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Emerald mineralisation in Colombia: Fluid

chemistry and the role of brine mixing

Article in Mineralium Deposita · November 2000

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Mineralium Deposita (2000) 35: 699±713
ARTICLE
D. A. Banks á G. Giuliani á B. W. D. Yardley
A. Cheilletz
Emerald mineralisation in Colombia: ¯uid chemistry and the role
of brine mixing
Received: 9 April 1999 / Accepted: 14 March 2000
Abstract Emerald mineralisation in Colombia is located
in two distinct zones along the borders of the Eastern
Cordillera, some 80 km apart. Mineralisation in the
western zone has been dated at ca. 35 Ma whereas in the
eastern zone it is 30 Ma older. Crush leach analysis of
the electrolyte chemistry of ¯uid inclusions contained in
emerald, quartz, calcite, dolomite and ¯uorite from both
zones, demonstrates that in each region brines associ-
ated with emerald mineralisation range between two
extremes with many samples yielding intermediate
compositions. Fluid 1, found mainly in emerald-hosted
¯uid inclusions, is dominated by NaCl with high Cl:Br
ratios indicating that the salinity was derived by disso-
lution of halite, most probably from the local salt beds.
Fluid 2, found notably in quartz hosted-¯uid inclusions,
is of similar salinity but contains less Na and signi®cant
concentrations of Ca±K±Fe±Cl and other cations. It has
lower Cl:Br ratios, more comparable with formation
waters, but is inferred to have obtained part of its sa-
linity by halite dissolution. Bivariate plots of almost all
cations have linear or sublinear trends regardless of the
mineral hosting the inclusions or the locality from which
the samples originated, demonstrating that mixing of the
two saline ¯uids has occurred. Because the same two
¯uids occur in both eastern and western zones, despite
the di€erence in space and time, it is inferred that ¯uid
compositions were rock controlled by similar interac-
Editorial handling: P. Lattanzi
D. A. Banks (&)
School of Earth Sciences, University of Leeds,
Leeds LS2 9JT, UK
G. Giuliani
I.R.D. and C.R.P.G./C.N.R.S., BP 20,
54501 Vandoeuvre-leÂs-Nancy Cedex, France
B. W. D. Yardley
School of Earth Sciences, University of Leeds,
Leeds LS2 9JT, UK
A. Cheilletz
E.N.S.G.-I.N.P.L. and C.R.P.G./C.N.R.S. BP 20,
54501 Vandoeuvre-leÂs-Nancy Cedex, France
Ó Springer-Verlag 2000
tions with evaporites and black shales in both instances.
It is proposed that beryllium was transported as Be±F
complexes in the NaCl-¯uid, and was precipitated as
emerald after mixing with the calcic brine caused pre-
cipitation of ¯uorite and parisite.
Introduction
The common association of emeralds is with igneous
and metamorphic rocks (Beus 1966; Sinkankas and
Read 1981), and the deposits in Colombia, which are the
principal source of the world's ®nest gems, are unique in
being hosted by black shales (Scheibe 1916; Forero
1987). The association between emeralds and magmatic
activity in other deposits clearly had an in¯uence on
early ideas for the origin of Colombian emeralds, which
were ®rst believed to be derived from magmatic ¯uids
(Oppenheim 1948). However, the lack of any contem-
poraneous igneous activity in the region provided a
signi®cant obstacle to the acceptance of this model.
Recent research has now provided a more robust model
for the origin of these deposits from evolved sedimentary
brines, based on evidence from a variety of geological
and geochemical investigations (Kozlowski et al. 1988;
Cheilletz et al. 1994; Ottaway et al. 1994; Cheilletz and
Giuliani 1996: Branquet et al. 1999).
The importance of saline ¯uids in the formation of
the Colombian emeralds is evident from studies of ¯uid
inclusions in quartz and carbonates (calcite and dolo-
mite), which are the gangue minerals of the hydrother-
mal veins, in ¯uorite and in the emeralds themselves
(Roedder 1963, 1972; Touray and Poirot 1968; Koz-
lowski et al. 1988; Giuliani et al. 1993a, 1995; Cheilletz
et al. 1994; Ottaway et al. 1994; Banks et al. 1995). They
have salinities up to 40 wt% eq. NaCl and are com-
positionally complex. There are two groups: those with
halite as the sole daughter mineral and those with mul-
tiple daughter minerals. Other daughter phases, identi-
®ed from scanning electron microscopy±energy
dispersive mode (SEM-EDS) and Raman spectra,
700
include sylvite, calcite, dolomite, sphalerite and parisite.
The presence of small amounts of N2 and CO2 has been
detected by Raman spectroscopy (Dele-Dubois et al.
1980; Giuliani et al. 1995). In general, the mineralising
¯uid can be considered a hypersaline brine and this
contrasts markedly with ¯uid inclusions found in
emeralds from igneous/metamorphic associated depos-
its. In these, the ¯uid is less saline, 10 wt% eq. NaCl,
and has greater concentrations of CO2 and other gases
(Grundmann and Morteani 1989; Nwe and Grundmann
1990; Souza et al. 1992; Martin-Izard et al. 1995).
Sulphur isotope studies of the ubiquitous pyrite,
which is intimately associated with emerald deposition
(Ottaway et al. 1994; Giuliani et al. 1995), clearly indi-
cate a single source of sulphide that was originally
