©2008 Society of Economic Geologists, Inc.

Economic Geology, v. 103, pp. 865–869

IDENTIFICATION OF AMMONIUM-BEARING MINERALS BY SHORTWAVE INFRARED REFLECTANCE

SPECTROSCOPY AT THE ESQUEL GOLD DEPOSIT, ARGENTINA

WALTER SOECHTING,
Minas Argentinas, San Luis 238, (oeste) San Juan, Argentina

NORA RUBINSTEIN,†
Universidad de Buenos Aires-Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET),
and Departamento de Geología, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires,
Ciudad Universitaria, (1428) Ciudad Autónoma de Buenos Aires, Argentina

AND MARTA GODEAS

Servicio Geológico Minero Argentino (SEGEMAR), Av. Julio A. Roca 651, 8° piso, sector 9, (1322)
Ciudad Autónoma de Buenos Aires, Argentina

Abstract
The Esquel low-sulfidation epithermal vein deposit in Chubut province, Argentina, is hosted by a Late
Jurassic bimodal arc assemblage. Shortwave infrared (SWIR) reflectance spectroscopy of vein samples using a
hand-held field spectrometer identified ammonium-bearing illite, jarosite, and adularia (buddingtonite) in
banded quartz displaying colloform and crustiform textures. The SWIR technique proved to be a rapid and
accurate means of detecting ammonium-bearing species, particularly buddingtonite, which provides evidence
for paleoboiling zones and thus of precious metal mineralization.

Introduction with minor sandstone, conglomerate, and limestones of Early

The Esquel gold-silver deposit is located in the southeast-
ernmost part of the Cordón de Esquel, 12 km northeast of the
town of Esquel, Chubut province, Argentina (Fig. 1). Sillitoe
et al. (2002) defined Esquel as a major low-sulfidation epi-
thermal gold vein deposit containing about 3 million oz (Moz)
of gold and 6.98 Moz of silver. A remarkable feature of the
deposit is the abundance of hydrocarbons associated with the
gold mineralization (Sillitoe et al., 2002), which are shown
here to be closely associated with ammonium-bearing alter-
ation minerals.
Shortwave infrared (SWIR) reflectance spectroscopy stud-
ies were carried out on vein samples using a hand-held field
spectrometer (PIMA II SP) in order to identify the ammo-
nium-bearing species. In this method, no sample preparation
is required prior to analysis. The reflectance spectrum ob-
tained consists of a background curve and characteristic ab-
sorption features. The resulting spectrum is compared with
the spectral library standards (specmin 3.0S for PIMA/SWIR,
Spectral/Mineralogical Database, CDROM) provided by the
supplier, Integrated Spectronics Co.. The spectrum also pro-
vides information about chemical substitution, the presence
of multiple phases, mixtures, water content, and crystallinity.
In the case of a mixture of two or more minerals (up to four),
the spectra are compared with mixed standards.
Local Geologic Setting
The Esquel deposit is hosted by the Lago La Plata Forma-
tion (Fig. 1), a Middle Jurassic bimodal arc sequence com-
posed of andesite and minor rhyolite (Haller and Lapido,
1980, 1982; Ramos, 1983). This unit overlies the Piltriquitrón
Formation, a sequence comprising organic-rich black shales
† Corresponding author: e-mail, nora@gl.fcen.uba.ar
Jurassic age that were deposited in an extensional marine
basin (Lizuaín, 1980; Urien et al., 1995).
In the studied area, the Lago La Plata Formation consists
mainly of subaerial andesite and basaltic andesite flows with
minor clastic and volcaniclastic horizons. It is cut by dacitic
stocks, rhyolitic domes, andesitic sills, and rhyolitic and inter-
mediate to mafic dikes. The dacite porphyry stocks have been
sericitized and pyritized, probably causing the widespread
pyritic zones that give rise to prominent color anomalies. Gar-
net-bearing rhyolitic domes lie immediately east and west of
the vein corridor but predate vein formation. The dikes are
structurally controlled by the vein-hosting faults and have
rhyolitic, andesitic, and basaltic andesitic compositions. The
intermediate to mafic dikes cut and, in turn, are cut by the
gold veins, implying that dike emplacement spanned the min-
eralizing event, whereas the felsic dikes appear only to pre-
date vein formation. An unaltered postmineralization an-
desitic sill caps the west-central parts of the vein corridor
(Sillitoe et al., 2002).
Galadriel Vein
The Esquel deposit is defined by north- to northeast-strik-
ing vein groups: Antonia, Ungoliant, Pinnacles, Elena, Gan-
dall, Julia, and Galadriel (Fig. 1), and Isengard (out of the
map area). The Galadriel-Julia corridor is the main group; it
dips 50° to 70° west and has a maximum width of 35 m (Silli-
toe et al., 2002).
Mineralogy
The Galadriel ore shoot comprises chalcedony and minor
quartz. The chalcedony is either white or dark gray due to py-
robitumen impregnation and shows evidence of multiple stages
of vein filling and brecciation. The vein shows crustiform,

