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 Journal of Volcanology and Geothermal Research 145 (2005) 81 – 96
www.elsevier.com/locate/jvolgeores

Mineralization associated with scale and altered rock and pipe

fragments from the Berlı́n geothermal field, El Salvador;
implications for metal transport in natural systems
Jasmin Raymond1, Anthony E. Williams-JonesT, James R. Clark
Dept. Earth and Planetary Sciences, McGill University, 3450 University St., Montréal, Québec, Canada H3A 2A7
Received 8 October 2003; accepted 17 January 2005

Abstract

Composite fragments sampled at solid collectors and drains of two-phase, re-injection, and vapour pipelines of the Berlı́n
geothermal field, El Salvador, consist mainly of sulphide- and electrum-bearing aluminium-rich amorphous silica scale,
sulphide- and electrum-bearing saponitic/vermiculitic clay from the reservoir, and altered metallic pipe linings containing As–S-
bearing iron oxide–oxyhydroxide grains. Siliceous and clay-rich precipitates contain concentrations of gold and silver in excess
of 180 and 8000 ppm, respectively, and appreciable concentrations of copper, lead, zinc, and antimony. Altered iron fragments
contain substantial arsenic.
Copper, lead, and zinc occur mainly as chalcopyrite, galena, and sphalerite, respectively, in amorphous silica and clay; near
the surface, chalcopyrite transported from depth alters to bornite. Gold and silver occur mainly as electrum, which deposited
with base metal sulphides in the clay precipitates, and amorphous silica at higher levels in the well. Electrum precipitates in the
wells due to the rapid drop in temperature and loss of H2S associated with boiling. The concentration of gold in vapour is ~4
times greater than that in water from associated wellheads. This suggests that gold can be transported efficiently by vapour, and
implies that such transport may be important in the formation of some hydrothermal ore deposits.
D 2005 Elsevier B.V. All rights reserved.

Keywords: geothermal scale; gold; amorphous silica; clay; vapour; boiling

1. Introduction

Geothermal systems were first recognized as

analogues of ore-forming hydrothermal systems by
Skinner et al. (1967), who reported the occurrence of
T Corresponding author. Tel.: +1 514 398 1676.
E-mail address: willyj@eps.mcgill.ca (A.E. Williams-Jones). copper- and silver-bearing minerals in opaline silica
1
Presently at Département de Géologie et de Génie Géologique, scales from surface installations of the Salton Sea field,
Université Laval. California, and by Weissberg (1969), who discovered
0377-0273/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jvolgeores.2005.01.003
82 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
significant Au–Ag concentrations in well cuttings
from the Broadlands field, New Zealand. Subsequent
studies by Brown (1986) and Clark and Williams-
Jones (1990) established that the processes which
control precipitation of gold and silver in geothermal
wells can be used to model directly the formation of
epithermal ore deposits. Geothermal scales and fluids
have been particularly valuable sources of information
for understanding metal behaviour in hydrothermal
systems (Henley, 1984; Krupp and Seaward, 1987;
Gallup, 1998a), and have demonstrated the importance
of phase separation (boiling) as a depositional mech-
anism. However, the possibility that vapour may be an
agent of base and precious metal transport was not
considered in these studies and, in view of recent
experiments demonstrating that these metals are
relatively soluble in aqueous vapour (cf. Williams-
Jones et al., 2002), it is something that merits
investigation in geothermal systems.
In this study, we report results of analysis and
modelling of scale, rock, and corroded pipe fragments
sampled from liquid and vapour pipelines of the
Berlı́n geothermal field, El Salvador. Previous scale
studies at Berlı́n noted the presence of iron oxide and
Fig. 1. Simplified geological map of the Berlı́n–Tecapa volcanic complex (modified from GESAL, 2001), showing the location of the Berlı́n
geothermal field and the distribution of studied wells.
oxyhydroxide, quartz, amorphous silica, native sul-
phur, pyrite, pyrrhotite, halite, and sylvite in similar
fragments (GESAL, 2002), but except for our
preliminary work (Raymond et al., 2003), did not
describe textural relationships among these phases or
interpret scale formation. The objectives of the current
study are thus to fully characterize the mineralogy and
geochemistry of sampled fragments, to evaluate their
origin, and to relate these findings to natural ore-
forming systems.
2. Geological setting
The Berlı́n geothermal field (Fig. 1), El Salvador,
is located 100 km east of San Salvador, on the flanks
of the Berlı́n–Tecapa Quaternary basaltic–andesite
stratovolcano, along the southern fault system of the
Central American graben (Wiesemann, 1975). The
Berlı́n–Tecapa volcanic complex is part of the San
Salvador Formation, and is one of nine volcanoes
occurring along a northwesterly trend parallel to the
trench axis of the Cocos plate, which is subducting
under the Caribbean plate (Carr and Stoiber, 1990).
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96 83

The Berlı́n–Tecapa volcanic complex (Fig. 1) is
characterized by basaltic to andesitic lava flows and
scoria, and andesitic to dacitic ignimbrites, which
were produced during two major eruptions that
accompanied the development of the Berlı́n and
Blanca Rosa calderas (GESAL, 2001). The Berlı́n
caldera forms a keyhole-shaped crater that opens
toward the north–northwest, and encloses the geo-
thermal field. Three distinct aquifers have been
identified in the field: (1) a shallow, low salinity
aquifer (1600 ppm NaCl equiv.; 200 to 300 m a.s.l.);
(2) a moderately saline intermediate aquifer (6600
ppm NaCl equiv.; near sea level) with temperatures of
150 to 200 8C, and a thickness of 500 to 700 m; and
(3) a deep (800 to 1200 m b.s.l.), saline aquifer that is
exploited for geothermal energy (Monterrosa, 1993;
Santos, 1995) and is responsible for scaling in wells
and pipelines. Fluids in the deep aquifer contain 8000
to 12 000 ppm NaCl equivalent (Monterrosa, 1993),
and have a pH of ~5 and a temperature of ~290 8C
(D’Amore and Mejia, 1999). The reservoir is hosted
by basaltic–andesite and andesite lavas interbedded
with minor tuff layers; these rocks have undergone
propylitic alteration, characterized by abundant quartz
and epidote, moderate chlorite and sericite, and minor
calcite and wairakite (CEL, 1999; GESAL, 2001).
3. Sample material and analytical methodology
Fourteen composite samples, consisting of mixed
scale, rock, and corroded pipe fragments, and ranging
in mass from ~2 to 22 g, were obtained from solid
collectors and drains (Fig. 2) attached to liquid-vapour
and re-injection lines of wells TR-2/TR-9 (WS-1 to 8),
the TR-4B/TR-4C water tank (WS-9), and vapour
lines (WS-10 to 14), during a maintenance operation
in February 2000. The system had been cleaned
previously in August 1999, and the wells remained
open throughout the period between the two cleaning
operations (L. Barrios, pers. comm., 2001). The
fragments constitute mixtures of material that origi-
nated in surface pipelines, at depth in the wells, and/or
in the reservoir. The fragments were detached and
transported by geothermal fluids to the solid collectors
and drains, where they were cemented by amorphous
silica. Samples were analysed by X-ray fluorescence
for major elements, by INAA for Au, As, and Sb, and
by ICP-OES (combined hydrochloric–nitric–perchlo-
ric–hydrofluoric acid digestion) for Ag, Cu, Pb, and
Zn. Selected samples, especially those with high
concentrations of precious and base metals, were
evaluated in detail by optical microscopy (transmitted
and reflected light), scanning electron microscopy
(SEM), energy dispersive spectrometry (EDS), and
electron microprobe (EMP) analyses. In addition, one
sample was analysed by X-ray diffraction to assess
clay mineralogy. Four water samples from the geo-
thermal reservoir, collected at wellheads TR-2, TR-9,
TR-4B, and TR-4C, one water sample from the re-
injection line at wellhead TR-8, and a sample of
condensed vapour from the separator connecting wells
TR-4C and TR-4B to the vapour line, were analysed
for cations by ICP-MS. These data were supple-
mented with Cl
, SO4=, HCO3
, and pH values for the
same samples obtained by La Geo S.A. de C.V.