sedimentary marine evaporitic sulphate. The d18O cal-
culated for water in equilibrium with quartz and
carbonate gangue is indicative of a rock-equilibrated or
basinal origin for the ¯uids (Giuliani et al. 1992),
whereas dD values of ¯uid inclusions suggest mixing
between a D-depleted water and a more D-enriched
formation water (Giuliani et al. 1997). Carbon isotopes
are indicative of mixing of C from oxidised organic
matter and from limestone.
As the result of ¯uid±rock interaction, the host black
shales have undergone intense albitisation and carbon-
ation with the depletion of many major and trace
elements (Kozlowski et al. 1988; Ottaway 1991; Giuliani
et al. 1993b). Altered shales have had almost all their
organic matter oxidised by the thermochemical reduc-
tion of sulphate to sulphide, and this accounts for the
abundant pyrite. In addition to wall-rock alteration,
mineral in®llings grew in veins and breccias. The
temperature and pressure during mineralisation has
been estimated at 290±360 °C and 1.12±1.06 kbar
(Cheilletz et al. 1994).
The ¯uid involved in producing the Colombian
emeralds is clearly unusual for this type of mineralisa-
tion, but its composition has been hitherto known only
from microthermometry, SEM and Raman studies. The
purpose of this study was to quantify the composition of
the ¯uids involved in the deposition of emeralds by
extracting the inclusion ¯uids using a crush-leach tech-
nique (below). The samples are amenable to this type of
analysis because each contains one dominant ¯uid
population, thereby avoiding the problem with bulk
extraction techniques of mixing di€erent ¯uid popula-
tions. With the data, we aim to more fully constrain the
source of the ¯uids and the geochemical processes that
led to this unique style of emerald mineralisation.
Geological setting
The emerald deposits are located in two narrow
polyphase thrust zones (Fig. 1), corresponding to the
original limits of the Cretaceous basin within the Eastern
Cordillera of Colombia (MeÂgard 1987; Schamel 1991).
The Cordillera is a fold belt of weakly metamorphosed
sediments overthrusting the Llanos Basin and the
Central Magdalena Basin. The Cretaceous and Eocene
series comprise marine sediments accumulated within
two back-arc basins and are up to 10 km thick. Inver-
sion of the basin occurred during late Miocene±Pliocene
Andean compression. The two zones of emerald miner-
alisation are located at the two fronts of the eastern
Cordillera some 80 km apart: in the east are the major
mining districts of GachalaÂ, Chivor and Macanal and in
the west are the districts of PenÄas Blancas, Coscuez,
Muzo and Yacopi (Fig. 1). 40Ar/39Ar dating of green
micas, associated with mineralisation, gives ages of
31±33 Ma and 35±38 Ma for the mines of Muzo and
Coscuez respectively in the western zone, but an age of
65 Ma for the Chivor±Macanal mines in the eastern
zone (Cheilletz et al. 1994, 1997).
In the east, the deposits are hosted by the Guavio±
Macanal black shales in the Cocuy palaeobasin which,
at the time of emerald formation (i.e. 65 Ma), reached
a temperature of at least 250 °C, which corresponds to a
sediment accumulation of 7 km (Fabre 1987). The
mineralisation is contained within the Berriasian horizon
of the Guavio series that is overlain by siliceous black
shales of the Valanginian Macanal series (Ulloa and
Rodriguez 1976). In the Chivor mining district, the
Guavio series lies unconformably on a Paleozoic base-
ment. It is composed from bottom to top of: siltstones
and siliceous black shales, carbonated black shale
sequences with intercalations of limestone lenses and
anhydrite beds (Branquet et al. 1999), limestone grading
to black shales intercalated with olistostromes. Emerald
mineralisation occurred during a phase of salt migration
accompanying extensional deformation.
In the west, the deposits are hosted within black
shales and intercalated dolomitic limestones of Valan-
ginian±Hauterivian ages (Rosablanca and Paja forma-
tions). The lithologies, from top to bottom are:
dolomitic limestones (Rosablanca formation) and
carbonated black shales (Hauterivian) which are the
principal emerald-bearing horizons, siliceous black
shales (Hauterivian) and mudstones (Barremian±Ap-
tian) of the Paja formation. The deposits are the
consequence of a compressive tectonic phase character-
ised by thrusts and faults (Laumonier et al. 1996).
The host black shales have su€ered intense ¯uid±rock
interaction and metasomatic alteration with striking
development of albitites and associated epigenetic
growth of calcite, dolomite, pyrite, micas and quartz
(Cheilletz and Giuliani 1996). The unaltered black shales
contain 19±35% of K-micas and 8±17% of K-feldspar,
but, where albitisation has occurred, these have been
completely replaced, predominantly by albite.
Emeralds are found within stratiform tectonic brec-
cias that are generally parallel to the bedding of the
black shales and comprise fragments of black shales,
unaltered and altered to albitites, in a matrix of pyrite,
albite and crushed black shale. Mineralised pockets,
containing emeralds and other associated minerals, are
located within the breccias. Two distinct phases of