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Sulfides constitute <3 vol percent of the vein. The ore

71°12’24” assemblage consists of pyrite and marcasite plus minor
Galadriel arsenopyrite, tetrahedrite-tennantite, galena, chalcopyrite,
N
sphalerite, pyrrhotite, bornite, bournonite, freibergite, stib-
nite, tellurides of silver, gold, bismuth, lead, and mercury, na-
tive gold, and electrum. The dark gray chalcedony is com-
monly but not consistently richer in gold than the white
variety (Sillitoe et al., 2002).
Host-rock hydrothermal alteration
An alteration halo several meters to tens of meters wide
Galadriel typically surrounds the vein. Illite dominates the host-rock al-
Sur teration, which grades outward from the vein through mixed-
Pinnacles layer illite-smectite and smectite-plus-chlorite zones to a pre-
Antonia existing greenschist-facies metamorphic assemblage. Locally,
and close to the contact with the vein, pyrobitumen-impreg-
nated massive silicification cut by chalcedony veinlets is ob-
served. Multidirectional calcite veinlets appear beyond the
42°53’00” silicification. The altered volcanic wall rock contains more
pyrite, marcasite, and arsenopyrite than the vein itself (Silli-
toe et al., 2002).

Elena Mineralogic Studies

Norte
Julia Petrography of the Galadriel vein
Ungoliant
Microscopic studies reveal that in addition to crustiform
Gandalf and colloform quartz textures minor comb-texture and zoned
Elena quartz crystals are also observed in the samples from the Gal-
Centro adriel vein. Microplumose, mosaic, and flamboyant recrystal-
lization textures are common. Interstitial illite is scarce, ap-
pearing only locally and stained by limonite.
Elena Adularia exists as aggregated or disseminated euhedral
Sur 0 300 m crystals in the hydrocarbon-impregnated quartz and chal-
cedony bands, with their long dimensions perpendicular to
References the banding (Fig. 2A). The crystals are commonly euhedral
Vein and up to 6 mm long (Fig. 2B) and their morphology corre-
Surface projection sponds to the subrhombic adularia type (Dong and Morrison,
of concealed vein
Andesite sill
1994). The adularia displays weakly developed argillic alter-
Tuffs ation and corrosion due to quartz replacement, which gives
Lago La
Andesites
Plata Fm.
rise to sieve texture (Fig. 2B, C). Quartz veinlets, as well as
Trachyte dome
Rhyolitic dike
minor illite plus limonite veinlets, also cut the adularia crys-
tals (Fig. 2D).
Shales Piltriquitrón Fm. 70º

