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A model of boiling for fluid inclusion studies: Application to the Bolaños Ag–
Au–Pb–Zn epithermal deposit, Western Mexico

Article  in  Journal of Geochemical Exploration · August 2011

DOI: 10.1016/j.gexplo.2011.04.005

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 Journal of Geochemical Exploration 110 (2011) 118–125

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Journal of Geochemical Exploration

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A model of boiling for fluid inclusion studies: Application to the Bolaños

Ag–Au–Pb–Zn epithermal deposit, Western Mexico
Carles Canet a,⁎, Sara I. Franco a, Rosa María Prol-Ledesma a,
Eduardo González-Partida b, Ruth Esther Villanueva-Estrada a
a
Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico
b
Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico

a r t i c l e i n f o a b s t r a c t

Article history: Boiling can be inferred from fluid inclusion microthermometry studies when a progressive increase in
Received 17 December 2010 apparent salinity is observed along with a decrease of homogenization temperature (TH) and depth, thus
Accepted 18 April 2011 reflecting the partitioning of non-volatile solutes into the liquid phase during steam loss. We propose a model
Available online 28 April 2011
for fluid evolution during boiling based on mass and heat balance equations, which establishes paths in the
TH-salinity space that can be compared with fluid inclusion data to confirm or discard boiling. Additionally,
Keywords:
Fluid inclusion microthermometry
the model allows calculating paleo-depths, for which the effect of steam bubbles lowering the hydrostatic
Enthalpy balance pressure is taken into account.
Boiling evidence The Bolaños Ag–Au–Pb–Zn deposit was selected to test the suitability of the proposed model, given that
Paleo-depth calculation previous work in this deposit emphasizes the role of boiling in ore deposition. The Bolaños deposit belongs to
Epithermal veins the low-sulfidation epithermal type and is genetically related to the final stage of formation of a graben-type
Hydrothermal system caldera. Microthermometry data show that the deeper the sample was taken, the higher is TH and the lower is
salinity (sample depths: 540, 500, 440 and 200 m below present surface). The overall range (n = 108) of
variation of TH and salinity is of 137°–279 °C and 2.4–10.9 wt.% NaCl eq., respectively. According to our model,
rising hydrothermal fluids in Bolaños underwent boiling from depths not exceeding 440 m (below present
surface). Conversely, below this level fluid evolution cannot be explained in terms of boiling, because the
increase of salinity is much greater than the expected considering solely the amount of steam lost during the
corresponding drop of temperature. The calculated paleo-depth for the lowest level of boiling in a Bolaños
vein is ~ 435 m. Neglecting the drop in fluid density due to steam bubbles may lead to serious
underestimations of paleo-depths.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Boiling is the most important process triggering metal deposition
in many ore deposit settings, in particular in epithermal systems (e.g.,
André-Mayer et al., 2002; Skinner, 1997). In the shallowest 2 km of
the hydrothermal systems, boiling is the main process controlling the
key chemical parameters for mineral precipitation such as pH, fluid
composition and mineral solubility. On the contrary, other processes
such as simple conductive cooling by wall rocks and mixing with cold,
dilute groundwater are much less influential in epithermal ore
formation (Drummond and Ohmoto, 1985; Hedenquist, 1991; Spycher
and Reed, 1989).
The term “boiling” will be used here in a strict sense, to refer to the
process of rapid separation of a gas phase largely consisting in water
vapor from a water(–salt) system, because of a temperature increase or
⁎ Corresponding author. Tel.: + 52 55 56224133.
E-mail address: ccanet@geofisica.unam.mx (C. Canet).
a pressure decrease (Fig. 1; Roedder, 1984; Henley et al., 1984). Hence,
we stress the difference between boiling and effervescence, the latter
being more appropriate for those systems rich in volatiles, particularly
in CO2, that are exsolved into the gas phase. The occurrence of CO2 in
hydrothermal fluids increases the vapor pressure along the liquid–gas
curve, lowering the “boiling point” temperature. This gas also contributes
to depress the freezing point of fluid, affecting salinity estimates based
on fluid inclusion measurements, and may lead, when not taken into
account, to significant overestimation of apparent salinities (Hedenquist
and Henley, 1985). Nevertheless, low CO2 concentrations (b3 mol%) are
expected in many epithermal deposits (Bodnar et al., 1985).
Many vein deposits have been found to be highly enriched in
precious and base metals in presumed boiling intervals, forming what
are known as “bonanza” high-grade ores (Fig. 2 C; Cole and
Drummond, 1986; Scott and Watanabe, 1998). Furthermore, the
precipitation of these metals has been corroborated in active
geothermal wells undergoing intense mass flow and boiling (Brown,
1986; Simmons and Brown, 2006). When it occurs in the deepest zone
of epithermal systems (below ~ 500 m), boiling produces a rise in pH