Fig. 1 Location of the studied emerald deposits in the eastern and
western mineralised zones of the Eastern Cordillera, Colombia
(modi®ed from the geological map of Colombia, 1988, scale
1:500,000, Ingeominas, BogotaÂ). The Lower Cretaceous sediments
enclose Late Cretaceous and Tertiary sequences. Size of emerald
symbol indicates the importance of the deposit
mineral deposition have been identi®ed by Giuliani et al.
(1995), namely stage 1, which is marked by the deposi-
tion of ®brous calcite, pyrite 1, albite, quartz and green
micas; stage 2a, marked by rhombohedral calcite,
dolomite, albite, pyrite 2 and some kerogens; and stage
2b, by the precipitation of emeralds along with pyrite 3,
parisite, (Ca,La)2Ca(CO3)3F2, rare earth element (REE)-
rich dolomite, ¯uorite and quartz. Emerald, parisite and
¯uorite are co-precipitated, followed by quartz.
Samples and analysis
Fluid inclusion-bearing samples of calcite, dolomite, quartz, ¯u-
orite and emerald from both the western emerald zones (the mines
at Yacopi, Coscuez, Pava, Cincho and Tequendama) and the
eastern emerald zone (the mines at Chivor, Palo Aranado, Guali
and Agua Blanca) have been investigated (Fig. 1). The majority of
the minerals studied: quartz, emerald and ¯uorite, are from stage
701
2b, commensurate with emerald deposition; however, carbonate
samples G112 and G107 are from stage 1, and carbonate and
quartz samples G103, G113 and 94±8 are from stage 2a.
Analysis of ¯uid inclusions was conducted using a bulk crush
leach method as described by Bottrell et al. (1988), Banks and
Yardley (1992) and Yardley et al. (1993). Samples were crushed to a
grain size of 1 mm and cleaned in aqua-regia where appropriate.
Contaminating mineral grains were removed by hand picking under
a binocular microscope and the samples further cleaned by boiling
in nitric acid and/or double distilled water. Quartz and emerald
samples had any adsorbed ions removed by placing them in an
electrolytic cell for 10 days. Clean, dry samples were crushed to a
®ne powder, in an agate pestle and mortar, and leached in double
distilled water for anion and alkali analysis, and in acidi®ed LaCl3
solution for cation analysis. Carbonates and ¯uorite contain ele-
ments in their structure that are of interest for this study, but will
contaminate the crush-leach analyses. Leaches from these minerals
were analysed for Na, K and anions only, whereas leaches of em-
erald and quartz were analysed for many additional elements. The
cations, Na, K, Ca, Mg, Al, Ba, Li, Sr, Fe, Mn, Zn and Cu, together
with B, were determined by inductively coupled plasma atomic
emission spectroscopy (ICP-AES), Na and K were also analysed by
¯ame emission spectroscopy (FES) and Cu, Pb, As and Be by
graphite furnace atomic absorption spectroscopy (GFAAS). The
anions, F, Cl, Br, SO4 and I, were determined by ion chromatog-
raphy. Na and K were determined on all leach solutions from all
minerals, so that all analyses were calculated initially as ratios to Na.
In addition to ¯uid inclusions, emerald also contains water in
the channels (up to 2.2% for Colombian emeralds; Zimmermann
702
et al. 1997). Because this water is normally released after heating to
above 600 °C (Giuliani et al. 1997) it is not likely to contribute to
the ¯uid analysed by crushing and leaching. Any structural ¯uid
released in our preparation procedure must be so weakly bound that
it is unlikely to fractionate components relative to inclusion ¯uid.
Microthermometric studies were performed on doubly polished
wafers using a Chaix±Meca heating-freezing stage. The equivalent
salinity of the ¯uids was determined from the temperature of halite
dissolution, and the chloride content obtained in this way provided
a normalisation constant to convert element ratios obtained by
crush-leach analysis to actual ¯uid compositions.
Results
The results of the crush-leach analysis are presented in
Table 1 for the western emerald zone and in Table 2 for
the eastern zone. The ¯uid analyses have been recalcu-
lated from weight ratios relative to Na, to their true
concentration in the ¯uid inclusions based on the Cl
content obtained from the microthermometry, using the
following method.
Cl (ppm) microthermometry=R analysed anions
relative to Na = F
True concentration (ppm)
ˆ F  element value relative to Na
The approximation involved in this method, which as-
sumes all salts produce a similar depression of freezing
point per unit mass of dissolved solid, can be justi®ed
because all the ¯uids investigated here are dominated by
NaCl.
Data quality
Uncertainties in element ratios depend only on the
analytical imprecision. Replicate analyses of samples
GG-19/20 yield di€erences that are <5% relative for all
elements except Be, where the precision is 20%, and I,
where results are semi-quantitative within a factor of 3
only. This is because of the extremely low concentrations
in the leach solutions, typically less than 0.5 and 0.1 ppb
respectively. Additional uncertainties in the recon-
structed compositions result from errors in the deter-
mination of salinity, both from spread in the data and
the assumptions in calculating total Cl. One test of the
validity of the analyses is the charge balance between
anions and cations. Ideally S+ve/S)ve charges should
equal 1 if all the species have been determined correctly,
but this is rarely the case for any natural water analyses.
In this study the charge balance is excellent for analyses
of this type, with all samples in Tables 1 and 2 having an
excess of +ve charges, typically of about 5%. A charge
imbalance can re¯ect a large error in one particular el-
ement, e.g. because of solid contamination or an unde-
termined species, but it is also likely that some error is
spread over all the analytes. In this study, the discrep-
ancy is most likely caused by the presence of carbonate
species that cannot be determined by our method.
The presence of solid impurities within the host
mineral (other than daughter crystals in ¯uid inclusions),
which are then dissolved in the crush-leach procedure, is
a major potential source of error. Of the minerals in-
®lling the veins, those most likely to contaminate the
analyses are ¯uorite, calcite, dolomite and pyrite. For
example, no analyses are reported for F, which, al-
though determined, was found to be either at the limit of
detection (equivalent to 1 ppm in the reconstructed
analyses) or so high (in carbonate samples) as to be
caused by contamination from a solid ¯uoride mineral in
the crushed sample. The presence of additional Ca and
Mg in analyses of quartz-hosted ¯uids is dicult to as-
sess because the ¯uids contain high concentrations of
Ca, and small calcite and dolomite daughter crystals are
often present. However, the charge balance is excellent
and the general levels of Mg are low so it is likely that
contamination is generally minimal. The concentration
of Fe in the ¯uid analyses is quite varied, yet the Fe:Mn
ratio of approximately 10 is the same in all samples; if
pyrite contamination was contributing Fe to the ¯uid
analyses this would not be the case.
Levels of Ba, Ca and SO4 in solution are limited by
the solubility of baryte and anhydrite, and these have
been estimated by extrapolating solubility data for the
two minerals in NaCl brines (Blount and Dickson 1969;
Blount 1977) to the P-T-X conditions during mineral
deposition (Fig. 2). The Colombian ¯uids are essentially
Na±Ca±Cl-brines and a signi®cant amount of Ca will be
ion paired with Cl (Williams-Jones and Seward 1989).
Therefore, total Ca concentrations in the ¯uid may be
greater than allowed by anhydrite solubility at any SO4
concentration. A signi®cant number of the samples have
Ba, Ca and SO4 concentrations close to or below the
limits allowable by anhydrite and baryte solubility at the
conditions of trapping, and so we are con®dent that solid
sulphate contamination has not occurred for these sam-
ples. A few ¯uid analyses lie well outside the saturation
curves for both baryte and anhydrite and we suggest that,
because in each case both sulphates appear supersatu-
rated, it is the SO4 concentrations that are too high. A
probable upper limit for the true concentration of SO4 in
the ¯uids is 500±600 ppm and, therefore, SO4 concen-
trations in samples GG-2/3/5/12/13/16 and G-103/107/
112/113 are likely to be too high because of contamina-
tion by a solid sulphate phase. Because Ca concentra-
tions are much higher than those of sulphate, and there is
no marked anomaly in Ba or Sr, anhydrite is the most
likely culprit, but this has not been con®rmed by obser-
vation. Sulphate minerals were not observed either in the
veins or by optical microscopy in the di€erent minerals,
but it is possible that insoluble sulphates may be present
at a size not readily resolvable by optical microscopy.
Ionic composition
The ¯uids associated with emerald precipitation in
stages 2a and 2b have total dissolved solids (TDS)
Table 1 Reconstructed composition of emerald-related ¯uids from individual mines (ppm). Salinity in equivalent wt% NaCl. S+ve/)ve charge balance of +ve and )ve ions. nd Not
detected