Fig. 2. Schematic sections showing solid collectors and drains from which composite samples were taken, and typical flow paths for Berlı́n
fluids: (A) location of samples related to wells TR-2 and TR-9, and (B) location of samples related to wells TR-4B and TR-4C. Composite
samples WS-1 to 7 and WS-9 to 14 are located by numbers 1 to 7 and 9 to 14, respectively. Geothermal infrastructure is labelled by letters: A,
back-pressure plate; B, solid collector; C, drain; D, separator; E, water tank; F, silencer; G, weirbox; and H, turbine.
84 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96

Fig. 2 shows typical flow paths for Berlı́n fluids. At Table 1

approximately 2000 m depth, the fluids boil at a Mineralogy of scale, rock and corroded pipe fragments in composite
samples W-1 to 14
temperature of ~290 8C in a radius of several metres
Minerals Siliceous Type 1 clay Type 2 Vapour line
around the wells (L. Barrios, pers. comm. 2002).
scale clay pipe frag.
Fluids enter the screened well, and continue boiling as
Early AS-1 VC
they rise rapidly to the surface under high pressure,
Later AS-2 VC VC VC
exiting the well at a temperature of ~145 8C. At the SVC VC VC
back pressure plate, pressure drops, and fluids flow at Qza C C C
lower pressures to the steam separator. Steam flows Amp R
through the vapour line to the turbine, and waste water Rt R
Ksp R
is eventually re-injected, either directly into the deep
Sl R
aquifer or the intermediate reservoir. Cp C C C
Sp C C C
Gl C C C
4. Mineralogy of scale, rock, and corroded pipe Pg R R
Bn C C R
fragments Tt R R
Py C C
Two dominant types of fragment, siliceous and Po C
clay-rich, both locally rimmed by amorphous silica, Act R R R
occur in composite samples WS-1 to 10 (Table 1). Gf R R
El R R R
Siliceous and clay fragments occur with clasts of
IOH C C
altered porphyritic lava and silicified tuff, monomi- AsS C
neralic plagioclase, quartz and epidote fragments VC=very common, C=common, and R=rare.
(from the reservoir), and corroded pipe fragments. Mineral abbreviations: AS=aluminium-rich amorphous silica,
Scale, rock, monomineralic, and corroded pipe frag- SVC=saponitic/vermiculitic clay, Qz=quartz, Amp=amphibole,
ments are locally cemented together by late-stage Rt=rutile, Ksp=K-feldspar, Sl=sylvite, Cp=chalcopyrite, Sp=spha-
aluminium-rich amorphous silica (or by quartz in lerite, Gl=galena, Pg=phosgenite(?), Bn=bornite, Tt=tetrahedrite,
Py=pyrite, Po=pyrrhotite, Act=acanthite, Gf=geffroyite, El=elec-
sample WS-10). Scale, rock, and corroded pipe trum, IOH=iron oxide/oxyhydroxide, AsS=As- and S-bearing iron.
fragments from vapour line samples WS-11 to 14 a
Only occurs in sample WS-10.
have been altered by acidic vapour, and are described
separately below.
generation of aluminium-rich amorphous silica (Fig.
4.1. Siliceous scales 3B) that has a similar composition but appears
fresher (not cracked and stained) than the primary
Approximately 94 vol.% of composite samples, silica. Siliceous scales in sample WS-10 are rimmed
except those from the vapour line, consist of by quartz. Based on semi-quantitative EDS analyses
siliceous scale fragments, comprising aluminium-rich (n=15), the average composition (anhydrous) of
amorphous silica that has two distinct modes of amorphous silica is 83 wt.% SiO2, 9 wt.% Al2O3,
occurrence: early cracked and stained, and later 5 wt.% K2O, and 3 wt.% CaO, and the silica/
bfreshQ. Siliceous scale fragments in samples WS-1, aluminium molar ratio is ~5.4; the early and later
WS-2, WS-5, and WS-10 consist of translucent, varieties of amorphous silica are essentially identical
aluminium-rich amorphous silica that is stained by in composition.
iron oxide/oxyhydroxide and exhibits colloform Early aluminium-rich amorphous silica scales host
(Fig. 3A) and cracked (Fig. 3B) textures. The dendritic and disseminated sulphides and electrum,
siliceous scales commonly have a base of altered variably constituting 1 to 5 vol.% of the siliceous
iron (pipe fragments) that is replaced locally by fragments. In general, the most abundant sulphide
pyrite. Siliceous scale and pipe fragments in samples minerals are chalcopyrite and sphalerite (~1 vol.%
WS-1, WS-2, and WS-5 are rimmed by a second each), followed by galena, bornite, Se-acanthite,
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96 85

