por
estar completamente insaturado. Los pozos H7, Hll y H23 pueden
320
(a)
SOBRESATURADOS
H tO
H-l
H-ll
H-r
-t
-IO
-II
-12
-1*
-14
-16
CdS04 =
-l<
-17
LOGK=6
-It
SOO
IZO
S40
TEMPCRATUKA MIOIOA
soo
ato
340
(C)
340
TCMPCRATUMA
WCMOA
sao
(c)
14
(c;
S08RESATURADOS
H-6
^-6
H-20
K
<
3
O
H-23
H-7
H-12
H-ll
-S
-S
INSATURADOS
-1.*
H-9
LOO K Cuarzo= 0.41- -^

4O
MCOWA
FIGURA. II
MO
(C )
SATURACIN DE SLICE, CALCIO, SULFATOS Y CARBONATOS

EN AGUAS GEOTRMICAS CON RESPECTO A LA SOLUBILIDAD
DE ANHIDRITA, CALCITA Y CUARZO.
330
presentar depsitos de sulfato de calcio por estar sobresaturados con respecto a la anhidrita. Los pozos H6 y H9 es probable que no presenten depositacin de sulfato de calcio por
estar insaturados con respecto a la anhidrita. Con respecto al
cuarzo la totalidad de los pozos estn insaturados, por tanto,
es probable que no haya depositacin de SiC>2 en la zona de
produccin. Sin embargo es probable que deposite SiO2 donde
haya cambios de fase; o bien cuando haya presencia de
hidrxidos de algn metal, los cuales actan como puente para
que se inicie la depositacin de slice. Esto puede ocurrir
como en el caso del pozo H16 present insaturacin con respecto al cuarzo, sin embargo haba depositacin de slice, pero
esto ocurri debido a la presencia de hidrxidos de fierro
productos d& la corrosin (Tello, E.H. 1989).
9.
CARACTERSTICAS ISOTPICAS DE LA FASE

LIQUIDA
YACIMIENTO Y GEOTERMOMETRIA ISOTPICA
DEL
En la tabla 5 se presentan los resultados del anlisis de

concentracin de oxgeno-18 y deuterio respectivamente, en
muestras de vapor de pozos de Los Humeros. Cabe mencionar que,
la base de datos incluye informacin sobre 16 pozos, los
cuales fueron muestreados en mayo de 1987, diciembre de 1988 =
Esto con el objeto de establecer la reproducibilidad de la
metodologa de muestreo, y de esta manera poder detectar
variaciones reales correlacionables con cambios en otros

parmetros fsicos y qumicos. En las mismas tablas se presen
tan las temperaturas de separacin de cada fase, y la entalpia
de mezcla solamente en los pozos Hl, H6 y H8, H13, H15 y H20
la muestra del vapor separado se tom a una temperatura dis
tinta que la temperatura de la muestra lquida. En los casos

de pozos equipados con separador de produccin, se tom la
muestra de vapor a la salida de este. En el caso de no contar
con separador se us un separador porttil para la toma de la
muestra de vapor, mientras que la muestra de agua separada se
tom en el vertedor. Con los resultados del anlisis de
concentracin de oxgeno-18 y deuterio en el lquido separado
y en el vapor separado, se calcul la concentracin de ambos
en la descarga total de los pozos, y los resultados se presen
tan en la tabla 5. Para estos clculos se utilizaron 2 proce
dimientos los cuales se describen a continuacin:a) Se utiliza
solamente los datos de concentracin de oxgeno-18 y deuterio
en la fase lquida analizada. Esto es para cuando se toma la
muestra de agua en el vertedor, se hace uso de las siguientes
ecuaciones:
<S18Odt=a180-eXv
(
1
0
)
5Ddt=aD-eXv
(11)
Donde Xv es la fraccin de vapor a la presin atmosfrica, que

en el caso de Los Humeros es de (0.073Mpa) y se calcula de
acuerdo con la ecuacin (4). Para el clculo del coeficiente
de particin (e) se hace de acuerdo con las siguientes ecuaciones:
e180 = 9.2 - 0.04tC
eD = 68 - 0.4tC
(12)
(13)
331
TABLA 5.- COMPOSICIN ISOTPICA DEL VAPOR SEPARADO DE LOS POZOS DE LOS
HUMEROS. LA ENTALPIA ESTA DADA EN kj/kg.
TEMPSE
POZO
H-1
H-1
H-6
H-6
H-7
H-7
H-8
H-8
H-9
H-9
FECHA
140587
290988
140587
290988
140587
280988
140587
280888
140587
270988
H-10
140587
H-10
280988
H-11
140587
H-11
280988
H-1 2 140587
H-1 2 290988
H-1 3 290988
H-1 5 280988
H-16
140587
H-16
270988
H-17
140587
H-17
280988
H-1 8 140587
H-1 8 290988
H-1 9 140587
H-20 280988
H-27 290988
ENTALPIA
1286
1248
1830
2382
2600
2492
2034
2249
2628
2757
2595
2662
2636
2527
1730
2265
2618
2431
2595
2662
2528
2662
VAPOR
C
127
160
144
150
139
136
138
139
172
170
124
216
248
248
261
139
120
128
170
163
175
144
194
178
192
152
119
OXIGEN-18
VAPOR
-5.45
-2.24
-3.76
-4.51
-3.18
-3.35
-4.17
-4.33
-1.47
-1.63
-3.56
-4.93
-2.52
-2.84
-1.38
-3.21
-4.19
-4.11
-4.34
-7.22
-3.72
-3.48
-1.87
-2.81
-2.96
-4.41
-3.29
DEUTERIO CARBON-13 DESCARGA TOTAL

VAPOR
EN EL GAS OXIGEN-18 DEUTERIO
-80.4
-3.5
-2.61
-77.6
-65.9
-2.35
-72.3
-70.6
-4.1
-2.09
-67.8
-71.5
-70.8
-3.88
-66.2
-3.7
-66.2
-3.18
-70.8
-2.91
-70.3
-73.8
-77.5
-3.3
-2.89
-72.7
-71.7
-3.42
-62.1
-68.0
-66.0
-68.0
-68.0
-64.3
-4.5
-60.1
-5.4
-4.0
-3.5
-67.3
-73.9
-69.3
-70.6
-82.2
-4.4
-64.9
-68.2
-46.0
-5.8
-53.4
-60.4
-3.2
-4.0
-71.7
-66.2
-1.47
-1.63
-3.56
-4.93
-2.52
-2.84
-1.38
-3.21
-2.2
-3.23
-4.10
-6.7
-3.72
-3.48
-1.87
-2.81
-2.96
-4.0
-3.29
-62.1
-68.0
-66.0
-68.0
-68.0
-64.3
-60.1
-67.3
-71.9
-68.4
-70.4
-81.6
-64.9
-68.2
-46.0
-53.4
-60.4
-71.3
-66.2
DEUTERIO Y OXIGENO-18 FUERON ANALIZADOS POR EL HE, MXICO

EL CARBONO-13 SE ANALIZO EN EL USGS LABORATORY. MENLO PARK, Ca.
donde (t) es la temperatura de saturacin a la altura de 2800

msnm que es la de Los Humeros.Estas ecuaciones 12 y 13 son
vlidas para temperaturas entre 80 y 100C.
b) Se utilizan los resultados de los anlisis de la fase

vapor separada, de acuerdo con las siguientes ecuaciones:
5180dt=5v180 +10 3 lna(Xa)
D dt =<SvD+10 3 lna (Xa)
(14)
(15)
donde Xa es la fraccin de agua a la temperatura de separacin

y se determina de acuerdo con la siguiente expresin:
Xa = Hv - Ho / Hv - Ha
332
(16)
donde Ho es la entalpia de mezcla, Hv y Ha son la entalpia del

v a p o r y l i q u i d o r e s p e c t i v a m e n t e a la t e m p e r a t u r a de
separacin. El coeficiente de particin (10 3 lna) se determina
de datos experimentales desarrollados por Botinga (1969).
En la figura 12 se encuentran graficados el contenido de

deuterio contra el contenido de oxgeno-18 de los pozos de
Humeros. Se puede observar en la figura
que los pozos presentan un corrimiento de oxgeno-18 caracterstico de fluidos
geotrmicos. Este enriquecimiento de oxgeno-18 se debe a que
el equilibrio agua-roca se llev a cabo a altas temperaturas.
Adems como referencia se incluy en la figura la composicin
isotpica del agua de manantiales y norias aledaos al campo.
Estos datos de deuterio, oxgeno-18 y tritio estn referidos
en la tabla 2.
Las muestras de Arteziano (47) y S.N. pizarro (M8) presentan un marcado corrimiento de oxgeno-18 respecto a la linea meterica, producto de la interaccin agua-roca
a altas temperaturas. La muestra proveniente de la laguna de
Alchichica ( M 3 7 ) presenta una composicin isotpica
c a r a c t e r s t i c a de a g u a s m o d i f i c a d a s por p r o c e s o s de
evaporacin a temperatura ambiente. El resto de los manantiales se u b i c a n en la l n e a de agua m e t e r i c a ( T e l l o ,
H.E.1988).
A
/LCHCHIC*
-24 -
-48 O
Di
U
Ul
Q
-72 -
-96 -
MANANTIALES
(DESQUEJA. TOTAL)
I POZOS
-120
-13
-11
-7
-5
-3
-1
OXIGENO 18
FIGURA 12.-
COMPOSICIN ISOTPICA DE MANANTIALES Y POZOS

DEL CAMPO GEOTRMICO
LOS HUMEROS, PUE.
333
10.GEOTERMOMETRIA ISOTPICA DEL CO2-CH4
Una extensiva investigacin de la composicin isotpica

del dixido de carbono y metano presente en fumarolas, manantiales calientes y fluidos geotrmicos se han llevado a cabo en
los ltimos 10 aos. Estas investigaciones se han realizado
con el objeto de: 1) Determinar si el contenido de
C en el
CO2 presenta alguna variacin significante en relacin con
cambios del gradiente geotrmico. 2) Probar la validez del
geotermmetro isotpico de CO2-CH4.
Ahora bien, el C02 es el compuesto ms abundante en los
fluidos geotrmicos investigados los cuales varan de acuerdo
con su ubicacin geogrfica. Las variaciones que presenta no
son al azar, ya que valores ms altos de 8 C estn asociados
con anomalas termales (Panichi y Tongiorgi, 1975). Por tanto,
las variaciones de S C en el C02 natural puede considerarse
como una herramienta auxiliar en la prospeccin de nuevas
reas geotrmicas.
Pequeas cantidades de metano e hidrgeno siempre

acompaan al CO2 en fluidos geotrmicos. Suponiendo que el
equilibrio isotpico ocurre entre C02, CH4, H2, y H2O a travs
de la reaccin.
CO2 + 4H2 = CH4 + 2H2O
(17)
El fraccionamiento isotpico observado entre los pares CO2

- CH4, H2O - H2 y H2 - CH4 han sido usados para evaluar la
temperatura a profundidad en varias reas geotrmicas (Craig,
1953; Hulston y McCabe,1962; Los datos isotpicos del contenido de SC
en el CO2 y CH4 para dos de los pozos de Los Humeros se refieren a continuacin.
POZO
FECHA
Tsep
5l3c
cH4
5l3c
CO2
T C
H17
14-V-87
175
-22.9
-4.O 400
H18
14-V-87
195
-24.6
-5.8
400
Cabe mencionar, que tanto el contenido de S C, como las

temperaturas fueron proporcionados por A.Truesdell
(comunicacin personal, 1988) . La constante de equilibrio para
el sistema C02 -CH4 ha sido calculada usando los grficos
elaborados
por Botinga (1969) para temperaturas entre O a 700
0
C. En el rango de temperaturas de inters geotrmico, por
ejemplo, de 100 a 400 C, los valores reportados pueden ser
determinados por medio de la ecuacin:
l'o3lna = -9.01 + 15.301 * 103T~1 + 2.631 * 106T~2
(18)
donde a = (13C/12C) CO2/ ( C/ 12C)CR4 y T es la Temperatura
expresada en K.
Si se aplica la ecuacin (18) para la evaluacin de la
temperatura, se debe suponer que existe equilibrio isotpico
entre el CO2 y CH4. Sin embargo, esta suposicin ha sido muy
criticada por varios investigadores entre ellos (Craig, 1963).
Por lo tanto, es importante discutir la validez y limitaciones
del geotermmetro isotpico de CO2 - CH4:
334
I) En todos los campos investigados, incluyendo Los

Humeros, el geotermmetro isotpico CG>2 - CH4 da temperaturas
generalmente de 50 a 200C ms altas que la temperatura medida
directamente en el cabezal.
II) El C02 y CH4 pueden estar en equilibrio isotpico
solamente cuando ambos se originen del mismo proceso qumico.
Esto es cierto para sistemas de baja temperatura como se ha
observado en gases naturales producidos por procesos bacterianos y no hay razn porqu no sea cierto tambin para sistemas
de alta temperatura (Panichi, C. , Ferrara, C., Gonfiantini,
R., 1976).
III) La 513C del metano vara de -20 a -30 %. en sistemas

geotrmicos. Mientras que, el metano que se origina
a ms
13
bajas temperaturas presenta valores ms negativos
de
C.
Para
el caso de Los Humeros los valores de <S13C varan de -22.9
(H17)
a -24.6
(H-18).
Esto es una evidencia de que la composicin isotpica del

CH4 refleja la alta temperatura a la cual se form o bien a un
intercambio sucesivo con el CO2 dentro del sistema geotrmico.
IV) Generalmente se admite que la velocidad de reaccin es
muy lenta en sistemas geotrmicos.
De acuerdo con lo anterior puede concluirse lo siguientes
a) Debido a la falta de equilibrio isotpico, las temperaturas evaluadas a partir de la composicin isotpica de CO, y
CH4 pueden no tener sentido (400C para el H17 y H18).
b) Sin
embargo, tambin puede ser que estas temperaturas sean respresentativas de fluidos ms profundos.
11. GEOTERMOMETRIA ISOTPICA DEL DEUTERIO EN H2 y CH4
Tambin se aplic la geotermometra isotpica del deuterio en H2 y CH4 a los pozos H17 y H18. Los resultados se
refieren a continuacin:
POZO
FECHA
Tsep.
S DR2
S DCH4
TC
H17
14-V-87
175
-435
-154 400 (D)
H18
14-V-87
195
-392
-155.5
430 (D)
530 (C)
donde (D) y (C) significa que el coeficiente de particin fue

calculado a partir de los datos experimentales desarrollados
p o r B o t i n g a ( 1 9 6 9 ) . Cabe m e n c i o n a r q u e estos v a l o r e s
analticos fueron proporcionados por A. Truesdell (1988). Como

se puede observar las temperaturas calculadas son muy altas.
Esto sugiere o bien que no exista el equilibrio isotpico o
que estas temperaturas sean representativas de fluidos de
origen ms profundo.
335
12o CONTENIDO DE 513C EN EL C02
(gas)
Se determin el contenido de
C en el CO^ en muestras de
gases de los pozos de Los Humeros.Como puede observarse en la

tabla 5 existe una diferencia bastante notoria en el contenido
de <S13C entre pozos localizados en ambientes volcnicos (Los

Azufres) y pozos
localizados en ambientes sedimentarios (Los
Humeros). La S 13C de rocas sedimentarias13
marinas (calizas) es
del orden de cero. Mientras que la 6 C de CO2 de origen

magntico es del orden de -7 a -8 %. para los pozos de Los
Humeros el contenido de 513C de CO2 en la muestra de gas vara
de -3.2 a -5.8 de acuerdo con lo anterior puede decirse que
existe un aporte de carbn de origen sedimentario. Siendo los

pozos Hl, H6, H8, Hll y H19 los que presentan un mayor aporte
de
C, adems de estar ms cercanos al alto estructural de
las calizas. Estos pozos estn ubicados en la parte noroeste
del campo. Los pozos H6, H12 y H18 los cuales estn ubicados
en la zona sur del campo, presentan valores ms negativos de
6 C lo cual refleja que si hay aporte de
C de origen
sedimentario, pero predomina el
C de origen magmtico0
Esto es cierto ya que los pozos H12 y H18 los cuales estn
ubicados cerca del crter de Maztaloya uresentan los valores
ms cercanos al valor que presenta el
13
C de origen magmtico
-7 a -8 %.(Figura 13).
13. CAMBIOS SECUNDARIOS EN LA COMPOSICIN QUMICA E ISOTPICA
DE LOS FLUIDOS.
La composicin qumica e isotpica de los fluidos producidos por los pozos productores de Los Humeros han sido utilizados en el modelo geoqumico del campo (Tello, H. E. 1989).
La existencia de procesos de mezcla, condensacin dentro

del campo han sido evidenciados, por medio de los anlisis
qumicos e isotpicos, el problema ahora es definir y delimitar las reas dentro del yacimiento geotrmico que son afectadas por esos fenmenos secundarios.
El presente trabajo representa un intento por correlacionar
un cierto nmero de parmetros geoqumicos. Por tanto, se ha

considerado adems de parmetros isotpicos, algunas especies
qumicas encontradas en los fluidos geotrmicos.
I Q
Los anlisis combinados de SO
y 6D como se menciono en
prrafos anteriores nos han servido para definir la

caractersticas isotpicas del vapor profundo y nos puede
ayudar a conocer las propiedades del agua ms somera que
pudiera estar recargando el acufero geotrmico. Adems de
indicarnos la direccin del flujo subterrneo.En la figura 14

se presenta una configuracin de isovalores de oxgeno-18 para
los pozos de Los Humeros. Se puede observar en esta figura que
los valores menos negativos se encuentran al sur de la zona
perforada y estos valores siguen una tendencia SE-NW lo cual
coincide con el alto estructural de las calizas. Esto sugiere
que existe un enriquecimiento en istopos pesados producto de
la interaccin del agua con calizas, a altas temperaturas.
336
6S9500
662500
665500
2178000
- 2178000
2175000
- 2175000
2172000 -
2169000
659500
2172000
2169000
662500
665500
Figura 13. Isovalores de carbono-13 (Los Humeros)
337
659500
662500
665500
2178000
- 2178000
2175000
<r
2175000
2172000
2172000
2169000
2169000
659500
662500
665500
Figura 14. Isovalores de oxigeno18 (1988) Los Humeros
338
En la figura 15 se presentan los isovalores de temperaturas medidas en los pozos a condiciones de equilibrio se puede
ver en esta figura que las temperaturas ms altas se encuentran en la parte norte de la zona perforada, concretamente en
pozos localizados dentro del colapso central, los pozos H4,
665500
659500
2178000
- 2178000
2175000
2172000
- 2175000
2169000
659500
2172000
2169000
662500
665500
Figura 15. Isotemperaturas medidas en Los Humeros.
339
Hll, H20 son los que presentan estas temperaturas las cuales
son mayores a 300C. Los pozos localizados en la zona sur del
campo en el Xalapasco Mastaloya tambin se detectan
temperaturas mayores a los 300C. Es importante hacer notar
que los pozos H13, Hl, H7 , H8 estn ubicados cerca de la
isolinea de 300C, y estn ubicados entre la falla de las
vboras y la falla de Los Humeros.
Al configurar los isovalores de temperaturas calculadas
por medio del geotermmetro de gases de D'Amore y Panichi
(1980) (Figura 16), se encontr que los valores ms altos
corresponden a pozos localizados en la falla de Los Humeros

(H7, H8, H10) y otros dentro del colapso central H17, H15, H16
y H9 (Tabla 3) .
De acuerdo con lo anterior puede concluirse que las zonas

ms importantes en cuanto a temperaturas se refiere pueden
clasificarse como sigue: 1) la zona del colapso central con
temperaturas medidas y/o calculadas de 307C hasta 384C. 2)
la zona del Xalapasco Maztaloya con temperaturas que van de

302 C a 356C y 3) el corredor central o falla de Los Humeros
con temperaturas medidas y/o calculadas que van de 267 a 315C
14. CONCLUSIONES
De acuerdo con su composicin qumica el agua producida
por los pozos de Humeros se clasifica en bicarbonatada-sdica,

sulfatada-sdica y clorurada-sdica. Al hacer la correccin de
la composicin qumica del agua separada de los pozos, se
encontr que el pozo Hl, produce en una zona de lquido dominante. El resto de los pozos de Los Humeros se encuentran
produciendo en una zona de dos fases.

De acuerdo con el estado de equilibrio los pozos Hl, H6,
H7, H8, Hll, H12, H20 y H23 pueden presentar depositaciones de
carbonato de calcio, ya que estn sobresaturados con respecto

a la calcita.El pozo H9 lo ms probable es que no presente
depositacin de carbonato de calcio ya que est insaturado con

respecto a la calcita. Con respecto a la anhidrita se concluye
que los pozos que pueden presentar depositaciones de sulfato
de calcio son los pozos Hll, H20 y H23 por estar sobresaturados con respecto a la anhidrita. El pozo H9 puede no presentar
depositaciones de sulfatos de calcio ya que presenta una gran
insaturacin con respecto a la anhidrita. Los pozos Hl, H8,
H12 estn en equilibrio soluto/mineral y los pozos H6 y H7
tienden al equilibrio por tanto, es probable que se deposite

sulfato de calcio. Con respecto al cuarzo la totalidad de los
pozos estn insaturados, por tanto, es probable que no haya

depositacin de slice en la zona de produccin. Sin embargo,
es probable que deposite SiO2 donde haya cambios de fase. O
bien cuando haya presencia de hidrxidos de algn metal, los

cuales actan como puente para que inicie la depositacin de
la slice.
340
659500
662500
665500
2178000
- 2178000
2175000
- 2175000
2172000
2169000
659500
- 2172000
662500
665500
2169000
Figura 16. laovalores del geotermo'metro de gases.
341
1 fi
Los pozos de Humeros, presentan un corrimiento de SO
caracterstico de fluidos geotrmicos. Esto indica que la
interaccin agua-roca se efectu a altas temperaturas. La
composicin isotpica del agua de los manantiales se agrupan
en su mayora en la linea de agua meterica (Tello, H.E.1988)o
Tambin se analiz el contenido de 513C en el CO2 en muestras de gases de los pozos de Humeros. Se13 encontr que existe
una gran diferencia en el contenido de <S C entre pozos localizados en ambientes volcnicos (Los Azufres) y pozos localizados en ambientes sedimentarios (Los Humeros), ya que en primer
lugar se sabe que la 8 C de rocas sedimentarias marinas
(calizas) es del orden de cero. Mientras que la <S13C de CO2 de
origen magmtico es del orden de -7 a -8 %. . Para los pozos
de Humeros la 13C de C02 en la muestra de gas vara de -3.2 a
-5.8, por lo que puede concluirse que existe un aporte de
carbn de origen sedimentario. Siendo los pozos Hl, H6, H8,
Hll y H19 los que presentan un mayor aporte de 513C de origen
sedimentario, lo cual se debe a que estn ms cercanos al alto
estructural de las calizas. Ahora bien los pozos H6, H12 y H18
los cuales estn ubicados cerca del crter de Maztaloya presentan valores ms negativos de 8 C (-4.1 a -5.8) lo cual
refleja que si hay aporte de 8 C de origen sedimentario, pero
predomina el 513C de origen magmtico.
De acuerdo con las temperaturas geotermomtricas de agua y
gases complementados con temperaturas medidas se encontr que
existen 3 zonas bien definidas, los cuales pueden definirse de
acuerdo a sus temperaturas como sigue 1) la zona del colapso
central con temperaturas medidas y/o calculadas de (307C a
384C), 2) la zona del xalapasco Maxtaloya (302 a 356C) y 3)
corredor central o falla Los Humeros con temperaturas de 267 a
315C.
RECONOCIMIENTO
El autor agradece al Ing. Marco Antonio Torres R., por el

apoyo recibido en la impresin final de este trabajo.
REFERENCIAS
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0C a 370C. Sciencie Institute, University of Icelan.
Arnorsson, S., Gunnlaugsson, E. 1982b. The chemistry of geothermal waters in Iceland II. Mineral equilibria and Independent variables controllings water compositions.Science Institute, University of Iceland.
Arnorsson, S., Gunnlaugsson, E. 1982. The chemistry of geothermal waters in Iceland III. Chemical geothermometry in geothermal Investigations. Science Insitute, University of Iceland.
342
Botinga, y., (1969). calculated fraccionation factors for

carbon and hydrogen isotope exchange in the system calcite
carbon-dioxide-graphite-methano-hydrogen-water vapor "Geochim.
Cosmochim. Acta, V. 33, p.49.
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in Geothermal areas. (Edited by Tongiorgi, E) C.N.R., Spoleto.
Craig, H., 1953. The geochemistry of stable carbon isotopes
Geochim. Cosmochim. Acta 33. pp. 49-64.
D'Amore, F. and Panichi, C. 1980. Evaluation of deep temperatures of hydrothermal systems by a new gas geothermometer.
Geochim, cosmochim. Acta, 44, pp. 549-556.
Ellis, A. J., and Mahon, W.A.J., 1977. Chemistry and Geothermal systems, Academic Press, New York. pp. 299 - 301.
Fournier, R.O., 1977. Chemical geothermometer and mixing
models for Geothermal systems Geothermics, vol. 5 pp.47 -49.
Giggenbach, W., 1986. Graphical techniques for the evaluation

of water/rock equilibration conditions by use of Na,K, Mg and
Ca-contents of discharge waters.Chemistry Division Department
of scientific and Industrial Research.Petone, New Zealand.
Giggenbach, W., 1988. Geothermal solute equilibria. Derivation Na-K-Mg-Ca-geoindicators. Geochim. Cosmochim. Acta, 52
pp.2749-2765.
Giggenbach, W., 1989. Techniques for the interpretation of

water and analyses in geothermal exploration. Chemistry
Division. Department of Scientific and Industrial Research. Petone, New Zealand.
Helgeson, C.H., Kirkham, D. 1969. Theore tical prediction of
thermodynamic Behavior of aqueous electrolytes at High pres-
sures and temperatures: II Debye-Huckelparameters for activity coefficients and relative partial molal properties. Departament of Geology and Geophysics,
University of California.
Hulston, J.R. and McCabe, W.J.,1962. Mass spectrometer measure
ments in the thermal areas of New Zealand carbon isotopic
ratios. Geochim. Cosmochim. Acta 26, 399-410.
Tello, H. E., 1984a. Qulmica de los fluidos de descarga del

pozo Humeros 1.CFE. Gerencia de Proyectos Geotermoelctricos
Informe 16-84. Morelia, Michoacan, Mexico.
Tello, H. E., 1984b. Metodologia para la estimacion de la
composicin de la fase liquida a descarga total y a condiciones de yacimiento. CFE. Gerencia de Proyectos
Geotermoelctricos. Informe GQ - 4 - 84. Morelia, Mich.,
Mexico.
Tello, H. E., 1986. Quimica de los fluidos de los pozos del

campo geotrmico de Los Humeros,Puebla. CFE. Gerencia de
Proyectos
Geotermoelctricos.
Informe
21-86.
Morelia,Mich.Mexico.
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Tello, H E., 1987. Caractersticas Geoqumicas de la descarga

de los pozos de Los Humeros, Puebla. CFE. Gerencia de Proyectos Geotermoelctricos. Informe 12-87. Morelia,Mich.,Mxico.
Tello, H. E.,1988. Caractersticas qumicas e isotpicas del
agua
de m a n a n t i a l e s aledaos al campo geotrmico de Los
Humeros. CFE. Gerencia de Proyectos Geotermoelctricos. Informe 22-88. Morelia, Michoacn, Mxico.
Tello H . E . , 1989a. Qumica de los fluidos de descarga del pozo

H-16. CFE. Gerencia de Proyectos Geotermoelctricos. Informe
68-89o Morelia, Michoacn, Mxico.
Tello, H. E. 1989b. Modelo geoqumico del campo geotrmico de
Los
Humeros,
Puebla.
C F E . Gerencia
de
Proyectos
Geotermoelctricos. Informe 07/89. Morelia,Michoacn,Mxico.
T r u e s d e l l , A . , 1988. R e s u l t a d o s a n a l t i c o s d e d e u t e r i o ,
oxgeno-18 y carbono-13 de los pozos de Los Humeros. Comunicacin personal.
344
GEOCHEMICAL REPORT ON THE CHALLAPALCA AND

TUTUPACA GEOTHERMAL AREAS, PERU
G. SCANDIFFIO
Ente Nazionale per 1'Energa Elettrica,
Pisa, Italy
D. VERASTEGUI, F. PORTILLA
Unidad Investigaciones Geotermales,
ELECTROPERU SA,
Lima, Peru
Resumen-Abstract
INFORME GEOQUMICO SOBRE LAS ZONAS GEOTERMALES DE CHALLAPALCA Y TUTUPACA,
PER.
Se muestran brevemente las
caractersticas ms sobresalientes de cinco
zonas termales que se encuentran en la parte sur del Per a lo largo de la
cordillera andina y cerca de la frontera con Chile y Bolivia.
Se han organi-
zado estas zonas en dos regiones:

Challapalca, que comprende Challapalca y Paucarani;
Tutupaca, que comprende Calacea, Calientes y Tutupaca.
Los datos geoqumicos se refieren principalmente a la composicin qumica

e isotpica del agua en determinados puntos;
si bien la composicin del gas
de estos caudales geotrmicos es casi desconocida, se obtuvieron indicaciones
muy favorables.
cuitos termales;
En las zonas de Calientes y Challapalca existen amplios cirsus temperaturas profundas deberan sobrepasar los 200C.
GEOCHEMICAL REPORT ON THE CHALLAPALCA AND TUTUPACA GEOTHERMAL AREAS, PERU.
The most
outstanding characteristics
of
five
thermal
zones,
located in the southern part of Peru along the Andean Cordillera
and near the border with Chile and Bolivia, are briefly discussed.
These zones were organized into two areas:
- Challapalca, comprising
- Tutupaca comprising
Challapalca and Paucarani;
Calacoa, Calientes and Tutupaca.
The geochemical data mainly regard chemistry and isotopes of

water
points;
even
if
the
gas
composition
of
these
geothermal
345
discharges
out.
is almost unknown, very
favourable
indications came
In the Calientes and Challapalca zones wide thermal circuits
exist; their deep temperatures should exceed 200 C.
1. Previous studies
The Challapalca and Tutupaca areas have been the subject of

studies by AQUATER-INGEMET [1] and Burgess [2],
The AQUATER survey regarded a region covering tens of thousands
of square kilometres, so that it can only be of interest for

general informations.
BURGESS, instead, carried out, with financial support of OLADE,
an a detailed study of the areas in question sampling 70 water

points.
Only
chemical
data
were
found
in
the
records
of
ELECTROPERU, the peruvian Agency attending to the development of
this
Coordinated
Research
Programme.
Isotopic
data
and
the
sampling map of the manifestations were missing.
2. Geologic outline and stratigraphy

This study regards an area of approximately 4500 sq km running
between
the
Western
Cordillera
and the
Peruvian
Plateau.
The
geological and structural setting is constitued by Mesozoic Units,

made up of terrigenous sediments, intensely deformed and folded
over which lie in unconformity the products of several volcanic
cycles spanning
glacial
or
from Lower Tertiary to Quaternary, and clastic
glacio-fluviatile
quaternary
deposits.
volcanics are the most widespread formations in the area.
346
However
From top downward the stratigraphie sequence is made up of:
Quaternary glacial or glacio-fluviatile erosion deposits;

Purpurini=i
Tutupaca
Upper Tertiary-Quaternary volcanic units;
Chila
=!l
Capillune formation=i|
Seneca volcanics
Limnic-Volcanic sequence;
Maure formation
=="
Huaylillas Volcanic Complex;
Huilacollo formation=i|
ow1"^
Tarata formation
=* Centre and SW
Toguepala Group;
Toquepala formation
NW
=^
Chachacumane format ion=ii Yura Grou
Atascapa formation
=^
P-
This
section
stratigraphie
of
Appendix
sequence
can
1C traced
be recognized
on the
in the AA'
geological
map
of the
Tutupaca area in Appendix 1A.
2.1 Tectonics, volcanism and thermal features

During
Tertiary
the
Andean
tectonic
in
this
area
was
characterized by brittle tensional features. The main phase dates

back to Miocene.
lineaments.
As
In places there was a reactivation of
result
the
region
was
divided
into
older
blocks
unevenly displaced, which could be responsible for the arising of
geothermal reservoirs.
Three main fault trends are distinguished, though some other
orientations occur: NW-SE (Andean), NE-SW (anti-Andean) and E-W;
some of thes trends can be seen in Appendixes 1A, IB and 1C.
Over the older ignimbritic basal complex (Huaylillas) several
central
volcanic
apparatuses
built
up
in
various
periods
of
activity and their products covered the whole area. Glacial or

glacio-fluviatile erosion have partly modified the morphology due
to the different volcanic cycles, but the most recent volcanics
remained almost unaffected by weathering.
Three
main
volcanic
phases
are
recognized:
a) Chila;
b) Tutupaca; c) Purpurini.
347
a) In a
first
period
spanning between
5 and
8.4 M.a.
activity was mainly effusive from central volcanoes
the
(Nazaparco,
Loma Pabelln, Novena, Jucure, Chila and San Francisco. The second
period
and
reactivated the former apparatuses between 2 and 4 H.a.,
gave
rise
predominantly
to
effusions
but
also
explosions
producing andsites.
b) This second
phase distributed
its products
over the whole
area, as isolated blocks, over the former volcanics. The glacial

and
glacio-fluviatile
erosion
has
strongly
altered
the
Chila
products while it has just touched the Tutupaca ones. The age of
Tutupaca volcano is estimated around 0.7 M.a., to the same period
should be ascribed also Yucamane, Yucamane Chico, Calientes, San

Francisco,
Casiri
predominant
with
and a few domes;

acid
products
again
(dacites),
effusive
activity
noteworthy
are
is
the
pyroclastic deposits of Yucamane.
c) The last volcanic phase (Purpurini), displaced superficial

domes,
probably
magmatism.
the
most
differentiated
products
of
regional
These domes of dacitic compositions could point to the
existence of magmatic chambers not at a great depth. In the local

morphology
the
domes
appear
as
isolated
shapes,
untouched
by
erosion, at times related to collapse structures.
Radiometrie age of Purpurini volcanics is around 0.1 Ma, of the
same cycle are Kere, Casiri and Paucarani.

The volcanic apparatuses related to the study zones of Tutupaca
and Challapalca are singled out in Appendixes 1A and IB.
Several
thermal
manifestations
are
known
(thermal
waters,
fumaroles, solfataras, geysers), almost all occurring close to the
youngest volcanic apparatuses, along Andean and anti-Andean fault

systems.
348
Fumaroles and geysers are mainly sited toward Tutupaca and

Calientes, while solfataras occur mostly around Paucarani sector.
Thermal waters spring almost always where there are fractures,
even having sometimes their final seepage through glacio-fluvial
covers.
Three circuits can be distinguished on the basis of spring
features :
1) subsurface freshwaters of meteoric origin infiltrating in
the volcanics and
outcoming
at the
contact between
lavas
and
pyroclastics as cold waters;

2) waters that through deeper circuit become contaminated by
geothermal fluids hosted by the permeable portion of the Capillune
formation, and rising as thermal waters of low salinity;

3) waters with higher temperatures and salinities, probably
from deep aquifers developed through regional fractures well below
the Huaylillas ignimbrites.

It is however difficult to distinguish "reservoir" and "cover"
geologic units because of the nature of the outcrops.

Mesozoic terrains have various lithologies and permeabilities
with a noteworthy silt-clay component; the limnic-volcanic upper
tertiary sequence can make up for a partial cover and is well

spread; volcanics could
act
as recharge
areas or covers
as
function of fissuring or/and hydrothermal alteration achieved. In
fact such alteration processes are known in the whole area, mostly
related to the occurrences at the highest temperatures, mainly as
deposits of kaolinite or silica/carbonate incrustations.

3. Sample collection and field determinations
The sampling carried out over a total of 11 days was mainly
performed
in three zones: Challapalca, Paucarani and Tutupaca.

349
Thirtyone manifestations were visited, 28 samples of water were

taken and 3 of gas; samples location is shown in Appendixes 1-1B.
Some of the water points recorded in the previous studies were not
found
owing
to
imprecision
as
to
their
location
or
to
the
(Calientes
and
impossibility of reaching them.

Water
Calacoa)
samples
were
of
later
others
sent
zones
to
not
Italy
visited
for
further
Unfortunately, for these samples, that proved
analyses.
to be of maximum
importance, some field determinations were not carried out and no

sample of gas is avalaible. Water samples were collected generally
in
separate
aliquots
for
analyses
of
major
and
trace
constituents, monomeric aluminum silica, stable isotopes (18O and

D) and tritium.
Temperature, pH, conductivity and alcalinity were determined in
the field. Major and trace chemical costituents
were analyzed in
ENEL laboratory in Italy; isotopes were analyzed in IAEA and DSIR
laboratories.
4. Water Chemistry
4.1. Classification of water samples (Tutupaca)
The analytical results of the fluids sampled in this area are

shown
in tables 1
identify
(waters) and 3 (gases) . The code CA and CS
manifestations
in
the
Calacoa
and
Calientes
zones
respectively.
The sample classification was mainly done by simple correlation
diagrams involving both major and trace chemical components.

In the Piper diagram of fig.l, all the samples of the Tutupaca
area (with the exception of TP12) are distributed in the NE and SE
350
Table 1 - Tutupaca water samples analyses
s = spring
Samplt;
Date
Cod. S.T
. T.f.pH.f.
C
CA1
CA2
CA3
CS1
CS2
CS3
CS4
TP10
TP11
TP12
TP1B
TP2
TP3
TP4
TP6
TP7
TP8
TP9
30/05/86
30/05/86
30/05/86
30/05/86
30/05/86
30/05/86
30/05/86
21/05/86
21/05/86
21/05/86
19/05/86
20/05/86
20/05/86
20/05/86
20/05/86
21/05/86
21/05/86
21/05/86
1755 S
1756 S
1757 S
1758 S
1759 S
1760 S
1761 S
1669 S
1670 S
1671 S
1660 S
1661 S
1662 S
1663 S
1665
1666 S
1667 S
1668 S
60.0
91.0
14.0
86.0
86.0
80.0
14.0
50.0
46.0
14.0
31.0
36.0
56.0
56.0
86.0
3.0
12.0
60.0
(:on.f. /Uc.f.
MS meq/l
6.30
7.96
1710
4130
3.8
3.2
7.65
7.04
6.94
5480
3980
5160
2.0
2.70
2.90
7.56
6.41
6.40
6.44
6.56
3.63
6.75
6.79
3.00
2100
2050
62
1790
2470
2840
3080
577
230
144
2100
0.0
0.0
2.9
2.2
10.9
10.8
11.2
0.0
0.0
0.0
1r.i. pH.l.
c
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
6.27
8.30
7.12
7.54
8.23
6.95
7.60
2.72
2.85
6.50
7.50
7.97
7.76
8.00
3.10
6.45
6.20
2.88
(:on.l. /Uc.l.
MS
meq/l
1740
2920
331
5600
5670
5580
353
2390
2260
67
2260
2760
2810
3030
7230
243
149
2420
3.6
3.6
1.1
2.1
3.2
2.4
0.4
0.0
0.0
0.4
7.9
10.3
10.1
10.8
0.0
0.7
0.5
0.0
Ca
Mg
Na
3.6 58.8
3.6 67.4
1.2 32.7
2.1 42.4
3.2 45.0
2.4 48.3
0.4 31.3
0.0 152.0
0.0 151.0
0.4
3.3
7.9 44.8
10.3
30.1
10.1
55.5
10.8
23.2
0.0 19.8
0.7 21.3
0.5 11.4
0.0 152.0
5.70
9.70
7.30
0.49
3.50
4.30
10.90
39.00
41.00
1.80
5.80
9.40
6.30
6.15
13.70
6.50
2.60
40.30
319.0
602.0
19.2
1270.0
777.0
1000.0
16.3
166.0
163.0
5.5
472.0
589.0
619.0
641.0
29.9
12.8
10.1
179.0
(Ic.l.
Cl
S04
HC03
Si 02
H3B03
Br
30.1
404.0 126.0225.8 530.0
53.0
702.0 368.0 195.3
766.0
9.5 77.1 73.2
4.6
0.0
1960.0 93.4122.0
969.0
99.1
1140.0 100.0176.9 836.0
54.9
1550.0 112.0134.2
850.0
42.5
1.2 124.0 24.4 50.0
6.7
162.0 1040.0
19.9
0.0 185.0
150.0 1020.0
0.0 178.0
18.7
1.2
8.6 24.4 46.0
2.5
36.6 322.0 314.0 0.0 109.0
45.9 428.0 372.0 659.0 172.0
43.6 444.0 390.0 659.0 120.0
49.9 452.0 412.0 683.4 126.0
18.1
1.7 248.0
0.0 190.0
3.4
1.5 66.4 0.0 42.0
2.0 32.2 0.0 38.0
4.8
23.8 168.0 1000.0
0.0 196.0
67.5
121.0
1.1
323.0
194.0
255.0
0.2
30.5
28.9
0.2
56.0
72.7
75.7
79.1
0.7
0.3
0.2
32.5
0.98
1.76
0.00
3.44
2.10
2.70
0.00
0.35
0.42
0.00
0.97
1.24
1.30
1.32
0.00
0.00
0.00
0.37
meq/l
0.00
0.60
0.00
0.50
0.30
0.30
0.00
0.00
0.00
0.00
0.70
0.50
0.80
0.00
0.00
0.00
0.00
0.00
Table 1 - ( cent.)
Sample Code
CA1
CA2
CA3
CS1
CS2
CS3
CS4
TP10
TP11
TP12
TP1B
TP2
TP3
TP4
TP6
1H7
TP8
TP9
2.00
3.20
1757 0.00
1758 2.70
1759 1.50
1760 1.80
1761 0.00
1669 4.30
1670 4.60
1671 0.00
1660 0.96
1755
1756
1661
1662
1663
1665
1666
1667
1668
1.00
1.04
0.00
0.28
0.16
0.00
4.80
Li
1.70
3.00
3.00
9.80
5.80
7.60
0.00
0.50
0.50
0.00
1.40
1.80
1.90
2.10
10.00
10.00
0.00
0.59
Rb
0.27
0.49
0.49
1.30
0.54
0.50
0.00
0.12
0.13
0.00
0.19
0.25
0.24
0.24
0.06
0.00
0.00
0.15
Cs
0.50
0.00
0.00
3.40
1.90
2.80
0.00
0.34
0.00
0.00
0.46
1.50
0.70
0.70
0.00
0.00
0.00
0.28
NH4
Sr
Ba
0.200 1.10 0.080

0.300 1.50 0.050
0.000 1.50 0.050
0.600 1.10 0.020
0.500 0.99 0.040
0.500 0.86 0.060
Zn
Sb
0.037 0.000
0.016 0.000
0.016
0.000
0.000
0.007
0.000 0.11 0.018 0.000
0.100 0.14 0.018 0.400
0.200 0.09 0.018 0.400
0.000 0.03 0.000 0.000
1.100 1.20 0.035 0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
1.00 0.001 0.000 0.000
1.400
1.100
0.200
0.000
0.000
0.200
1.50
1.40
9.00
0.17
0.13
0.04
0.039
0.028
0.011
0.010
0.024
8.000
0.000
0.000
0.081
0.000
0.000
0.420
0.000
As
1.60
2.80
0.01
9.30
Fe ALT
0.420
0.220
0.000
0.030
0.270
0.000
0.000
0.200
Al.M
0.000
0.000
0.000
0.000
5.60 0.080 9.000 0.000

8.00 0.440 0.120 0.000
0.00 0.020 0.000 0.000
0.33 29.00 35.50 0.000

0.29 27.20 34.90 0.000
0.00 0.000 0.000 0.000
0.49 0.760 9.000 0.170
0.67 0.000 0.000 0.000
0.51 0.470 0.050 0.000
0.000
0.61 0.000 0.000 0.000
0.000
0.000
0.000
0.000
0.00
0.02
0.02
0.35
1.800
0.000
0.000
32.20
6.500
0.000
0.000
23.80
0.210
0.000
0.000
0.000
TDS
TAN
TCAT
5180
5D
meq/l
meq/l
o/oo
o/oo
1550 17.7
2703 30.7
157 3.1
4789 59.2
3179 37.1
3892 48.3
241
1866
1821
3.0
26.2
25.5
69
0.6
1858 23.5
1727 30.6
1764 31.4
1797 32.5
550
5.2
1.4
165
102 0.7
1864 25.6
18.3 - 1 1 . 78 -91.0
32.2 -11.28 -89.3

3.6 -11.36 -82.6
61.4 -12.67 -111.4
38.6
48.5
3.3
18.6
18.6
0.6
24.4
29.3
31.7
31.2
5.3
3.7
1.3
19.4
-13.36 -112.3
-14.04 -118.4
-14.13 -111.3
-13.44 -103.4
-14.11 -104.9
-13.16 -96.6
-13.36 -102.8
-13.39 -105.8
-13.46 -103.3
-12.86 -100.4
-11.84 -102.6
-12.73 -98.2
-13.34 -96.2
-14.20 -106.1
Tnt.
U.T.
1.2
0.4
2.0
0.4
0.4
5180/S04 534S/S04 A l t .
o/oo
o/oo m.
-6.00
3600
2900
3000
9.20 4340
-3.00
2.7
0.7
2.2
0.6
0.7
1.7
0.3
0.4
2.10
2.50
8.20
0.00
0.00
0.00
0.00
0.00
0.00
12.80
12.60
0.00
0.00
0.00
0.00
0.00
4315
4280
4320
4390
4330
4260
4120
4140
4050
4040
4480
4140
4140
4290
Table 2 - Challapalca water samples analyses

s = spring
SampU;
Date
Cod. S.T. T.f.pH.f.

C
PA1
PA2
PA3
PA4
PC1
PC10
PC2
PC3
PC4
PC5
PC6
PC7
PCS
PC9
17/05/86
17/05/86
17/05/86
17/05/86
14/05/86
16/05/86
14/05/86
14/05/86
15/05/86
15/05/86
15/05/86
15/05/86
16/05/86
16/05/86
1656
1657
1658
1659
1673
1682
1674
1675
1676
1677
1678
1679
1680
1681
S
S
S
S
S
S
S
S
S
S
S
S
S
S
45.0
9.0
62.0
38.0
43.0
18.0
87.0
8.0
12.0
72.0
22.0
58.0
24.0
68.0
(:on.f. /Uc.f. r.i. pH . I .:on.l.

(
/Uc.l. Pilc.l.
MS meq/l
6.59
5.05
6.50
5.98
6.81
6.72
7.92
9.02
8.20
6.12
6.28
6.10
6.72
6.10
1010
294
1880
890
1350
473
5460
339
292
207
475
4570
550
4630
11.2
0.0
4.5
4.5
3.8
1.9
1.4
0.0
0.0
0.7
0.0
4.4
1.8
3.1
c
20
20
20
20
20
20
20
20
20
20
20
20
20
20
MS meq/l
7.53
3.84
7.28
7.12
7.17
6.84
7.35
6.75
6.67
6.75
6.75
7.05
7.06
7.10
1120
274
1930
1040
1470
611
6190
314
291
220
506
4050
502
3860
10.6
0.0
4.4
4.3
3.7
1.9
1.2
1.0
1.2
0.6
1.5
3.7
1.7
2.9
Ca
Hg
Na
75.6
15.8
65.3
93.8
35.2
23.2
67.6
18.1
28.9
8.7
15.6
43.1
16.5
38.7
35.40
5.80
38.30
29.10
16.30
17.00
0.44
3.60
7.30
0.72
12.20
17.60
10.90
10.10
127.0
12.8
241.0
93.1
249.0
67.2
1420.0
37.2
16.4
26.6
59.1
848.0
65.9
807.0
S04
HC03
Si 02
H3B03
Br
3.7 116.0
42.9
0.6 125.0
4.2
90.3 498.0 70.8
31.0
6.1 344.0
29.4 354.0 41.4
95.0 58.7
16.4
91.9 2320.0 75.5
5.4 79.0
8.9
5.1
6.5 66.2
1.0 41.7
8.2
14.8 102.0 16.4
98.1 1330.0 107.0
84.2 29.6
10.1
84.0 1240.0 98.7
677.3
0.0
274.6
268.5
231.9
115.9
85.4
61.0
73.2
42.7
90.3
268.5
109.8
189.2
192.0
53.0
244.0
132.0
137.0
85.4
273.0
37.4
43.4
120.0
93.9
210.0
99.9
165.0
4.0
0.4
147.0
4.5
91.8
8.4
591.0
1.7
1.5
0.6
10.2
233.0
17.7
220.0
0.00
0.00
1.65
0.00
1.18
0.12
7.42
0.00
0.00
0.00
0.21
5.28
0.36
4.96
0.00
0.00
0.50
0.00
0.30
0.00
1.30
0.00
0.00
0.00
0.00
0.60
0.00
0.70
Cl
meq/l
10.6
0.0
4.4
4.3
3.7
1.9
0.6
1.0
1.2
0.6
1.5
3.7
1.7
2.9
Table 2 - ( cont.)
Sample Code
PA1
PA2
PA3
PA4
PC1
PC10
PC2
PC3
PC4
PC5
PC6
PC7
PCS
PC9
1656
1657
1658
1659
1673
1682
1674
1675
1676
1677
1678
1679
1680
1681
Li
Rb
0.12 0.16 0.19

0.27 10.00 0.00
022. 1.00 0.38
0.21 0.15 0.17
0.22 1.75 0.19
0.20 0.15 0.00
1 .84 11.50 1.10
0.22 0.03 0.00
0.30 0.03 0.00
0.15 0.00 0.00
0.20 0.17 0.00
0.86 4.90 0.76
0.24 0.30 0.04
1 .04 4.70 0.76
Cs
0.00
0.00
0.28
0.50
0.76
0.00
5.70
0.00
0.00
0.00
0.00
2.50
0.00
2.60
TAN
TCAT
180
meq/l
meq/l
0/00
o/oo
U.T.
0.000 0.35 5.500 0.050 0.000 605 13.6

0.000 0.00 0.250 6.400 0.100 235 2.6
0.000 4.50 0.140 0.050 0.170
1416 20.0
0.000 0.36 5.400 0.070 0.000 742 11.7
0.53 0.016 8.000 0.000 3.30 0.000 0.110 0.090 971 14.6
0.24 0.020 0.000 0.000 0.11 0.000 0.000 0<t)00
372 5.8
1.50 0.065 0.026 0.000 18.60 0.000 0.070 0.050 4893 68.4
0.15 0.010 0.000 0.000
0.05 0.000 0.000 0.000 192
2.8
0.19 9.000 0.000 0.000 0.05 0.000 0.000 0.000 185
2.8
0.13 0.043 0.007 0.000 0.02 0.390 1.100 0.210 212 1.6
0.17 0.000 0.014 0.000 0.32 0.020 0.080 0.000 416 4.7
1. 500 1.50 0.170 0.000 0.000 12.30 0.070 0.050 0.050 2917 44.1
0. 000 0.15 0.000 0.000 0.000 1.30 0.000 0.000 0.000 337 4.8
1. 500 1.500.1900.000 0.000 11.400.2000.0000.000 2698 40.1
13.3
1.9
19.2
11.9
14.7
5.9
67.5
3.0
2.9
1.9
4.7
43.0
4.8
-15.84 -117.5
0.7
-14.37
-14.74
-15.96
-15.25
0.5
0.1
0.3
NH4
0.400
0. 000
0.600
0.900
0. 100
0. 000
0.700
0.000
0.000
2. 400
0. 000
Sr
0.71
0.11
0.60
1.10
8a
Zn
Sb
As
Fe A l . T Al.M TDS
0.120 0.000
0.010 0.073
0.210 9.000
0.023 0.000
TP1B
TP4
TP6
PC6
Date
20/05/86
20/05/86
20/05/86
15/05/86
C02
%
N2
%
H2S
ppm
CH4
ppoi
65.65
93.54
98.75
22.90
34.00
6.17
1.24
77.10
2
0
0
363
277
0
2
-10.95
-11.68
-12.96
-3.76
-16.64
-14.57
-16.58
40.0 -14.58
Tab. 3 - Chemical analyses of gases
Sample
-16.76
H2
CO
ppm
ppm
4.2
2.9
450.0
4.2
2.0
15.4
48.6
6.5
-111.5
-118.6
-121.7
-119.0
-125.6
-104.9
-99.2
-103.0
-89.2
-124.6
-116.9
-126.2
-116.3
T r i t . 5180/S04 34S/S04 A l t .
o/oo
o/oo m.
4600
4600
4750
0.2
3.0
-1.50 4540
4370
4420
4395
4360
6.4
4370
0.5
4700
4200
4350
0.0
2.8
0.0
0.5
0.0
1.20
4380
4370
100
Cl- + S04
..TP7
n
::TF
+ TP12
ra
+
+
CA
TP2
+ TP4
100
Fig.
HC03- + C03
- Piper diagram for Tutupaca area water samples.
quadrants. Points TP7, TP8, TP12, CA3, and CS4 are cold meteoric
waters
with
maximum
temperature
of
14 "C
and
TDS
ranging
between 70 and 240 mg/1.

TP6, TP9, TP10 and TP11 are hot acid waters, the first of wich
is a boiling pool
(86 C) with a TDS
of 550 mg/1, whereas the
others have a temperature varying between 46 and 60.4C and a TDS

around 1850 mg/1. TP6 and TP9 are located in the quebrada Azufre
Grande, the other in the quebrada Azufre Chico. Along the shores
of these torrents, located in two large faults beneath the slopes

of Tutupaca volcano, many warm and hot springs are present.
Their chemical characteristics are similar displaying a high
earthy-alkaline
sulphate
component
(approximately
alkaline sulphate component of some 25%; the
rest
60%)
and
is alkaline
chloride.
355
All the other samples of the Tutupaca area are located in the
SE quadrant, where the alkaline chloride waters are found.
For better discrimination the Piper diagram was plotted with
chlorides as separated anin

chloride
samples
can
be
(fig.2). In this
clearly
figure the rich
distinguished
into
three
subgroups.
The first includes the samples TP1B, TP2,
TP3 and TP4,
which
are hot samples with temperature ranging between 31 and 56C and a
TDS
around
1750-1850
mg/1; their
composition
is
alkaline
bicarbonate chloride with a high sulphates percentage. In the zone
where these samples are located there are many emergences of warm
and hot springs and numerous streams with considerable flowrate
that may interact.
100
Cl-
n
+
TP8
Q)
TP9
+ TP6
TP12
ra
-2.
CA
+ CA2
T
^TPS
+ TP4
.00
Fig. 2
356
HC03-
S04--
- Piper diagram w i t h Cl as separated a n i n .
The second subgroup is composed of the samples CA and CA2,

these were taken in the zone of Calientes, several kilometres away
from the water points with the code TP. Their temperature values
are 60.5 and 91'C respectively (this latter, decidely higher than
the water boiling point at the emergence altitude, is probably
justified
by
the
formation
of
superheated
chloride component exceed 65%, the TDS
steam);
the
sodium
ranges between 1550 and
2700 mg/1 and the SiC>2 content, very high, is respectively 530 and
766 mg/1.
The third and last subgroup includes the samples CS1, CS2 and
CS3, located
about 15 km to the west of the Tutupaca volcano.
Their temperatures and TDS are very high ranging 80-86C (boiling
point)
and
3200-4800
mg/1 respectively;
the
sodium
chloride
component varies between 86 and 93% and the SiOo content between
836 and 969 mg/1.
In fig. 3 is shown the relative Cl, S04 and HCO3 content of all
the previous described water points. On the basis of this diagram,
excluding the cold waters from the discussion,
the samples TP6,
TP9, TP10 and TP11 (hot acid waters), located in the left corner,
could be considered as steam heated
waters enriched mainly
in
geothermal H2S. This statement is actual for the water point TP6,
the upper one sampled in a creek where some mud pools and steaming
pools are present; as regard the others three, the total absence
of gas, along the lower part of both the streams Azufre Grande and
Azufre Chico, leads one to believe that the conspicous presence of
sulphates, rather than to an H2S oxidation, is linked to a sulphur

oxidation. This is a product of the past activity of the Tutupaca
volcano in such large amounts that not
far from the summit a
sulphur mine exists.
357
STEAM HEATEa WATERS
o.
60
80
100
40
S04 (mg/l)
Fig. 3
The
samples
chloride
with
- Relative Cl, S04, HC03 content.
TP1B, TP2,
a
high
TP3
sulphates
and
TP4
percentage)
(alkaline
are
found
bicarbonate
in
the
"peripheral" waters sector of the diagram. These mixed samples can
be considered the boundary part of a geothermal system, leaving

the central core, the deeper chlorinated inflow uprising at the
surface reduces, but the CO2 and H2S, reaching surface nappes rich
in oxygen, give aggressive solutions that can considerably alter

the
host
formations
and
produce
alkaline
bicarbonate-sulphate
waters. In the Tutupaca area the peripheral waters retain a slight
deep
liquid
content.
358
phase contribution and this explains
its
chloride
All the samples in the SE quadrant of fig. 2 are also in the

upper sector of fig. 3, in particular CS1, CS2 and CS3 are located
in the "mature waters" zone and can
be used for geothermometric
purposes.
The linking between these alkaline chloride waters and the

previous "mixed waters" is clearly appears in fig. 4, where the
relative content of Li, Rb and Cs is shown: the representative
points cluster in the same area of the diagram proving that a

single deep liquid feeds the manifestations.
Another diagram that provide general
informations about any
steam and gas inflow contribution is the fig. 5 one, where the
relative content of Cl, H3BO3 and NH4
is shown. The
chloride
0,
i i i i i i i i i
100
i i~i i i i i i i ] i i i i
80
60
RB (mg/L) * 4
Fig. 4
- Relative content of Li, Rb, Cs.
359
40
60
Cl (mg/i)
Fig. 5
concentration
is
- Relative content of NH4, Cl, H3BO3.
direct
function
of
the
water-rock
equilibration process, H3BO3 behave in a similar way, but prove to

be
enriched
where
phenomena
of
steam
inflow
occur;
the
NH4
concentration, finally, in addition to phase separation phenomena,
may depend on gas inflow.