Western emerald zone

Muzo district

Yacopi Coscuez Cincho Pava Tequendama

Emerald Quartz Fluorite Quartz Emerald Quartz Quartz Emerald Fluorite Quartz Quartz Quartz Calcite Dolomite
GG-2 GG-3 GG-4 GG-5 GG-6 GG-9 GG-16 GG-7 GG-17 GG-18 94±8 GG-19 G107 G103

Stage 2b 2b 2b 2b 2b 2b 2b 2b 2b 2b 2a 2b 1 2a
Salinity (%) 38 40 41 35 38 41 42 37 37 39 41 41 25 35
Na 100,376 94,019 115,526 54,590 130,946 106,484 92,542 94,823 95,616 63,557 103,599 110,776 79,975 103,619
K 22,585 19,556 9,472 11,622 5795 14,833 10,467 18,813 1491 11,567 5449
Ca 44,027 6746 59,847 16,821 43,302 18,931
Mg 639 1062 250 5424 115 3082 111
Ba 1064 118 250 303 67 966 432
Li 2031 944 2212 1261 1454 4322 432
Sr 1605 144 250 228 38 1347 399
Fe 23,791 4300 3822 10,772 344 21,749 13,071
Mn 3308 420 620 1005 38 3044 653
Pb 131 30 61 60 26 112 87
Zn 573 196 370 199 57 928 676
Cu 115 393 nd nd 96 228 22
As 17 78 65 370 67 38 11
Be 0.57 0.92 0.48 0.19 1.0
Cl 224,007 240,815 245,448 211,091 230,082 248,415 254,132 224,306 224,502 230,481 247,813 227,371 140,343 211,269
Br 80.2 328.1 333 100.6 36.7 118.4 65.8 39.7 11.4 99 390 150.7 33.7 91.4
I 4.5 0.9 5.1 0.2 0.3 0.9 3.0 1.9 0.9 1.6 5.0 2.7 0.5 1.0
SO4 6491 1567 nd 1189 463 238 658 166 nd nd 558 24 11321 1017
Cl:Br (m) 6294 1654 1660 4728 14,128 4728 8703 12,733 44,382 5249 1431 3401 9384 5208
S+ve/)ve 1.05 1.01 1.09 1.03 1.09 1.02
703
704

Table 2 Reconstructed composition of emerald-related ¯uids from individual mines (ppm). Salinity in equivalent wt% NaCl. S+ve/)ve
charge balance of +ve and )ve ions. nd Not detected

Eastern emerald zone

Chivor district Macanal district

Palo Aranado Chivor Guali Agua Blanca

Emerald Emerald Emerald Quartz Quartz Quartz Calcite Calcite

GG-10 GG-11 GG-12 GG-13 GG-20 GG-15 G112 G-113

Stage 2b 2b 2b 2b 2b 2b 1 2a
Salinity (%) 40 38 40 31 31 40 25 34
Na 122,677 116,142 98,923 76,239 68,344 78,554 70,182 105,495
K 8829 5888 10,248 12,389 8796 17,415
Ca 15,972 19,151 32,556 31,855 32,356
Mg 3606 1568 6440 1435 385
Ba 196 198 604 1503 652
Li 1165 430 1959 2549 2090
Sr 356 407 1048 1524 825
Fe 6747 5086 9388 4579 23,252
Mn 736 569 1108 1025 2176
Pb 124 54 115 315 383
Zn 282 174 366 950 997
Cu 74 104 495 nd 825
As 331 92 782 48 39
Be 1.2 0.48
Cl 242,430 230,202 240,698 188,232 183,208 242,078 131,294 195,814
Br 55.5 27.4 51 87.7 42.8 23.8 71.5 318
I 0.68 0.36 2.61 3.1 1.5 2.2 1.4 5.1
SO4 232 352 1966 997 nd 614 20,332 10,173
Cl: Br (m) 9844 18,935 10,637 4836 9648 22,922 4139 1388
S+ve/)ve 1.04 1.01 1.09 1.08 1.00

reported here are in agreement with those reported

in studies of ¯uid inclusion decrepitates and of daughter
minerals. Kozlowski et al. (1988) and Giuliani et al.
(1993a, 1995) found that decrepitates contained
chlorides of Na, K, Ca, Fe, Mn and Cr, either singly or
as mixtures, and daughter minerals included halite,
sylvite, calcite, dolomite, sphalerite, parisite and Zn-
carbonate.