Location of the SWIR reflectance spectroscopy

studied samples
Fault
Road
FIG. 1. Geology of the area of the Esquel gold deposit (Galadriel, Gal-
adriel Sur, Ungoliant, Pinnacles, Antonia, Julia, and Elena veins), showing
locations of studied samples. Taken from Sillitoe et al. (2002).
cockade, and carbonate pseudomorphic replacement tex-
tures; drusy texture with vugs lined by prismatic quartz crys-
tals is also common. Minor illite occurs as isolated flakes and
discontinuous bands in the colloform chalcedony. Coarse-
grained adularia is present as thin bands in the colloform
chalcedony and yielded a K-Ar minimum age of 161 ± 4 Ma
(Sillitoe et al., 2002).
Using SWIR reflectance spectroscopy, three ammonium-
bearing minerals were identified in samples from the Gal-
adriel vein (see Application Note 3; SWIR Reflectance
Spectroscopy Applied to Ammonia Minerals, Integrated
Spectronics). Ammonium-bearing illite (brammallite: Deer et
al., 1992), ammonium-bearing jarosite, and ammonium-bear-
ing adularia (buddingtonite: Barker, 1964) were detected as
mixtures.
Figure 3A shows the spectrum of ammonium-bearing il-
lite, whereas Figure 3B is a mixture of ammonium-bearing
jarosite and ammonium-bearing illite. Figure 3C represents
a mixture of buddingtonite and ammonium-bearing illite.
Figure 3D is of a mixture of ammonium-bearing jarosite,
ammonium-bearing illite, and buddingtonite, whereas in
Figure 3E a mixture of montmorillonite and buddingtonite
is observed.

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A B

a a

C D
a
a a

FIG. 2. Typical adularia from the Esquel gold deposit. A. Hand sample showing adularia crystals (arrow) perpendicular to
banding in gray chalcedony. B. and C. Rhombic adularia crystals (a) corroded by quartz. D. Adularia crystal cut by quartz
veinlet.

The clay minerals replacing buddingtonite and the jarosite
are interpreted as supergene alteration products, on the basis
of microscopic observations.
Laboratory-based FT-IR analysis
In order to verify the results of SWIR spectroscopy, a mid-
infrared Fourier transform spectroscopic analysis was carried
out on an adularia concentrate from the Galadriel vein, where
dark gray chalcedony is present. The infrared spectrum was
recorded on a Nicolet FT-IR 510P Fourier transform spec-
trophotometer using the KBr pellet technique, as employed
at the Instituto de Química Física de los Materiales, Medio
Ambiente y Energía, Universidad de Buenos Aires.
The spectrum of the analyzed sample (Fig. 4) was com-
pared with the buddingtonite standard supplied by Sadtler
Research Laboratories, Inc. (Sadtler Standard Spectra, In-
frared Grating Spectra, Volume 1: Minerals, Philadelphia
1973) and with data provided by Voncken et al. (1993). Both
spectra are comparable not only in terms of the pattern but
also in the wave number of the absorption features. The typ-
ical ammonium features for buddingtonite are at 3,070,
2,850, 1,430, and 710 cm–1; however, the anticipated feature
at 3,290 cm–1 is absent. The remaining features are probably
caused by montmorillonite, one of the alteration products of
buddingtonite detected by the SWIR spectroscopy and
microscopic studies. The infrared results show the presence
of ammonium ion and are consistent with those provided by
SWIR spectroscopy.
Discussion
The presence of ammonium ion in minerals is due to sub-
stitution of K+ by ammonium (NH4+). This process takes
place in illite, montmorillonite, interlayed illite-smectite,
muscovite, alunite, jarosite, and adularia, giving rise to am-
monium-bearing mineral species; neither the minerals nor
country rocks display any physical changes (Baugh, 1995).
Several studies have used remote sensing imagery to detect
ammonium-bearing alteration minerals, although only a few
of them tested the accuracy of the technique using hand-held
field spectrometers (e.g., Baugh et al., 1998; Felzer et al.,
1994). However, Yang et al. (2001) used this technique exclu-
sively to characterize the hydrothermal minerals (including
buddingtonite and ammonium illite) in the Broadlands-
Ohaaki geothermal field.
At the Esquel deposit, SWIR reflectance spectroscopy suc-
cessfully identified ammonium-bearing illite, jarosite, and
adularia (buddingtonite), which was confirmed in the labora-
tory. Previous work on other epithermal gold deposits in Ar-
gentina, including Pan de Azúcar (Godeas and Litvak, 2004),
El Pantanito (Godeas and Rubinstein, 2004), and El Peladar