Excluding the cold waters, whose NH4 content is zero and lie on
the
diagram
base,
in
the
lower
part
are
located
the
most
representative alkaline chloride samples, where the NH. content is

very reduced. Subsequently the group of acid waters TP10,
TP11
is encountered, this
confirms their
low
steam
TP9 and
inflow;
higher values of NH4 content the samples TP4, TP3 and TP1B
at
is met,
for this "mixed water" group the supply of deep gases has already
been underscored.
360
At the top of the diagram is located TP6, where the presence of

condensed steam were evident even if the presence of gas is not
particularly abundant. The gas sample associated with this water

point (see table 3) contains H2, relatively high quantity of CO,
but H2S and CH4
are below the detection limit, making any gas
geothermometry unreliable; the tritium content of the associated

liquid phase (1.7 T.U.) is, finally, quite comparable with that
found in the cold waters. This situation agrees with a mixing

between a local groundwater, that circulates
in hot subsurface
rocks and boils without reaching high temperature and pressure,

and a deeper gas
which encounter this fluid and considerably
enriches it in NH and SO..
4.2.
Classification of water samples (Challapalca)
The analytical results of the fluids sampled during the survey

in this area are reported in tables 2 (waters) and 3 (gases) . The
samples with
PA
code
identify manifestations
of the
Paucarani
zone.
The classification of samples was carried out in the same way
as for the preceding area.

In the NE quadrant of Piper diagram
alkaline sulphate bicarbonate

alkaline
sulphate
sample
PA2
( fig. 6) the earth-
samples PA4, PC4

are
found;
the
and the earthfirst
has
temperature of 38 C and a TDS of 740 mg/1, the others are cold and
characterized by a TDS lower than 250 mg/1. Sample PA1 (45C and
605 mg/1)
located along the dividing line between the NW and SW
sectors is a alkaline earth-alcaline bicarbonate sulphate water.

In this latter sector
TDS,
aroud
200
the PC3 and PC5 samples are found; their
mg/1, is
similar,
but
the
temperature
quite
different: the first is a cold water, the second a steaming pool

(72C).
361
At the boundary between SW and

PC10,
SE sectors are located PCS and
alkaline earth-alkaline bicarbonate chloride tepid samples
with a TDS around 350 mg/1.
Other 6 samples, PA3, PCI,
PC2,
PC6, PC/ and PC9
are found
well inside the SE quadrant. These mainly alkaline chloride waters

have temperatures ranging between 42C and 86.9 C and TDS between
1 and 5 g/1.
Excluding PA3 belonging to Paucarani thermal zone,
all these last samples either line up in the diagram
or show a
good correlation between chloride content and temperature.

The same conclusions can be drawn from the triangular Cl, SO4
HCO3 diagram (fig.
7) , where, the all the water points found in
the SE quadrant of fig. 6, fall into a line in the "mature waters"

area.
100
Cl-
+ PC4
fPA2
>PA4
0)
. +
PAi
ra
z .-
+ PC 10
ia
+PC3
i PCS
+ PA3
+ PC5
+ PC1
+ CS
............ .1......
100
Fig. 6
362
+PC
.. i..... .,..__,.. i _..._.. i... ........
HC03- + S04
- Piper diagram with Cl as separated anin for

Challapalca water samples.
TI
I I I I I I I T I I I I I I I I I T I I I I I I I I M
I I I I I I I I I II
I I I I I I I I
S04 (mg/l)
Fig.
- Relative content of Cl, SO, HCO-,.
This trend is evidently due to a dilution process of a deep

water whose most representative uprising end-member
is the PC2
sample.
4.3.
Geothermometry
Fig.
8 and 9 show the Na, K, Mg diagram [3] for the two areas
samples of Tutupaca and Challapalca. The deep temperatures for the
most representative springs CS1 and PC2, evaluable from the Na/K
ratios, are respectively 215C and 20CTC that is 20- 30C higher
than those computable with the K/Mg ratios. This shift could be
explained
in
terms
of
the
different
re-equilibrations
rates
363
Na1000
100
K/100
Fig.
Mg 0.5
- Na, K, /~Mg triangular diagram for Challapalca area water samples.
involving the considered cations during the deep fluid uprising at

the surface. Both the geothermal areas present dilution phenomena
are as confirmed, in the corresponding diagrams, by the samples
points lining between the most important springs
(CS1,
PC2)
and
local groundwaters (right corner in the diagrams).

Also
in
fig.
10
(where
the values
of
10*Mg/ (10*Mg+Ca) are
plotted vs. lO*K/(10*K+Na)[3]) springs CS1 and PC2 fall very close
to
the
equilibrium
curve
confirming
the
reliability
of
the
geothermometric estimation. These temperatures, however, should be

considered as the minima to be found in the reservoirs.
As
regard
the
SiO2
geothermometer
values,
these
must
critically evaluated: PC2 spring (Challapalca area) and CS1,
364
be
CS2,
Na/1000
100
MG0.5
Fig. 9
- Na, K, 7~"Mg triangular diagram for Tutupaca area water samples.
CS3 springs (Tutupaca area) are steaming ones; on the hypothesis

of the "quartz adiabatic cooling" the resulting deep temperatures
are over
186C
[4]
for the the
former
area and 265C
for the
latter.
The former value is consistent with the Na/K and K/Mg results
for the same water point, the second is decidedly higher. As above
200 C the re-equilibration speed of SiO2 is very high and not even
massive phenomena of boiling can explain this incongruence, the
only explanation to justify the concentration found is that the
thermal
fluids meet formations with SiO2 which
can easily be
leached. These latter could be the ignimbrites schematized in the
365
10 Mg
10 K
Fig.
10 - 10 K/(10 K + Na) vs. 10 Mg/(10 Mg + Ca) diagram for both the areas.
geological section of the Tutupaca area (see appendix 1C). In this
case, the SiO2 content would be controlled by the amorphous phase

and the resulting equilibrium temperature ranging between 185 C
and
200C
[4]
perfectly
merging
the
solute
chemical
geothermometers values.
At last in fig. 11 are shown the log
spring
composition
vs.
temperatures
(AP/K) values for PC2
ranging
between
120C
and
240 C (with the only constraint of the calcite equilibration at

the
different
volcanic
rock
temperatures)[5].
components,
and
The
the
curves
phases
for
derived
hydrothermal alteration converge at a value around

closed to the Na/K temperature.
366
series
from
of
their
210C, very
Sample PC2
Added Carbon to solut.
13.17 mmol/Kg
120
140
160
180
200
220
240
260
Temperature C
Fig. 11 - Log AP/K values vs. temperature.
5. Remarks on the isotopic data
The
relative
results
of water
points
sampled
for
isotopic
analyses are given in tabs. 1 and 2. The SD vs. <518O diagrams for
the Tutupaca and Challapalca areas are shown in figs. 12 and 13.
The first shows a substantial shift (at least two <S18O units)
for the samples CS1, CS2 and CS3 confirming that these are fluids
with high deep temperatures.

The second (fig. 13) the cold samples PC3, PC4 and PC11, which
considerably swerve from this one, are brook waters subjected to

daily cicles of freezing and thaw and could, in the warmer hours,
partially evaporate. This last process certainly is at the base of
367
-70
O
<N
X
-90
-110
1 30~
I I I I I I 1I I I I I 1I I I 1I I
I I I I I I I I I I I I I 1! I I 1I
I I I I I I I II I I i 1 I I ! I I I
-13
15
I I I I I I I I I I I I 1I I I I I I
12
-11
180 IN H20
Fig. 12 - 6 D vs. <518O diagram for Tutupaca water samples.
-60-1
-80-
o
IE
zj
100-
-120
-140
-18
-16
-14
-12
Fig. 13 - S D vs. ^0 diagram for Challapalca water samples,
368
the
isotopic
composition
characterized
by
a small
of
PCS
flow
(72C,
rate,
212
results
mg/1)
which,
isotopically
very
increased: <S18O = -3.76, SD = - 89.2.
These evaporation phenomena are confirmed by the lining of all

the points till now mentioned on a straight line with the equation
<SD = 1.53*<S18O - 81.6
"evaporation
line".
(R2 = 0.96)
further
which can exatly taken as the
support
is
constituted
by
the
position of sample TP6, which also evaporates, that even located

in the Tutupaca area, falls on the same line.
As
regard
the
remaining
points,
sample
PC2,
the
most
representative of the reservoir deep fluid, shows an appreciable

oxygen shift of about three <518O units; PC7,
and PC10 can be considered as

this
deep
fluid
with
PC9,
PCI,
PC6,
PC8
mixings in different percentages of
surface
groundwater
whose
isotopic
composition should be: <518O = -16.85, SD = -126.5.
The SD vs. Cl content diagram of fig. 14, furtherly confirms

this hypothes is.
f.3
100- O
O
CM
) i.
C)
o
-120*
O
o o
500
1000
15002000
2500
Cl (mg/l)
Fig. 14 - 5 D vs. Cl diagram for Challapalca water samples.
369
To
end
up,
the
tritium
content
of
the
samples
decreas,
generally, as a function of TDS and temperature with the exception

of TP6; here, notwithstanding a temperature of 12C, the tritium
value is 1.7 T.U. confirming the large supply of groundwater.
The 180C and 240C temperatures computable for the exchange

reaction of
18
between dissolved sulphate and water [6] for the
CS2 and CS1 samples also agree with the chemical geothermometers
results.
6. Gas chemistry
The number of free gases found in the two areas, not taking
into
account
rather
the
small.
Calacoa
The
and
Calientes
manifestations
are
zones
not
characterized
visited,
by
is
a very
reduced gas flow. Moreover, some samples were damaged during the
air freight.
Shortly, for the Tutupaca area only three gases are available,
while for Challapalca the only gas resulted so polluted to loose
any meaning. The few analytical results are in tab. 3.
The composition of TP1B and TP4 agree with the assumption of a
mixture between
a thermal fluid and surface waters initially in
equilibrium with the atmosphere. Instead TP6 contains an higher

quantity of H2 confirming
a stronger interaction of surface water
with a deeper gas of vulcanic origin.
7. Conclusion
In the Tutupaca and Challapalca areas exist geothermal fluids,
their temperatures should be higher than 200C. As regard the

former, samples coming from the Calacoa and Calientes zones, even
if some tens of kilometers far each from the other, seem to be the
emergecy
of
the
same
big
thermal
different hydrologic circuits with

370
system
or,
at
least,
similar characteristics.
two
References
[1] AQUATER - INGEMET (1980) - Proyecto de Investigacin

Geotrmica de la Repblica del Per - Regin V. Lima PER.
[2] BURGESS
PERU:
W.G. (1985) Proyecto Integrado del Sur,

contribution to the geothermal assessment.
WD/OS/85/19.
[3] GIGGENBACH, W.F. (1988) - Geothermal solute equilibria.

Derivation of Na-K-Mg-Ca geoindicators. GEOCHIMICA ET
COSMOCHIMICA ACTA. 52, 2749-2765.
[4] FOURNIER, R.O. & POTTER, R.W. (1982) - A revised and
expanded
silica
quartz
geothermometer.
GEOTHERMAL
RESEARCH COUNCIL BULLETIN. 11, 3-9.
[5] REED, M. & SPYCHER, N.
(1984) - Calculation of pH and
mineral equilibria in hydrothermal waters with application to geothermometry and studies of boiling and
dilution. GEOCHIMICA ET COSMOCHIMICA ACTA.
48,
1479 -
1492.
[6] MIZUTANI,
Y. & RAFTER,
A.T.
Oxygen
composition of sulfates. NZ J SCIENCE, 12, 54-59.
isotopic
371
U)
~J
to
Appendix 1
LOCATION OF THE INVESTIGATED THERMAL ZONES IN SOUTH PERU
Appendix 1A
GEOLOGICAL MAP OF THE TUTUPACA AREA
Appendix 1B
MAP OF THE CHALLAPALCA AREA
-j
-t-
> -- ' Av-s-Mt^fti

./( %!ifjf|'
y
te^ -k^l w^n

'
J-X
, \
J^, ~C"
/'
. v ,J
^s^^S^^ -M -- * ^j^^t ^
/?r^x^S;~^"H0,"-)"^ T'""*.
^ j-^-^t.'"?"';^!-*\
i,ci^.1,^ vi.'Giv/ S\
"''
S)S4
!*>*
''-.
^1"
''* /^-^
'"
v TV.,,
/
"
,-,<l^L '< ^-p-rv-v '-*%;""; / ^ x
êitoj""' ^X^/O^^ ^ , , x
^^^^S^^-^^'^rV/v^^^tv V<,
I l \ \ u \ ^ll ^ *
1
/^
7
/N^'x ^x N;^^ f *^\^ \-)

X\ 4 >__
A>-r -lI>N- /"- - ' -Â

\ V
^'J-- '-V *v
Appendix 1C
SCHEMATIC GEOLOGICAL SECTION OF THE TUTUPACA AREA
(see Appendix 1A)

VOLCAN TUTUPACA
avas
pi roc last i cos (tufos)
" " " (redeposition)

ignimbrite
VOL CAN LOP E7 EX TRA NA
5500
RIO CALIENTES
5000
500
4000
-igmmbrite
J50U
-areniscas
3000
LEYENDA
DEPSITOS ALUVIALES Y FLUVIO.
GLACIARES
\ Qp-VlcZ VOLCNICO TUIL'PACA CALIENTES
lUv-XVl TtO-Vicl VOLCNICO Pf?E-TUTUPACA CALIENTES

L"l'\-':';] T-Co Fm. CAPILLUNE
KTI-to
f'PUPO TOOUEPALA
JSKI-/U GRUPO YURA

MANANTA C A L I E N T E
GEOTHERMAL EXPLORATION BY GEOCHEMICAL METHODS

OF THE THERMAL AREA EL PILAR-MUNDO NUEVO,
STATE OF SUCRE, VENEZUELA
F. D'AMORE, G. GIANELLI
Istituto Internazionale per le Ricerche Geotermiche,

Pisa, Italy
E. CORAZZA
Istituto di Geocronologia e Geochimica Isotpica,

Pisa, Italy
J. JAUREGUI, P. VRELA
Direccin General Sectorial de Energa,

Ministerio de Energa y Minas,
Caracas, Venezuela
Resumen-Abstract
EXPLORACIN GEOTRMICA MEDIANTE MTODOS GEOQUMICAS EN EL REA TERMAL DE EL

PILAR-MUNDO NUEVO, ESTADO DE SUCRE, VENEZUELA.
En 1985-1986 se efectu un estudio geoqumico en la zona de El Pilar Hundo Nuevo, pennsula de Paria, Estado de Sucre, Venezuela.
El objetivo era
hacer comprobaciones para una posible explotacin geotermoelctrica de la zona, que se caracteriza por muchas manifestaciones naturales con temperaturas
del orden de 80-100C.
Mediante una serie de clasificaciones diferentes de las muestras de agua
y gas, fue posible hacer una seleccin de las composiciones qumicas ms importantes que permitieron obtener indicaciones geotermomtricas tiles.
Para
evaluar algunos de los parmetros del depsito, se han aplicado al mismo tiempo varias tcnicas geotermomtricas basadas en la interaccin fluido-roca.
La zona en cuestin parece prometedora respecto a la recuperacin de recursos geotrmicos de entalpia elevada; parece que hay un depsito profundo
con salinidad relativamente baja (< 5 000 ppm), con salmuera neutra a temperaturas que se calculan entre 250 y 300C y con presin parcial de CO elevada. Se supone que existe un segundo depsito a menos profundidad, con temperaturas del orden de 200-220C.
La accin de ambos depsitos est dominada
por el agua, y parece que se produce la ebullicin a 160C, a un nivel muy poco profundo.
El nivel piezomtrico (elevacin de 150 m) regula la distribu-
cin en la zona de fumarolas y manantiales de agua.
La autoobturacin hace
377
posible la acumulacin de fluidos, al menos en el depsito profundo,

puede realimentarse con agua meterica del lugar.
el cual
Se deduce que a cierta pro-
fundidad hay un batolito que proporciona calor a los fluidos profundos.
GEOTHERMAL EXPLORATION BY GEOCHEMICAL METHODS OF THE THERMAL AREA EL

PILAR-MUNDO NUEVO, STATE OF SUCRE, VENEZUELA.
A geochemical survey was carried out in 1985-86 in the El Pilar - Mundo Nuevo area, Paria
peninsula, state of Sucre, Venezuela. The aim was to ascertain a possible geothermoelectric
exploitation of the area, characterized by many natural manifestations with temperatures in the range
80- 100C.
Through a series of different classifications of water and gas samples it was possible to operate
a selection of the most significant chemical compositions that allowed useful geothermometric
indications. Several geothermometric techniques based on fluid-rock interaction have been applied at
the same time to evaluate some reservoir parameters.

The area of concern seems to be promising for the recovery of high enthalpy geothermal
resources; a deep reservoir appears to be constituted by a relatively low salinity (< 5000 ppm), neutral
brine with computed temperatures between 250 and 300C and high C2 partial pressure. A second
shallower reservoir is supposed to exist, with a temperature of the order of 200 - 220C. Both
reservoirs result to be water-dominated, and boiling appears to take place at 160C, at a very shallow
level. The piezometric level (elevation 150 m) regulates the areal distribution of water springs and
fumaroles. Self-sealing allows accumulation of fluids at least in the deep reservoir which can receive
its recharge from local meteoric water. A batholith is inferred at some depth, supplying the heat to the
deep fluids.
INTRODUCTION
From the Preliminary Report on the Evaluation of the Geothermal Potential of north-eastern
Venezuela (Gonzales et al., 1981), and also from the results obtained in the Geothermal Resources
Inventory in eastern and central Venezuela (Hevia and Di Gianni, 1983; Urbani, 1984), the El Pilar Mundo Nuevo area, located in the isthmus of the Araya-Paria peninsula, state of Sucre, Venezuela
(Fig. 1), was selected as the one with the highest priority. The geothermal assessment of the Paria
peninsula allowed this area to be selected as the most promising for a geothermoelectric exploitment.
The reason for this choice is due to some characteristics suggesting a local accumulation of
geothermal fluids, like the highest density of surface manifestations in Venezuela as well as of high
temperature springs (80 - 100C) and of the peculiar chemical composition of the discharged fluids.
Urbani (1989) gave a preliminary assessment of the area and proposed a model implying a
geothermal reservoir with a temperature of 200 -250C.
378
.SEA*
* ATI ANTIC
Stau of SMCft O C E A N
CPAB - Cariaco pull-apart
basin
CG
- Cariaco graben
GG
- Guaranos graben
SOG
- San Juan graben
EPFS - El PHar fault

system
SFF
- San Francisco fault
UF
- rica fault
BF
- Bohordal fault
LBF
- Los Bajos fault
ESF
- El Soldado fault
r
r
Area of interest (El Pilar-Casanay

geotherraal district)
Geolonical map
sc."1:25.000
Geological map
Zone of highest temperature springs
sc. 1:10.000
Towns
22
39
Springs
x Tree hydrocarbons
A Cerro La Pica
""- Fault traces
Fig. 1. Location of thermal springs in the Araya-Paria isthmus, stale of Sucre (from Urbani,1984,
modified), and geostructural sketch map (from Vrela and Hevia, 1990, modified). The
center-most rectangle is represented in detail in Fig. 2.
20km
In the years 1985 and 1986 several thermal manifestations were sampled and analyzed with the
purpose of a regional survey from the Cariaco gulf to the Paria gulf, and inland to the San Juan
valley, thus characterizing the boundaries of the interest area outlined in Fig. 2 (Campos, 1981;
Gonzales, 1981; Juregui etal., 1985; Juregui et al., 1986; D'Amore and Gianelli, 1986; Hevia and
Juregui, 1988). Many more analyses of diluted waters, both from cold and hot springs, are reported
in Hevia and Juregui (1988), namely for the central area. The location of springs in Fig. 2 was
derived from the map in the same article by Hevia and Juregui (1988).
The marginal springs shown in Fig. 1 have been included in the present work with the purpose
of a better evaluation of the thermal anomaly in the central area. In spite of their thermality (up to
55-60C) and of their salinity, since the beginning of the survey these springs demonstrated by their
compositions to be related to marginal circuits. Their locations are roughly aligned E - W on the active
El Pilar fault trace or on secondary ones related to it.
The geothermal manifestations in the area of concern (Fig. 2) form a hydrothermal system,
constituted by several boiling springs of sodium chloride type, associated with large alteration zones
with fumaroles and mineral deposits of sulfur, gypsum, anhydrite, calcite, and silica. Being only of
shallow origin, fresh diluted waters are found sparsely in the whole area, including also the
fumarolic zones.
In this study several geothermometric techniques based on fluid-rock interaction have been
applied at the same time, with the aim of a better definition of the thermal potential of the field. The
survey allowed also a thorough test and intercomparison on the reliability of different methods in
evaluating the main reservoir parameters. The interpretation of data is based also on a selection of
available samples, depending on their modifications that might occur during their ascent to the
surface; this selection was applied both to water and to gas samples. Notwithstanding the high
density of the tropical vegetation covering the studied area, enough geological and structural
information has been obtained, as briefly exposed in the geological chapter.
Though the above limitations are objective, the study encouraged by the involvement of IAEA
certainly allowed some conclusions to be reached about the high geothermal potential of the El Pilar Mundo Nuevo system, positively ascertaining high thermal conditions at depth and possibly a sealing
that produces the condition necessary for a true geothermal field: the fluid accumulation.
The interpretation given in this work may give useful indications for further steps of the
survey, like deep explorative drillings.
GEOLOGICAL BACKGROUND
The northeastern region of Venezuela is located in a transition zone at the contact between the
SE end of the Caribbean plate and the NE edge of the South American plate. Such a contact is poorly
defined, and it is marked by a wide strip affected by deformation and block faulting. This character is
the consequence of the stress generated by the right transcurren! movement and the oblique collision
of the Caribbean plate toward ESE, against the counterclockwise turning South American plate. The
result at depth is a transcurrent strain (at the base of the thinned continental crust which is near the
380
- '\
\ m
O NH 4 -S0 4 springs (fumaroles)
UJ
00
N a - C l springs
A Diluted w a t e r s
Houses
Fig. 2. Location of thermal springs in the area of concern, El Pilar - Mundo Nuevo. Elevations are in
m a.s.l. (from Hevia and Juregui, 1988, modified). Dashed lines represent the
hydrogeological pattern.
\\ MV.J\/
rW*
ductile-frage limit, at a depth of some 15 km) and pressure deformation along the dominating
directions NNW-SSE, E-W, and NW-SE; in turn this is complicated by the pre-existing directions
(e.g. N 70 E) as well as by some more directions complementary to the previous ones (SW-NE,
N-S). The block faulting takes place either through faulting with variable directions around NW-SE,
or through reactivation of old faults (rica, San Francisco, Santa Rosa, and others more,
delimitating the Caribbean plate), or else through recent faults like Bohordal, Los Bajos, El Soldado
(Fig. 1).
An important feature is the clear steady decrease from W to E of the right transcurrent E-W
movement, between the Cariaco graben (almost 100 km), the Cariaco gulf (25-40 km) and the
western part of the Araya-Paria isthmus (20-25 km), reaching a full stop in the Cerro Las Minas
"push-up" block (Vierbuchen, 1984). This is in agreement with the interpretation given by Speed
(1985) about the present transcurrent activity of the El Pilar fault system, as the consequence of a
suture resulting from the angular collision in this area between the two plates.
After the Paleocene-Eocene great displacements that gave the region its basic architecture, the
main deformations took place in middle Miocene (Macsotay et al., 1986), in Pliocene-Pleistocene,
and in Quaternary. The most recent evidence are the marine terraces in the Araya peninsula, uplifted
12 and 8 m, 125000 and 25000 years ago respectively; another consequence is the subsidence proved
by microgravimetric methods in the area around and ESE of El Pilar (Bravo et al., 1986), as well as
in other areas of the SE quadrant. According to all authors working in the area the above inference is
supported by the interpretation of the present seismicity.
In the central area Mundo Nuevo - Las Minas - El Pilar the compressive deformation toward S
and SE produced many scales, faulted folds, wedges either raised or lowered, structures like
semigraben or klippen, all of them with an average vergency to SE.
Since in the region almost all contacts and the same stratigraphic column have been altered
tectonically, the following list represents the formations and the lithologies of the area:
- Barranquin formation (KB): average or very coarse quartz sandstones, shales, calcarenites
and limestones. Age: Barremian. Thickness: 600-1200 m.
- El Cantil formation (KEC): clear massive limestones and some calcarenites. Age: Albian.
Thickness: 300-700 m.
- Querecual formation (KQ): limestones with alternated dark shales. Age: Turonian-Coniacian.
Thickness: 150-300 m.
- San Antonio formation (KSA): limestones, hard siliceous shales and some shales and
sandstones. Age: Maestrichtian. Thickness: 200-400 m.
- Tunapuy formation (KMT): phyllites and calcareous schists, either quartz-graphitic or
micaceous, with intercalations of lenses of metamorphic limestone, of some quartzites and of
quartz-mica-chlorite schists. Age: lower Cretaceous. Thickness: 800-1500m.
- Gliinimita formation (KMG): sericitic-graphitic phyllites, marls, meta-arenaceous limestones.
Age: lower Cretaceous. Thickness: 200-300 m.
- Lechozal complex (KTpL): informal name for a mixture of deformed fragments of
metamorphic rocks (KMT, KMG, KM Macuro, etc.) and of sedimentary rocks (BB, KSA, etc.).
Age: undetermined, later than Paleocene-Eocene. Thickness: 100-150 m.
382
- Chaguaramas complex (Ts-QCH): informal name for a polymictic conglomerate or mixture of
reworked clasts, ranging from a coarse conglomerate to a fine sandstone and to a pelite, of greenish
color. It results from the demolition of the southern edge of laminations and scales, and from other
erosive products of metamorphic rocks (KMT, KMG, etc.) as well as of sedimentary rocks like KB
and KSA. Thickness: 500-800 m.