Cation variations

Na is the dominant cation present in this set of samples

Fig. 2 Plots of SO4 versus Ba and Ca concentrations in ¯uid
inclusions. Dashed lines represent the maximum concentrations
allowed constrained by the solubility of baryte and anhydrite
between 350 and 420 g/l, whereas the stage 1 calcites
have lower TDS of 250 g/l. Remarkably there are no
systematic di€erences in the ¯uid chemistry of samples
from the eastern and western zones. Emerald-hosted
¯uids are dominated by Na and Cl and have the lowest
concentrations of all other elements, while quartz-hosted
¯uids have signi®cant concentrations of Na, Ca, K
and Fe with a range of Na:Ca ratios from di€erent
mines that is consistent with estimates from microther-
mometry (Cheilletz et al. 1994). The dominant species
and occurs over a wide range of concentrations. For this
reason, bivariate element plots against Na have been
constructed for all the cations analysed except Be
(Fig. 3). All the plots display clear linear or sublinear
negative correlation with Na, regardless of the locality
or the mineral hosting the ¯uid inclusions, with three
exceptions. The relationship of Mg and As with Na is
c
Fig. 3 Bivariate plots of Na versus the other cations determined in
the ¯uid inclusions. Values are the analyses reconstructed to the actual
concentrations in the inclusions using the salinity determined from
microthermometry. All the plots have strong negative correlations
irrespective of location or host mineral, except for Na versus Mg and
As where there are di€erent trends for emeralds and quartz +
¯uorite, and for Na versus Pb where the ¯uids from the eastern and
western zones are distinctive
705
706
di€erent for emerald-hosted inclusions compared with
those hosted by quartz or ¯uorite, whereas the plot of
Na versus Pb has di€erent slopes for deposits in the east
and those in the west.
The simplest explanation for the linear trends are
that they either represent mixing of two di€erent ¯uids
in di€erent amounts or progressive reaction of a single
¯uid with a single wall-rock. Fluid mixing could either
have occurred prior to the ¯uids being trapped in
inclusions, or could be the result of mixing two
di€erent generations of ¯uid inclusions during crush-
ing. However, if it were a random mixing of di€erent
¯uid inclusion generations during crushing, then it is
unlikely that there would be a clear distinction
between the composition of emerald- and quartz-
hosted inclusions.
Anion variations
Cl is by far the dominant anion and is at almost constant
concentration in the inclusion ¯uids during emerald
deposition. There is no correlation between Cl and the
other anions or with the dominant cation Na. SO4 is the
only other species present in signi®cant concentrations
with apparently higher levels in carbonate-hosted ¯uids.
However, the highest values probably result from con-
tamination by solid sulphates. Br and I appear to have a
weak correlation with each other, but the magnitude of
the errors associated with the I analyses must cast some
doubt on this.
Origins of salinity
High salinity brines are not uncommon in sedimentary
sequences, and a range of origins has been proposed.
The likely possibilities are: (1) a simple connate origin
preserving brines present after seawater evaporation
(White 1965) (2) dissolution of evaporites in the rock
sequence (Carpenter 1978; Hanor 1979) and (3) en-
hancement of salinity by shale-membrane (Graf 1982) or
reverse osmosis (Knauth and Beeunas 1986). The cur-
rent consensus is that in the vast majority of brines the
salinity has its origins in seawater, as a result of either
surface processes or halite dissolution, whereas subsur-
face processes of salinity enhancement are generally in-
signi®cant. In contrast, the cation content of brines has
typically evolved from its original composition through
dissolution/precipitation and diagenetic reactions with
host rocks. Only Cl and Br are considered conservative
enough to be of use in determining the origins of brines
(see Fontes and Matray 1993 for a review of the con-
servative nature of halogens) as, in the absence of halite,
¯uid±rock interactions do not normally a€ect their
concentrations in solution except through dilution or,
more rarely, concentration accompanying hydration
reactions.
Halogen ratios as a guide to sources of salinity
Seawater contains 19,350 ppm Cl and 67 ppm Br (data
in Fontes and Matray 1993) and on evaporation both
increase, maintaining a constant ratio, until the onset of
halite precipitation. From this point Br becomes
progressively enriched in the residual brine as halite
precipitation proceeds (the Br ion is much larger than
Cl, and substitutes poorly into the halite lattice, distri-
bution coecient 0.032; Holser 1979), and eventually
reaches a concentration of 2300 ppm. The ®rst halite
to precipitate contains 65±75 ppm Br (Holser 1979;
Herrmann 1980), but, as halite precipitation proceeds,
the Br enrichment results in higher concentrations in the
precipitating salt, until at the end of halite precipitation
concentrations of 200 ppm Br in halite are possible.
Lower Br concentrations in halite are also possible;
Stoessell and Carpenter (1986) estimated there should be
27 ppm Br in halite at thermodynamic equilibrium and
Land et al. (1988) found similar values in recrystallised
diapiric halite. Initially, evaporites may have porosities
as high as 40±50% (Sonnen®eld 1984) and, therefore,
may contain appreciable residual bittern ¯uid, enriched
in Br, in both pores and ¯uid inclusions, as well as Br-
depleted halite. It follows that minor dissolution of
newly formed halite can release a brine with higher Br
concentrations than would be expected if pure halite
were being dissolved. Despite these complications, the
Cl:Br ratio is generally believed to distinguish brines that
are evaporated seawater (Cl:Br ˆ 290) from those that
are residual bittern ¯uids and have precipitated halite
(Cl:Br < 290), and from those that result from halite
dissolution (Cl:Br  290). However, Land and Prez-
bindowski (1981) and Stoessell and Carpenter (1986)
suggested that recrystallisation of halite in the presence
of a halite-saturated ¯uid will release Br, yielding small
amounts of a low Cl:Br brine despite some halite
dissolution.
Origins of salinity in the emerald-related brines
The Cl:Br characteristics of ¯uid inclusions in minerals
precipitated during and immediately after emerald
mineralisation, from the western and eastern emerald
zones, are shown in Fig. 4. The chloride contents
reported here are greatly in excess of halite saturation at
surface conditions. Cl-contents of 200,000±260,000 ppm
correspond to halite saturation at 160±320 °C, whereas
the two lowest salinity data points are close to salt sat-
uration under surface conditions. In both emerald zones,
all the ¯uid inclusions have Cl:Br ratios much greater
than that of seawater and this is indicative of halite
dissolution. Both sets of data lie on the same trend of
varying Cl:Br at essentially constant salinity, with the
exception of the stage 1 calcites and lower salinity
quartz-hosted ¯uid inclusions from the eastern minera-
lised zone, which de®ne a parallel trend at lower salinity.
In general, ¯uid inclusions in emeralds have higher Cl:Br