Fig. 3. Photomicrographs and backscattered electron images of scale and corroded pipe fragments. (A) Photomicrograph in plane-polarized
transmitted light of chalcopyrite dendrites (Cp; black) hosted by early colloform aluminium-rich amorphous silica (AS-1; translucent) on an
altered iron pipe fragment (IOH; black), and rimmed by the second generation of aluminium-rich amorphous silica (AS-2; translucent). (B)
Photomicrograph in plane-polarized transmitted light of early cracked and stained aluminium-rich amorphous silica (AS-1; translucent), on an
altered iron pipe fragment (IOH; black). The entire scale fragment, including the base, is rimmed by a second generation of bfreshQ aluminium-
rich amorphous silica (AS-2; translucent). (C) Backscattered electron image of Se-acanthite (Act; white) in a chalcopyrite dendrite (Cp; medium
gray), hosted by early aluminium-rich amorphous silica (black). (D) Backscattered electron image of galena (Gl; white), with sphalerite (Sp;
medium gray), chalcopyrite (Cp; dark gray), and Se-acanthite (Act; light gray), hosted by early aluminium-rich amorphous silica (black). (E)
Backscattered electron image of spherulitic type 1 saponitic/vermiculitic clay (SVC; medium gray) rimmed by late-stage amorphous silica (AS-
2; medium gray). This fragment contains small sylvite grains (Sl; white), and is adjacent to a large grain of probable phosgenite (Pg; white). (F)
Backscattered electron image of electrum and galena (El and Gl; both white) in sphalerite (Sp; medium gray), locally rimmed by chalcopyrite
(Cp; dark gray), hosted by type 1 saponitic/vermiculitic clay (black). (G) Backscattered electron image of chalcopyrite (Cp; dark gray) replaced
by bornite (Bn; medium gray), both with inclusions of galena and later probable phosgenite (Gl and Pg; white), hosted by type 1 saponitic/
vermiculitic clay (black). (H) Backscattered electron image of bornite (Bn; dark gray) with galena inclusions (Gl; white), replaced by
tetrahedrite (Tt; light gray) at grain margins; hosted by type 1 saponitic/vermiculitic clay (black).

geffroyite(?), tetrahedrite, and electrum (b1 vol.%
each). Energy dispersive spectrometric analyses (n=4
acanthite; n=3 geffroyite) indicate that the stoichiom-
etry of acanthite is Ag1.8[S0.7Se0.3], and that for
geffroyite(?) is (Ag2.3Cu4.0Fe3.7)(S7.4Se0.6); the iden-
tification of geffroyite is tentative, as the quality of the
analyses was limited by the extremely fine grain-size
of this mineral (V3 Am).
Sulphide dendrites contain individual grains (Fig.
3A,C) that are V5 Am in diameter, and consist
dominantly of chalcopyrite, with lesser fine-grained
sphalerite, galena, acanthite (Fig. 3C), and geffroy-
ite(?). Sphalerite and galena are commonly replaced
by chalcopyrite, and acanthite and geffroyite(?) occur
at chalcopyrite grain margins. Late-stage bornite and/
or tetrahedrite locally replace the sulphide dendrites.
86 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96