- Los Arroyos formation (TmLA): informal name for deep trench turbiditic sediments with a
composition generally pelitic. Age: middle Pliocene. Thickness: 600-1000 m.
- Guatamarito formation (TpsG): informal name. Clear calcareous shales and greenish-gray
clays from lagoons and marshes of upper Pliocene. Thickness: 150-400 m.
- Mamporal formation (QM): clear polymictic conglomerate, poorly cmented, with layers of
fine sandstone. Age: upper Quaternary. Thickness: 300-800 m.
- Recent sediments from alluvium and flooded plains. Thickness: from a few meters to more
than 100 m.
The recharge of water takes place through the intensive faulting of the rocks all over the area.
The sealing could be provided by some low permeability lithologies of the above mentioned
formations, or by a self-sealing, or else by the compression of certain sections of the fault planes.
Approximately 8 km to the north of the area with thermal manifestations several apophyses of
a granitic porphyrite outcrop, with an age of 5 Ma (Moticska, 1987). This area corresponds to a
gravimetric anomaly suggesting the presence of a great sized intrusive body, either granitic or
granodioritic (Vierbuchen, 1984); possibly this intrusion is constituted by rocks derived from the
recent igneous phase related with the volcanic activity in the southernmost section of the Lesser
Antilles arc (Schubert and Sifontes, 1983). According to the gravity model by Vierbuchen (1984) the
top of the intrusion can be located at a depth of 6-9 km. The batholith has a maximum extension of
about 10 km, and a maximum thickness of 5 km (undefined width). A hypothesis about the heat
source can be forwarded, attributing it to the pressure stresses producing the fracturing and the
deformation of the plate edges, and capable of generating heat anomalies in the deep crust, up to the
local melting. The heat anomaly would produce a high heat flow capable of generating deep
reservoirs of hot fluids. The hot fluid uplift can take place through fracture systems associated to
faults, the most known directions of which are NNW-SSE and N-S, as resulting from the
distensional discharge of the compression of blocks limited by minor faults.
The geological conditions of the region are highly favourable to the presence of reservoirs at
depth, with a medium-high enthalpy.
CLASSIFICATION OF WATER SAMPLES

The results of water analyses are given in Table 1 for the main components; trace elements for
selected samples are given in Table 2. Table 3 reports dÔ, QD and tritium values for samples
collected in May 1985. Fig. 3 is a r O vs. dD diagram for the rainwater values of the Maracay area
(Venezuela, Lat. 10.25N, Long. 67.65W) and Barranquilla area (Colombia, Lat. 10.88N, Long.
383
TABLE 1. Chemical analyses for main components of the springs in the El Pilar area. All analyses
performed at 25C, expressed in mg/\; temperature and pH are measured in the field;
conductivity is in nS/cm; blanks = not determined.
sample
date
t'C
pH
conductivity
Na
Ca
7
12
13
14
15
106
114
5/85
2/86
5/85
5/85
5/85
677
596
68
794
69
4930
825
400
287
273
188
364
263
130
136
229
181
122
110
371
179
11 7
252
577
763
675
689
634
939
650
290
2/86
6/86
983
86 5
80
100
99 5
97 5
480
5/85
497
595
5060
779
147
466
373
17
5/85
5/85
5/85
5/85
87
954
904
82
42
85
622
650
1070
18
45
106
28 3
15
39
040
092
46
47
49
50
51
109
110
111
112
22
24
39
77
88
M2
19
31
36
42
52
53
59
65
66
71
78
83
115
116
5/85
5/85
5/85
4/86
536
285
1331
2660
2750
6
3
1
0
280
435
1300
6930
3 5
07
5640
3 1
575
236
364
285
3/86
3/86
435
394
493
3/86
275
240
278
3/86
599
1 83
5/85
5/85
476
244
284
392
6 16
691
605
667
565
588
5/85
5/85
5/85
5/85
5/85
5/85
5/85
5/85
5/85
4/86
5/85
4/86
5/85
5/85
4/86
5/85
2/86
2/86
240
70
305
324
37
32
53
465
295
697
684
661
63
63
632
67
738
635
65
701
58
644
654
340
33
32
43 5
37
355
332
4780
4030
5710
3
3
3
6
2
2430
3600
3490
3020
1130
7
6
3
8
2
7
2
4
5
477
908
1030
816
176
658
990
87
94 8
725
31
713
888
573
28 1
63 8
6 3
52
50
38
69 5
63 2
4 8
6 2
4 0
39
461
852
927
609
1
1
1
0
2
2
19
5
3
2
6
4
6
6
9
7
3
7
35
85
7 5
25
66
Mg
13 5
21 7
082
42 1
16 1
74 8
10
8 8
30 1
162
78 3
035
55
579
21 5
34
381
16 1
276
251
743
15 7
176
191
232
203
42 4
141
36 8
195
106
295
1
12
1
1
143
146
904
124
144
179
169
108
95 5
147
21 2
18 2
5
3
5
7
82
1 5
1 4
05
03
8 8
57
09
142
4 0
0 7
0 7
304
143
78 3
136
52
98
Cl
1540
1900
1415
1220
1870
1400
705
1190
68
4 7
2 2
2 2
4 7
0 4
4 4
10
0 9
2 5
2 5
1 8
SiO2
NH4
129
350
222
262
150
27
144
143
78 1
26
13
154
144
49
430
76
152
109
877
465
59 5
287
474
1160
1140
482
3170
1870
545
1130
257
117
0
0
0
0
0
0
0
0
0
0
28
26
25
86
29
36
SO4
166
177
168
63 5
827
123
116
157
HCO3
76 5
201
45 2
77 3
53 8
1090
2590
1720
1420
39
637
35 4
29
13
279
167
152
147
98 5
87
12
11 5
6 4
111
96
9 8
10 5
8 1
80
348
329
262
182
399
338
540
281
290
336
420
241
409
314
345
8 9
28 7
13
62 2
20 2
96 3
139
24 8
24 4
16 0
9 6
0
14 8
19 9
0
5 3
22
29
353
11 4
11 3
435
89
137
85
10 3
61 5
i75
462
403
45
1080
304
16 6
0 05
0 05
065
0 04
0 03
<001
008
68 8
7 4
103
187
25 8
66
691
54
309
33 7
24 5
45 2
42 3
17 7
70 9
341
85 3
537
149
657
56 5
36 1
36 5
33 5
5
8
1
4
3
8
33
21
22
26
8
5
9
2
13 6
12 3
18 7
42
25
13
13
24
18
15
58
15
15
4
5
2
1
0
2
2
9
1
23
3
5
3
9
4
4
8
2 6
0 24
62
4 5
29
I 4
0 05
0
0
0
0
0
0
0
1
0
2
2
3
2
8
3 1
06
5
7
04
0 3
<0 01
0 2
02
2 2
1 7
0 4
008
TABLE 2. Chemical analyses for trace elements of selected springs, El Pilar area. All analyses performed at 25C, expressed in ppb; n.d. - not determined
sample
Rb
Cs
As
Br
NO3
Ba
Sr
Al
AlOnXO
Fe
Sb
Pb
Zn
H2S
7
13
14
15
11800
11400
9900
15400
5200
5100
4000
6300
2700
2400
2500
3200
1000
1100
1500
1100
8100
7100
5000
9300
2500
910
<200
<200
370
270
390
620
1800
1700
1100
2100
1800
1900
1600
1700
40
<30
90
60
20
<20
<20
40
10
150
30
20
230
180
130
870
500
460
390
530
<5
<5
<5
<5
1600
1200
290
1100
9000
1800
1500
110
6500
<200
50
3600
1800
60
<20
1900
190
470
<100
17
<10
<IO
<400
<400
<400
<400
<400
<400
<400
<10
<10
80
20
40
40
100
120
<100
160
100
<100
740
200
<200
<200
<200
<200
<200
<200
<200
40
40
<30
100
70
<30
40
180
300
<100
<100
140
<100
<100
<500
<500
<500
<500
<500
<500
<500
720
800
1000
500
10600
430
54900
160
320
60
n.d.
n.d.
130
n.d.
1100
90
1900
2100
22500
560
6100
30
<30
<30
120
<30
<30
30
<20
<20
<20
<20
30
<20
60
<5
<5
<10
30
<40
<40
<40
<40
<40
<40
<40
4400
13800
2800
920
770
4000
160
*
740
110
980
1400
540
<40
<40
<40
<40
<40
<400
<400
<400
<400
<400
10
30
80
20
570
<100
1000
870
190
3700
115000
7900
2800
<200
3600
2030
80
930
440
4600
1700
910
3900
3900
1100
1200
<500
3400
1100
<30
40
<30
<30
<30
<20
<20
<20
<20
<20
80
10
130
<10
60
170
220
190
150
90
260
400
460
600
150
20
<5
180
<10
<10
50
<40
<40
<40
<40
<400
<400
<400
<400
<10
<20
240
<200
<200
3300
80
<30
130
20
210
130
<500
<500
<500
<500
100
<30
<30
30
<20
<20
<20
<20
250
140
30
80
20
<30
40
<30
40
30
60
20
7
7
20
<IOO
<100
<100
<100
<40
<400
<400
<400
<400
<400
<400
50
10
10
20
50
20
590
260
130
330
380
120
<200
3300
<200
10200
4000
6900
160
40
90
180
140
180
600
<500
<500
<500
<500
<500
<30
<30
<30
<30
<30
<30
<20
n.d.
n.d.
<20
<20
<20
<10
<10
20
<10
<10
<10
40
70
30
30
50
90
80
18
45
46
47
49
50
22
24
39
77
88
52
59
83
M2
19
31
36
42
66
71
<10
<10
<io
1200
<10
<10
610
830
580
<40
<40
<40
<40
<40
<10
O Al is expressed as total Al and monomeric Al (separated in the field)
oo
400
<100
370
410
500
360
300
320
30
<30
30
<30
20
10
50
60
30
130
<5
<5
<5
7
<5
<5
<5
<5
<5
<5
1700
100
670
380
790
790
<100
730
590
<100
<100
660
<100
730
380
TABLE 3. Isotopic composition of HÔ. 5 is in / SMOW. *518O for 804.
sample
7
13
14
15
15
4
6 18 O
-2.45
-2.59
-3.14
-1.88
+6.6*
6D
T.U. (1.0)
-17.8
-20.0
-17.3
-16.0
1.2
0.1
-3.63 - 1 9 . 2
17
18
45
45
46
47
49
50
-2.77
-0.33
-0.18
-1.88
-2.67
-3.76
-0.39
- 7.4
+ 0.7
+ 7.3
- 0.4
- 6.9
- 4.8
+ 0.2
22
24
39
77
88
-3.81
-3.29
-3.61
-3.91
-3.90
-21.2
- 9.2
-18.4
-23.6
-20.5
M2
19
31
36
42
52
59
66
71
83
-3.45
-3.91
-4.06
-3.70
-3.88
-3.73
-3.71
-3.86
-4.00
-4.24
-16.8
-19.5
-19.5
-18.5
-19.2
-18.6
-18.1
-20.0
-20.2
-20.2
2.2
3.1
1.4
1.5
1.1
3.4
0.5
0.6
5.1
0.7
9.4
4.2
0.9
0.3
74.78W), as well as some average rainwater values of Venezuela and Colombia (from IAEA,
Vienna; R. Gonfiantini, personal communication). A slope of 8 seems fairly reasonable, although the
average rain values might not be fully representative of the average ones in the El Pilar area.
The chemical classification of waters was accomplished taking into consideration: i) absolute
concentrations of the main components characterizing each type of water; ii) correlations among
selected components.
Five types of waters can be recognized on the basis of the former method. In Fig. 4 the five
water types are exemplified by particular samples.
386
10-
-10-
Q
-30H
O a
-50-
1 2 3 4
-70-
-10
-8
-6
-4
-2
180
Fig. 3. Rainwater 5^80 versus 5D (/ SMOW) in northern Venezuela and Colombia. 1: average in
Venezuela; 2: average in Colombia; 3: Barranquilla area (Colombia); 4: Maracay area,
Venezuela.
Na
K
xlO
Ca Mg Cl HC03 S04 NH4 B Li Rb Cs SiQ2

10
KlO 10 xlO 3 !03 10
Na
K Ca Mg
ID
10
Cl
B Li Rb Cs SiO?
x1010 <103 103 xlO
Mixed water
NAC water
80-
nnn
n
Na HC03 water
NH4 S4 water
80
XL
O
80
diluted water
-Q.
diluted water
40-
n n n___n
n n PI 1 1 n n
Fig. 4. Examples of the Five types of waters, as described in the text.

387
Group 1). The first group consists of seven samples (7, 12, 13, 14, 15, 106, 114). Complete
chemical analyses are available for springs 7, 13, 14, and 15 only, sampled in 1985. From Piper's
(1944) modified diagram (Fig. 5) it is evident that this is a homogeneous group of sodium-chloride
type waters. They are all located along an east-west strip of about 3 km in length, from El Palmar to
Los Chirriaderos (see map of Fig. 2). The most representative water sample (15) is reported in Fig. 4
for almost all chemical components (in meq/1). Despite its homogeneity some interesting differences
can be observed in Fig. 6 where sample 39 (located 15 km to the south) is also reported for
comparison (only samples collected in May 1985 are represented). In this figure several components
are plotted versus chloride (ppm). It is evident that, as the Cl concentration decreases, the Mg and
alkalinity increase, whereas Na, K, Li, Rb, Cs, Br, Nlfy, and B decrease. The SO4/H2^ ratio also
increases, due mainly to a decrease in H2S (oxidation). From stable isotope data (Table 3) the waters
show almost the same D values (=18 i 1.5/), while the dÔ value is -1.9% for sample 15,
decreasing progressively towards -3.14% of sample 14 and to -3.6% for sample 39, in proportion to
the Cl content. The high arsenic content (over 1 ppm) in these waters is an indication of its
accumulation in the geothermal water from a deepe and hot source. Antimony also is quite high in
these waters: in sample 15 it is just less than 1 ppm.
Despite the fact that the tritium content of fresh water is about 13 T.U., little tritium is
apparent in these waters, at least in samples 13 and 15 which were the only ones analyzed in this
group.
Group 2). It includes spring 4 (o Carlos) only, located about 15 km east of the first group.
The water chemistry shows an unusual composition: it contains about the same amount of Cl as
spring 14, but more Ca, Mg, Na, as well as very high values of 804 and of HCC>3. Figures 4 and 5
show the complex chemistry of this water.
Group 3). One typical group of waters is that of the NH4-S4 springs located in the fumarolic
fields of the Mundo Nuevo - Los Mereyes area (springs 45, 46, 47, 49, 50, 51, 112) and of El
Salvaje - Buena Esperanza area (springs 17, 18, 109, 110, 111). Their peculiar composition is put
into evidence in Figures 4 and 5.
Group 4). The fourth group of waters is of the Na-HCC>3 type (springs 22, 24, 39, 77, 88),
located far west and south of the area of concern El Pilar - Mundo Nuevo. They are all accompanied
by emissions of CO'2. Their chemistry is evidenced in Fig. 4 for sample 77, and in Fig. 5; they
usually contain large amounts of Mg. In Fig. 6 spring 39 is reported because of its Cl content in
excess of 500 ppm, despite its relative distance from the springs of Group 1. Compared to the
waters containing Cl reported in Fig. 6, its Na content increases with a decrease in Cl, whereas K,
Li, Rb, Br, B and NH3 decrease; this is the consequence of its high HCC>3 content.
Group 5). This is made of low salinity waters (< 1000 ppm), with pH between 6 and 7. A
distribution can be made on the basis of their geographic location. Springs 52, 59, 65, 78, 83 and
388
Fig. 5. Piper's (1944) modified diagram plotting compositions of waters from Groups 1, 2, 3, and 4.
M2 are located in the Mundo Nuevo area. Springs 115 and 116 are located west of El Salvaje and
north of Los Chirriaderos ( 1 - 2 km); these are typical local groundwaters of the Ca-HCC>3 type, as
shown in Fig. 4 (for sample 83). Springs 19, 31, 36, 42, 66 and 71 are all located west of the Los
Mereyes - Mundo Nuevo area (see example in Fig. 4). Springs 31 and 36 in the Casanay - La
Florida area are characterized by relatively higher Mg and 804 contents with respect to the others of
this group.
Fig. 7 shows the 3D versus dÔ diagram for the waters of Groups 1, 2, 4, and 5. All
samples but Group 1 are positioned on the meteoric line (Fig. 3) at dD = -19/ and dÔ = -4/
approximately. Diluted waters can be considered as representative of the local meteoric ones. All
sodium bicarbonate waters except spring 24 fall on the meteoric line, at about the same point as
diluted waters. The lack of an isotopic shift of bicarbonate waters can be an indication of
low-enthalpy systems in spite of the emerging temperatures. The position of spring 24 can be
explained taking into consideration its recharge from Cerro El Pato, with an elevation in excess of
600 m; a negative shift for dÔ can also be explained by an exchange with C2: the manifestation
emits a huge amount of free gas with respect to the water flow. Springs of Group 1 show an evident
positive shift in dÔ, up to two units (spring 15), suggesting a high temperature water-rock
interaction.
389
Fig. 6. Plot of some components against chloride for some selected springs, from the central ones
(center and right) to a peripheral one (left), showing the steady changes in major and minor
components. Chemical components are in ppmv.; 3'Ô in %<> SMOW.
390
201004,36.39.52.59
Q-10-
31,71.19,42,66.88
83
20-30-40 H
-7
-6
-5
-4
-2
-1
Fig. 7. 5D versus 5O diagram for the waters of Groups 1, 2, 4, and 5. The meteoric line is
reported also (from Fig. 3). The oxygen isotopic shift for Na-Cl waters is marked by a broken
line.
Fig. 8 shows the isotopic composition for the NH4-S4 type waters (Group 3). The values
are scattered over the diagram from about 0 to about -4/ of 3Ô, across the meteoric line; the
exchange with CC>2 of the associated gas can displace the points toward more negative values. The
points fall along a straight line with a slope 3 which can be interpreted as due to condensation and
evaporation processes at about 100C; this line intercepts the meteoric line at more positive 3D values
with respect to the springs of other groups. The positive shift in 5D can be explained by an exchange
with H2S of the associated gas phase, depending on the relative amounts of K^S and water.
"Most geochemical techniques may with confidence be applied only to specified types
of fluids with limited ranges of compositions. For instance, most ionic solute
geothermometers "work" only if used with close to neutral waters containing chloride as
the major anin. Any such interpretation of geothermal water samples, therefore, is best
carried out on the basis of an initial classification e.g. in terms of their major anions Cl,
SO4 and HC03" (Giggenbach and Goguel, 1989).

In the C1-HCO3-SO4 diagram of Fig. 9 the five groups of waters show the importance of
three main geochemical processes: a) steam heating from the absorption of high temperature,
H2S-containing, "geothermal" steam into groundwater; b) uprise of neutral, low sulfate, high
chloride, "geothermal" waters along the C1-HC3 axis, close to the Cl corner; c) dilution by neutral,
but high-bicarbonate waters. Considerable caution is required in the application of most
"geo-indicators" for sulfate or bicarbonate waters, because the observed chemical composition is
mainly due to attack of acidic gases on the local matrix rock. It is evident that all waters of Group 1
follow almost a linear trend toward the shallow bicarbonate waters, starting from spring 15 which is
391
20-
Fig. 8. dD versus d^Ô diagram for the NH4-S4 springs of Group 3 (see text).
0,50
HCO,/Cl
STEAM - HEATED WATERS
112-51-109-110-111
115-53-65-116
Fig. 9. Cl - HCO3 - SO4 diagram (after Giggenbach and Goguel, 1989) for all five groups of waters.
The hatched area represents "mature" waters; symbols represent: solid circles waters of Group
1, open circles waters of Groups 2 and 4, crosses waters of Group 3, open squares waters of
Group 5.
392
regarded as the most "mature" water and which is likely to be the most representative of the deep
reservoir. With respect to spring 15, the other Na-Cl waters become more and more enriched in Mg
and bicarbonate upon dilution; this has been evidenced also in Fig. 6. All low salinity waters (Group
5) fall in the vicinity of the bicarbonate corner; some waters far from the interest area show a certain
scatter, like the ones from Pantoo and Casanay areas (Fig. 1). Springs 22 and 39 (out of the interest
area) show a relatively high content of Cl, likely to be related to a mixing with salty waters in recent
sediments, from which they can strip also oxidized organic matter, like nitrates. Spring 4 also shows
a high Cl content associated with a high sulfate, consistent with a saturation temperature for anhydrite
close to 50C. The relatively high Br (6 ppm), sulfate, Ca and Mg values, and its location subjected to
sea flooding, might indicate that a fraction of this water is likely to be related to a marine source. Its
isotopic composition, shown in Table 3, is consistent with a meteoric origin and a circulation within
marine sedimentary formations, at low temperature.
Spring 24, located few kilometers south of Las Minas, is a typical sodium bicarbonate water; it
shows anomalous contents of ammonium and mainly nitrate. The associated gas has a very high flow
rate and contains large amounts of methane (close to 20 % in volume). All these evidences are in
favor of a circulation in sediments rich in organic matter.
In the interest area the waters falling near the left corner of the diagram are generally acidic.
Fig. 9 shows that springs 17 and 18 also contain a significant amount of bicarbonates. These two
springs (not acidic) are associated with the most powerful gas emissions east of the Mundo Nuevo
area. All these waters are interpreted as cold groundwaters that have been heated and contaminated by
geothermal steam. Indeed, all these springs are characterized by a strong bubbling of gas containing
large amounts of H^S. One interesting feature of these waters is their large seasonal variation of pH.
During the rainy season oxidation of FTjS is stronger and the pH lower (less than 2).
It is interesting to point out that bicarbonate waters, such as 4, 22, 24, 31, 36, 39, are
surrounding the interest area of geothermal upwelling. Besides, the high sulfate and the steam-heated
waters in the interest area are encountered at the higher elevations (see Fig. 2). In particular in the
eastern area, while the Na-Cl waters (El Palmar - Los Chirriaderos) are found below 150 m, the
steam-heated waters and the main gas flows (El Salvaje - Buena Esperanza) are found at elevations
between 200 and 400 m. The piezometric level can be defined by the elevation of springs 14 and 15,
about 130 - 150 m. In the Mundo Nuevo - Los Mereyes western area only acidic springs (as well as
diluted bicarbonate waters) are found; indeed the whole area has an elevation between 350 and 400
m. Then (if locally present) the deep and chloride-rich waters are not allowed to reach the surface
because of their lower piezometric level. The circulation system is complicated by many shallow
waters which can also influence the composition of gases, e. g. oxidizing F2S and H2-
The Cl-Li-B diagram shown in Fig. 10 is here proposed only for water samples where
chloride is above 10 % in weight among anions. According to Giggenbach and Goguel (1989):
"The alkali metal probably least affected by secondary processes is Li. It may, therefore, be
used as a "tracer" for the initial deep rock dissolution process and as a reference to
evaluate the possible origin of the two important "conservative" constituents of thermal
waters, Cl and B."
393
Cl/100
001
0.20
B/4
Fig. 10. Li - Rb - Cs diagram (Giggenbach and Goguel, 1989) for selected waters (Cl > 10% in
weight among anions) (see Table 2); SW = sea water.
All waters of Group 1 fall in a single cluster, showing a leaching of rocks, possibly reaching a
"maturation" stage. Sample 4, and to a further extent 22 and 39, show a chloride enrichment: this is
consistent with an addition of sodium chloride-rich waters (tectonic lows filled with marine
sediments and/or sea water at high tide).
In the Li-Rb-Cs diagram (Fig. 11) the Na-Cl waters cluster again around a composition which is
consistent with the dissolution of an acidic rock, like rhyolite. Rhyodacitic subintrusive rocks (as
discussed in the geological chapter) outcrop just north of the area, within a distance of 6 - 10 km.
These three rare alkali elements, being little reactive, are conservative of the rock composition and can
be leached only at depth; their ratios are not affected by shallow processes (Giggenbacb and Goguel,
1989). Only in waters of Groups 1 and 2 it was possible to find measurable concentrations of Rb
and Cs. These neutral waters (at least for their deep components) possibly have lost Rb due to uptake
in K-silicates, but not Cs.
As an introduction to the next chapter dealing with water geothermometry, the Na-K-Mg
diagram proposed by Giggenbach and Goguel (1989) has been used only for qualitative classification
(Fig. 12). All points representing waters of Group 1 fall aligned in a straight pattern from the Mg
corner of shallow waters to the farthest sample 15. This is an indication that they all form a single
family, confirming the previous observations. The relative position of the alignment is due mainly to
the Na-K and K-Mg geothermometric equations chosen by Giggenbach and Goguel. It is evident that
in this case the use of the two geothermometers yields an inconsistency. In spite of the general
reliability of Giggenbach and GoguePs (1989) geothermometer, the Ca concentration should be
taken into account in sedimentary rocks, like in this case. Different temperature calibrations of the
394
100
IOCS
Fig. 11. Triangular plot for Li, Rb, and Cs (after Giggenbach and Goguel, 1989, modified) for
selected waters (see Table 2).
Na/1000
K/100
"VMg
Fig. 12. Triangular plot for Na, K, and Mg (after Giggenbach and Goguel, 1989, modified).
Temperatures are in C.
395
empirical K-Mg curve result in changes of the "full equilibration" and temperature lines. In any case,
the diagram suggests that all these waters are likely to be partially equilibrated or mixed waters, the
least immature being again spring 15.
CLASSICAL WATER GEOTHERMOMETRY

Empirical cation geothermometry has been used as a first attempt to calculate the sub-surface
temperatures of the springs. A particular emphasis will be given to the sodium chloride waters, with
the aim of evaluating the thermal conditions of the deep reservoir, even though all these waters appear
to be affected by some dilution processes, on the basis of the classification outlined above.
It is well known that many different geothermometers (Table 4) rarely give the same computed
temperatures. Table 5 summarizes the results obtained using some among the given geothermometers
for the high salinity groups of waters (Groups 1, 2, 4). Geothermometers should be used carefully,
and some comments are necessary for their application.
Silica geothermometer: Quartz (conductive cooling) can be used with a certain confidence for all
the sampled springs except for the Na-Cl waters. For this group in fact the relatively low computed
temperatures (of the order of 160C in the El Palmar - Aguas Calientes zone) have been interpreted as
the ones at which the gas phase separates from the liquid phase owing to boiling and cannot be
assumed to be representative of the deep reservoir temperatures. Fig. 13 is a dissolved silica enthalpy plot (Truesdell and Fournier, 1977) for determining the temperature of a hot water
component mixed with a cold water, yielding a warm spring water. Group 1 only is reported in the
diagram; considering among the sodium chloride waters the ones between the boiling point and the
point where all local diluted waters merge, the extrapolation to the quartz solubility curve gives a
temperature of 250C approximately. Of course, this temperature is only indicative of a high enthalpy
system, namely because of the few data available. For Na-bicarbonate waters (Group 4) temperatures
computed from the chalcedony equation are also reported in Table 4, considering low enthalpy
systems (t< 150C).
Na - K geothermomcten Several Na-K geothermometers can be applied; all of them lie in a
broad band between the albite-microcline and the albite-adularia curves (Fig. 14; from Fournier,
1990); empirical curves tend to converge above 300C. In Table 5 Arnorsson's (1983)
geothermometer only was used as an instance for Na-K calculated temperatures. For the Na-Cl
waters the Na/K ratio appears to give too high temperatures, as if Na were deficient with respect to
pure albite. For springs of Groups 2 and 4 a Na-K geothermometer based on montmorillonites has
been applied (as in Fig. 14) In fact, it must be taken into account that in sedimentary basins exchange
reactions involving clay minerals can substantially change the Na/K ratio (see also Henley et al.,
1984). The computed temperatures are much lower than the ones obtained by application of the Na-K
geothermometer based on feldspars.
Na - K - Ca geothermometer: It takes into account reactions involving exchanges of the three
elements with a mineral solid solution (Fournier and Truesdell, 1973). Fournier (1990) makes several
comments on the application of this geothermometer for waters with reservoir temperatures below
200C, of sodium bicarbonate type, and/or rich in Mg (see also Giggenbach, 1989). The composition
396
TABLE 4 - Equations expressing the temperature dependence of selected chemical

geothermometers. For each geothermometer used in Table 5 there is an abbreviation;
concentration units are in mg/Kg, except for Fouillac and Michard (1981) (molar units).
Geothermometer
Equation
Source
731 ^- - 273
4.52 - log SiO
Amorphous silica
tC =
Chalcedony (TCH)
tC = 4 69
1(32
S;Q
Quartz (maximum steam loss)
tC =
1522
-273
- log SiO2
Quartz (no steam toss) (TQC)
tC = 5 ^ f c
Na-K
Na-K
tC =
5.75
-273
"2?3
Fournier (1981)
(<250C)
Fournier (1981)
(<250C)
Fournier (1981)
(<25(f C)
Fournier (1981)
856
-273
0.857 +log (Na/K)
tC =
Truesdell(1976)
833
-273
0.780 + log (Na/K)
____ 933
Na-K(TNK)
(<250C)
0.993+
Tonani(1980)
273
ll5
Amorsson(1983)
Na-K(TNK)
AmOISson(1983)
Na-K
f0/"*._ _____1L1 /_____
Na-K
tr = ____*178____ . 273
1.470 + log (Na/K)
Na-K
t o c=
K-Mg(TKM)
JTl
Fournier (1981)
1.483 + log (Na/K)
1.750
1390
+ log (Na/K)
t0M1-273
13.95-log (K2/Mg)
Nieva and Nieva (1987)
.2?3
Giggenbachetal. (1983)
Giggenbachetal. (1983)
397
TABLE 4. (continued)
ft>
2200 ==r-273
5.470 -log(Li/VMg)
Kharaka and Manner (198 9)
Na-Li
tC =
1590
^-273
0.779 + log (Na/li)
Kharaka et al. (1982)
Na-Li (TNL) <ci<o 3 M)
fC =
1000 > rr *\ ~ * i J
0.389 + log (Na/Li)
Fouillac and Michard (1981)
1195
.x - 273
0.130 + log (Na/Li)
Fouillac and Michard (1981)
Li-Mg CTM L)
Na-Li (ci>o 3 M)
Na-Ca
tC =
1096.7
-273
3.080 -log(Na/VCa)
Tonani(1980)
K-Ca
tC =
1930
-273
3.861 -log(Na/VCa)
Tonani(1980)
Na-K-Ca(TNKC)
fC =
1647
- 273
bg(Na/K)+p[log(VCa/Na)+2.06]+2.47
Foumier andTruesddl (1973)
P = 4/3 for t<100C, = 1/3 for t>lOOC
Na-Ca-Mg(TNKCM)
tOTNKC-DEL (see below)
Fournier and Potter (1979)
1 Compute t by TNKC
If t<70C, no correction to TNKC
2 Compute R = (Mg/(Mg + Ca + K)) 100 (in equivalents)
If R>50, no correction to TNKC (cold environment)
3 Compute DEL - correction to TNKC
If 5<R<50 and T is computed by TNKC
DEL - 10 66-4 7415R+325 87(log R) 2 -l 032 105(log R) 2 /T-1 968 107(log R) 2 /T 2 +l 605 107(log R)Vr 2
If 0 5 <R<5 and T is computed by TNKC

DEL = -1 03+59 971 log R+145 05(log R) 2 -3671 l(log R)2/T-1 61 10 7 log R/T2
If DEL <0 5, no correction
4 To compute R- Ca - Ca(ppm)/(1000 20 04)
K = K(ppm)/(1000 39 102)
Mg = Mg(ppm)/(1000 12 156)
18
5 O
1 000 In a - 2.88 (lO6!'2)- 4.1

1000 + 5
1000
398
MacKenzie and Truesdell (1977)
TABLE 5. Temperatures (in C) computed by water geothermometers
sample
TQC
TCH
TNK
TNKA
TNKC
TNKCM
TNL
TML
TKM
4
7
12
13
14
15
22
24
39
110
161
159
158
124
162
84
66
69
81
271
349
364
355
319
352
125
74
59
140
125
231
190
228
145
291
63
34
85
281
322
73
142
173
169
155
246
67
23
86
121
164
150
159
138
231
66
55
-25
153
281
280
278
258
291
93
94
85
77
88
106
114
74
86
142
123
42
55
136
206
357
330
61
97
133
91
268
249
63
62
168
167
106
147
87
67
...
87
70
138
129
53
34
37
54
29
333
324
331
100
70
TQC: quartz, no steam loss (Fournier, 1981)
TCH: chalcedony (Fournier, 1981)