Fig. 4 Cl versus Cl:Br molar ratio of ¯uid inclusions relative to the
trend followed by evaporating seawater (data from Fontes and
Matray 1993). All the ¯uid inclusions lie above the evaporation line
indicating that a portion of their salinity was derived from halite
dissolution. Inclusions in stage 1 carbonates have lower salinities
(25 wt% eq. NaCl) but Cl:Br ratios comparable to the other samples.
Emerald-hosted inclusions tend to have the highest Cl: Br ratios,
although one quartz and ¯uorite have the highest ratios
ratios than those hosted by quartz or carbonates,
although there is some overlap. There are large varia-
tions of Cl:Br ratios within individual deposits, e.g. at
Chivor (Table 2) where the range of ratios is 19,000 (in
emerald) to 5000 (in quartz). Thus the variation seen is
not related closely to the local geology but is evidence of
two distinct ¯uids. The I:Cl versus Br:Cl plot (Fig. 5)
likewise demonstrates that the ¯uid inclusions have low I
values that are also typical of brines derived from
evaporite dissolution. They compare with ¯uid inclu-
Fig. 5 Log(I:Cl) versus Log(Br:Cl) molar ratios of ¯uid inclusions,
which are depleted in both Br and I and are indicative of evaporites.
There is a trend towards higher levels of I as the concentration of Br
increases. Fluids for locations where evaporites are known to be
involved are shown for comparison. Data for Hansonburg, Bohlke
and Irwin (1992a); Salton Sea, Williams and McKibben (1989);
seawater and bulk earth are from the compilation of Bohlke and Irwin
(1992b)
707
sions from Hansonburg (Bohlke and Irwin 1992a) and
contemporary ¯uids from the Salton Sea (Williams and
McKibben 1989), both of which have dissolved evap-
orites. Evidently, the black shales were not a signi®cant
source of I or Br at the time of the hydrothermal ac-
tivity. A clear di€erence between the emerald ¯uids and
other brines reported to result from halite dissolution, is
that the high salinity of Colombian brines demonstrate
an origin under low-grade metamorphic conditions.
The importance of halite dissolution in controlling
the chemistry of the brines is shown in Fig. 6, a plot of
Na:Br versus Cl:Br that removes the e€ects of concen-
tration or dilution from a consideration of the source of
the solutes. The majority of ¯uid inclusion analyses
follow a linear trend, which could be generated by ad-
dition or removal of NaCl to or from a ¯uid with a
constant Br concentration. Emerald-hosted inclusions
tend to have higher Cl:Br and Na:Br ratios than inclu-
sions hosted by other minerals and approach values
consistent with dissolution of primary halite. In the
western zone, salt diapirs are found in the vicinity of the
emerald mines and show evidence of repeated cycles of
brecciation, dissolution and recrystallisation of the salt.
We cannot link the breccias to the speci®c tectonic
events responsible for emerald mineralisation; however,
the diapirs, could be a potential source for the high sa-
linity ¯uids. Analyses of the salt shows they have a wide
range of Cl:Br and Na:Br ratios that are much greater
than those of primary halite and indicate a substantial
amount of Br has been removed (McLaughin and Arce
1971). The present Br content of halite from the local
salt diapirs (18±65 ppm) is less than would be expected
in primary halite but typical of recrystallised halite, thus
con®rming that Br may have been lost during interac-
tion with a halite-equilibrated ¯uid. In the eastern zone,
Branquet et al. (1999) report that the albitised and
Fig. 6 Na:Br versus Cl:Br molar ratios of ¯uid inclusions that follow
an approximate linear trend are indicative of dissolution or
precipitation of halite. The inset compares halite from two local salt
diapirs (McLaughin and Arce 1971) with primary halite and ¯uid
inclusions. Cl:Br and Na:Br ratios are signi®cantly higher and indicate
that the halite has recrystallised and lost Br
708
carbonised sequence originally contained evaporites as
shown by phantom nodules, chicken wire and tepee
structures. The dissolution of an evaporite horizon,
initially containing halite, appears to be the major pro-
cess in controlling the formation of the breccia layer just
below the albitites in Chivor.
There are three likely models that can explain the
variation in Cl:Br ratios, and hence the origin of the high
salinity brines that existed throughout the region during
emerald mineralisation: (1) varying degrees of interac-
tion with progressively recrystallising halite bodies, (2)
dissolution of halite by ¯uids of variable initial salinity
and Br content and (3) mixing of two types of brines of
di€erent origins and halide characteristics. The ®rst
possibility would give a range of Cl:Br ratios; however,
the ¯uids trapped in early precipitating minerals would
have lower Cl:Br ratios than ¯uids trapped in minerals
precipitating later because the reservoir of Br in the re-
crystallising halite would become progressively depleted
with time. This is inconsistent with the data that show
that Cl:Br ratios of inclusions hosted by emeralds are
greater than those of younger quartz. In the second
possibility, the highest Cl:Br ratios would result from
interaction of low salinity waters with halite, whereas the
more Br-rich ¯uid would have started as Br-enriched
formation waters that retained their Br as they inter-
acted with halite. It is possible that simple dissolution of
halite by di€erent ¯uids, one with signi®cant initial Br
and the other with none, could generate Cl:Br ratios at
either end of the extremes observed. However, the range
of ratios observed indicate that ¯uid mixing also oc-
curred. The third model, ¯uid mixing, can generate the
observed variations in the Cl:Br ratio, but the fact that
the salinity of the extreme ¯uids is the same is strongly
indicative of interaction with solid halite at similar, low
grade metamorphic temperatures.
Overall, the evidence points to the mixing of two
brines of similar salinity during the main stage of em-
erald mineralisation. This is consistent with the results of
cation analyses, but the varying Cl:Br ratios of the ¯uids
cannot be explained by ¯uid±rock interaction, as the
cation analyses can be. The NaCl dominated, high Cl:Br
ratio, ¯uid (¯uid 1) can only have been derived from the
dissolution of halite by a low-Br ¯uid. This may have
been primary halite from evaporite horizons, which
would give Cl:Br ratios close to the maximum of the
emerald-hosted ¯uid inclusions, and/or the Br-depleted
halite of the local diapirs. The possibility exists that,
even in the samples where the Cl:Br ratio is greatest,
some mixing with the Br-enriched ¯uid (¯uid 2) has
occurred thereby lowering the Cl:Br ratio from values
that would be generated by dissolution of the salt dia-
pirs. In fact, the ¯uid inclusions in one ¯uorite sample
have Cl:Br ratios equivalent to that of the recrystallised
halite. Fluid 2 has the lowest Cl:Br ratios and signi®cant
amounts of cations other than Na. It may have origi-
nated as the residual Br-rich ¯uid left as halite precipi-
tated from evaporating seawater, but it dissolved halite
during burial and heating. Addition of NaCl to raise the
salinity from 30%, typical of highly saline formation
waters, to the 40% now in the ¯uid inclusions would
produce Cl:Br ratios almost identical to the lowest val-
ues we have found.
We conclude that ¯uid 1 was the product of disso-
lution of halite under low grade metamorphic conditions
in a low salinity, possibly meteoric water, whereas ¯uid 2
may be a pre-existing formation water that interacted
with halite under similar metamorphic conditions.
The ¯uids in stage 1 carbonate-hosted inclusions are
the least saline, and did not reach halite saturation,
whereas stage 2 carbonate-hosted inclusions are more
saline but have lower Cl:Br ratios. The salinities and
Cl:Br ratios are indicative of halite dissolution but it is
uncertain what the ¯uids originally were. The three
carbonates with the highest Cl:Br ratio (lowest Br con-
tent) ¯uid inclusions would be consistent with halite
dissolution by either fresh water or seawater, whereas
the carbonate with the lowest Cl:Br ratio (highest Br
content) ¯uid inclusions is not. The much greater Br
concentration is more consistent with a bittern ¯uid
dissolving halite.
Wall-rock reactions accompanying mineralisation
At the sites of mineralisation, the bituminous and partly
carbonaceous marine shales have su€ered two major
types of alteration: albitisation and carbonation. In the
former type of alteration the mineral composition is
dominated by albite, 45±92%, with lesser amounts of
mica, <20%, quartz, <19%, and pyrite, <10%. In the
latter type, calcite + dolomite range from 5 to 55%,
followed by albite at 25 to 45%, quartz at 4 to 48%, and
pyrite at <10%. The relationship between the two types
of alteration is not always clear, although in the eastern
zone carbonation is superimposed on bleached albitised
rocks. In a study of the elemental changes in the black
shales, produced by the alteration processes, Giuliani
et al. (1993b) found that albitisation was accompanied
by a major increase in the concentration of Na and de-
creases in K, Mg, Al, Ti, Si and P, whereas carbonation
increased the Ca and Sr content and produced dramatic
decreases in the majority of the other elements (Ba, Be,
Cr, Rb, Sc, U, V, B, Th and organic carbon). Conver-
sion of all of the original feldspar, typically 8±17%, in
the black shales is insucient to produce the much
higher concentrations of albite observed after alteration.
Additional albite could have resulted from the con-
version of micas, chlorite and quartz, and for phyllosi-
licate-rich rocks is likely to have been accompanied by
leaching of Al.
The ¯uid inclusions in emerald, ¯uorite and quartz
date from the end of the mineralising event (stage 2b)
and they post-date initial alteration of the black shales
by the hydrothermal ¯uids. The deposition of emerald
and ¯uorite is considered to be synchronous, and to
predate the deposition of quartz. There has been intense
¯uid±rock interaction and this must be re¯ected in
 709