Sphalerite (1 to 20 Am), chalcopyrite (1 to 30 Am), Table 2

galena (1 to 10 Am), and pyrite (10 to 35 Am) also Average composition (wt.%) and stoichiometry of saponitic/
vermiculitic clay
occur as disseminated grains in the early aluminium-
wt.% Type 1 (n=24) Type 2 (n=6) Type 3a (n=7)
rich amorphous silica; pyrite grains are typically
isolated and are generally not intergrown with other SiO2 39.37 38.25 37.52
TiO2 0.01 0.01 0.01
sulphide minerals. Chalcopyrite locally rims galena,
Al2O3 5.91 6.98 9.84
sphalerite, and electrum grains, and is locally replaced Fe2O3 11.78 13.61 4.40
by bornite and tetrahedrite. The main gold- and silver- MnO 0.37 0.60 0.14
bearing minerals in early amorphous silica are MgO 16.53 15.13 26.17
electrum, acanthite, and geffroyite(?). Acanthite CaO 1.25 1.28 0.13
Na2O 0.20 0.14 0.04
(Fig. 3D) and geffroyite(?) (both 1 to 3 Am) occur at
K2 O 0.19 0.31 0.02
the margins of chalcopyrite and sphalerite grains. Total 75.61 76.31 78.27
Electrum occurs as 1 to 3 Am diameter inclusions in
chalcopyrite, bornite, and sphalerite grains. Stoichiometry
Late-stage aluminium-rich amorphous silica hosts Si 1.31 1.27 1.25
Al 0.17 0.21 0.29
minor disseminated chalcopyrite, sphalerite, galena Ti 0.00 0.00 0.00
and pyrite, and traces of electrum. Chalcopyrite grains Fe3+ 0.22 0.26 0.08
range from 30 to 100 Am in diameter, enclose galena Mn 0.01 0.01 0.00
and electrum, and are locally replaced by bornite, Mg 0.41 0.38 0.65
acanthite, geffroyite(?), and tetrahedrite. Sphalerite Ca 0.02 0.02 0.00
Na 0.00 0.00 0.00
grains (5 Am diameter) enclose galena and electrum,
K 0.00 0.00 0.00
and are locally replaced by acanthite and geffroyite(?). Sum 10.24 10.25 9.67
Pyrite grains are locally intergrown with chalcopyrite Si/Al 7.53 6.20 4.31
and galena, and are typically 10 to 40 Am in diameter. Mg/Fe 1.85 1.47 7.84
Electrum, acanthite, and geffroyite(?) are the main Jeol JXA-8900L electron microprobe WDS analyses; ZAF correc-
gold and- silver-bearing minerals in the later amor- tion; 15 kV, 20 nA; 20 s peak counts; 5 Am beam; total Fe as Fe3+;
phous silica, but are less abundant than in the early stoichiometry based on 22 oxygen equivalents; analytical totals are
less than 100 wt.% due to the likely presence of water, which cannot
amorphous silica. be analysed by this method.
a
From vapour line (sample WS-13).
4.2. Clay-rich precipitates
indicate that the clay does not contain Na (thus
Clay-rich fragments comprise approximately 5% of eliminating loughlinite), and that compositions are
the composite samples. Most of these fragments similar to saponite or vermiculite. Thus, the clay has a
appear to have formed in the geothermal reservoir as structure that is similar to sepiolite or montmorillonite,
they are not attached to altered pipe substrate. Three but a stoichiometry that more closely resembles
types of clay have been distinguished based on mode saponite or vermiculite. Similar clays have been
of occurrence, composition, and associated minerals; reported to occur in wells and pipes at other geo-
all types are characterized by high concentrations of thermal fields (cf. Reyes and Cardile, 1989).
magnesium and iron and high silicon/aluminium
ratios, and stoichiometries that resemble saponite or 4.2.1. Massive to well-crystallized clay-rich fragments
vermiculite (Table 2). Separates containing type 1 clay (type 1)
were hand-picked from sample WS-2 under a Most (~95%) clay-rich fragments are brown to
binocular microscope, and were analysed qualitatively yellow–brown coloured and massive to well-crystal-
by powder diffraction using a Rigaku D/MAX-2400V lized with conspicuous to distinctive spherulites (Fig.
X-ray diffractometer. The resulting spectrum is con- 3E), and are locally rimmed by late-stage aluminium-
sistent with a clay mineral having a structure similar rich amorphous silica (samples WS-5 and WS-7) or
to sepiolite, loughlinite, or montmorillonite, with a quartz (WS-10). Type 1 clay fragments contain traces
major reflection at ~7 2. However, EMP analyses of sylvite and up to 45 vol.% of sulphide minerals.
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
Table 3
Compositions of composite samples (scale, corroded pipe, and rock fragments) from solid collectors and drains at Berlı́n
Sample Location Major elements (wt.%) Trace metals (ppm)
SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O LOI Au* Ag As* Cu Pb Sb* Zn Total
WS-1 TR-2/9 S. collector #1 L+V line 65.99 0.02 9.25 6.40 0.07 0.71 1.22 1.73 3.23 9.99 31.100 1840 158 3133 3474 40.5 2920 99.80
WS-2 TR-2/9 S. collector #2 L+V line 62.08 0.02 8.63 8.30 0.12 2.29 1.10 1.64 2.85 10.48 187.000 1140 150 5707 7278 49.7 6100 99.59
WS-3 TR-2/9 Drain #2 L+V line 59.57 0.04 8.57 17.18 0.14 0.19 1.43 1.66 3.00 8.34 2.530 358 162 451 347 25.8 364 100.33
WS-4 TR-2/9 Drain #3 L+V line 70.84 0.02 8.57 5.48 0.06 0.10 1.08 1.82 2.62 9.27 9.320 580 94 680 379 31.8 332 100.09
WS-5 TR-8 Drain #2 re-injection line 62.54 0.10 8.98 7.31 0.16 2.55 1.78 1.75 2.70 9.99 149.000 1210 345 6203 4261 28.5 4260 99.54
WS-6 TR-8 Drain #1 re-injection line 72.78 0.02 8.35 2.03 0.07 1.34 1.16 1.74 2.92 9.15 18.800 206 69 895 1041 66.4 829 99.90
WS-7 TR-8 Drain #2 re-injection line 74.87 0.02 7.72 1.41 0.06 1.24 1.03 1.79 2.70 8.75 17.800 79 49 738 843 52.9 705 99.86
WS-9 TR-4B/4C Water tank – – – – – – – – – – 7.920 61 50 290 119 6.6 188 –
WS-10 TR-4B/4C Drain #1 V line 67.56 0.02 8.19 2.85 0.05 1.61 1.21 1.47 2.82 9.06 148.000 8100 393 9772 10490 240.0 14500 99.23
WS-11 TR-4B/4C Drain #3 V line – – – – – – – – – – 1.100 22 1040 1878 27 17.2 3330 –
WS-12 TR-4B/4C Drain #7 V line 1.01 0.02 0.60 96.28 0.31 0.04 0.08 0.15 0.02 3.00 0.915 39 740 544 25 18.8 212 101.72
WS-13 TR-4B/4C Drain #9 V line 1.38 0.09 0.51 94.36 0.32 0.04 0.09 0.14 0.02 4.59 0.439 bd/l 1860 779 bd/l 36.0 387 101.91
WS-14 TR-4B/4C Drain #14 V line 1.41 0.04 0.64 80.36 0.24 0.12 0.06 0.21 0.02 18.22 4.500 20 11300 1587 92 67.9 175 102.70
D. L. (ppm): 60 35 120 30 30 95 15 75 25 100 0.002 5 0.5 10 3 0.2 30
–: insufficient sample material for analysis.
Major elements by XRF, trace metals by ICP-OES except where noted by * INAA. Note that totals may be high due to reporting of total Fe as Fe2O3, and that the sums include data
for additional analysed elements that are not included in the table.
Abbreviations: S=solid, L=liquid, V=vapour, D.L.=detection limit, and bd/l=less than detection limit.