TNK: Na-K (Arnorsson, 1983)
TNKA: Na-K from clay equilibrium (Fournier, 1990)
TNKC: Na-K-Ca (Fournier &Truesdell, 1973)
TNKCM: Na-K-Ca-Mg (Fournier & Potter, 1979)
TNL: Na-Li (Fouillac & Michard, 1981)
TML: Mg-Li (Kharaka & Mariner, 1989)
TKM: K-Mg (Giggenbach et al., 1983)
of CO2-rich waters tends to be controlled by the attack of carbonic acid on feldspars (and on other
mineral phases); this will cause water composition to plot off the empirical composition trends that
result from NaCl geothermal fluids in equilibrium with feldspars. The NKC temperatures for waters
of Group 1 appear to be significant of the deep reservoir conditions, ranging between 250 and 290C.
Na-K-Ca-Mg geothcrmometcn The presence of relatively high contents of Mg tends to lower the
temperatures given by the previous geothermometer; Fournier and Potter (1979) introduced the Mg
correction. About this geothermometer, Fournier (1990) made the following comments:
"Mg concentrations in geothermal fluids decrease rapidly as temperature increases and all
Mg-rich fluids found in nature have undergone water-rock reaction at a relatively low
temperature. Furthermore, as geothermal fluid flows from a high-temperature environment
399
to lower temperatures, it appears to pick up significant amounts of Mg from the

surrounding rock relatively easily and quickly. This leads to major ambiguity in the
application of the Fournier and Potter (1979) Mg correction; that is, a truly
low-temperature water may require a Mg correction to give a correct temperature, but a Mg
correction applied to a high-temperature water that has picked up Mg during upflow will
yield too low a reservoir temperature."
The Mg correction for the springs here considered appears to give reasonable results only for
bicarbonate waters. For NaCl springs the decrease of the calculated temperature is in correlation with
the decreasing salinity; it seems to confirm that the whole Group 1 constitutes a family of mixed
origin waters, among which spring 15 is the purest term.
K - Mg and Mg - Li geothermometers: Giggenbach et al. (1983) and Kharaka and Mariner
(1989) proposed these two empirical geothermometers respectively, using equations based on water
compositions of well fluids. Application of both geothermometers to the springs of Group 1 yields
lower temperatures than the ones inferred in the deep reservoir because of the possible uptake of Mg
during ascent, along with dilution. According to Fournier (1990)
700-
600-
500O>
^
O5 400-
JE
CM
300 H
200-
100-
0100
200
300
Enthalpy (cal/g)
Fig. 13. Dissolved silica vs. enthalpy diagram (from Truesdell and Fournier, 1977) for selected
samples. Solid circles represent Na-Cl waters; all groundwaters fall within the solid square.
400
3.00
2.50-
-~
05
5 1.50H
1.00-
0.5060
3.50
3.00
200 250 300 C

i . i
i
100
i
2.50
2.00
1.50
1000/T(K)
Fig. 14. Variation of log (Na/K) as a function of the reciprocal of absolute temperature. Theoretical
curves for low albite - microcline, low albite - adulada and Na-montmorillonite K-montmorillonite calculated using equilibrium constants in Arnorsson (1982). Various Na/K
geothermometers are labelled VG (Giggenbach et al., 1983), RF (Fournier, 1979), DN (Nieva
and Nieva, 1987), SA (Arnorsson, 1983), AT (Truesdell, 1976), FT (Tonani, 1980). (After
Fournier, 1990).
"Water-rock exchange reactions involving Mg proceed relatively fast at low

temperatures and K //Mg and Li//Mg ratios appear to be good indicators of the last
temperature of water-rock equilibration in an ascending water. A contributing factor in this
apparent fast reequilibration is that both Mg and Li tend to be minor constituents in most
thermal waters, so a relatively small amount of reaction involving one or both of these
constituents may have a large effect on the ratios of cations remaining in solution. When
there is good agreement in the temperatures estimated using K//Mg, Li//Mg, and other
geothermometers (particularly Na-K-Ca and silica), one can be fairly certain that
water-rock equilibration has occurred at the estimated temperature and that there has been
little water-rock reaction during subsequent flow to the surface. Agreement between
K//Mg and Li//Mg geothermometer temperatures, but higher temperatures estimated using
other geothermometers, may indicate a relatively short time in a reservoir at intermediate
depth and intermediate temperature where water-rock reequilibration occurs only in respect
to the most reactive phases."
In this study the Na bicarbonate waters follow the former proposition (equilibrium), while the
Na-Cl waters (as always, possibly except spring 15) contain significantly more Mg (and less Li) than
initially was present in the deep reservoir water (dilution).
401
Na - Li gcothermometen Two geothermometers of this type have been proposed by Fouillac and
Michard (1981) and by Kharaka et al. (1982) (Table 4). In Table 5 only the temperature computed
according to Fouillac and Michard's (1981) equation is given. Since Na is a major constituent and Li
a minor one, slight changes in the latter (e.g. exchanges in sedimentary formations) can heavily
modify the Na/Li ratio. It is used here only to differentiate the high temperature sodium chloride
system (Group 1) with respect to the low enthalpy sodium bicarbonate waters (Group 4). The high
temperature calculated for spring 4 by means of this geothermometer is worth of attention, because of
its geographic location: the temperature might be interpreted as the deep reservoir original
temperature, before any possible reequilibration in a shallow and low enthalpy reservoir. Moreover,
application of the TNL geothermometer often results in overestimated temperatures, possibly because
it has been calibrated mostly in granitic systems.
K - Ca geothermometer A chemical reaction governing CC>2 pressure through the formation of
calcite in a full equilibrium system corresponds according to Giggenbach (1988) to:

Ca-Al-silicate + K-feldspar + C2 = K-mica + calcite
(1)
The temperature dependance of this univariant reaction is given by:

log PC02 = o- 168 t-3.78
(2)
where ?CO2 *s 'm ^>ar an& * m CAs an example, this equation gives 2.6 bar at 250C and 18 bar at 300C. A possible relation
linking CC>2, Kand Ca in a full equilibrium system is (Giggenbach, 1989):
3 K-feldspar + CC>2 + Ca2+ = K-mica + calcite + 2 K+
(3).
Its PcC>2 dependence corresponds approximately to:
log (CK2/CCa) = log PC02 + 3-0
(4)
where Cs are concentrations in mg/1.

For spring 15 this geobarometric equation gives a PcO2 f 1-2 bar, consistent with a reservoir
temperature close to 230C if calcite is considered a stable phase. This is the same temperature as that
computed by the K-Mg geothermometer.

As a general conclusion on the application of the aforementioned geothermometers, the general
remarks by Fournier (1990) are to be regarded consistent with the results obtained in this study:
"In evaluating cation geothermometer temperatures, attention must be given to possible
effects of continuing water-rock interactions and mixing of different waters during upflow.
In addition, variations in estimated cation geothermometer temperatures may result from
variations in the mineralogy of the reservoir rocks that are reacting with the fluid. The
complete conversion of all feldspar in contact with reservoir water to smectite or illite will
generally lead to erroneous cation geothermometer temperatures. In particular, this is a
likely source of error when dealing with CU2-rich waters that contain mostly NaHCO3Additional errors arise from not taking into account activity coefficients of both the solid
and ionic reactants. Under the best conditions cation geothermometers have an uncertainty
of at least 5 - 10C, and commonly much greater than 20C.
402
Even with their inherent uncertainties, cation geothermometers can be very useful for
estimating approximate temperatures in geothermal systems and for investigating effects of
water-rock partial reequilibration during upflow. Reactions involving Na and K appear to

proceed very slowly while those involving Mg appear to proceed relatively quickly. In this
regard, the salinity of a solution is an important factor because a given amount of reaction
of highly saline fluid with wall rock during upflow will have little effect on the ratios of the
major cations in solution. On the other hand, the same amount of reaction of a dilute
solution with wall rock may drastically change cation ratios. Therefore, cation
geochemistry applied to hot-spring waters is likely to be most reliable for saline waters and
least reliable for dilute water. Increasing Mg , in general, and decreasing K/V~Mg and
Li//Mg, in particular, are very sensitive indicators of water-rock reequilibration with
decreasing temperature and of mixing of high- and low-temperature waters."
Some more remarks can be made about the results reported in Table 5. The general trend of
temperatures follows the classification groups made on the basis of salinities and chemical
compositions. Sodium chloride waters of Group 1 show in general a strong thermal anomaly
centered in the area of the order of 1 - 2 km^ between El Palmar and Aguas Calientes. The thermal
anomaly is likely to be extended 3 - 4 km westward, as far as spring 14 (Los Chirriaderos). All these
waters appear to be more or less affected by dilution and mixing with a shallow diluted water, as
already outlined. In spite of this, the composition of spring 15 (El Palmar) allows a first evaluation of
the deep thermal conditions to be made through the geothermometers presented in Table 5. As
mentioned before, the temperature calculated from quartz for this spring might well represent the
temperature of the flashing point. One can suppose that a liquid phase (equilibrated at high
temperature with quartz) rising from the deep reservoir is cooled by conduction and becomes
oversaturated in silica; at a certain shallow depth, depending on local structural and physical
conditions, the liquid phase starts boiling, segregating a gas phase. The sudden increase in
concentration of silica and the violent expansion of the gas phase produce a stirring of the residual
liquid, and as a consequence precipitation of silica. The solid phase thus produced can be partially
deposited locally in the fractures and/or carried to the surface by the upflow; it is then eliminated at the
sampling point by filtration of the sample. The explanation for the whole process was proposed by R.
Celati (personal communication, 1986).
The average temperature calculated for spring 15 by means of the other classical
geothermometers is of the order of 290 50C, with all the already outlined limitations. It is worth
noting that the use of the isotopic S4-H2O geothermometer reported in Table 4 (Mackenzie and
Truesdell, 1977) gives a temperature of 206C for the same spring. This represents the isotopic
equilibrium temperature between water and sulfate ion. Of course, water collected from this spring
does not necessarily have the same isotopic composition as the deep hot water because of possible
steam losses or dilution and mixing phenomena which here are not accounted for. The temperature
obtained from the isotopic geothermometer can represent the equilibrium between water and
anhydrite, below which solid sulfates dissolve yielding sulfate ions. That is, above this temperature
S4 and HSO4 species are not present in the solution; this is supported by the calculated
403
oversaturation of anhydrite found for this water for temperatures above 200 - 230C. In the deep
reservoir instead sulfur is supposed to be controlled by the E^S - pyrite equilibrium.

Temperatures computed for spring 4 (Group 2) by TQC, TNKCM, TNKC, TNKA, TKM,
TML are of the order of 132 16C, indicating a situation of medium enthalpy as can be inferred by a
leak from a deep reservoir and a later reequilibration.
Temperatures computed for bicarbonate waters of Group 4 (ruling out the TNK and TNL
geothermometers) are all below 100C. As an example, spring 22 can be considered representative of
the group; it is located south of the anomaly, with an emerging temperature of 48C and an average
calculated temperature of 69 15C.
From the geothermal point of view Group 5, including all diluted waters, was not taken into
account, having been considered too immature for having any significance. The NKC computed
temperatures are in any case lower than 50C.
GEOTHERMOMETRY AND SATURATION INDICES
Despite the fact that all the classical geothermometers indicate a strong thermal anomaly localized
in the El Palmar - Aguas Calientes area, the range of values is pretty wide for a precise temperature
evaluation. Application of fluid-mineral equilibria governing the chemical composition of water can
decrease the uncertainty with regard to the temperature estimates for the deep aquifers (e.g.
Amorssonetal., 1982; Michard and Rockens, 1983; D'Amore et al., 1987; Celati etal., 1991). This
can be achieved by the analytical determination of monomeric aluminum (AP+) and (AKxJOw)2' wth
x = OH", F-, SO^-, etc. and z = 3 - wy. Monomeric aluminum must be separated in the field.
The method by Arnorsson et al. (1982) was used through the computer program WATCH in
order to calculate the water speciation and the saturation indices for several hydrothermal minerals.
The Saturation Index (SI) is the logarithm of the ratio (at a given temperature) between the
activity product for hydrolysis reaction of a given mineral (AP) and its thermodynamic equilibrium
constant (K). Assigning a decompression temperature (that is when a two-phase system is produced
in the ascending fluid) equal to the quartz geothermometer temperature and a SiC>2 concentration
corresponding to quartz saturation, it is possible to calculate at selected temperatures the pH, the
speciation of the fluid (as activities of aqueous species), and then the saturation indices. These
saturation indices are plotted versus temperature for a number of selected minerals. For each mineral
the intersection of the SI vs. temperature curve with the zero line gives its equilibrium temperature.
Considering the uncertainty of measured Al concentration and of the thermodynamic data, the field of
stability for a given mineral is assumed to be between temperatures corresponding to a saturation
index of 0 0.25. Table 6 reports the temperature range for selected minerals andsprings (4, 15, and
22). For sodium chloride waters spring 15 was chosen as the most representative. The values of the
saturation indices vs. temperature for spring 15 is reported in Fig. 15. Taking into consideration the
maximum temperatures of the 0.25 range, the following high temperature mineral assemblage can
be found for spring 15: albite (293C), K-feldspar (288C), Mg-chlorite (305C), calcite (275C),
epidote (268C). The computed mean temperature is 286 15C; this is very close to the value of
291C given by the TNKCM geothermometer. On the other hand, considering the minimum
404
temperatures of the 0.25 range, a different mineral assemblage can be also found in the diagram:
albite (226C), K-feldspar (210C), wairakite (225C), prehnite (235C), calcite (225C), anhydrite
(225C). This gives a mean temperature of 224 8CC. This temperature is comparable with that of the
TKM geothermometer (231C).

This bimodal distribution of temperatures can be interpreted as two limiting thermal conditions
existing in different and independent parts of the reservoir: a deep zone characterized by temperatures
close to 290C and a relatively shallow zone with a temperature of about 225C. If spring 15 is
partially mixed, the bimodal distribution is the result of the mixing. Of course, the choice of mineral
species is somewhat arbitrary, at least in the early survey phase, until proved by drill cores. This
method cannot be applied with confidence to the other sodium chloride waters because their higher
dilution and mixing produce large variations of the computed saturation indices of minerals.
Waters of spring 4 (Group 2) and of sodium bicarbonate springs (Group 4) appear to be in
equilibrium with the following minerals: albite, K-feldspar, laumontite, montmorillonites (Table 6
and Fig. 16). Undersaturation for alumosilicates such as epidotes, prehnite, Mg-chlorite, can be
ascribed to the incompatibility of the reservoir temperature with the stability ranges of these high
-6
200
250
300
350
T(C)
Fig. 15. Saturation indices vs. temperature (see text) for selected minerals, for spring 15 (at quartz
saturation).
405
temperature mineral phases. This type of waters, always accompanied by free gas, may be the result
of a release of CC>2 at depth from hydrolysis of limestones and interaction of the produced carbonic
acid with silicate minerals at relatively low temperatures. All waters of Group 4 yield temperatures
lower than 100C with the "classical" geothermometers; saturation indices give consistent indications
within a temperature range of 60 to 90C.
For spring 4 (see Fig. 17) the computed temperature is 104 8C, in spite of its high chloride
content; it confirms a contribution of a deep component, with reequilibration at low temperature. The
presence of the deep component is witnessed by the relative abundances of conservative species like
Li, Rb, Cs, Cl. Waters of Groups 2 and 4 are noteworthy for the agreement between the temperatures
computed by the method of saturation indices and by the "classical" geothermometers.
TABLE 6. Computed temperature range (C) for equilibrium conditions of selected mineral species.
Equilibrium occurs when SI = 0.000.25. Spring numbers as column headings.
mineral
system
15
22
Albite
Na-Al-Si-O
26033 (x)
Adulara
Microcline
K-Al-Si-0
K-Al-Si-O
28929
oversat. t>232
K-FeldsparO)
Prehnite
Epidote
Zoisite
Wairakite
Mg-Chlorite
K-Al-Si-O
Ca-Al-Si-O-H
Ca-Fe-Al-Si-O-H
Ca-Al-Si-O-H
Ca-Si-O-H
Mg-Al-Si-O-H
249139 (x)
Calcite
Ca-C-O
Anhydrite
Ca-Si-O
241 6
2644
2325
2337
3022
(x)
(x)
(x)
(x)
(x)
705
undersat. t>60
undersat.
855
undersat.
906
(x)
undersat. t>90
undersat.
112112 (x)
undersat.
undersat.
undersat.
undersat.
undersat.
undersat.
250125 (x)
oversat. t>48
oversat i>59
oversat. t>200
undersat.
oversat. t>82
undersat
undersat.
undersat.
Na-Montm.
Na-Al-Si-0-H
oversat.< >
881
10311
(x)
K-Montm.
K-Al-Si-0-H
oversat. t>205
Ca-Montm.
Mg-Montm.
Muscovite
Laumontite
Ca-Al-Si-O-H
Mg-Al-Si-O-H
K-Al-Si-0-H
Ca-Al-Si-O-H
821
9911
(x)
93+1
110+1
(X)
941
110+1
(X)
oversat/ )
oversat/ )
2
oversat/ )
oversat/2)
oversat. t<H5
794
(x) This symbol indicates the use of the mineral for equilibrium temperature evaluation (see text)
(') Assumed with a structural state intermediate between microckne and adulara
(2) Oversaturated in the temperature range 200-325C
406
oversat. t<!40
10215
(x)
-6-
80
T(C)
100
saturation).
- 6-
~4
'
80
100
TC)
"io
'
iS
'
8~
saturation).
407
GAS GEOCHEMISTRY
Gas classification
In Table 7 the gas compositions as vol. % are given; analyses were carried out on total dry
gases. Data are reported after correction for C>2, considered as an index of air contamination. In order
to use the gas composition as a tool to evaluate deep temperatures, a classification of gases was made
by means of three suitable diagrams.
Fig. 18 is a diagram comparing the main component C2 against two reduced and reactive
parameters: CH4 and the sum H2 + H^S. Methane is an ubiquitous component of all kinds of gases ;
it is one of the slowest species to equilibrate (Giggenbach, 1982) with respect to "faster"
components. The samples in the diagram follow a certain geographic distribution from E to W and to
marginal springs: the compositions of the eastern samples, occurring from El Palmar as far as El
Salvaje, show important concentrations of 2 and/or H^S. Moving farther to W (Mundo Nuevo Los Mereyes) the gases show lesser and lesser of these components, up to nil (or close) in the gases
associated with the marginal bicarbonate waters. An exception is the gas of spring 88, with high
concentrations of H2S (and to a lesser extent of H2) in spite of its marginal position, its low salinity
and its low (< 100C) temperature computed by water geothermometry.
Another classification is given by the reduced and hydrogenated minor components H2, H2S,
CH4, in the plot of Fig. 19. A geographic trend similar to what obtained from Fig. 18 can be seen in
this diagram, the marginal gases being richer in methane. The shift to the right, that is toward the
2S - CF4 edge, of gases associated with NaCl springs like 7, 14, and 15 can be explained as a
hydrogen loss. The most likely reason for this can be a steam loss from the original fluid, of which
the high elevation gas emissions like 17 and 18 represent the gas fraction; the NaCl springs instead
represent the liquid fraction. It should be pointed out that the former are within 1.5 km of the springs,
at an elevation about 200 m greater. The gas composition of 17 and namely of 18 samples is thus
here considered as the most representative one of the gas at equilibrium in the deep reservoir, the
corresponding water being represented by spring 15. A second hypothesis for the H2 loss can be
reequilibration in water during ascent. The gases from the Mundo Nuevo - Los Mereyes area lie in an
intermediate position between 17 and 18 gases and the methane corner. The explanation for not being
these gases in the same position in the diagram as samples 17 and 18 can be attributed to a certain
contamination of the deep gases in the latest stages of their ascent, that is after separating from the
liquid phase at the piezometric level (as already mentioned in the water classification): in the area in
fact the villages tap local water tables at very shallow depths. The least affected by this oxidation is
the gas from spring 45, the strongest gas manifestation in the area. The position of sample 52
(air-contaminated and associated with a diluted neutral water, the richest in tritium) is odd: it is clearly
the result of oxidation in the surface water. Because of the large amount of C>2 found in the gas, its
position in the diagram suggests that if no oxidation did occur (complete loss of 2 and partial of
2S) its point would shift toward the position of gas 18. The same can be valid for sample 88.
408
TABLE 7. Composition of free gases in springs, El Pilar area. All analyses expressed in vol %; n.d. = not determined; blank = not detected.
sample
C02
H2S
CH4
H2
N2
AT
He
CO-104
7
14
15
17
18
98.5
97.3
89.0
93.2
92.4
0.51
2.01
2.90
0.97
1.90
0.074
0.092
5.40
3.49
1.54
2.9-10-4
0.0084
0.041
0.43
0.52
0.85
0.57
7.40
1.89
3.65
0.018
0.012
0.114
2.5-10-3
4.3-10-3
traces
traces
traces
2.4-10-3
2.5-10-3
4.4
5.0
6.3
3.1
3.3
94.6
1.09
3. HO- 4
4.27
2.7-10-2
4.2-10-3
3.3
45
45
46
47
49
50
95.9
96.4
96.0
95.6
97.2
95.4
0.33
0.27
0.081
0.09
0.17
0.21
2.25
1.84
2.26
2.42
1.50
2.39
0.063
0.076
0.033
0.058
0.062
0.028
1.71
1.38
1.61
1.84
1.01
1.92
5.7-10-3
3.6-10-3
5.1-10-3
8.2-10-3
3.7-10-3
7.4-10-3
1.5-10-3
1.1-10-3
1.7-10-3
2.2-10-3
7.8-10-4
1.6-10-3
4.8
n.d.
0.9
0.24
1.4
0.96
22
24
24
39
77
95.8
71.3
79.4
98.9
1.73
3.0
2.73
1.04
2.37
28.3
4.6-10-2
traces
0.45
2.46
25.7
18.4
5.5-10- 4
1.38
3.50
5.5-103.9-10-2
2.5-10-2
1.6-10-2
0.49
2.9-10-4
1.1-10-3
1.6.10-2
9.2
0.2
n.d.
0.2
1.0
1.8
23.4
0.34
6.6-10-2
5.9-10-3
2.6.10-3
n.d.
0.37
88
96.2
67.2
52
83
72.0
91.2
1.15
3.11
2.77
2.6-10- 4
2.7-10' 4
n.d.
4.0-10- 4
2.0-10- 4
6.5-10'4
1.2-10-
5.93
2.9. 10traces
COz/100
AAAAAAAAA'(Hj.Hj.SJxK)
Fig.
18. Triangular diagram for CC>2, Cffy and (H2 + H^S). Crosses refer to the easternmost
springs in Fig. 2, from El Palmar to Los Chiorriaderos and from Buena Esperanza to El
Salvaje; open circles represent the Mundo Nuevo - Los Mereyes area; triangles represent
peripheral springs, as in Fig. 1.
/\
Fig.
19. H2S-H2-CFI4 triangular diagram. Symbols as in Fig. 18, except solid circles identifying
true fumaroles (Buena Esperanza - El Salvaje).
410
The diagram built on the N2-Ar-He inert components (Fig. 20) (Giggenbach et al., 1983;
Giggenbach and Goguel, 1989) yields more information about the origin of gases as well as on the
effect of air contamination. The He corner, named "crustal", represents radiogenic helium, as can be
obtained from a long residence in old rocks; the N2 comer is close to the "magmatic" gases, nitrogen
being an ubiquitous component, also in its non-atmospheric fraction. Along the N2 - Ar edge the two
end points of air and water-dissolved air are lying; the air-saturated water generally represents the end
member on this side. Most samples cluster into two distinct compositions: one groups all fumaroles
(with associated condnsales as the acidic waters of Group 3) in a position intermediate between the
"crustal" and "magmatic" end members; the second group includes all gases associated with neutral
"real" thermal springs. Once more, samples 17 and 18 appear to be the most representative of the
deep gas, lying right on the "crustal"-"magmatic" line; the gases from the Mundo Nuevo - Los
Mereyes area appear to be more or less contaminated by an atmospheric component supplied by
air-saturated water. In particular, gases from springs 52 and 83 (diluted neutral waters) are more
heavily contaminated by dissolved air. For what the central study area is concerned, these results
confirm that any geothermometry based on gas equilibria becomes significant only when the air
contamination is small: reactive species (namely H2) in fact can reequilibrate at low temperature.
N,/100
HexlO
Fig. 20. Inert gas triangular plot (N2, He, Ar) (after Giggenbach et al., 1983).Solid circles represent
true fumaroles (Buena Esperanza - El Salvaje); open circles represent gases associated with
Na-Cl waters; X's refer to the Mundo Nuevo - Los Mereyes area; squares and triangle refer to
peripheral waters.
411
Among gases associated with bicarbonate waters (all falling near the air-saturated water end
member) exceptions are shown by gases 5 (o Carlos) and the two ones from the Cariaco gulf (77
and 88). All of these are right on the El Pilar fault trace or on secondary ones, and in spite of their
apparently odd location there can well be a contribution from deep gases. This anomaly was pointed
out also in the section dealing with waters, namely for conservative species, e.g. Li.
Gas Geothermometrv.
On the basis of the above information the geothermometric methods based on gas equilibria
will be applied only to some gases considered as the most representative.
The gases from manifestations 18 (El Salvaje, to the east) and 45 (Mundo Nuevo, to the west)
were tested by means of the method by Saracco and D'Amore (1989). This method takes into
consideration the three contemporary equilibria:
CH4 + 2H2O = CO2 + 4H2
(5)
H2 + 3/2FeS2 + 2H2O = 3H2S + l/2Fe3O4

CH4 + 3CO2 = 4CO + 2H2O
(6)
(7)
A numerical approach is used to solve a set of three non-linear equations derived from the
above equilibria:
4 log (H2/CO2) - log (CH4/CO2) = 4.635 log T - 12144.08/T + 6.69
+ 4 lo A
- 3 log A
- lg A
-4
3 log (H2S/CO2) - log (H2/CO2) = - 0.412 log T - 10318. 15/T + 17.25

+ 3 log AH2S - 2 log ACOZ - lo AH2 ' 2 'g PCO2
(9)
4 log (C0/C02) - log (CH4/CO2) = 0.719 log T - 12913.84/T + 4.73

3
A
+ 4 log ACO - ig co2 - ig ACEU
where T is in K, PcO2
IS
(1)
ê partial pressure of CO2 at equilibrium, and Aj is a term
containing the reservoir vapor mass fraction y and the distribution coefficient B of the gas i between
steam and liquid (Bj is the ratio between the concentrations in the steam and in the liquid):
Ai = y + (l-y)/B i
(11)
if y > 0 (steam present in a two-phase fluid), or:

A= l/Bjd + y - y B j )
if y < 0 (liquid, vapor-depleted system).
The unknowns are three: T, PcO2> an^ v-
412
(12)
For gas 18 the following results are obtained:

T = 250C;
y = 0.001;
P C O2 = 2.8atm;
the computed redox conditions are the following:

log P02 = -37.7;
log P S 2 =-13.4,
consistent with the values computed in many geothermal fields (D'Amore and Gianelli, 1984).
For gas 45 the results are:
T = 230C;
y = 0;
Pcc>2=1.0atm.
As pointed out by Giggenbach (1987) this method, used to evaluate the reservoir parameters,
involves several species at the same time, with the limiting assumption that all of them are still found
in the sample in the representative proportions as originally present in the reservoir. Hence, the
computed temperatures above shown are to be considered minimum values for the reservoir if
reequilibration (and oxidation at shallow depth) are actually occurring during the ascent to the
surface, with different reaction rates for each species and with different solubilities.
Calculation of deep temperatures for "good quality" samples can be achieved through use of
carbon monoxide in equilibrium with the other main carbon components CC>2 and CIfy and with
water, according to equation (7) (Bertram! et al., 1985; D'Amore et al., 1987; Giggenbach, 1987;
Chiodini and Cioni, 1989). Fig. 21 was taken from Giggenbach (1987), plotting the CH4/CC>2
versus CO/C2 molar ratios. In the figure two major redox buffers are considered: one supposing
2 - SC>2 coexistence for a magmatic gas phase, and another (more interesting for geothermal
systems) involving a general reaction likely to control the redox state:
4(FeOL5) = 4(FeO) + 02
(13)
+
where the bracketed entities represent Fe2 and Fe^ incorporated in an unspecified iron
oxide or an iron-aluminum mineral assemblage. For this buffer two curves are shown, according to
different equilibrations in the liquid phase or in the vapor phase. In the upper right part isotherms
refer to the equilibration temperatures in the vapor phase, while in the lower part they refer to
reequilibration in the liquid phase. In Fig. 21 the four most representative gases for the study area are
reported: 17, 18,45, and 46. At the first glance the points fall on the curve of the iron buffer referring
to the liquid phase; the same result was found according to the previous method. The calculated
temperatures range from 250 - 260C for the El Salvaje - Buena Esperanza area (eastern zone) to 220
- 270C for the Los Mereyes - Mundo Nuevo zone. The other gases (not reported) fall in a scattered
way, outside the liquid-vapor area, for temperatures between 200 and 300C. This does confirm the
local high temperature anomaly, but it confirms also what stated above about the non-equilibrium
state of these gases, due to vapor loss and/or oxidation phenomena during the late stages of ascent.
The carbon monoxide content can also be used to estimate the CC>2 partial pressure using
(Chiodini and Cioni, 1989) the following chemical equilibrium:
C02 + H2 = CO + H20.
(14)
Arranging the expression of the equilibrium constant, the following relation is obtained
(D'Amore, 1990):
413
5-
0Cvj
o
C)
O)
-5-
-10-
-8
-7
-6
-5
-4
log (CO/CO2)
Fig. 21. CH4/CO vs. CH4/C2 molar ratios for the application of the CO geothermometer (after
Giggenbach, 1987) applied to selected samples (see text).
= -491 + 192.4/T + 0.979 log T + log (CO/H2) -log AC + log AH2
(15)
where T is in K and A as defined in equations (11) and (12).