composition of the ¯uids preserved as inclusions. It was

noted above that although most emerald-hosted ¯uids
are dominated by NaCl (¯uid 1) and are relatively rich
in Mg, ¯uids in other hosts, and especially late quartz,
generally have higher concentrations of other cations.
Patterns of cation variation and the in¯uence of host
mineral are summarised in Fig. 3. Variations from a
¯uid initially derived by evaporite dissolution may be
kinetically limited, re¯ecting approach to equilibrium
during wall-rock alteration, or may result from the
bu€ering of ¯uid composition by di€erent wall-rocks,
and the mixing of ¯uids. In view of the similarity of ¯uid
compositions from the eastern and western zones, it is
most probable that ¯uid compositions were controlled
by the local rocks, which are the same in each area, i.e.
black shales and evaporites, and which experienced the
same P±T conditions during mineralisation (Branquet
et al. 1999). The linear or sublinear trends observed in
Fig. 3 can be explained by mixing of these two end-
member ¯uids at each of the mineralised zones. Fig. 7 Na±Ca±K plot of emerald and quartz-hosted ¯uid inclusions
There is an obvious question as to why two ¯uids compared with formation waters (oil-®eld brines, Carpenter et al.
from separate original sources should then experience 1974) and ¯uids derived from the dissolution of evaporites (Rustler-
di€erent wall-rock interaction patterns afterwards. A Salado formation, Bodine and Jones 1990). Emerald-hosted ¯uid
possible explanation is that the migration paths and inclusions are comparable with evaporite-derived ¯uids and the quartz-
hosted inclusions are comparable with the formation waters. The
rates of these ¯uids re¯ect ongoing deformation and inclusions de®ne a trend with variable Na at a constant Ca:K ratio
faulting, such that the in¯ux of waters from di€erent
reservoirs was in part accompanied by di€erent char-
acteristic ¯ow paths or ¯ow rates.
The concentrations of alkali and alkaline earth ele-
ments in the ¯uid inclusions are higher than the levels
found in comparable brines. This is partly caused by the
higher temperatures than oil-®eld brines, whereas salin-
ities are higher than those of most geothermal ¯uids of
equivalent temperature. The ratios of the dominant ca-
tions, Na, Ca, K (Fig. 7) in the two end-member ¯uids
and their mixtures do broadly conform with modern
examples of these types of ¯uids, i.e. ¯uids derived by
dissolution of evaporites (brines from the Rustler and
Salado formation, Bodine and Jones 1990) and metal-
rich formation waters (oil-®eld brines, Carpenter et al.
1974). However, potassium is higher relative to sodium
and calcium in the inclusion ¯uids than in the majority
of the modern ¯uids because of bu€ering at higher
temperatures. Other alkalis: Li, Sr and Ba, (Fig. 8) show
a clear trend of variable Li at a constant Sr:Ba ratio
indicating that while Sr and Ba were bu€ered Li was not.
Each of the elements is signi®cant because the greatest Fig. 8 Li±Sr±Ba plot of emerald and quartz-hosted ¯uid inclusions
concentrations are usually found in di€erent reservoirs. compared with formation waters (®lled circles oil-®eld brines,
Lithium normally resides in clay minerals and micas, Ba Carpenter et al. 1974; open circles Alberta Basin, Connolly et al.
1990). The inclusions de®ne a trend with variable Li at a constant
is derived mainly from feldspars and Sr is present in Sr:Ba ratio
both feldspars and carbonates. In this respect, the in-
clusion ¯uids do not compare closely with formation
waters (Carpenter et al. 1974; Connolly et al. 1990) that The inclusion ¯uids also contain high concentrations
are dominated by Sr and can have signi®cant Li, but are of the metals Pb, Zn, Fe and Mn. These are shown in
depleted in Ba. There are instances where Ba concen- Fig. 9a±c, as bivariate plots versus Fe, and display clear
trations comparable to the inclusion ¯uids have been linear trends. The Fe and Mn concentration in the in-
found (MacPherson 1989) but only in low-SO4 ¯uids. clusion ¯uids covers a large range, yet is maintained at a
High Ba in the Colombian ¯uids is again likely to re¯ect constant Fe:Mn ratio of approximately 10 regardless of
higher temperature. the mineral host or location. The signi®cance of Fe and
710
Fig. 9 Bivariate plots of Fe versus Pb, Zn and Mn in the ¯uid
inclusions and for comparison metal-rich oil-®eld brines (Carpenter
et al. 1974). The concentrations of Pb and Zn in the ¯uid inclusions
are generally equivalent to the range in the oil-®eld brines; although
some ¯uid inclusion values are higher; however, the Fe and Mn
concentrations in the ¯uid inclusions are substantially higher. For Fe
versus Pb there is a clear distinction between inclusions from the east
and those from the west
Mn was discussed by Bottrell and Yardley (1991) who
showed the Fe:Mn ratio of low grade metamorphic ¯uid
was controlled by its redox state for similar wall-rock
Fe:Mn ratios. Where the ¯uid was hematite bu€ered,
Mn concentrations were equivalent to or greater than Fe
concentrations, but in more reduced ¯uids Fe was pre-
sent at much higher concentrations and Fe:Mn was >4.
The ratio found in the ¯uid inclusions in this study (10)
indicates that the ¯uids giving rise to emerald minerali-
sation were reducing, at least by the time of trapping.
This agrees with both Ottaway et al. (1994) and Giuliani
et al. (1995a) who showed that reduction of sulphate to
sulphide occurred during deposition of emeralds.
Pb and Zn are important because they normally
reside in di€erent clastic reservoirs. Lead is concentrated
in feldspars that contain little zinc (Brown 1972) whereas
high zinc concentrations have been found associated
with clays where they are thought to reside as adsorbed
or interlayer base-metal ions (Carpenter et al. 1974). In
contrast to the other transition metals, which have
constant ratios irrespective of locality, this is not the case
for Pb. The Pb:Fe ratio (Fig. 9a) of the inclusion ¯uids is
greater in the eastern mineralised zone than in the west.
Transport of beryllium and the origin of the emeralds
Kozlowski et al. (1988), Ottaway et al. (1994) and
Cheilletz et al. (1994) have shown that Be was partially
removed from the black shales during hydrothermal
alteration. Ottaway et al. (1994) suggest that Be resided
with Cr and V in the organic portion of the shale and
was released when the organic matter was consumed
during thermochemical reduction of sulphate. Cheilletz
et al. (1994) found 3.2 ppm Be, 208 ppm Cr and
892 ppm V in a K-mica and suggest that, initially, Be, Cr
and V were incorporated into K-micas precipitated at
the vein margins. Emerald precipitation is restricted to
the ®nal phase of mineralisation and is associated with
REE-dolomite, ¯uorite and parisite in drusy cavities.
Ottaway et al. (1994) suggested that Be was trans-
ported as OH) complexes based on solubility studies by
Renders and Anderson (1987). However, Wood (1991,
1992), in a study of the solubility of bertrandite/phe-
nakite with di€erent ligands, showed that it was ¯uoride
or mixed ¯uoride±carbonate complexes that were by far
the most ecient at transporting Be. Concentrations of
several hundred ppm Be can be achieved in solution as a
¯uoride complex, whereas as hydroxide complex con-
centrations were predicted to be less than 1 ppm. In this
case, beryllium can be deposited from solution by in-
creasing the pH or by decreasing the free ¯uoride ac-
tivity. The association of emerald with ¯uorite and
carbonate therefore points towards ¯uoride ‹ carbo-
nate complexing as being predominant.
In this study we have found that the highest con-
centrations of Be correlate with the highest concentra-
tions of Na in the ¯uid inclusions (Fig. 10), but the large
uncertainties in the Be analyses mean that the trend is
not as good as other elemental correlations. Neverthe-
less, it is likely the Na±Cl dominated ¯uid was respon-
sible for transporting Be in solution. Leaching of Be may
have been a signi®cant consequence of interaction with
normal wall rock if (1) the wall rocks were dominated by
phyllosilicates and (2) the early stages of wall-rock in-
teraction were dominated by reaction of F, leaching Be
(and Al) and inhibiting take-up of Ca until all F was
consumed. Alternatively, ¯uid 1 may result from inter-
action with previously albitised wall rocks, such that
there was little potential for cation exchange. In either