87
88 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
Chalcopyrite, sphalerite, and galena occur as dissemi-
nated grains (up to 60 Am diameter), and sphalerite
also occurs as acicular grains filling cracks in clay
fragments. Chalcopyrite commonly rims or is inter-
grown with sphalerite (Fig. 3F), and fine-grained (V3
Am) acanthite and geffroyite(?) occur near the margins
of chalcopyrite and sphalerite grains. Bornite locally
replaces chalcopyrite (Fig. 3G) and sphalerite, and
tetrahedrite (Fig. 3H) locally replaces chalcopyrite,
sphalerite, and bornite. Chalcopyrite, bornite, and
sphalerite contain inclusions of galena and electrum
(average 2 to 5 Am in diameter; Fig. 3F). Galena is
locally altered to a Pb- and Cl-bearing phase (EMP-
WDS scans also suggest elevated peak counts for C
relative to adjacent grains), tentatively identified as
phosgenite (Pb2(CO3)Cl2).
4.2.2. Rock fragments pervasively altered to clay
(type 2)
Massive saponitic/vermiculitic clay similar to type
1 clay occurs in altered reservoir rock fragments,
which contain remnants of K-feldspar, rutile, and
amphibole. This type of clay-bearing fragment is rare,
and occurs only in sample WS-5 (re-injection line).
Chalcopyrite, sphalerite, and galena (up to 25 vol.%)
occur as disseminated grains (up to 30 Am in
diameter) in type 2 fragments. Chalcopyrite rims
sphalerite and galena. Fine-grained (1 to 3 Am)
acanthite occurs at the edges of chalcopyrite and
sphalerite grains, and is locally intergrown with
bornite. Chalcopyrite is locally replaced by bornite,
and galena by phosgenite(?). Chalcopyrite, bornite,
and sphalerite host inclusions of galena and fine-
grained electrum (2–3 Am in diameter).
4.2.3. Altered clay fragments from the vapour line
(type 3)
Clay fragments from the vapour line sample are
opaque and appear unstable. They contain more
magnesium and aluminium, but less iron and alkalis
(Table 3) than those from two-phase/re-injection lines
samples. Type 3 clay fragments contain mineral
assemblages similar to those of type 1 and 2.
4.3. Vapour line fragments
Altered iron fragments are more abundant in
vapour line samples than in two-phase and re-
injection line samples, and therefore are probably of
local origin. Some fragments may also have been
detached and transported to the vapour line (i.e.,
originated from well casings/linings or two-phase pipe
linings), but these are indistinguishable from in situ
fragments. The pipe fragments consist of iron oxide/
oxyhydroxide and locally contain small grains (5 to
10 Am diameter) of an As–S-bearing iron phase.
These grains have an average composition of 17 wt.%
As and 10 wt.% S, but elemental proportions vary
widely; in some cases, the composition approximates
that of arsenopyrite. The altered iron fragments are
locally replaced by intergrowths of pyrite and
pyrrhotite.
Monomineralic chalcopyrite and covellite frag-
ments also occur in vapour line samples, and have
embayed rims. Covellite was observed only in sample
WS-14, and is rimmed by pyrite. Gold- and/or silver-
bearing minerals were not observed.
Quartz occurs as distinct monomineralic fragments
and as grains accreted to altered pipe fragments in
sample WS-13; it also rims and cements composite
fragments in sample WS-10. In sample WS-13, quartz
fragments are corroded and embayed, and thus appear
to have been locally out of equilibrium with the
vapour.
5. Paragenesis
The mineral paragenesis for an idealized well/
surface pipeline sequence is summarized in Fig. 4.
The first mineral to precipitate in response to geo-
thermal production appears to have been saponitic/
vermiculitic clay, which filled open space and
pervasively altered reservoir rocks in the production
horizon adjacent to the well. Traces of sylvite in type
1 clay minerals were likely formed by evaporation of
brine trapped in pores during sample collection.
Amorphous silica and saponitic/vermiculitic clay did
not precipitate together, as they do not occur in the
same scale fragments (except where the latter forms
composite clasts cemented by late-stage amorphous
silica or quartz in surface pipes). The precipitation of
late-stage amorphous silica likely occurred after fluids
entered surface pipelines.
Millimetre-size fragments originating in the reser-
voir and the well column were transported by
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
Fig. 4. Schematic mineral paragenesis of composite samples from
surface pipelines. The paragenetic sequence is plotted versus
distance from well and surface structures, but is not drawn to scale.
Mineral precipitates from two-phase and re-injection lines are
plotted on the right, and corrosion products and minerals forming in
the vapour line on the left. Geothermal infrastructure is labelled with
letters: A, back-pressure plate; D, separator; and E, water tank.
Mineral abbreviations are the same as those used in Table 1.
geothermal fluids to the re-injection and vapour lines.
Quartz probably formed in the vapour line because it
only occurs in samples WS-10 and WS-13. Since
quartz has the same mode of occurrence as late-stage
amorphous silica (i.e., rims and cements fragments),
and the enthalpy of the steam is substantially higher
than that of the corresponding liquid, it is possible that
quartz formed by re-crystallization of amorphous
silica.
Chalcopyrite, galena, sphalerite, pyrite, and elec-
trum precipitated throughout the well column and
occur in both siliceous and clay-rich scales. These
minerals started to precipitate early, probably in the
reservoir, and continued to do so in the well and
surface pipelines. Pyrite also precipitated throughout
the well column, as it replaces metallic pipe substrates
and occurs as disseminated grains in amorphous
silica. Chalcopyrite precipitated later and/or at higher
89
elevations in the well than sphalerite and galena, as it
generally rims the latter minerals. Electrum co-
precipitated with these base metal sulphides. The
deposition of precious and base metals occurred
throughout the well and surface pipelines, but late-
stage amorphous silica hosts only minor abundances
of these minerals.
Late-stage replacement minerals occurring close to
the wellhead and/or the back-pressure plate, where
transported fragments experienced abrupt changes in
pressure and temperature, include acanthite, geffroy-
ite(?), bornite, and tetrahedrite after chalcopyrite and
sphalerite, tetrahedrite after bornite, and phosgenite(?)
after galena. Acanthite co-precipitated with bornite
and the latter with tetrahedrite. Tetrahedrite to bornite
volume ratios increase with distance from the well
along surface pipelines, indicating not only that
tetrahedrite formed later than other sulphide minerals,
but also that it formed mainly after the fragments had
been transported to the surface. The presence of
tetrahedrite in sample WS-2 indicates that some
tetrahedrite also formed in the two-phase line.
Additional deposition of sulphides occurred when
fragments were transported into the vapour lines.
Pyrite replaced iron oxide/oxyhydroxide, and co-
precipitated locally with pyrrhotite. Covellite, which
occurs only in vapour line samples, may have
replaced transported chalcopyrite fragments; however,
chalcopyrite and covellite were not observed together.
Sample WS-10 contains the greatest abundance of
tetrahedrite, suggesting that some tetrahedrite formed
in the vapour lines. Arsenic- and sulphur-bearing iron
minerals are also interpreted to have formed in the
vapour lines because they were only observed in
sample WS-14.
6. Bulk compositions of composite fragment
samples
Concentrations of SiO2, Al2O3 and Fe2O3 in
samples from drains and solid collectors of two-phase
and re-injection lines (WS-1 to 7) range from 60 to 75
wt.%, 8 to 9.5 wt.%, and 1.5 to 17 wt.%, respectively
(Table 3). The proportions of these oxides reflect the
dominance of amorphous silica in the samples, and to
a lesser extent, the presence of metallic pipe frag-
ments. Sample WS-10 is from a drain located at the
90 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96

entry of the vapour line connecting wells TR-4C and
TR-4B to the turbine, and has a similar composition to
samples WS-1 to 7, suggesting that most fragments in
sample WS-10 were imported into the vapour line.
Samples WS-1 to 10 contain significant concentra-
tions of gold and silver; WS-2 contains the highest
concentration of gold (187 ppm), and WS-10 the
highest concentration of silver (8100 ppm). Copper,
lead, and zinc concentrations are also elevated in these
samples; up to ~1 wt.% Cu, ~1 wt.% Pb, and ~1.5
wt.% Zn in WS-10. Gold correlates positively with
Cu, Pb, and Zn (R 2N0.86) in two-phase and re-
injection line samples collected from wells TR-2/9
(WS-1 to WS-7), which reflects the co-precipitation of
electrum with chalcopyrite, sphalerite, and galena
evident in textural relationships. Silver has only a
weak positive correlation with Au (R 2=0.23) in these
samples, but correlates strongly with Se (R 2=0.94)
reflecting the control of Ag by Se-acanthite and
geffroyite(?).
Vapour line samples WS-11 to 14 consist mainly of
corroded pipe fragments (~97 vol.%) that appear to
have formed predominantly in situ due to the highly
acidic environment, as well as minor scale and rock
fragments that were transported to the vapour line (~3
vol.%). The principal oxide is thus Fe2O3 (80 to 96
wt.%). The concentration of arsenic is significantly
higher in vapour line samples (up to 11 300 ppm) than
in those from the two-phase/re-injection lines. Con-
centrations of Sb are comparable in vapour and two-
phase/re-injection line fragments; the two highest
concentrations, 240 ppm and 68 ppm, are both from
samples collected from drains in vapour lines, WS-10
and WS-14, respectively. Gold concentrations in