This equation is almost independent of the temperature and the steam fraction . Between 130
and 320C, and neglecting the effect of "y":
log PC02 = 3.52(0.1) + log (CO/H2)
(16)
The effect of considering a pure liquid phase will increase the computed log ?CO2 by abut
0.2 units, considering the difference in solubilities between CO and H2- Application of equation (16)
to the four samples appearing in Fig. 21 gives a range of CC>2 partial pressures close to 2 bar in the El
Salvaje - Buena Esperanza and of the order of 10 bar for the Mundo Nuevo - Los Mereyes areas
respectively.
414
The empirical gas geothermometer proposed by D'Amore and Panichi (1980) gives
temperatures of 264 and 289C for gases of springs 17 and 18 respectively, considering a
PCQ2-dependent correction term of 10 bar because of the composition constraints:
t(C) = 24775/(2 log(CH4/C02) - 6 log (H2/CO2)- 3 log (H2S/CO2)

-71ogPc02 + 36.05)-273
(17)
Considering a liquid-dominated geothermal system, an attempt was made to apply the H2/Ar
geothermometer proposed by Giggenbach and Goguel (1989). According to these authors in the case
of boiling springs the H2/Ar ratio (when no oxidation from O2 nor Ar pollution from atmospheric
sources occur) appears to provide valid information on the thermal conditions within the deep
equilibrated liquid phase. This method has been proposed and up to date tested only for high enthalpy
systems; in the case of low enthalpies it needs further refinement. The equation used is:
t(C) = 70 (2.5 + log (H2/Ar))
(18)
The calculated temperatures are 321 and 331C for gases 18 and 17 respectively, and 258 and
232C for gases 45 and 46 respectively. These temperatures are in general agreement with the ones
already found by gas and water geothermometry, thus confirming a liquid-dominated system at high
enthalpy.
D'Amore et al. (1989) proposed a geothermometric method devised for low enthalpy systems
which can be applied to thermal springs where the gas is associated to water. The method is based on
the calculation of the CO2 pressure either from water chemistry and from gas composition. There is a
temperature at which the two PcO2>s are equal. This can be considered the temperature at which the
gases are in equilibrium with the water sample at some point in the reservoir. This method of
comparison of the two PcO2>s
can
be use(^ as
geothermometer if the water sample is truly
representative of the reservoir water, where it is possible to assume steam fraction to be totally absent
in the reservoir. Using the chemical equation (5) and expression (8) with y = 0, the computed ?CO2
changes very rapidly with temperature. Table 8 lists the temperature-dependent term (KBT) of the
following equation:
lgPcO2 = KBT - log(H2/CO2) + 1/4 log(CH4/CO2)
(19)
Using the water composition and starting from the field measured temperature, pH and
alkalinity it is possible to calculate the new values for pH and ?CO2 fr eacn temperature, e.g. by
means of the program WATCH by Arnorsson et al. (1982). Change of P<X)2 w'tn increasing
temperature is moderate and smooth.
The limitations of this method are mainly due to attainment of full equilibrium of the gases
involved in the chemical reactions considered (different reactions can be used), and to the water
which must be representative of the liquid phase in the reservoir. As an example, this method was
applied to the o Carlos spring (water sample 4 and gas sample 5, a few meters away) and for spring
15 with the gas of samples 17 and 18. To calculate PcO2 in
me water
of spring 15 a decompression
temperature of 160C was chosen (as resulting from the silica geothermometer), taking into account
the loss of carbonic acid as CO2 during boiling. This method gives a convergency of computed
415
TABLE 8. Temperature-dependent term KBT in eq. 19

(t in C)
KBT
40
50
60
70
75
80
90
100
110
120
125
2's
-6.352
-5.945
-5.582
-5.233
-5.071
-4.905
-4.589
-4.307
-4.021
-3.758
-3.648
130
140
150'
175
200
225
250
275
300
325
KBT
-3.516
-3.290
-3.100
-2.607
-2.169
-1.796
- 1 .443
-1.110
-0.808
-0.470
of 2.5 bars at about 90C for o Carlos and between 13 and 15 bars at a temperature of 306
8C for the high temperature example (15, 17, 18), as shown in Fig. 22. The obtained temperatures
are consistent with the ones calculated by the previous methods. Besides, the higher PcO2 obtained
at 300C with this method is consistent with 2.3 atm calculated with the method by Saracco and
D'Amore(1989)at250C.
CONCLUSIONS
The results of the geochemical survey indicate that the studied geothermal area can be
promising for the recovery of high enthalpy geothermal resources in the El Pilar - Mundo Nuevo
area.
About the springs outside the area of concern, chemical evidences indicate that some leaks
from the deep reservoirs must exist, namely for spring 4 (o Carlos), with computed reservoir
temperatures generally in excess of 100C, but lower than 150C. This temperature is still of interest
for the exploitation of a low enthalpy system. Its position right on a fault plane of the El Pilar fault
system is in favor of a deep contribution.
The springs with NaCl waters, located in the El Palmar - Aguas Calientes - Los Chirriaderos
' area and the fumaroles located both in the Buena Esperanza - El Salvaje and in the Mundo Nuevo Los Mereyes areas are the result of a high local convective heat flow. A local heat source can be
postulated in a young magmatic body at an indefinite depth of some kilometers. Its residual
temperature at the top can still be high enough to justify the heat transmission to the fluids. The
416
5-
ra
oo 3O
equilibrium
equilibrium
o
40
60
80
temperature (C)
100
100
200
300
temperature(C)
Fig. 22. Computed ?CO2 vs- temperature for water and gas compositions, for selected samples, in
order to obtain the equilibration temperature between gas and water (see text).
inference of this magmatic body is justified by the occurrence of outcrops of rhyodacitic subintrusive
rocks (5 Ma; Sifontes and Santamara, 1972), located in the metamorphic unit about 6 km north of the
main zone of thermal manifestations. These rhyodacitic subintrusives are likely to be apophyses of
the deep batholith, possibly granitic or granodioritic; other younger intrusions not outcropping are
also possible to exist in the region just below the thermal area.
The local permeability is a consequence of the long-lasting and intensive deformations of the
zone; the recent and present episodes are related to the active El Pilar right lateral strike-slip fault
system (and to other systems complementary to the main structural feature) connected with the
displacement of the southern end of the Lesser Antilles arc with respect to the continent. Possible
recharge areas are located on both sides of the El Pilar fault: north of it the metamorphic formations
are highly fractured, and south of it limestones are fractured too by secondary tectonics. Both sides
form elevations in excess of 200 - 400 m of the fluid manifestations.
The zones with higher temperature manifestations are affected by carbonate, sulfate, and/or
silica mineralizations. Self-sealing phenomena can exist at depth, thus allowing the formation of an
impermeable cover confining the fluid into a possible reservoir. Shallow oxidation is witnessed by
the remains of some old sulfur mining works in the study area; the fresh water wells in the villages
indicate the presence of shallow water tables that can mix with the thermal fluids of deep origin.
The processing of geochemical data led to some hypotheses on the chemical and physical
characteristics of the reservoir fluids, as well as on their modifications during ascent. All the
following considerations are summarized in Fig. 23.
417
--300
--150
GAS+STEAM |_J
LIQUID
BOILING + GAS SEPARATION (t =160 C
--0
LLI
O
---150
ce
<
o
LU
ce
1000
Fig. 23. Sketch summarizing the possible model inferred for the geothermal field centered in Las
Minas (Fig. 2), in a section approximately N - S, from Aguas Calientes to Buena Esperanza
and farther uphill. Some selected springs and fumaroles are labelled along the topographic
surface. Symbols represent: 1, the gas phase; 2, the liquid + gas and steam (2 phases); 3, the
liquid phase; 4, the dominant phase(s). Stippled areas represent possible aquifers. The true
reservoir is the deeper one; the shallow resrvoir is not certain to exist: it can be merely the
mixing and partial reequilibration level (see conclusions in the text).
A deep hot reservoir is inferred at a temperature of about 300C; it is constituted by a sodium

chloride neutral water, without any free steam (y = 0), with a CC>2 partial pressure of about 14 bar.
Considering all classifications, a mixing results to be active for all springs, the "purest" being water
15; various geothermometric methods give the highest calculated temperatures for this spring. Being
this the least diluted (TDS = 3650 ppm), the total salinity in the deep reservoir cannot be much
higher, of the order of less than 5000 ppm, taking into account a dilution of 10 % approximately
(from Fig. 9) and a silica loss.
The lower temperatures obtained by the SO4-F2O geothermometer (206C) and the bimodal
distribution of temperatures obtained by water geothermometry indicate that a second reservoir is
likely to exist, separated from the hotter one and with temperatures in the range of 200-230C. The
mixing with water of this second reservoir yields a dilution of the NaCl water and increases the
relative concentrations of Mg, 804 and HC3.
418
Considering the highest silica content (spring 15) a boiling temperature in the range
160-170C is found; the result is the production of a two-phase system, in which the steam-gas phase
migrates toward springs 17 and 18, while the liquid phase outcrops as spring 15. The piezometric
level at an elevation of 150 m approximately controls this phase separation of the manifestations: all
fumaroles are found at higher elevations than the low-gas Na-Cl springs. For all fumaroles the most
reliable temperatures computed by gas geothermometry are found around 250C. This difference from
the maximum temperatures of the deep reservoir obtained by water geothermometry can be due either
to equilibration in the upper reservoir or to interaction with shallow fresh waters. Using the boiling
point curve for liquid H2O at low salinity and assuming a certain connection between the deep
reservoir and the surface, the high temperature reservoir can be estimated to lie at a depth greater or
equal to 1100 m. The shallow reservoir, with a temperature of the order of 220C, may also be
present at a depth of a minimum of 300 m.
The relative position in the inert gas diagram (N2-He-Ar) of the most important fumaroles
(namely 17 and 18) indicates for certain a deep origin of these gases (no meteoric contribution). The
high He content can be explained only by a long residence of the fluid in the reservoir rocks (this was
found e.g. at Larderello). This supports a possible accumulation of the fluid in the deep reservoir,
which is inferred to be generally sealed by the rock alteration.
The geothermal system is supplied by groundwater derived from meteoric water which can
originate from the two high elevations on both sides of the El Pilar fault: Cerro La Pica to the north
and Cerro El Pato to the south, both higher than 600 m (recharge areas).
Heat and gas (mainly C2) are assumed to be supplied by a buried batholith which heats a
convective cell of neutral pH, chloride type, water, and with a two-phase condition in the upper zone.
This steam separation process gives rise to the fumaroles; steam can be absorbed by local
groundwater, with oxidation of H2S and production of steam-heated sulfate and bicarbonate waters
rich in boron and ammonia. Hybrid waters can be the result of mixings between the deep waters and
shallow ones.
The outflow of chloride waters depends on local structural and topographic conditions:
because of lateral flow the spring can be found kilometers away from the hot upflow point of the
geothermal system. The high relative permeability for the gas phase generally yields a direct vertical
upflow from the reservoir, thus defining clear geographic distributions. In this area the main steam
upflows are localized at Las Minas and between Mundo Nuevo and Los Mereyes (Fig. 2), where
eventually exploratory wells can be localized.
ACKNOWLEDGEMENTS
This work has been performed within the framework of the IAEA coordinated research
program on the "Application of Isotope and Geochemical Techniques in Geothermal Exploration in
Latin America (Research Contract No. 3994/R2/IG), which is executed with the financial support of
the Government of Italy. The Italian National Research Council (CNR) also gave a financial
contribution to this program.
419
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422
ORIGINS OF ACID FLUIDS IN GEOTHERMAL RESERVOIRS

A.H. TRUESDELL
US Geological Survey,
Menlo Park, California,
United States of America
Resumen-Abstract
ORGENES DE LOS FLUIDOS CIDOS DE DEPSITOS GEOTRMICOS.

Los fluidos cidos en depsitos geotrmicos son raros.
sistemas geotrmicos
relacionados con volcanismo
reciente
Su presencia en
(Tatn, Sumikawa,
Miravalles) indica probablemente que el fluido en el depsito geotrmico pro-
viene de fluido volcnico

feldespatos y micas.
incompletamente neutralizado por
la reaccin con
El vapor recalentado que contiene HC1 (Larderello, Los
Geiseres) forma cido cuando se condensa o se mezcla con lquido a temperaturas moderadas (<300C).
El origen del vapor con HC1 es la reaccin del NaCl
slido con las fases minerales de la roca a temperaturas elevadas (>325C).

En Los Humeros se produce criptoacidez cuando se forma y neutraliza la acidez
del HC1 sin alcanzar la superficie.
ORIGINS OF ACID FLUIDS IN GEOTHERMAL RESERVOIRS.
Acid fluids in geothermal reservoirs are rare. Their occurrence in geothermal systems
associated with recent volcanism (Tatun, Sumikawa, Miravalles) probably indicates that the geothermal reservoir
fluid was derived from volcanic fluid incompletely neutralized by reaction with feldspars and micas. Superheated
steam containing HCl (Larderello, The Geysers) forms acid where it condenses or mixes with liquid at moderate
temperatures (<300C). The origin of steam with HCl is reaction of NaCl solid with rock minerals at high
temperatures (>325C). Cryptoacidity occurs at Los Humeros where HCl acidity is formed and neutralized
without reaching the surface.
Introduction
The occurrence of acid fluid in well discharges from geothermal wells is of great theoretical and
practical interest. Chemical substances in geothermal fluids have been proposed to originate
from leaching of rocks by hot water (e.g. Ellis and Mahon, 1964) or from neutralization of
volcanic fluids (e.g. Giggenbach, 1981). Because volcanic gases and condnsales where they
discharge at the surface are acid, the occurrence of acid reservoir waters in some geothermal
fields associated with volcanic activity supports the hypothesis that neutral geothermal fluids
also originate from volcanic fluid. Deep, hot, acid water has not been successfully exploited
and some wells (and fields) have been abandoned as a result. Acid carried in superheated steam
that condenses only at the surface can be neutralized but at additional cost. Distinguishing the
cause of acid fluid production can assist in management decisions involving treatment or
isolation of acid reservoir fluids and possible abandonment of wells or fields.
423
In some fields, acid waters that come to the surface through springs or drill holes originate
from acid reservoir fluids. In others, boiling of high-temperature neutral or acidic brines or
reactions in vapor-halite-silicate assemblages generates HC1 gas that is carried in superheated
steam and becomes corrosive when the steam condenses, usually at the wellhead. Ascending
superheated steam containing HC1 may also mix with overlying neutral waters to produce acid
solutions that rapidly corrode and scale well casings, possibly without acid fluid appearing at
the surface. Analyses (in milliequivalents per liter) of related acid and neutral geothermal waters
and steam condnsales are given in table 1.
TABLE 1. SELECTED ANALYSES OF ACID GEOTHERMAL RESERVOIR WATERS AND RELATED

WATERS (in milliequivalents per litre unless otherwise specified)
No
Well or
Temp
spring
<C
pH
Na
Ca
Mg
Fe
SO,)
Cation
Aruon
Cl
mmol
mmol
sum
sum
excess
28
377
46
HCOj
Tatun
1 Hsinpeitou
2 E101
3 E102
70
175
250
13
4
98
12
72
424
297
396
103
123
854
12
62
13 1 86
4 35 19
48
496
31 1
199
108
1 66
24
376
0206
67
972
105
15
228
0005
101
024 0041 0022 129

0095 0041 0079 322
265
48 8
104
109
158
66
504
172
91 4
277
169
153
89
564
128
407
93 6
114
136
170
104
114
21 5
175
70 8
45
367
503
123
!25
33 1
46 3
Sumikawa
4 Tamagawa
5 S-2
6 S-2A
7 S-4
8 Yakeyama
240
245
280
88
26
76
04
253
1 33
66
15
854
018
42 8
17
0007
34 8
341
987
373
227
175
11
286
15 6
107
13 1
5 17
123
361
526
293
140
739
0741
0204
0361
00093
153
858
165
0171
165
95
165
228
5 83
657
5 37
107
122
109
115
129
111
0 065
196
1410
0 169 0 1
185 151
1600 1100
1 06
0964
0808 3 17 22
137
227
145
145
138
274
Yellowstone
9 Green Drag
10 Echinus G
11
Ear
12 Unnamed
85
93
94 5
88
29
3
9 21
22
126
696
138
1 28
152
013
0532 003 00012 11 6

00128 001 00065 0011 0076
235
235
238
22
8 1
962
108
977
673
849
683
250
>250
340
59
31
26
073
0957
0065 17
1 66
00818 135 119
330
330
667
348
0826 0123010500008 000540592

00074
0021
00032 0932 3 16
300'
316
270
29
77
85
739
215
128
342
653
6 02
--
4 27
0521
227
308
27
07
1 96
15 6
1 17
0 574 10
11 5
0 689 10 6
Miravalles
13 PGM 2
14 PGM2A
15 PGM Av
16 G 2
17 G-4
18 G-6
34
19
325
0 0 1 100047 112
1 26
1 39 113
0012 00036 109
017
144
887
185
1600
00683 482
0 667
1 48
48 1
0 777 78 6
Krafla
19 KG 12
20 KG 12v
0208
-
1 1
Los Humeros
21 H-4
22 H-16
23 H-l
0665
0716
1 25
48
036
001
00033
-
143
742
272
024 0 19
398 236 109
2 56 2 84 11 3
214
154
222
812
Sources of analyses 1-3.CH Chen (unpublished), 4. Ozawa et a] (1973) 5-7, Sakai et al (1986), 8, White et al (1963): 9-12, Roweet al
(1973) and Thompson and Yadev (1979). 13-15. Majruen et al (1990). 16-20. Truesdell et al (1989) and Orkustofhun unpublished data,
21-23, CFE (1990)
Other significant consDtuents (in meq/1) for analyses (#) Al #1. 17 3. #Z 24, #3. 15 6, 4, 17 6, and #8. 37 8 NRi #17.41 6, #18,486. and
#21.05 F#4. 63. and #11. 14 Mn #1 0 6. #17. 6 8, and #18. 26 6 Li #9, 0.5. #11. 0 75. #13. 097. #14. 1 1, and #15. 1 0
424
Acid C1-SO4 Waters with Excess Chloride

Some reservoir water analyses show "excess" chloride defined as chloride equivalent
concentrations
significantly
greater
than the sum of equivalent concentrations of cations other
+
++
++
than H . (High Fe
and Mn
in well discharges originate from reaction of H+ with casings,
and these ions are also not included in the sum of cation equivalents.) These waters must have
had at least part of their acidity introduced as HC1, most probably from a volcanic source.
Chloride excess waters from geothermal reservoirs are apparently rare, although many
examples of similar waters are found in crater lakes or associated with active volcanoes (White
et al., 1963, table 19). Only the Tatun system in northernmost Taiwan has been sufficiently
explored to show excess chloride waters present in a distinctly geothermal reservoir. Other
areas may have similar reservoirs but have not been drilled.
The geology of the Tatun field has been described by Chen (1970) and the chemistry of
reservoir waters briefly reviewed by Truesdell et al. (1989). The Tatun geothermal field covers
an irregular area about 5 x 10 km within the circular Plio-Pleistocene Tatun volcanic group.
This volcanic center has a long history of activity and some morphologically young volcanoes
but there are no historic eruptions or published rock dates. The geothermal reservoir is
developed partially within andesitic flows and tuffs but mostly within the underlying 900-m
thick Miocene Wuchishan Sandstone consisting chiefly of thick beds of orthoquartzite
containing only quartz, kaolinite and minor alunite, and elemental sulfur. Within the reservoir
andesites are highly altered.
Reservoir waters range in salinity but have chemical compositions similar to each other and to
the Hsinpeitou spring at the western margin (table 1, analyses 1-3, and figure 1). The deep
reservoir water at Tatun probably has a pH of 1.5 to 2, chloride from 3500 to 13000 ppm, and
a temperature of 250 to 300C (references in table 1). Steam boiled from this water contains
HC1 gas. Condnsales from a shallow well producing dry steam contained 3500 ppm HC1 at
pH 1 (Ellis and Manon, 1977) and condnsate with 400 ppm Cl was collected from a
superheated fumarole (Truesdell et al., 1989). The chloride excess at Tatun has not been
neutralized by reaction with rock because the reservoir contains no minerals (e.g. feldspar or
mica) capable of neutralizing acid. The Tatun field was finally abandoned because no means
was found to prevent rapid corrosion of casings.
a E-101
O E-102
+ Hsinpeitou
3
4->
JO
+-I
03
o 02
c
o
O
O)
pH
Na
Ca
Mg
Fe
Cl
S04
Al
Figure 1. Schoeller diagram of analyses (in meq/1) of well waters and a spring water from the
Tatun, Taiwan field. In a Schoeller diagram the slopes of lines connecting logarithmic
concentrations indicate ratios and are not changed by boiling or mixture with dilute waters or
steam condnsate. pH values are shown directly. Data sources are given in table 1.
425
Other waters with chloride excess are closely associated with active volcanism. An example is
the famous Tamagawa hot springs on the western slope of Mt. Yake, north-central Honshu,
Japan. These springs (table 1, analysis 4, and figure 2) discharge 9300 1/m at 98C containing
about 3 g Cl/1, comparable on a yearly basis to an erupting volcano in the amount of heat and
material transported (Ozawa et al., 1973). The Sumikawa geothermal field on the north slope
of Mt. Yake produces mostly low-Cl (100-400 mg/1) neutral waters with one well producing
acid SO4-C1 water (discussed later). The relation between the neutral waters, high-SU4 acid
water, and high-Cl acid waters occurring within 5 km has never been examined.
Acid discharge of well 4 at Los Humeros, Mexico, well 12 at Krafla, Iceland, and acid steam
condnsate at The Geysers, California, and Larderello, Italy, are also excess chloride waters
but were formed by a different mechanism involving transport of HC1 in superheated steam.
These areas will be described later.
Acid SO4-C1 Reservoir Waters

Acid waters with SO4-C1 acidity are found at the margins of several geothermal systems
associated with recently active andesite volcanoes. In these fields the acid zones were
penetrated by a small number of wells that produced acid fluid from the outset or after
deepening. These wells were soon abandoned or used as injectors so geochemical data are
limited. The best documented examples are well S-2 at Sumikawa, Japan, and well PGM-2 at
Miravalles, Costa Rica. Each of these wells became acid after deepening. Analyses of flashed
waters from these wells before and after deepening and of a typical neutral water of each field
are given in table 1 (references in the table).
Well S-2 at Sumikawa was originally drilled to 900 m and deepened 5 months later to 1065 m
with the intention of increasing the flow. The fluid produced before deepening had high excess
steam (2428 J/g total enthalpy) and elevated Cl, SC<4, Ca, Mg and Fe relative to other
Sumikawa well waters but was at near neutral pH (table 1, analyses 5-7, and figure 2). During
the first few months of production, Cl and S4 increased but fluid pH remained neutral. After
10
o
S-2
O S-2A
cr
QJ
E
c
B
cu
cu
o
c
o
A
+
x
S-4
Tamagawa
Yakeyama
D3
-1
-2
-4
pH
Na
Ca
Mg
Fe
Cl
S04
Al
Figure 2. Schoeller diagram of analyses (in meq/1) of waters from Sumikawa, Japan wells and
associated acid springs, on the flanks of ML Yake volcano. Data sources are given in table 1.
426
deepening (S-2A), the water no longer had excess steam (~1090 J/g enthalpy), but had much
higher $64, Fe, Ca and Mg, and lower Na, B and HCOs, with pH values below 3. Oxygen
isotope compositions were initially similar to those of other Sumikawa waters and increased
0.8 permil after deepening, but deuterium compositions were initially 5 permil higher than
other waters and became 12 permil higher after deepening (MMC, 1990). The Cl in the acid
water was a little lower than the initial Cl but still higher than Cl in other well waters although
there was no chloride excess.
The chemical evidence for the source of the acidity is equivocal. Higher Cl and SC4 compared
to other Sumikawa waters might suggest less dilution with meteoric water and less reaction
with rock to neutralize acidity and precipitate S4 as anhydrite. Alternatively, the S-2 acid
water could be a mixture of normal Sumikawa water with acid SO4-C1 spring water similar to
the Yakejama water (table 1, analysis 8) but higher in S4 relative to Cl. Higher 6D and 5O are
consistent with evaporation at surface boiling temperatures, suggesting a component of
surface-evaporated, acid-sulfate water. The mixing of shallow high-SC4 water with deep highCl water has been suggested to be the origin of acid S4-C1 waters in the Palimpanon and
Bacon-Manito fields of the Philippines (Robinson et al., 1987) and of acid SC4-C1 hot-spring
waters at Yellowstone National Park, USA (table 1, analyses 9, 10, and figure 3). The
deuterium contents of the Yellowstone waters were intermediate between those of neutral highCl waters and of evaporated, deuterium-rich acid-SU4 waters formed by oxidation of H2S
(Truesdell et al., 1977).
10
Green Dragon
Echinus Geyser
Ear Spring
Unnamed
cr
o>
c
o
8 o
O)
O
-2
pH
Na
Ca
Mg
Fe
Cl
S04
Figure 3. Schoeller diagram of analyses (in meq/I) of acid and neutral spring waters from
Yellowstone National Park, USA. Data sources are given in table 1.
At Miravalles, Costa Rica, acid high-SC4 water was discharged from well PGM-2 after it was
deepened from 1200 m to 2000 m in 1984 (table 1, analyses 13, 14, and figure 4). Before
deepening the well had produced water similar to other wells with neutral pH but slightly
elevated 804. After deepening (PGM-2A),pH decreased to 2.2 and SC<4, Mg and Fe increased
greatly with smaller increases in Na, K and B, and decrease in Ca. The increased Fe probably
resulted from acid corrosion of the casing suggesting that the reservoir pH was probably lower
than 2.2. This water showed almost no change in Cl and no excess Cl indicating that the acidity
was associated with higher SO4 not Cl.
427
10
o PGM-2
O PGM-2A
A PGM-Ave
cr
03
0)
u
c
o
U
O)
-2
-4
pH
Na
Ca
Mg
Fe
Cl
S04
HC03
Figure 4. Schoeller diagram of analyses (in meq/1) of well waters from the Miravalles field,
Costa Rica. Data from Mainieri and Vaca (1990).
As at Sumikawa the chemical evidence does not indicate a definite origin for the acidity. Acid,
high-SO4 waters could have had a volcanic origin or could have been formed at the surface by
oxidation of H2S. These acid-SC>4 hot-spring waters are well known and occur in almost every
geothermal system where steam escapes at the surface. Most of these spring waters contain
cations leached from adjacent rocks but some are nearly pure, dilute sulfuric acid (table 1,
analysis 12). However, in order to increase SO4 in PGM-2 from 2 meq/1 to 16 meq/1 with only
1% change in Cl requires a concentration of S4 in the mixing water exceeding 1400 meq/1 or
about 65000 ppm S4. This is about 20 times the most concentrated acid-SU4 water reported
by White et al. (1963). An acid-SO4 water mixing to produce the acid S-2A discharge at
Sumikawa would have to be twice as concentrated. Although not impossible, the existence of
these waters seems very unlikely.
A Volcanic Origin for Acid C1-S4 and SO4-C1 Waters
Acid S4-C1 waters at Sumikawa and Miravalles seem most likely to be immature volcanic geothermal waters not fully equilibrated with feldspar, mica, and Fe minerals in the reservoir.
Giggenbach (1981, 1988) suggests that volcanic fluids containing acid, oxidizing gases
"mature" to form neutral, reducing geothermal waters by reaction with rock minerals including
feldspars, mica, and reduced iron oxides and silicates. HC1 is neutralized to NaCl, and SO2
disproportionates to H2S and H2S4, which may then precipitate as alunite and anhydrite. The
chemically distinct acid waters at Tatun and at Sumikawa and Miravalles appear to have
resulted from different reaction paths during maturation. At Tatun, S4 is present in variable
amounts but is not as important as HC1 in producing acidity. At Miravalles, acid and neutral
waters differ mainly in S4 with nearly the same Cl. Sumikawa seems intermediate. At Tatun,
conversion of SO2 to SO4 and precipitation as anhydrite and alunite appears to have preceded
neutralization of HC1. At Miravalles, HC1 neutralization apparently preceded SC2 disproportionation which produced additional acid. Sumikawa may be similar to Tatun but with more
neutralization of acid and less precipitation of sulfate.
Sulfur isotopes in SC4 from Miravalles (Giggenbach and Corrales, this volume) and from
Palimpanon and Bacon-Manito fields in the Philippines (Robinson et al., 1987) have been
428
analyzed to determine whether SC4 was produced by surface oxidation of H2S or by deep
addition of SO2- These isotope analyses were not entirely definitive and the interpretations
were quite different. In the Philippines fields most S^S values were near zero permil, which
was interpreted to indicate that all sulfur was originally present as H2S and that H2S had
oxidized near the surface to acid-SO4 water, which infiltrated the geothermal reservoirs.
Analyses of Miravalles SO4 were interpreted to show that mixing with surface-produced acidSC4 water had not occurred and that S4 was of deep origin. It is unfortunate that detailed
analyses of Philippine acid waters are not available for geochemical interpretation.
HC1 in Superheated Steam