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10 10
A Sample 2 C Sample 4 (b)
Standard Standard
8 8

6 6

4 4

2 2

0.0 0.0

1400 1600 1800 2000 2200 2400 1400 1600 1800 2000 2200 2400
Wavelength (nm) Wavelength (nm)

10 10
B Sample 4 (a)
E Sample 6
Standard Standard
8 8

6 6

4 4

2 2

0.0 0.0

1400 1600 1800 2000 2200 2400 1400 1600 1800 2000 2200 2400
Wavelength (nm) Wavelength (nm)

10
D
Sample 5
Standard
8

0.0

1400 1600 1800 2000 2200 2400

Wavelength (nm)

FIG. 3. Spectra of Esquel ammonium-bearing minerals. A. Sample 2b. Ammonium-bearing illite. B. Sample 4. Mixture
of 60 percent ammonium-bearing jarosite and 40 percent ammonium-bearing illite. C. Sample 4a. Mixture of 80 percent
buddingtonite and 20 percent ammonium-bearing illite. D. Sample 5. Mixture of 50 percent ammonium-bearing jarosite, 30
percent ammonium-bearing illite, and 20 percent buddingtonite. E. Sample 6. Mixture of 70 percent montmorillonite and
30 percent buddingtonite.

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2850
40 3070
30
% Transmittance
1430
20
10
0 Baugh, W.M., 1995. Quantitative remote sensing of ammonium minerals, in
-10
4000 3000 2000 1500 1000
Wavenumbers (cm-1)
FIG. 4. Infrared spectrum of buddingtonite from Galadriel vein. Arrows
indicate the typical ammonium features.
and El Bagual (Godeas and Litvak, 2006) also determined the
presence of ammonium-bearing minerals.
Among others, Baugh (1995) and Baugh et al. (1998)
pointed out that the ammonium likely originates from buried
organic matter, from which it is leached and transported by
hydrothermal fluids. The presence of buddingtonite and am-
monium-bearing jarosite and illite in the Esquel deposit sup-
ports the hypothesis that organic matter derived from the
black shales of the underlying Piltriquitrón Formation was in-
corporated in the ascending hydrothermal fluid. Sillitoe et al.
(2002) suggested that the hydrothermal system provided the
heat necessary to generate petroleum that migrated into the
Esquel veins and was eventually converted to pyrobitumen by
continued passage of the hot gold-bearing fluid.
Concluding Remarks
SWIR reflectance spectroscopy carried out on samples
from the Esquel epithermal gold deposit allowed identifica-
tion of ammonium-bearing alteration minerals. The presence
of buddingtonite, in particular, confirms that there was cont-
amination of the ascending hydrothermal fluid by organic
matter, probably prior to the boiling stage.
SWIR reflectance spectroscopy proved to be useful for
quick and accurate detection of ammonium-bearing species,
particularly buddingtonite, a mineral that provides evidence
of paleoboiling zones (Browne, 1978) and thus, potentially, of
precious metal mineralization.
Acknowledgments
We thank Orquídea Morello (Comisión Nacional de En-
ergía Atómica) for preparing the buddingtonite concentrate
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869
for infrared spectroscopy analysis, Richard Sillitoe for im-
provements to the manuscript, and Servicio Geológico
Minero Argentino (SEGEMAR) for permission to publish.
Comments provided by T. Cudahy and M. Hannington
greatly improved the manuscript.
November 3, 2006; April 10, 2008
710
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