Table 4
Compositions of Berlı́n geothermal waters and vapour condensates (ppb) at 25 8C
Sample TR-9 TR-2 TR-4B TR-4C TR8A TR-4B/4C D.L.
Location P Wellhead P Wellhead P Wellhead P Wellhead RI Wellhead Separator
Na 3 440 000 4 230 950 2 380 000 3 070 000 4 470 000 1825 5
Mg 286 202 1230 155 118 220 1
Al 335 196 1935 89 105 9 2
Si 272 000 369 000 347 000 286 000 372 000 8160 50
K 702 000 923 000 543 000 652 000 942 000 666 10
Ca 110 000 94 200 29 600 45 900 117 000 bd/l 50
Ti 119.3 131.1 194.0 107.7 127.6 8.0 0.1
Mn 116.6 117.2 181.5 70.9 124.6 66.5 0.1
Fe 409 bd/l 8080 117 429 130 5
Ni 14.4 34.6 604.9 117.5 82.3 45.9 0.3
Cu 64.4 bd/l 119 48.3 13.2 3.6 0.2
Zn 23.1 21.1 27.4 145 86.0 17.6 0.5
As 9490 11 800 16 700 7750 12 800 10 1
Se bd/l bd/l bd/l bd/l bd/l 0.9 0.2
Mo 37.1 35.3 69.3 61.6 40.0 0.2 0.1
Ag 1.1 0.5 bd/l 0.6 0.3 bd/l 0.2
Cd 0.18 0.15 0.24 0.27 0.13 0.02 0.01
Sb 34.5 77.7 524.7 57.8 298.7 1.6 0.5
Au 0.013 0.005 0.002 0.003 0.004 0.012 0.002
Hg bd/l bd/l bd/l bd/l bd/l bd/l 0.2
Pb 10.2 15.1 57.2 21.4 85.5 0.1 0.1
*Cl
4 164 000 5 889 800 3 560 000 5 916 000 8 191 000 3040 NA
*SO4
8800 4420 2000 10 200 12 000 15 100 NA
*HCO
3 9030 5092 15 130 7320 21 000 NA NA
*pH 6.32 6.43 6.98 6.06 6.31 4.56
Abbreviations: P=production, RI=re-injection, NA=not available, D.L.=detection limit, bd/l=less than detection limit.
All data (except those noted *) by ICP-MS; * data from La Geo S.A. de C.V. Samples were acidified (pH b2) after pH was measured in the field.
Note that anion concentrations are insufficient to balance total cation charge in data columns 1 to 3, and may be under-reported. The fifth data
column represents a boiled water sample collected at re-injection well TR-8A, and the sixth data column is a vapour condensate from the TR-
4B/TR-4C separator.
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
vapour line samples WS-11 to WS-14 are appreciable
(ranging from 0.4 to 4.5 ppm), although lower than in
two-phase/re-injection line fragments, and approach
those of some economic epithermal deposits.
7. Fluid compositions
Geothermal waters (Table 4) sampled at production
wellheads TR-9, TR-2, TR-4B, and TR-4C (at 25 8C)
have moderate salinity, with Cl
, SO4=, and HCO3

concentrations averaging 4882 ppm, 6.4 ppm, and 9.1
ppm, respectively. The principal dissolved cations are
sodium (3280 ppm), potassium (705 ppm), silicon
(3185 ppm), and calcium (70 ppm). All wellhead
liquids have a near-neutral pH at 25 8C, averaging 6.5.
Concentrations of Au, Ag, Cu, Pb, Zn, As, and Sb
average 0.006, 0.6, 58.0, 26.0, 54.2, 11435, and 173.7
ppb, respectively.
Vapour condensates sampled at the separator
connecting wells TR-4B and TR-4C contain much
less Cl
(3 ppm), but considerably more SO4= (15
ppm) than corresponding wellhead liquids. These
differences are interpreted to reflect preferential
partitioning of sulphur species into the gas phase,
and chlorine into the liquid phase during boiling (cf.
Drummond and Ohmoto, 1985). Concentrations of
Na, K, Ca Si, Ag, Cu, Pb, Zn, Sb, and As are much
lower in the mechanically separated vapour than in
corresponding wellhead liquids (TR-4B and TR4-C).
The very low concentration of As is particularly
surprising given the relative abundance of this
element in vapour line fragments, and may indicate
loss of As during sampling. By contrast, the gold
concentration in vapour is considerably higher than
those in all wellhead liquids except for TR-9, and
about four times higher than in corresponding well-
head liquids (TR-4B and TR4-C).
The respective concentrations of Cl
, SO4=, HCO3
,
Na, K, Ca, and Si in boiled water sampled at the head
of re-injection well TR-8A are 3165, 5.4, 14, 635,
130, 15, and 52 ppm higher than in corresponding
liquids sampled at production wellheads TR-2 and
TR-9. The behaviour of the trace metals is more
irregular. Zinc, Pb, As, and Sb concentrations are 64,
73, 2155, and 243 ppb higher, respectively, in the
boiled water, but Cu, Ag, and Au are 51, 0.5, and
0.005 ppb lower than in wellhead liquids.
91
8. Discussion
8.1. Formation of aluminium-rich amorphous silica
and clay-rich precipitates
Aluminium-rich amorphous silica scales are known
to form in many geothermal fields around the world
from near-neutral pH, moderately saline brines (Gal-
lup, 1997). The average temperature at which pure
amorphous silica saturates during one-step adiabatic
boiling of Berlı́n fluid is ~170 8C (Martı́nez, 1997).
However, aluminium-rich amorphous silica is less
soluble than its aluminium-free counterpart, and has
been observed to precipitate at temperatures ~25 8C
above the saturation point for the latter (Gallup,
1998b). By contrast, the average wellhead temper-
ature is ~145 8C. We therefore conclude that early
aluminium-rich amorphous silica formed in the wells,
which is consistent with the mineral paragenesis.
The colloform texture of aluminium-rich amor-
phous silica in Berlı́n wells suggests that amorphous
silica was supersaturated (cf. Rimstidt, 1997) and
precipitated as a gel. It is thus possible that aluminium
and alkalis were incorporated directly into the sili-
ceous gel by adsorption; the gel then dehydrated after
the fragments were sampled, producing aluminium-
rich amorphous silica with desiccation cracks as
described earlier. Alternatively, it is possible that
aluminium reacts with dissolved silica and forms
precipitates through reactions (Gallup, 1997, 1998b),
such as:
2AlðOHÞ83 þ 14SiðOHÞ4 YAl2 O3 d14SiO2 þ 31H2 O
2AlðOHÞ