Fig. 10 Bivariate plot of Na versus Be in the ¯uid inclusions showing
an increase of Be with Na. Be was most probably dissolved in the Na-
Cl ¯uid
event, ¯uid 1 can be interpreted as little-modi®ed since
leaving the halite bodies, except for acquisition of
F-complexed cations, whereas ¯uid 2 underwent a more
extensive wall-rock reaction, with extensive exchange of
Na and probable loss of F and F-complexed metals. If
this is the case, all the brine types appear to exhibit
evidence of modi®cation by wall-rock interactions,
though to di€ering degrees. The relatively high concen-
trations of K, Ca, and Fe in ¯uid 2 are consistent with
interaction of mica and feldspar-bearing shales at mildly
elevated temperatures, whereas the very high Na
concentration in ¯uid 1 is dicult to reconcile with
signi®cant interaction with primary wall-rock. Never-
theless, the evidence cited above suggests that, in certain
conditions, Be may have been leached from wall-rocks
and introduced in ¯uid 1. We suggest that mixing of the
Ca-rich ¯uid with the Na±Cl ¯uid caused precipitation
of ¯uorite and parisite, and hence destabilisation of Be±
F complexes and growth of emerald.
Conclusions
The Colombian emerald deposits were formed from
brines that migrated through a deforming, evaporite-
bearing, sedimentary sequence under low grade meta-
morphic conditions. Although the brines have many
similarities to formation water, their high salinity and
detailed chemistry betray their origin at elevated tem-
perature (ca. 320 °C). In detail there are two distinct, but
equally saline, ¯uids in both the eastern and western
emerald districts, and interactions of these ¯uids are
believed to play a key role in emerald mineralisation.
One ¯uid, dominated by NaCl (¯uid 1) and with low
concentrations of other elements, is very low in Br and
was probably derived from the dissolution of halite by a
low salinity water at elevated temperatures. The other,
dominated by Na±Ca±Cl (¯uid 2) and with signi®cant
711
concentrations of many other elements, including Br,
was probably a residual ¯uid resulting from the precip-
itation of halite from evaporating seawater, that simi-
larly dissolved halite, under metamorphic conditions, to
attain its ®nal salinity. The two ¯uids also experienced
di€erent patterns of wall-rock interaction with the more
Br-rich ¯uid (¯uid 2) undergoing more extensive cation
exchange. Linear trends exhibited by cations versus Na
and halogens when all analyses are considered, indicate
that there was mixing of the two ¯uids. The similarity of
elemental ratios in the eastern and western emerald
zones shows that ¯uids composition was rock-bu€ered
by the same rock types in each instance: evaporites and
black shale.
Wall-rock alteration by hydrothermal ¯uids was an
important factor in the mineralising process, the rela-
tionship between ¯uid types and alteration types has not
been totally resolved. From the high metals content of
the Na±Ca±Cl ¯uid it is possible that this ¯uid was
responsible for much of the alteration of the black
shales, including oxidation of the graphitic material.
Although the Na±Cl ¯uid has an equivalent anion con-
centration and could therefore have leached similar
levels of cations from the black shales, the analyses of
¯uid inclusions clearly shows that this has not happened
to any great extent. It is more likely that the Na±Cl ¯uid
either reacted only brie¯y with the wall rocks, or inter-
acted only with previously altered black shales, now
composed of albite and carbonates with lesser amount of
mica, quartz and pyrite, which had been stripped pre-
viously of much of the leachable cations, but yielded Be
(and Al) to this F-rich ¯uid. Emerald precipitation is
inferred to be linked to the mixing of the two brine
types, such that Ca in the calcic brine reacted with F in
the Na±Cl brine, precipitating ¯uorite and carbonates
and destabilising Be±F complexes.
Acknowledgements We thank the reviewers and editor for their
constructive comments that helped to improve the paper. The study
was supported by NERC grant GR3/11087.
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