The appearance of superheated steam containing HC1 at the major vapor-dominated geothermal
systems of Larderello and The Geysers has led to several studies of its occurrence and origin
along with programs to mitigate its corrosive effects. At Larderello, HC1 was first observed in
1960 (Allegrini and Benvenuti, 1970; D'Amore et al., 1977) and at The Geysers, in the mid1980s (Haizlip and Truesdell, 1988). The almost simultaneous appearance of HC1 in many
wells at Larderello was probably caused by widespread drying of the reservoir and to a large
extent HC1 disappeared when liquid injection was begun (Truesdell et al., 1989). The solubility
of HC1 in solutions differing in temperature, pH, and Cl concentrations was calculated by
Haizlip and Truesdell (op. cit.) who concluded that at The Geysers and Larderello (240260C), HC1 is transported only in superheated steam because below 300C it is very soluble in
neutral liquid and would have been removed from the vapor if condnsate were present.
Saturated steam from the normal Geysers reservoir (table 1, analysis 16, and figure 5) has little
Cl, but superheated steam at normal and high temperatures may have high HC1 concentrations
indicated by acid condnsate with high Cl and high Fe and Ca (analyses 17, 18). The origin of
the HC1 in these fields is related to high-temperature reactions but whether it forms mainly from
boiling of near-neutral NaCl brines or from reaction of halite with silicates (D'Amore et al.,
1990) is still controversial.
At The Geysers and Larderello, HC1 in steam seems closely related to the existence of hightemperature zones below the main vapor-dominated reservoir (Walters et al., 1988; D'Amore et
al., 1990). At The Geysers these high-temperature zones are at the same pressure as the vapor
cr
,
c
o
o G-2
C> G-4
A G-6
03
c
o
o
c
u
D)
O
-2
-4
pH
Na
Ca
Mg
Fe
Cl
S04
S02
Figure 5. Schoeller diagram of analyses (in meq/1) of water collected in condnsate traps from
a low-Cl (G-2), and high-Cl (G-4) normal-temperature wells and from a high-temperature,
high-Cl (G-6) well at The Geysers, USA.
429
reservoir and 50 to 100C higher in temperature. Fluid in these zones must be superheated
steam with only absorbed liquid or high-Cl brines possibly present. These zones contain
distinct, high-gas, high-B, high oxygen-18 steam and HC1 that is either an original constituent
(if a volcanic origin is assumed) or has resulted from boiling of brine or from halite-silicate
reactions. In most areas of The Geysers where HC1 occurs, steam is sufficiently superheated
that the first condensation occurs at the wellhead and corrosion can be prevented by injection of
alkaline solutions.
HC1 in superheated steam occurs in many places, mostly related to active volcanoes. In well
KG-12 at Krafla, Iceland, superheated steam containing HC1 appeared in late 1979 and
disappeared in 1982 (table 1, analyses 19 and 20 before and after superheating) with HC1
content closely proportional to the degree of superheating and the rate of flow (Truesdell et al.,
1989). The KG-12 acidity was mitigated by mixing the steam with two-phase discharge from
another well. The Krafla occurrence was clear evidence that HC1 could appear in any hightemperature (>325C?) geothermal field in which superheated steam appeared. The Cl
concentration in waters from KG-12 (table 1, analysis 19) and nearby wells is normally
relatively low (<100 ppm) but brines are occasionally encountered and evaporation in the
reservoir may be the origin of the brine or possibly halite, which produced HC1 in KG-12. As
at The Geysers and Larderello, the appearance of superheated steam is related to the local or
widespread depletion of liquid in the reservoir and a decrease in reservoir pressure. Injection of
liquid water will recharge liquid in the reservoir and in most cases raise pressures and eliminate
HC1 in steam.
Los Humeros, Mexico, an Unusual Case

The Los Humeros geothermal field in the state of Puebla, Mexico, is located in a large caldera
at the eastern end of the Mexican volcanic belt. The productive reservoir is mainly developed in
andesites and andesite tuff underlain by hornfels and calcareous skarn. There are several
petrographic and fluid inclusion studies of Los Humeros reservoir rocks (Arnold and
Gonzales-Partida, 1987; Prol, 1988; Viggiano and Robles, 1988; Prol-Ledesma and Browne,
1989). Chemical analyses of fluids (tables 1 and 2) and some downhole-temperature
measurements were provided by the Comisin Federal de Electricidad (CFE) and the Instituto
Investigaciones de Elctricas (HE). A report by Gutierrez-Negrin and Viggiano (1990) and one
by HE (1990) provided additional data on the history of well H-16.
Most wells of Los Humeros have high total fluid enthalpy and produce all or almost all steam at
the wellhead. Of well fluids collected before 1990 only those from well H-l (table 1, analysis
22, and figure 6) were low enthalpy and originated as almost entirely liquid water in the
reservoir (about 0.7 liquid fraction when produced to 4 bars). Other wells had liquid fractions
from zero to 0.4 but most were less than 0.1. With high total enthalpy and small liquid
fractions the reconstruction of reservoir fluid concentrations is difficult because boiling is
almost certain to have caused some mineral precipitation in the reservoir or wellbore.
Well H-l is one of the shallowest of the field (1450 m TD) and produces relatively little excess
steam (fluid enthalpy, 1311 100 J/g). The measured temperature at bottomhole was 260C in
agreement with geothermometer calculations (quartz saturation 260 10C; Na/K (Fournier)
265 10C). It is probable that H-l fluid is typical of the main aquifer at Los Humeros (table
2, analyses 1-5). Fluids from six other wells have average flashed Cl concentrations similar
(25 ppm) to that of well H-l (95 28 ppm) and give similar geothermometer temperature
indications (figure 7). Other wells have a wide range of measured and calculated Cl
concentrations but also have similar indicated reservoir temperatures (figure 7). Measured pH
values of all (except H-4) fluids after flashing are generally neutral to alkaline (pH 7.5 to 8.5,
rarely as low as 6.5).
430
TABLE 2. SELECTED ANALYSES OF FLASHED WATER FROM LOS HUMEROS WELLS H-l, H-16
AND H-4 (in mg/L unless otherwise specified)
Source: Comisin Federal de Electricidad (1990)
No.
Date
1 82/06/10
2 85/01/10
3 89/06/06
Enthalpy
pH
Na
Ca
Cl
HCOj
1220
8.5
250
43
74.4
1240
8.5
294
49
0.2
96.4 173
293
1340
8.24 290
48
1.9
95.1
2660
2660
7.79
7.76
7.73
7.7
7.54
8.21
9.24
9.12
8.64
8.92
28.8
7
7.7
10.3
7.2
255
SO4
116
123
225
240
116
694
675
187
803
Well H-16
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
86/02/14
86/03/18
86/06/12
87/07/14
88/06/24
88/08/11
89/01/20
89/02/14
89/09/09
89/10/13
2660
2310
2330
2500
7.2
82/08/19
82/08/30
82/08/30
83/01/24
83/03/08
83/03/08
83/03/15
83/04/21
2.9
2.9
6.2
6.6
8.5
8.5
4.95
540
600
695
494
372
430
636
632
420
586
26.6
32.2
28
54
40
29
29
44.2
32
208
309
263
1.86 298
1
212
210
210
393
450
900
144
54.'
54.7
73.:
524
523
1.2 212
0.9 99.3
279
464
66
170
150
285
4
15.3
26 96
72
33
47
7
37.4 6.7 0.2
53
7.5 0.0
30
4
0.0
130
0.0
208
63.3 61
506
472
97
951
106
585
40
26.9 1150
333
36.6
150
197
1680 944
1880 1020
1900
1080
191
1660 651
95.2 1180 1080
166
691 534
192
197
94.6
142
248
187
270
220
194
367
875
551
216
465
350
11 .3 2320
11.6
29 .2 4230
18.9
69
400 400
18.4 481
41
42
17.3 287
52 .2
10.8 303
32 .7 376
372
Notes: 2-inch orifice plates were used for H-l samples after 1983 and all H-16 samples presented
here; orifice plate sizes for H-4 samples are not known. "--" indicates not available, not analyzed,
or not detected.
10
a H-4
O H-16
A H-1
cr
2
+->
g
D)
-4
pH
Na
Ca
Mg
Cl
S04
HC03
Figure 6. Schoeller diagram of analyses (in meq/1) of waters from two wells affected by deep
HCl and of a normal well at Los Humeros, Mexico.
431
3000
* Total discharge
a Aquifer liquid
a Flashed liquid
100
200
300
400
500
600
Chloride, mg/kg
Figure 7. Enthalpy-Cl diagram of average fluids from wells at Los Humeros, Mexico, with
lines showing steam loss for average H-l discharge and for the highest chloride well (H-l 1,
data for H-2, H-4 and H-19 are not sufficient to plot).
Well H-l6 was described in detail by Gutierrez-Negrin and Viggiano (1990) and IIE (1990).
This well was drilled to 2048 m total depth and showed several likely production zones as
indicated by intensive faulting and lost circulation, a definite deeper zone from 1750 m to total
depth, and shallower, less well-defined zones above 1650 m to possibly 1300 m or above. The
lower zone (in andesite and hornfels) was entirely in the amphibole facies characterized by the
appearance of amphiboles and garnet. The measured temperatures in the lower production zone
were 300-319C but temperatures of 380-400C have been measured in other wells. The upper
production zone (in andesite) was mainly epidote facies but extended to the amphibole facies.
Measured temperatures were 230-290C. Quartz-saturation geothermometer temperatures of
fluid from this zone were variable but centered on 270C similar to those from well H-1.
After initial production in 1985, the flow of this well progressively decreased and in 4 years
nearly stopped flowing. The partially slotted liner installed from 1400 m to total depth was
raised and found to be highly corroded in its lower part (1420-1432 m depth) with only 50 m
of unslotted and 20 m of slotted liner recovered. The middle part of the liner (1415-1420 m
depth) was scaled completely with Fe oxides and sulfides in the outer part and amorphous
silica with some Fe minerals in the inner part. The upper part of the liner was lightly scaled.
The chemistry of H-l6 well fluids (table 2, analyses 6-16,

and figures 6 and 8) went through a
remarkable evolution (Gutierrez-Negrin and Viggiano, op. cit.) in which HCOs, which was
originally the major anin, decreased from 450 to 55 ppm and then increased to 520 ppm while
chloride increased from 210 to 300 ppm and returned to 210 ppm. During this period the pH
(after flashing) decreased from about 8.5 to 7.5 and then increased to 9.0, B decreased from
1900 to 600 ppm and Ca decreased from 7 to about 1 ppm. Other species (Na, S2) showed
less definite decreases.
In December 1989 the lower zone was isolated by a plug at 1570 m and a new slotted liner was
installed, after which the well produced entirely from the upper zone and the fluid chemistry
stabilized. The flow after December 1989 was about that measured when the well was first
drilled but the enthalpy decreased from near 2660 to 2400 J/g (Luis Quijano Len, pers.
commun., 1990) suggesting that the lower zone had contributed heat but little fluid.
432
3.5
2.5
g
'^
(o
M
(U
1.5
c
o
o
05
O
0.5
-0.5
85.5
86.5
87.5
88.5
89.5
Year
Figure 8. Changes in concentrations (in mg/1) of selected constituents of flashed discharge

fluids from well H-16, Los Humeros, Mexico.
The chemical reactions that led to the corrosion and scaling may be interpreted from the
wellhead chemistry and the character of the scale. The initial production was from both deep
and shallow zones. The shallow water was similar to that of well H-l (table 2, and figures 6
and 8) and is represented by samples taken in early 1989 after the lower zone was sealed off by
scaling or had been cemented. The deep zone produced superheated steam containing HsBOs,
HC1, and H2S along with C2 and other gases. In the upper part of the slotted liner the
superheated steam mixed with water from the shallow reservoir and partially condensed to
produce an acid high-Cl, high-B solution that attacked the casing and rock minerals including
plagioclase, other feldspars, and possibly calcite.
These reactions increased brine concentrations of Fe, SO2, Na, and Ca, and neutralized some
of the acid. Before complete neutralization, sulfide was present as H2S and did not react with
Fe++,+ and SiO2, present in high concentrations from solution of rock silicates, was stabilized
by H ions so that amorphous silica did not precipitate although it was highly supersaturated.
With further neutralization by reaction with casing, rock minerals, and HCC3 from the upper
reservoir, H2S was converted to HS and stabilization of supersaturated amorphous silica
ended, producing the scale composed mostly of Fe sulfide and amorphous silica. Oxidation of
Fe+2 to Fe+3 caused by fluid mixing resulted in minor precipitation of Fe oxides. In the
mixture, SC4 from the shallow water had been present as HS4 along with elevated Ca++
(from acid attack of rock minerals) and with neutralization, HSO4 became SO4 and anhydrite
precipitated. With sealing off of the deep zone, acid attack of rock minerals ended so that Ca
decreased strongly (to equilibrium with anhydrite) and Na decreased moderately.
Concentrations of B and Cl decreased as contributions from the deep fluid ended. The
corrosion and scaling had continued from the first tests in 1986 with a decreasing contribution
of deep fluid caused by progressive scaling until the deep flow was cut off entirely between
September 1988 and January 1989. The lowest pH values and the highest B and Cl
concentrations were near the beginning when the proportion of deep flow was greatest. This
interpretation is similar to those of HE (1990) and Guterrez-Negrin and Viggiano (1990).
433
Other wells in the central zone probably produce from both upper and lower zones and may
have similar problems. Well H-4, just south of H-16, produced HC1 to the wellhead with so
much corrosion that it was necessary to plug and cement it shut (table 2, analyses 17-24, and
figure 6). The short history of well H-4 is similar to that of well H-16 but more extreme
(figure 9).
ra
E
03
o
c
u
O)
-1
82.5
83
83.5
84
Year
Figure 9. Changes in concentrations (in mg/1) of selected constituents of flashed discharge
fluids from well H-4, Los Humeros, Mexico.
Well H-4 was drilled to 1880 m total depth. There were two permeable zones between 900 and
1400 m and between 1700 and 1800 m. Measured temperatures were about 300C at 1100 m,
significantly higher at this depth than in most other wells. Measured temperatures below 1100
m seemed to decrease but petrology of samples from 1400 m depth did not indicate low
temperatures (Prol-Ledesma and Browne, 1989). Initial fluid production in mid-August 1982
was neutral, but within 2 weeks, pH had dropped below 3.0. The well was flowed and
samples were taken intermittently until April 1983 but rapid wellhead corrosion was observed
and the well was finally cemented and abandoned. During the first 2 weeks of production,
flashed Cl concentrations immediately increased from 60 to 500 ppm and pH, initially 7.2,
decreased to 3.7 and stabilized at 2.9. Over the same period B increased from 460 to 4000 ppm
and HCOs, initially 60 ppm, disappeared entirely. Other species showed irregular changes; Na,
K and Ca increased and Si2, NH4 and SO4 decreased. When sampled in January and March
1983, these changes had generally reversed, the fluid was neutral or alkaline (pH 6.6 to 8.5)
with B (18 ppm) and Ca (0.2 ppm) much lower and HCO3 (800-1100 ppm) much higher than
in any 1982 samples. Again other changes were irregular but Na, K and Cl generally decreased
while SiO2, NH4 and 864 generally increased. After March 1983, most of these changes were
again reversed, with lowered pH and HCOs ar>d increased B and Cl.
The changes in H-4 fluid with time are similar to those in H-16 fluids and undoubtedly H-4
went through the same history of liner corrosion and progressive plugging leading to
elimination of deep fluid influence. In H-4 the deeper fluid was blocked by scale in March
1983 but reappeared later, possibly having broken through or bypassed the scale.
434
Conditions in the Deep Los Humeros Reservoir
During the initial production from wells H-16 and H-4 a mixture of shallow and deep fluids
was produced. The wellhead enthalpy of early H-16 production, combining deep and shallow
fluids, was 2662 J/g and the enthalpy of the upper fluid alone (after scaling had blocked the
deeper fluid) was 2400 100 J/g. From mass balance calculations (using 2500 J/g shallow
discharge), the deep contribution would be 65% if it were saturated steam (2750 J/g at 300C),
50% if it were superheated to 2830 J/g, and 25% if superheated to 3150 J/g. The observation
that the flow of the repaired well (producing from the upper zone only) was nearly equal to the
initial flow from both zones probably rules out major production from the deeper zone and
suggests that the deep fluid was highly superheated steam.
This high enthalpy steam probably was not produced by equilibrium boiling from liquid. Steam
from evaporation of 30% NaCl brines at 350C would have an enthalpy of only 2890 J/g; and
higher temperature evaporation would produce steam with lower enthalpy (calculations by J.L.
Haas, Jr., quoted in Truesdell and White, 1973). If the deep zone fluid was 25% of the total
and had an enthalpy of 3150 J/g, then it would have a temperature of about 410C at the
pressure of the upper reservoir (about 85 ba). This steam would not be compatible with liquid
water unless the water were highly saline or tightly adsorbed on rock surfaces. This suggests
that the lower reservoir contains only superheated steam and that temperatures near 400C exist
not far below the bottom of well H-16. A temperature near 400C has been observed at Los
Humeros (Guterrez-Negrin and Viggiano, 1990) although the well and depth are not available.
The high-temperature reservoir found at Los Humeros beneath a normal temperature reservoir
is analogous to the high-temperature zones underlying vapor-dominated reservoirs in the
northern part of The Geysers. The main difference is that the shallower reservoir at Los
Humeros is liquid dominated, and therefore, pressures in both reservoirs are higher.
The Origin of Deep Fluid Constituents
In the earlier discussion of changes in fluid chemistry it was shown that the constituents
contributed from the deep reservoir were all soluble in superheated steam or resulted from acid
attack of casing and wallrock. The "primary" constituents HC1, B and H2S are also present in
the shallow reservoir (with HC1 represented as NaCl). It is also observed that in the natural
state before drilling there is no evidence of acid fluids. The andesite contains calcite, feldspars,
and mica; the hornfels and skarn are composed in part of carbonate rocks and normally contain
calcite. If superheated vapor in the deep reservoir contained significant HC1 and B in its natural
state, then it would be expected that minerals such as calcite and feldspars would not occur and
that boron minerals such as tourmaline would be found. The lack of mineralogical evidence for
deep acid or high boron suggests that the deep fluids observed in H-16 and H-4 may be in part
artifacts of drilling formed by flows of shallow water down the wellbore.

A shut-in drill hole penetrating both the shallow, liquid-filled reservoir and the deep reservoir
containing only high-temperature steam would be a conduit for downward flow of liquid
between the two zones. Liquid flowing down the well would quickly vaporize as it reached the
high-temperature zone and it would precipitate salts and evolve gases. Some constituents such
as B (as HsBOs) would partition between solid and vapor. The continued downflow of upperzone water could cause accumulation of significant quantities of alkali chlorides (mainly halite)
and sulfates, boric acid, and amorphous silica and release CC>2 (from HCOs) and NH3 (from
NELO into the steam. The steam in contact with this deposit of salts would have high H3B3
and significant HC1 formed by halite-silicate reaction. With production of the well, gases and
volatile salts would be drawn upward to mix with the shallow reservoir water with the results
discussed earlier. If this idea is correct, then shallower drilling at Los Humeros could have
avoided the formation of acid steam as well as its introduction into drill holes.
435
Summary
Acid reservoir fluids in geothermal fields seem to originate from either the introduction of
volcanic fluids or from the volatilization and transport of HC1 in superheated steam. A minor
source may be infiltration of surface acid-SO4 waters formed by oxidation of H2S. With the
exception of the high-Cl waters of the Tatun field, acid reservoir waters of volcanic origin seem
to exist on the margins of geothermal reservoirs and do not represent a major part of the total
fluid. Acid from volatilization of HC1 is expected to appear in boiling high-temperature
reservoirs as they lose reservoir liquid and start producing superheated steam. The occurrence
of superheated, high-HCl steam at Los Humeros, Mexico, is unusual because the steam is
produced by flow from a deep dry reservoir to a shallower water-saturated reservoir with
strong corrosion and scaling resulting from fluid mixing and reaction with casing and rock. It
is suggested that the acid steam is an artifact of exploitation and could be avoided by shallower
drilling.
Acknowledgments. The author wishes to thank Luis Quijano Len and Enrique Tello Hinojosa
of the Comisin Federal de Electricidad de Mexico for the use of unpublished data for Los
Humeros and for enlightening discussions of well H-16. He also wishes to thank Alfredo
Mainieri P. and Leonel Vaca C. of the Instituto Costarricense de Electricidad for discussions
and data for Miravalles well PGM-2, and Mitsubishi Metals Corp. (Japan) for data on
Sumikawa well S-2. Partial support of the International Atomic Energy Agency in the Los
Humeros study is gratefully acknowledged. He also thanks his colleagues, in particular
Donald White and Werner Giggenbach, for many discussions of acid fluids in the earth.
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obturacin de pozos de Los Humeros: Informe IIE/11/3753A, 15 p.
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vapor-dominated reservoir exceeding 600F at The Geysers, Sonoma County, California:
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438
IAEA INTERLABORATORY COMPARATIVE GEOTHERMAL

WATER ANALYSIS PROGRAM
W.F. GIGGENBACH, R.L. GOGUEL, W.A. HUMPHRIES
Division of Chemistry,
Petone, New Zealand
Resumen-Abstract
PROGRAMA DEL OTEA PARA ANLISIS COMPARATIVOS DE AGUAS GEOTERMALES ENTRE

LABORATORIOS.
La composicin qumica de tres muestras de aguas geotermales de Nueva

Zelanda
se determin en 22 laboratorios, incluyendo los que participan en el
programa coordinado de investigacin para Amrica Latina sobre "Aplicacin de
tcnicas isotpicas y geoqumicas en la exploracin geotrmica". Aqu se presentan y discuten los resultados de esta intercomparacin.
Con arreglo a lo
previsto, los resultados indican que algunos laboratorios tienen capacidad

para realizar anlisis qumicos de elevada calidad, mientras que otros deben
mejorar considerablemente su rendimiento para obtener resultados que puedan
utilizarse en la exploracin geoqumica de zonas geotrmicas.
No obstante, en
gran medida corresponde a cada laboratorio evaluar su propio rendimiento y
adoptar decisiones con respecto a las posibles maneras de mejorarlo.
IAEA INTERLABORATORY COMPARATIVE GEOTHERMAL WATER ANALYSIS PROGRAM.
The chemical composition of three samples of geothermal waters from

New Zealand was determined by 22 laboratories, including those
participating in the coordinated research programme for Latin America on
"The application of isotope and geochemical techniques in geothermal

exploration". The results of this intercomparison are presented and
discussed. As expected, the results show that some laboratories have the
capacity to produce high quality chemical analyses, while others must

improve their performance considerably in order to obtain results which
can be used for the geochemical exploration of geothermal areas. To a

large degree, however, it is up to individual laboratories to assess
performances and decide on possible avenues of improvement.
439
INTRODUCTION
Application of recently developed techniques for the evaluation of chemical and
physical conditions over the deeper part of a geothermal system relies heavily on the
availability of sufficiently complete and accurate analyses of the fluid discharges. The
range and sophistication of these techniques can be expected to increase considerably
within the near future putting great demands on the reliability of laboratories
involved in geothermal fluid analysis. The most promising way to check on the
present state of reliability of laboratories involved in geothermal projects, and to
identify possible lines of improvement, consists of a comprehensive interlaboratory
analysis program.
A number of national or regional interlaboratory water analysis programs have been

carried out. Most of these, however, were restricted to little mineralised potable or
irrigation waters or waters of interest in environmental pollution studies. The
number and type of constituents covered by these programs are generally quite
different from those determined in geothermal investigations.

The only interlaboratory chemical analysis program involving many countries and
including geothermal water samples was organised by Chemistry Division, DSIR. The
results are reported by A J Ellis (1976). For a number of constituents (Li, SO4, As,
NH3, Rb, SiO2) more than half of the laboratories reported values outside an
acceptable range, for the rest only 80% of the data were considered acceptable. The
scatter exposed during this study revealed serious deficiencies in analytical accuracy
and the need for general improvement and standardisation of analytical procedures.
In view of this and its involvement in many geothermal projects, the International
Atomic Energy Agency decided to initiate a purely geothermal intercomparison water
analysis program within the framework of the Coordinated Research Program on the
Application of Isotope and Geochemical Techniques in Geothermal Exploration in
Latin America. Chemistry Division, DSIR, New Zealand was asked to organise the
collection and distribution of suitable samples and to carry out an initial assessment
of the results.
440
TIMETABLE
13.08.85 - Distribution of announcement of program to some thirty laboratories

involved in geothermal projects, together with a questionnaire as to the range of
species able to be analysed. Of the 25 replies received by the end of 1985, all stated
the ability to analyse for Na, K, Mg, Ca, Cl and SO4; 23 were able to determine pH,
Li, F, HCO3; 22 to determine Fe and SiO2; 21 B and NH3; 18 Rb, Cs, Al, As; 12
Hg, Br, I, D, 180.
30.12.85 to 1.1.86 - Collection of three sets of twenty liter, filtered and two preserved
one litre water samples.

15.01.86 - Distribution of three 500 ml samples by airmail to 25 laboratories together
with covering letter and reply forms to acknowledge receipt of samples (by end of
February) and to report analytical results (by end of April 1986). As expected, only a
fraction of laboratories acknowledged receipt or submitted results by the deadlines
and a reminder was sent on

02.07.86 - enquiring about the fate of the samples sent. In due course, it was learnt
that all had arrived safely, with some leakage reported for two or three bottles. By
the extended deadline of

31.10.86 - twenty more or less complete lists of analytical results had been received.
LIST OF PARTICIPATING LABORATORIES
The selection of laboratories participating in the Intercomparison Program is largely

based on their present or past involvement in IAEA projects.
Facultad Ciencias, Universidad Mayor de San Simon
Calle Sucre Final, Cochabamba, BOLIVIA.
Coordinador rea Materials Primas, Instituto de Asuntos Nucleares
Apartado Aereo 8596, Bogot D.E., COLOMBIA.
441
Instituto Costarricense de Electricidad
PO Box 10032, San Jos, COSTA RICA.

Instituto Ecuatoriano de Electrificacin (INECEL)
Casilla 565-A, Quito, ECUADOR.

Comisin Ejecutiva Hidroelctrica del Rio Lempa
Avenida Norte, San Salvador, EL SALVADOR.

Institute Mixte de Recherches Geothermiques, BRGM
BP 6009, 45060 Orleans Cedex, FRANCE.

Laboratoire de Geochimie des Eaux, Universite Paris 7
F 75 251 Paris Cedex 05, FRANCE.
Instituto Nacional de Electrification
6a Ave. 2-73 Zona 4, Guatemala City, GUATEMALA.
Geological Survey of India
Ghandi Bawan, Lucknow 226 001, UP, INDIA.

P T Geoservices
JL Setiabudhi 81, Bandung, INDONESIA.

Oil and Gas Technology Development Center, LEMIGAS
PO Box 89 JKT, Jakarta, INDONESIA.

Isotope Hydrology, IAEA
PO Box 100, A-1400 Vienna, AUSTRIA.
Laboraterio Chimico Fsico, ENEL-UNG

56044 Larderello (PI), ITALY.
442
Ocean Research Institute

1-15-1 Minami-Dai, Nakano-ku, Tokyo 164, JAPAN.
Comisin Federal de Electricidad
Apartado Postal 31-C, Morelia, 58000 Midi., MEXICO.
Geothermal Research Centre, DSIR Chemistry Wairakei
Private Bag, Taupo, NEW ZEALAND.
DSIR Chemistry
Private Bag, Petone, NEW ZEALAND.
Electropem S.A.
Edif. "La Torre" of. 903, Centro Cvico, Lima, PERU.
PNOC Energy Development Corpoation, Geothermal
Port Bonifacio, Metro Manila, THE PHILIPPINES.
Geological Survey Division, Dept. of Mineral Resources
Rama 6 Road, Bangkok 10400, THAILAND.
Vernadsky Institute of Geochemistry, Academy of Sciences of the USSR
Kosygin St. 19, 117 975 Moscow, 5-334, USSR.
Ministerio de Energa y Minas
Torre Oeste - Piso 17 - Parque Central, Caracas 105, VENEZUELA.