4 þ 14SiðOHÞ8YAl
4 2 O3 d14SiO2 þ 31H2 O
þ 2OH

However, the low concentration of aluminium
(~100 to 2000 ppb; Table 4), the relatively high
solubility of aluminium–silicate scale (500 ppm at 150
8C; Gallup, 1998b), and the comparable solubility of
amorphous silica scale make direct precipitation of
Al-bearing silica scale at Berlı́n unlikely. We therefore
conclude that incorporation of aluminum in amor-
phous silica by adsorption is a more plausible
explanation for the formation of these scales. Late-
stage aluminium-rich amorphous silica that rims
fragments does not exhibit colloform textures, which
92 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96

may indicate lower degrees of supersaturation in the
two-phase line.
The saponitic/vermiculitic clay is similar to that
reported from the Philippines by Reyes and Cardile
(1989) and from Iceland by Kristmannsdottir (1983).
The clays are massive to spherulitic, have the optical
and chemical characteristics of saponite/vermiculite
(relatively high Mg and low Al), and a structure similar
to sepiolite/montmorillonite. Kristmannsdottir (1983)
suggested that such clays precipitate as Fe- and Mg-
rich and Al-poor silicate gels that recrystallize to a
mineraloid. This hypothesis may not be applicable at
Berlı́n, as most clay appears to be well crystallized,
suggesting formation near equilibrium conditions.
Reyes and Cardile (1989) suggested that this type of
clay could form by the decomposition of bentonite
(Na-rich montmorillonite used in drilling mud), and its
reconstitution into saponitic/vermiculitic clay. This
hypothesis could apply at Berlı́n, as the clay has a
structure similar to montmorillonite. However, type 1
clay fragments exhibit a spherulitic texture, suggesting
that some clay precipitated in fracture and void space
in the reservoir near the well column. Furthermore,
type 2 clay-rich fragments clearly formed by alteration
of the reservoir rock, as indicated by preserved textures
and relicts of K-feldspar, amphibole, and rutile. Clay-
rich clasts from the vapour lines (type 3) have lower Si/
Al and higher Mg/Fe ratios than type 1 and 2 clays, but
similar mineral assemblages, suggesting that such
fragments were transported and altered in situ by
late-stage acidic liquid/vapour.
8.2. Precious and base metal deposition
Chalcopyrite, bornite, galena, sphalerite, and elec-
trum have been reported from numerous geothermal
fields, including Salton Sea, USA (Skinner et al.,
1967), Ohaaki and Rotokawa, New Zealand (Brown,
1986; Warren et al., 1998; Reyes et al., 2002), and
Cerro Prieto, Mexico (Clark and Williams-Jones,
1990), where they are interpreted to have precipitated
due P to boiling-induced changes in temperature, pH
and [S]. Geochemical modelling shows that gold at
Berlı́n also precipitated due to fluid boiling.
Log fO2-pH diagrams (Fig. 5) were constructed at
reservoir (average 290 8C for wells TR-2 and TR-9;
Table 5) and wellhead temperatures (145 8C) to model
the deposition of gold at Berlı́n; calculations were
based on fluid and gas chemistry from well TR-2
(Tables 4 and 6), which is the best candidate to model
gold deposition since most siliceous scales were
collectedPfrom well suite TR-2/TR-9. The diagrams
assume [S]=0.003 and 0.0003 P m at 290 and 145 8C,
respectively. The values for [S] and pH (4.7) at 290
8C (reservoir conditions) were calculated using gas
(Table 6) and liquid (Table 4) compositions for well

Fig. 5. Log fO2-pH diagrams for 290 and 145 8C at saturated vapour pressure, showing predominance fields for aqueous sulphur species (dashed
lines), stability fields for Fe–O–S minerals and bornite–chalcopyrite (solid grey lines), and solubility contours (solid black lines) for gold
(Au(HS)


2 ); the data for Au(HS)2 were taken from Benning and Seward (1996), calculated using the HCh software package (Shvarov Yu and
Bastrakov, 1999). The grey shaded bar for 290 8C (pH 4.7), and the grey shaded dot for 145 8C represent possible fO2-pH conditions for
mineralizing fluids at Berlı́n.
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96 93