Four other laboratories had agreed to participate, but had failed to supply results by
the extended deadline of 31.10.86.
DESCRIPTION OF WATER SAMPLES
The three water samples used in the Intercomparison Program were obtained from
geothermal areas on the North Island of New Zealand.
443
TABLE 1
Chemical analyses reported for sample 001 collected from a clear, colorless,
boiling (97.5) spring at Waikite on 31.12.85 (in mg/kg).
Lab No.
01
02
03
04
05
06
07
08
09
10
11
13
14
15
17
18
19
20
21
22
23
25
median
"true"
PH
Li
8.1
7.6
8.0
7.7
8.0
8.4
7.6
8.2
8.1
8.1
8.2
8.3
7.7
7.9
7.7
7.9
7.8
8.2
8.0
8.4
8.4
8.3
8.0
8.0
2.0
2.0
1.9
2.5
2.0
0.8
2.4
2.2
2.2
2.0
2.4
2.3
2.0
2.0
.
2.0
2.3
2.1
2.1
1.6
2.1
2.0
2.0
Na
197
2.3
200
178
200
186
183
220
197
191
202
200
199
192
206
193
182
186
210
144
203
196
196
K
7.2
6.0
8.0
2.5
6.9
5.8
7.8
8.0
7.5
7.2
6.8
8.0
9.8
10.3
7.1
6.9
9.4
7.9
6.4
6.8
6.8
7.2
7.2
Rb
0.09
.
0.10
.
0.70
<.10
0.06
0.14
0.20
0.30
0.09
.
0.10
0.08
0.09
<.10
0.10
0.10
Cs
0.29
0.30
.
.
2.60
<.10
0.11
0.17
0.40
0.80
0.40
0.26
0.28
0.27
0.28
0.28
Mg
0.21
0.20
0.21
1.00
1.25
0.54
0.21
2.70
0.23
0.17
0.21
4.00
<.10
0.20
0.22
.
0.18
0.07
0.28
0.22
3.73
0.23
0.21
0.21
Ca
7.9
8.0
8.2
8.0
7.9
16.4
8.0
14.3
7.6
7.8
8.7
6.0
7.0
7.0
8.3
.
7.3
9.6
10.0
8.0
10.2
7.9
8.0
8.0
Al
<.05
<.03
0.04
0.02
<.10
0.01
Fe
As
<.01
<.20
0.31
.
0.92
.
0.39
0.38
.
.
-
1.8
2.0
.
1.9
1.3
2.2
1.9
2.0
2.0
2.2
1.9
2.3
2.4
2.1
2.2
2.8
2.0
2.0
<.50
.
1.20
0.51
.
.
.
<.02
0.02
0.45
0.01
0.80
0.01
.
<.06
.
<.02
.
0.01
0.02
0.02
0.04
<.01
<.10
0.32
.
.
0.23
.
.
0.32
0.30
Cl
138
128
133
298
137
136
125
250
130
125
133
140
153
109
129
124
133
136
152
135
121
131
133
133
Br
-
SO,
34
<.5
0.4
0.4
0.8
0.4
0.1
0.4
0.4
29
35
23
29
36
33
32
31
36
31
26
96
32
33
34
29
25
36
56
32
33
33
HCOj
278
344
303
307
287
259
299
299
299
293
298
299
301
300
302
278
287
315
295
254
305
300
280
1.2
1.3
1.2
1.1
3.5
1.3
1.6
1.3
5.4
1.5
1.4
1.1
0.1
1.5
.
1.4
1.3
1.3
SiO,
150
57
149
283
142
185
154
141
144
146
134
146
152
130
146
160
25
143
146
146
TABLE 2
Chemical analyses (in mg/kg) waters collected from the weirbox of well WK66 and Wairakei on 30.12.85. The enthalpy of the well
at the time of sampling was 1020 J/g, steam was separated at 166 and 100C.
Lab No.
01
02
03
04
05
06
07
08
09
10
11
13
14
15
17
18
19
20
21
22
23
25
median
"true"
PH
8.5
6.5
9.5
8.5
8.6
8.9
8.2
8.3
8.8
8.5
8.3
8.7
8.4
8.5
8.4
8.6
8.5
8.0
8.7
8.5
7.7
8.4
8.5
8.5
Li
10.7
11.0
10.7
12.6
9.4
1.2
11.0
10.0
11.4
10.9
10.4
12.0
11.9
10.3
10.7
10.2
10.4
11.2
10.8
7.8
11.2
10.7
10.7
Na
1158
1130
1170
1050
1442
1187
1200
1225
1150
1090
1170
1100
1180
1308
1170
1130
1045
1099
1200
7149
1180
1170
1170
Rb
169
149
164
13
174
176
230
200
167
168
186
160
156
187
163
163
204
166
171
86
168
167
167
2.2
2.8
1.8
4.5
2.3
0.2
3.3
2.5
2.5
2.1
2.1
2.6
2.0
2.1
14.2
2.2
2.2
Cs
2.0
1.9
2.5
2.0
5.0
0.3
2.2
2.5
3.2
.
2.0
1.9
2.0
2.0
18.4
2.0
2.0
Mg
0.004
.010
2.70
19.82
0.05
.
<.01
0.16
0.20
<.10
0.04
0.002
<.01
0.08
<.01
0.04
0.05
0.05
0.004
Ca
Al
Fe
20.2
20.0
19.7
18.0
18.9
41.8
12.0
21.4
18.7
19.0
21.6
12.0
17.3
16.5
20.0
16.2
19.6
22.1
20.0
.
16.8
19.7
20.0
0.5
0.3
2.0
.
427
0.5
0.6
.
0.2
,
0.4
0.3
0.4
.
.
0.4
0.4
<.01
<.50
.
1.00
0.34
.
<.01
<.01
0.04
.
0.05
1.00
0.004
0.06
.
<.02
.
.
0.04
<.01
As
3.8
4.1
4.1
.
2.0
.
.
4.7
.
.
.
4.2
.
.
2.8
.
.
4.1
4.0
F
3.3
7.0
.
.
1.4
.
.
3.7
7.6
9.5
7.6
8.0
6.9
1.5
7.8
.
9.5
7.5
8.4
.
9.3
7.6
7.6
CI
1950
1970
1960
2710
2363
2010
2487
2700
1975
1933
1960
1955
1965
1991
1960
1970
1960
1969
1995
1970
1630
1952
1970
1970
Br
.
5.3
.
.
4.3
5.3
.
1.6
5.4
.
.
4.1
.
2.9
4.3
4.3
SO,
32
34
34
30
27
38
34
.
34
37
37
39
35
90
37
37
35
33
28
37
65
35
35
35
HCO3
<5
54
49
39
27
49
49
7
49
29
29
23
96
<1
48
48
5
81
<5
41
33
40
<5
B
25
33
25
23
52
.
26
23
36
29
25
.
28
.
24
27
26
.
27
26
26
SiO,
596
283
588
234
29
8
683
647
481
110
135
497
590
610
175
105
580
52
582
382
590
TABLE 3
Chemical analyses (in mg/kg) reported for waters collected at Morere, New Zealand, on 1.1.86
from a 47 spring associated with a natural gas discharge. The waters contained suspended
iron hydroxides, removed by filtration.

Lab No.
01
02
03
04
05
06
07
08
09
10
11
13
14
15
17
18
19
20
21
22
23
25
median
"true"
PH
7.2
6.9
7.0
7.2
7.0
7.4
7.0
7.1
7.2
7.0
7.0
6.9
7.0
7.0
6.9
6.9
7.0
7.1
7.2
7.1
7.3
7.3
7.0
7.0
Li
Na
Rb
Cs
Mg
Ca
Al
Fe
As
4.5
5.0
4.8
20.8
5.0
0.8
5.1
4.8
3.3
4.6
5.9
6.0
12.0
3.5
4.8
4.3
2.4
4.9
4.8
4.6
4.8
4.6
6690
84
65
72
11
198
67
162
108
83
82
85
90
60
583
82
74
110
83
82
71
90
82
84
0.07
0.40
2.10
<.10
0.50
0.04
0.17
0.50
6.20
0.10
0.10
0.06
0.13
0.12
0.13
0.10
.004
<.10
-
9
75
81
406
90
198
81
168
76
76
77
63
73
65
75
74
81
83
100
174
78
80
80
2750
<.05
.
.
.
.
<.03
0.02
0.02
.
0.40
.
_
0.11
0.10
0.15
<.50
0.14
4.60
0.34
0.12
.
<.10
0.03
0.81
0.14
200.0
<.01
.
0.28
0.29
<.02
.
0.06
0.14
0.15
<.01
.
3.1
.
.
.
<.01
.
0.01
7025
6660
6000
7208
6064
5200
640
6770
6540
6780
6800
6400
7692
6770
6590
6364
6497
7000
1580
6880
6660
6700
1.16
<.10
<.001
0.20
22.50
<.10
0.15
<0.01
<.10
-
0.10
0.004
3000
2770
2620
2893
249
2800
3274
2660
2730
2790
3506
2738
2225
2720
2690
2856
2856
2300
2882
2600
2760
2760
0.10
<.05
<.01
-
<.01
<.01
F
0.9
1.0
1.7
1.0
0.4
1.4
1.8
0.9
0.2
0.6
1.5
1.3
.
1.1
0.8
1.0
_
1.1
1.0
1.0
CI
15670
16470
15800
26680
16072
15537
15900
20000
16320
14775
15600
15750
15408
17176
15650
15800
15660
15755
15964
15800
13461
15374
15800
15800
Br
57
.
57
58
.
.
2
63
.
.
.
51
.
.
57
57
SO4
<3
.
26
4
47
<10
75
<1
<1
6
.
1
<1
60
6
_
<5
78
6
<3
HCO,
SiO2
28
-
44
42
44
38
84
40
48
54
45
46
37
46
.
42
.
42
45
.
28.4
13.7
30.0
-
44
73
44
29
7340
40
35
41
46
39
49
85
42
38
39
31
76
45
39
42
42
30
47
44
44
50.1
583.0
3.6
56.0
27.7
34.0
27.6
26.0
23.0
25.0
.
25.5
25.4
26.5
<50.0
55.0
35.0
27.0
27.0
The lowest salinity samples was collected on 31.12.85 at Waikite from a natural
boiling spring (97.5). The waters are clear and colorless and deposit minor amounts
of silica. The springs are located at the NW- margin of the Taupo Volcanic Zone
and are possibly associated with the Waiotapu - Te Kopia geothermal systems.
The intermediate salinity samples represents the weirbox discharge from well WR66
at Wairakei collected on 30.12.85. The discharge enthalpy at the time of sampling
was 1020 J/g, steam was separated at 166 and 100C. The water was clear and
colorless, minor amounts of amorphous silica accumulated on the cellulose filters.

The highest salinity sample was collected at Morere, an area of warm springs (47)
on
the East Coast of the North Island. The waters are associated with copious discharges of methane and deposit considerable amounts of ferric hydroxide (FeOOH)
in flow channels. The waters are also characterized by high iodide contents which
impart a yellowish color to the samples after prolonged exposure to air.
Three samples were taken at each location. A twenty litre samples, pressure (N2)
filtered through cellulose acetate (Millipore) filters, two one litre samples each
filtered and acidified with 5 ml of cone. HNO3 and preserved with 5 ml 30% formalin
respectively. All sample containers, including sample bottles sent to participants, had
been cleaned by treatment with half-concentrated HNO3 and rinsing with distilled water.
The samples bottles were number with the first two digits representing the labo-
ratory, the last digit the type of water; Waikite (001), Wairakei (002), Morere (003).
RESULTS
The analytical results for the three geothermal water samples as received from 21
laboratories by mid November 1986 are given at least seven results were reported,
some laboratories reported results for a number of other species, they are shown in
Table 4.
Excess significant figures given are rounded off, otherwise the data are shown as
received in spite of some obvious typing, transcription or dilution errors such as a
value of 427 mg/kg of Al reported for 092, a Na-content of 640 given for 083, a Ca447
TABLE 4
Chemical results for constitutents analysed only sporadically

(in mg/kg and / (SMOW))
Lab.
Lab.
Waikite (1)
15
44.0 01
17
<0.4 05
06
09
11
14
15
17
median
Wairakei (2)
01
11
0.1
15
60.0 05
17
<.4
06
09
21
0.3
11
14
15
17
median
0.2
Morere (3)
11
26.901
15
30.0 06
17
30.0 09
21
29.5 11
17
median
30.0
NH,
Lab.
0.04 01
0.2510
21
<0.02
<0.02
0.04
0.04
0.70
<.10
0.04
0.2311
1.2510
0.30 21
0.32
0.34
0.84
1.00
0.22
0.33
10.20 01
8.1008
11.50 10
12.10 21
11.40
11.40
Sr
Lab.
0.06
14
49.00
21
Hg
Lab.
<.0002
01
09
10
16
18
.0009
0.05
0.1014
88.50
21
0.11
<.0002
.0006
231
208
200
213
210
14
21
01
09
10
16
18
.0076
.0023
01
09
SD
SIS0
-44.6 -6.53
-42.9 -6.32
-6.10
-41.8 -6.45
-45.7 -6.70
-45.2 -6.45
-41.8
-38.8
-39.8
-40.5
-4.72
-4.65
-4.60
-4.65
-5.00
-40.2 -4.65
-15.7 +3.90
-12.0 +3.93
10
+3.60
16 -35.4 +4.11
-
-15.0 +3.90
content of 249 for 063, a HCO3-value of 7340 for 073, a B-value of 583 for 063, and a
K-value of 583 for 153. Also Na-values for 232 and 233 are likely to have been
interchanged, Sr-values for 101 and 102 are likely to be ng/kg. The occurrence of
such errors even in data sets submitted to an intercomparison program illustrates the
need for rigid checking procedure of analytical data and for good "book-keeping"
practices.
Samples Oil, 012 and 013 were analysed at Chemistry Division, DSIR, New Zealand
by use of an iterative procedure. The waters were first analysed by comparison with
individual standards for each species. On the basis of these results, three artificial
waters were recreated gravimetrically with chemical compositions closely matching
those of the original waters. These artificial waters were then used as standards for
448
the re-determination of the original samples thus eliminating matrix effects and
chemical interferences. The results obtained can be expected to be as close to "true"
values as possible for the species Li, Na, K, Rb, Cs, Mg, Ca, Sr, Al, Fe, As, B and
SiO2 determined by atomic absorption or emission spectrophotometry.

The remaining parameters pH, F and NH 3 were determined by use of specific
electrodes against gravimetric standards on samples stabilised by HNO 3 or formalin,

sulfate was determined gravimetrically as BaSO4, HCO3 by blank-corrected alkalinity
titration (Giggenbach and Goguel, 1986).

Samples 001 and 002 were chemically stable and analytical values for all three sub-
samples (filtered, acidified, preserved with formalin) agreed closely. Both filtered
and formalin treated samples of 003 (morere) continued to precipitate minor
amounts of iron hydroxide, the filtered and acidified ones turned yellow due to the
oxidation of iodide, the formalin treated one remained colorless.
EVALUATION
Due to the large diversity of analytical techniques applied by a wide range of
laboratories of possibly highly variable standards, statistical techniques based on the

assumption of normal distribution around a mean are of little value. In order to
minimise the effects of far outliers, a technique based on the distribution of
observations around the median value of a given samples has been chosen. The "boxwhisker"-plots, as proposed by Tukey, (1977) were modified as shown in Figs 1 to 3.
There the analytical data for a given species, normalised to the median value are
presented on a logarithmic scale. The boxes extending to the left and right represent
each 25% (quartile) of the data deviating to higher or lower values thus
encompassing 50% of all data. Values outside this range are indicated by their
laboratory number. The size of the boxes *'c an indication for the error associated
with the determination of a given species by the "better half of laboratories.
Of the species considered in Figs 1 to 3, for some the scatter of results is within a
reasonable range (pH, Li, Na, K, Ca, F, Cl and B) for all three samples, for some,
however, the range of results exceeds the two order of magnitudes covered (Rb, Mg,
449
1/5
median
1/2
2x
5x
median
H*
Li
No
@@[
@~c
Rb
IVg
<ix
vJ
|I
f\^
S*^t
\u/
\ii/
20
196
72
010
/f?^
û/

21
vc5!(_
06
Fe
-*-U 17
80
11 02 05 15 oT OO4
--09 1021
0 ^HD-0
HIJ@ -
a
sq
028
1 1 06 23 J3021
(ISS ]-@@d5i -@
Co
20
133
<3SgHI ]
MOO,
B
?L
@@ I
Cs
80
1 ~ -
(M2><SX!3EH
330
300
toit
so2
130
]@<5^
146
(mg/kg)
o1
0.2
Fig. 1 -
03
04
' 06
'
' 10
'
'
' ' 10 x
Comparison of analytical results for sample 001 (Waikite) in terms of
deviations from median. Best estimates of "true" values are indicated by
heavy bars
Boxes contain 25% of values deviating to higher or lower
values. Arrowed boxes indicate data outside the range of the figure.
1/5
nedian
85
107
1170
167
22
20
005
197
Ca
Fe
+J0910
J?_L __ _ __
11
U_ __ __ __ __
0 2 W I 5 0.04
76
197O
35
40
26
382
Q2
0.1
Fig. 2 -
03
Comparison of analytical data reported for sample 002 (Wairakei).

Dashed lines enclose values too widely scattered to permit meaningful
statistical evaluation. Arrowed number indicate detection limits given.

450
median
1/5
Csl'OHJ
Fig. 3 -
-"020617-22
19
13
Comparison of analytical results for sample 003 (Morere). For details see
captions Fig. 1 and 2.
Fe, SO4, HCO3). In these cases any statistical treatment with the aim to arrive at the
"true" composition of the samples is futile. In order to be able to select a range of
analytical results most likely approaching this "true" value, the laboratories were
classified in terms of the number of results outside the two quartiles shown in Figs 1
to 3 for pH, Li, Na, K, Cs, Ca, F, Cl, B and SiO2. Four groups of laboratories are
distinguished:
TABLE 5
Number of outliers:
Laboratory:
0-1
2-4
09
02
5-10
06
10-20
04
11
03
07
05
17
10
13
08
19
20
14
15
25
22
21
23
By use of the data reported by the first, most reliable group, together with those
obtained at Chemistry Division, DSIR (01) an attempt was made to derive a best
estimate of the "true" composition of the three samples.
451
For sample 001, these estimates are very close to the median values derived earlier,
except for iron for which a value below the detection limit of 0.01 mg/kg was
accepted. The same conclusion for iron was reached for water 002. In addition, the
DSIR value of .004 nig/kg was accepted for Mg and a value of <5 mg/kg for HCO3,
well below the median values. A HCO3 value of 40 mg/kg was obtained here at
DSIR as the result of a simple alkalinity titration. After correcting for the effects of
the considerable amounts of the weak acids H3BO3 and H4SiO2 present, by "back
titrating" the samples with NaOH from pH 3.8 to their original pH (Giggenbach and
Goguel, 1986), the amounts of HCO3, however, were found to be below the detection
limit of the technique employed. Most of the low values reported for SiO2 are likely
to represent monomeric silica contents. As most silica geothermeters are based on

total silica contents, the much higher total silica contents as determined by AA are
accepted as "true" values.
A special effort was made to determine Cs in sample 003, therefore, the very low
value of 0.004 mg/kg as measured by DSIR is adopted. Similarly an upper limit of
0.05 mg/kg is accepted for Al, of 0.15 mg/kg for iron. The iron content of the
acidified sample was 0.90 mg/kg but had dropped to 0.15 mg/kg in the filtered
samples by the time they were sent out. They may have decreased further during
shipment. Again a blank corrected lower value of 30 mg/kg was taken for HCO3,
with sulfate likely to be well below the limit of 3 mg/kg.

These best estimates of the true composition of the three waters are shown in Figs 1
to 3 as solid bars, they may be used to judge the accuracy of individual values.
DISCUSSION
A detailed point by point discussion of the results is beyond the scope of this general
evaluation. Some general conclusions, however, may be drawn.

One of the major uses of chemical data is geothermal investigations consists of the
valuation of water-rock equilibration conditions at deeper levels. Application of such
geo-indicators relies largely on Na, K, Mg, Ca and SiO2-contents of the discharges. A

look at the results reported by the "better half of laboratories , as indicated by the
size of "boxes" in Figs. 1 to 3, shows that the errors for Na, K and Ca are within
452
reasonable limits (5-10%) for all three samples. For Mg, however, scatter increases
rapidly with decreasing concentrations. For sample 003 containing 80 mg/kg, the
scatter is within 10-15%, it increases to a factor of three for sample 001 (0.21 mg/kg)
and spans several orders of magnitude for sample 002 (0.004 mg/kg).
The effects of these errors on the evaluation of water-rock-equilibration temperatures

by use of a recently proposed technique (Giggenbach, 1986) are shown in Fig. 4. For
Waikite (001) the apparent range of K/Na-temperatures extends from 100 to 200,
K/Mg-temperatures from 60 to 140. For wairakei (002), most data points are close
to the measured and the full equilibrium temperature of 260. The results for 042,
052, 232, however, would give a completely unrealistic picture. Even for the high Mg
water 003, an unacceptable scatter is observed. The range of silica contents reported
for the low (27 mg/kg) to intermediate (146 mg/kg) silica waters (003, 001) are
reasonable.
CI/100
Li
Fig. 4 -
B
Evaluation of K-Na and K-Mg-water-rock equilibration temperatures
(Giggenbach, 1986) by use of analytical results reported for Na, K, Mg for
Waikite (001), Wairakei (002) and Morere (003) geothermal discharges.
453
There silica is largely present in the monomeric form and colorimetric and atomic
spectroscopic values agree. In the case of the high silica water from Wairakei (002),
however, the discrepancy of values obtained by the two techniques becomes
unacceptable.
Another application of geochemical data consists of the evaluation of possibly source
components by use of "conservative" components such as Cl, B and one of the alkalis
Li, Rb, Cs In Fig. 5 relative Cl, Li and B contents are shown for all three waters.
Again considerable uncertainties are introduced by the scatter in the data reported by
some laboratories.
The main reason for likely errors in the analysis of low HCO3 waters has been
discussed above (lack of back titration with NaOH to account for the presence of B,
Na/1000
K/100
Fig 5 -
300*
200*
K / Mg - terrperatunt (*C)
Relative Cl, L and B - results reported for Waikite (001), Wairakei (002)
and Morere (003) geothermal discharges.
454
SiO2 and other weak acids). Sulfate results for the two higher sulfate waters (001,
002) are quite reasonable, most of the laboratories could not cope with the very low
sulfate water 003 for which much too high values were reported.
Accurate Al data are required in many computer studies of water-aluminium silicate
equilibration, but only less than half of the laboratories report results for this
constituent and then often only detection limits. The few values given are within an
acceptable range, in contrast to results for iron, another species required in the
computer simulation of mineral-water interactions. All three waters are likely to
contain iron in very low amounts (<.05 mg/kg), values reported, however, range
beyond 1.0 mg/kg.

Of the constituents determined only by a few laboratories, iodide values for Morere
(003) are very consistent but appear to be unreliable for the other two waters. The
variations in NH 3 reported may be due to some interference from biological activity
in the unstabilised samples. The agreement of the results by many laboratories for
Wairakei (002) and Morere (003) with the DSIR results, obtained on acidified and
sterilised samples, suggests that biological effects were not important. Strontium
values agree for the Morere water (003), as do Hg-data.

Interlaboratory checking procedures are obviously much better developed for isotopic
measurements. Most deuterium and oxygen-18 values are well within acceptable
ranges of 27 and 0.27 respectively, except for 003. There some problems may
have been introduced by the high salt content of this water.
RECOMMENDATIONS
The major purpose of the present intercomparison program was the identification of
deficiencies in the analytical procedures of laboratories involved in the geochemistry

of geothermal systems. The results obtained clearly show that there is ample room
for improvement. To a large degree, however, it is up to individual laboratories to
assess their performance and to decide on possible avenues of improvement. In some
455
cases this may involve upgrading of existing facilities, eg, analysis of Mg and SiO2 by
atomic absorption spectrometry rather than wet chemical techniques; the
introduction of more suitable techniques or the application of stricter calibration and
quality control procedures. Only very minor errors are likely to have been introduced
by the use of the simple sampling technique. Considering eg, the excessive range of
iron values reported, only little would have been gained by distributing a second
acidified sample.
REFERENCES
Ellis A.J. (1976) The IAGC interlaboratory water analysis comparison programme.

Giggenbach W.F. (1986) Geothermal solute equilibria, derivation of Na-K-Mg-Ca
geoindicators. Geochim. Cosmochim. Acta 52, 2749-2765.
Giggenbach W.F. and Goguel R.L. (1986) Methods for the collection and analysis of
geothermal and volcanic water and steam samples. Chem. Div., DSIR, Report, pp.60.
Tukey J.W. (1977) Exploratory Data Analysis. Addison-Wesley Publ. Comp. 27-56.
456
LISTA DE PARTICIPANTES
Eduardo ALMEIDA, Jefe del Proyecto Geotrmico, Instituto Ecuatoriano
de Electrificacin, Quito, Ecuador
Peter
BLATTNER,
Institute
of
Nuclear Sciences, Department of
Scientific and Industrial Research, Lower Hutt, Nueva Zelandia
Egizio CORAZZA, Istituto di Geocronologia e Geochimica Isotpica,
Pisa, Italia
Werner GIGGENBACH, Chemistry Division, Department of Scientific and
Industrial Research, Petone, Nueva Zelandia
Roberto
GONFIANTINI, Organismo Internacional de Energa Atmica,
Divisin de Ciencias Fsicas y Qumicas, Vienna, Austria
Pablo
HERNNDEZ
PANAMEO,
Jefe
del Centro de Investigaciones
Geotrmicas, Comisin Ejecutiva Hidroelctrica del Rio Lempa,
San Salvador, El Salvador
Julieta JAUREGUI, Proyecto Geotrmico, Ministerio de Energa > Minas,
Caracas, Venezuela
Alfredo LAHSEN, Decano de la Facultad de Ciencias Fsicas y Naturales,
Universidad de Chile, Santiago, Chile
Alfredo
MAINIERI,
Jefe
del
Proyecto
Geotrmico,
Instituto
Costarricense de Electricidad, San Jos, Costa Rica
Karla MIRANDA, Proyecto Geotrmico, Instituto Nicaragense de Energa,
Managua, Nicaragua
Rafael MURILLO, Jefe del Laboratorio Qumico de Miravalles, Instituto
Costarricense de Electricidad, San Jos, Costa Rica
David
NIEVA,
Jefe del Departamento de Geotermia, Instituto de
Investigaciones Elctricas, Cuernavaca, Morelos, Mxico
Pietro NOTO, Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Hector PANARELLO, Instituto de Geocronologia y Geologa Isotpica
(INGEIS), Universidad de Buenos Aires, Argentina
Costanzo PANICHI, Istituto Internazionale per le Ricerche Geotermiche,
Pisa, Italia
Javier RODRGUEZ C., Departamento de Qumica, Universidad Mayor de San
Simn, Cochabamba, Bolivia
Alberto RODRGUEZ M., Decano de la Facultad de Ciencia y Tecnologa,
Universidad Mayor de San Simn, Cochabamba, Bolivia
Alfredo ROLDAN M., Jefe de la Seccin Geoqumica, Instituto Nacional
de Electrificacin, Ciudad de Guatemala, Guatemala
Giovanni SCANDIFFIO, Unita Geotrmica Nazionale, Ente Nazionale per
l'Energia Elettrica (ENEL), Pisa, Italia
Jos Luis SIERRA, Direccin de Desarrollo Geotrmico, Ente Provincial
de Energa del Neuqun, Neuqun, Argentina
Paolo SQUARCI, Director, Istituto Internazionale per le Ricerche
Geotermiche, Pisa, Italia
Enrique
TELLO,
Oficina
de
Geoqumica,
Comisin
Federal
de
Electricidad, Morelia, Michoacn, Mxico
Alfred H. TRUESDELL, Geological Division, Branch of Experimental
Geochemistry and Mineralogy, U.S. Geological Service, Menlo
Park, California, USA
Leonel
VACA,
Proyecto
Geotrmico,
Instituto
Costarricense de
Electricidad, San Jos, Costa Rica
Pablo VRELA, Coordinador General del Proyecto Geotrmico, Ministerio
de Energa y Minas, Caracas, Venezuela
Eulalia
VIVES,
Proyecto
Geotrmico, Instituto Costarricense de
Antonio
YOCK,
Proyecto
Geotrnr-,o,
Instituto Costarricense de
Gian Maria ZUPPI, Dipartimento di Scienze della Terra, Universit di
Torino, Torino, Italia
457
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ESTUDIOS GEOTERMICOS CON TECNICAS ISOTOPICAS Y GEOQUIMICAS

Publicamos en el prsente volumen

We are publishing in this volume the papers presented at

may be used in future, and to form and train a number of Latin

Resumen del Programa coordinado de investigation ..................................................

Reservoir characteristics of the vapor dominated geothermal field of Copahue, Neuqun,

Geothermal exploration by geochemical methods of the thermal area El Pilar-Mundo Nuevo,

RESUMEN DEL PROGRAMA COORDINADO DE INVESTIGACION

El PCI para la America Latina sobre el empleo de tcnicas

principales lineas de investigacin y los campos geotrmicos

los nueve paises participantes.

Argentina; Volcan Copahue, Volcan Domuyo, Epulafqu, todos en

Colombia; Paipa en la Cordillera Oriental;

constituye un solo campo geotermico compartido por los dos

Guatemala; Lago Amatitlan, Zunil, San Marcos y Tecuamburo, en

Mexico; Los Humeros, Estado de Puebla;

Los isotopos ambientales se utilizaron principalmente

geotermico, la mezcla de aguas geotermicas con otras aguas, y

interacciones agua-roca y las perdidas de vapor. Por primera

subduccion (vease memoria de Giggenbach y otros,

La geotermometria isotopica se limito a unos pocos

(metano-CO2 y metano-hidrogeno) probablemente reflejan el

superior a la de la zona de almacenamiento geotermico.

utilizaron ampliamente en geotermometria, asi como paia el

SUMMARY OF THE CO-ORDINATED RESEARCH PROGRAMME

The CRP for Latin America on the Use of Isotope and

The first research contracts were awarded towards the end

Due to the remoteness and high elevation of many of the

Bolivia; Laguna Colorada, Empexa and Volcan S a jama, on the

Colombia: Paipa in the Cordillera Oriental;

Costa Rica: Volcan Miravalles in the Cordillera de Guanacaste;

Mexico: Los Humeros, state of Puebla;

Isotopic geothermometry was limited to a few cases,

RESERVOIR CHARACTERISTICS OF THE VAPOR

* Ente Provincial de Energa del Neuqun,

El caiapo geotrmico de Copahue-Caviahue, se puede dfinir

RESERVOIR CHARACTERISTICS OF THE VAPOR DOMINATED GEOTHERMAL FIELD OF COPAHUE,

1.1. LOCATION AND GEOLOGY

The climate is Patagonic, and that of high mountain, depending of

This episode Mas over with the formation of a

km average radius calders.

ty and to the great explotions produced by variations in the dynamic,

blocks that originate an

the border of the caldera that produced a set of priphrie eruptions.

m and is producing dry vapor of similar characteristics of COP-1

the ENTE PROVINCIAL

DE ENEBGIA DEL NEU-

During three field trips performed in the 1985/1987 period,

the geothermal field model. Based on this model, a third exploration

ICOPfl-2 ft! Poro COP I

flND ISOTOPIC flNflLVSIS OF CONDENSEES ONO COLD ONO HOT UWrERS

: ng/l : g/l : g/i : q,a : .3/i1

d*l vol c-in

20 : 3,6 : 1,7 ! < o,os

Isotop] c flnlyin: INGEIS.

ISOTOPIC HNftLVSIS OF COP-1 RNO COP-2 UELLS.

DfirE : s/ei : i/85

Ch-nicl ftnlylis: flPft-EPEM.

RESULTS AND DISCUSSION

3.1. METEORIC WATER LINE