Table 5 WS-1 to 7. These metals are assumed to be

Calculated reservoir temperatures (8C) for studied wells using transported predominantly as chloride complexes,
various cation geothermometers
and to have deposited in response to the increase in
Well (Na–K) (Na–K) (Na–K) (Na–K) (Na–K) T average
pH and decrease in temperature that accompanied
1 2 3 4 5
boiling.
TR-9 281 296 287 286 280 286
TR-2 291 303 294 293 291 294
TR-4B 298 308 300 298 298 300 8.3. Comparison of Berlı́n to epithermal precious
TR-4C 287 301 291 290 286 291 metal systems
1: T (8C)=933/[0.993+log (Na/K)]
273.15 (Arnórsson et al.,
1983). Base and precious metal concentrations in Berlı́n
2: T (8C)=1390/[1.75+log (Na/K)]
273.15 (Giggenbach, 1988). wellhead fluids are generally lower than those
3: T (8C)=1217/[1.483+log (Na/K)]
273.15 (Fournier, 1979). reported from many other geothermal fields (e.g.,
4: T (8C)=1289/[1.615+log (Na/K)]
273.15 (Verma and Santoyo,
Gallup, 1998a,b; Henley, 1984). Nevertheless,
1997).
5: T (8C)=856/[0.857+log (Na/K)]
273.15 (Truesdell, 1976). Berlı́n fluids are actively precipitating Au and Ag
in scales and reservoir rocks in concentrations
comparable to those of economic ore deposits,
and the siliceous scales forming in the wells are
TR-2, adjusted to represent equilibrium with quartz,
analogous to low-sulphidation epithermal veins.
sericite, epidote, and chlorite (which occur in the
Amorphous silica precipitates instead of quartz
reservoir; GESAL, 2001), using the programs SOL-
because the Berlı́n geothermal fluids are super-
VEQ
P and CHILLER (Reed, 1982). The values for saturated and deposition occurs rapidly. The
[S] and pH (5.7) at 145 8C (wellhead conditions)
absence of adularia and sericite in Berlı́n wells,
were assumed to decrease and increase, respectively,
which are common in low-sulphidation epithermal
from the reservoir values by 1 log unit due to boiling
systems (Cooke and Simmons, 2000), is likely due
of fluids. Gold was assumed to be transported as
to the incorporation of Al and K by amorphous
Au(HS)2
, the most stable complex for conditions in
silica. Although smectite is common in alteration
the well (pH ranges from ~4.7 to ~5.7 from reservoir
assemblages formed by weakly acidic fluids in
to wellhead, respectively), and to precipitate accord-
hydrothermal systems, it generally does not host
ing to the reaction:
much mineralization. However, significant Au and
AuðHSÞ
þ
2 þ H þ 1=2H2 OYAuðsÞ þ 2H2 SðaqÞ
Ag precipitated in the saponitic/vermiculitic clay
þ 1=4O2 from the reservoir at Berlı́n. Such saponitic/vermic-
ulitic clays appear to be unique to geothermal
In the reservoir, the upper and lower limits for environments, and may form in response to the
fO2 (between
30 and
35) are constrained by the extremely accelerated boiling process around the
pyrite–hematite and pyrite–pyrrhotite boundaries, for wells.
which calculated gold solubilities range from 1 to
10 ppb. At the wellhead, fO2 (near
48) is 8.4. Vapour transport of metals
constrained by the co-existence of bornite, pyrite,
and chalcopyrite, and the calculated gold solubility One of the most interesting features of the
is b1 ppb. The decrease P in temperature, increase of Berlı́n scales is the occurrence of appreciable Au,
pH, and decrease in [S] due to boiling reduced
gold solubility sufficiently to cause its precipitation
in well scales at depth. Other metals, such as Ag, Table 6
Cu, Pb, and Zn, are also interpreted to have Dry gas compositions for well TR-2 (mol%)
precipitated due to boiling, as electrum co-precipi- Ar H2 N2 CH4 H2S He CO2 NH3 Ys XH2O
tated with sphalerite, galena, and chalcopyrite, and 0.214 1.186 2.068 0.209 9.881 0.196 86.697 0.091 0.276 0.997
gold and silver concentrations correlate positively Data obtained from La Geo S.A. de C.V.
with those of Cu, Pb, and Zn in composite samples Abbreviation: Ys=steam fraction.
94 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
As, and Sb in composite samples from the vapour
lines. Silver, Cu, Pb, and Zn also occur in
significant concentrations in vapour line samples,
but appear to reflect deposition prior to transport of
the fragments into the vapour lines. Greater
concentrations of Au, As, and Sb in samples
further along the vapour line from wells TR-4B/
4C (compare WS-14 with WS-11 to 13; Fig. 2B)
suggest that some Au, As, and Sb were precipitated
directly from vapour. Arsenic in particular has been
previously reported to be precipitated from vapour
in geothermal systems (e.g., Reyes et al., 2002).
The fluid chemistry at Berlı́n supports the idea that
significant gold is also transported in the vapour, as
the condensate sample taken at the separator
contains about four times as much Au as the
corresponding production wellhead liquids (TR-4B/
4C). Arsenic and antimony precipitated as an As–
S-bearing iron phase (sample WS-14) and as
tetrahedrite (sample WS-10), respectively; the form
of precipitated gold in the vapour line samples is
unknown.
Volatility data (cf. Williams-Jones et al., 2002)
indicate that As and Sb are the most volatile ore-
related metals after Hg, and suggest that these
metals were transported by vapour. By contrast,
Au has very low volatility suggesting that it should
have negligible solubility in the vapour. However,
experiments by Archibald et al. (2001) indicate that
hydration greatly enhances Au solubilities in aque-
ous vapour, and that significant concentrations can
be transported as hydrated chloride complexes.
Considering the importance of H2S in enhancing
Au solubility in aqueous liquids, and the fact that
H2S partitions strongly into vapour, it is also likely
that complexes involving H2S play an important role
in increasing Au solubility in aqueous vapour.
Finally, we note that the evidence presented above
for the transport of gold in vapour is consistent with
reports of high gold concentrations in vapour-rich
fluid inclusions (Ulrich et al., 1999) in some ore
deposits.
9. Conclusions
Mineralized fragments originating in the Berlı́n
geothermal field are composed mainly of sulphide-
and electrum-bearing aluminium-rich amorphous
silica scale and saponitic/vermiculitic clay precip-
itates. Siliceous scales formed in the wells as a gel,
which incorporated aluminium and alkalis by adsorp-
tion. Clay precipitated in the reservoir, filling void
space, and altering reservoir rock. Scale, rock, and
corrosion fragments were cemented by a second
generation of amorphous silica, after transport into
two-phase and re-injection lines. Gold deposited as
electrum in well scales due to decreases in temper-
ature, H2S depletion, and increases in pH that
accompanied fluid boiling.
Fragments transported into the vapour lines and in
situ pipe linings were altered by steam acidity.
Antimony and arsenic were transported in the vapour
line due to their relatively high volatilities, and
precipitated as tetrahedrite (after bornite) in trans-
ported scales, and as an As–S-bearing iron phase in
altered pipe fragments. Gold was transported into the
vapour lines as a hydrated gas species by the slightly
acidic chloride vapour, as indicated by higher
concentrations of Au in condensed steam relative to
wellhead fluids.
This study of mineralized fragments from drains
and solid collectors of the Berlı́n field shows that
precious metal-bearing siliceous well scales are
analogous to epithermal veins and are deposited by
boiling. The significant Au, As, and Sb concentrations
in vapour line fragments suggest that geothermal
vapour pipelines provide an active environment in
which to study the role of vapour in metal transport.
Future research in such systems may furnish addi-
tional information with which to evaluate mineral
deposit models.
Acknowledgements
We wish to acknowledge support from Ing. Luz A
Barrios, Elizabeth de Enriquez and La Geo S.A. de
C.V. during this study. Funding was provided by
grants to A.E. Williams-Jones from NSERC and
FQRNT, and to J. Raymond from GEOTOP, the
Society of Economic Geologists, and the Geological
Society of America. We are also grateful for the
comments of reviewers D. Gallup and T. Ulrich
which significantly improved the manuscript. Special
thanks go to S. Archibald who provided valuable
 J. Raymond et al. / Journal of Volcanology and Geothermal Research 145 (2005) 81–96
help and guidance, and to E. Labrecque who helped
initiate the project in El Salvador.
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