0375-6742/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2011.04.005
 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125
Fig. 1. Scheme showing fluid evolution and its entrapment as fluid inclusions, in the P–T
space. (A) Homogeneous trapping of rising fluid, as aqueous fluid inclusions, at the
lower levels of an hydrothermal system. Since the moment of fluid inclusion formation,
P–T evolution within the inclusion is constrained by an isochore (line of constant
density, black arrows), up to its intersection with the L + V univariant curve. Note that
the temperature of homogenization (TH) is below the trapping temperature (Tt);
actually, temperature and pressure conditions during fluid inclusion formation are
unknown and cannot be directly deduced from TH. (B) Fluid trapping (heterogeneous)
during boiling, at shallower levels of the same hydrothermal system, resulting in the
formation of both liquid- and, eventually, vapor-rich fluid inclusions. In this case, Tt is
equivalent to the TH value for the liquid-rich inclusions, and trapping pressure (Pt) can
be directly deduced from the boiling curve. The scheme is an idealization that considers
that fluid rises adiabatically, and univariant curves were drawn considering pure water.
due to the CO2 loss to the gas phase, causing destabilization of metal–
chloride complexes and thus the precipitation of base-metals and
silver (Drummond and Ohmoto, 1985). Conversely, gold, which forms
complexes with sulfur (Seward, 1973), precipitates at shallower
depths where boiling causes H2S loss (Brown, 1986; Hedenquist and
Fig. 2. Examples of mineralogical and fluid inclusion “classic” evidences of boiling in epithermal deposits, from the Veta Madre vein of the Guanajuato District, Central Mexico: (A) Adularia
euhedral crystals reflecting a pH increase of the hydrothermal fluid during boiling; (B) Large crystals of bladed calcite formed by the release of CO2 to the vapor phase during boiling;
(C) “Bonanza” ores rich in native gold and silver-bearing minerals, caused by a loss of H2S during boiling; and (D) Fluid inclusions showing variable liquid-to-vapor (L – V) ratios due to
heterogeneous fluid trapping during boiling. Abbreviations: Au – native gold, Cc – calcite; Cpy – chalcopyrite, KF – potassium feldspar (adularia); Prg – pyrargyrite; Q – quartz.
119
Henley, 1985). H2S is much more soluble than CO2 and, when it
exsolves CO2 had already been completely lost and pH suffers no
major changes (Henley et al., 1984). So it is a drop in sulfur fugacity
and temperature which triggers gold precipitation (Brown, 1986;
Simmons and Browne, 2000).
Boiling in epithermal systems may be a key exploration criterion,
especially for epithermal gold deposits (e.g., Del Blanco et al., 2009).
Apart from them, boiling is relevant to the genesis of other types of
hydrothermal ore deposits that form near or at the earth surface or
seafloor, as manganese-oxide veins (e.g., Rodríguez-Díaz et al., 2010)
and volcanogenic massive sulfide (VMS) deposits (e.g., Large, 1992).
Finding boiling evidence points out not only possible high-grade
zones, but also can be used to constrain paleo-depths based on the
principle that during boiling vapor pressure equals hydrostatic
pressure (Haas, 1971). Thus, several mineralogical and fluid inclusion
boiling evidences have been established for mineral exploration
purposes (e.g., Simmons and Browne, 2000). For instance, occurrence
of hydrothermal breccias in epithermal environments is usually
accepted as boiling evidence, taking into account that an increase in
fluid pressure within a vein may result in hydraulic fracturing and,
thus, in a sudden drop in pressure (Berger et al., 1983; Cole and
Drummond, 1986; Jobson et al., 1994; Jébrak, 1997). Additionally,
adularia and platy calcite are widely taken as indications of boiling
(Fig. 2A and B). The cause of adularia precipitation is the release of CO2
during boiling, which causes a pH increase of the solution and,
consequently, a shift to the adularia stability field from that of illite
(e.g., André-Mayer et al., 2002; Browne, 1978; Browne and Ellis,
1970):
− þ
KAl3 Si3 O10 ðOHÞ2 þ 6SiO2 þ 2HCO3 þ 2K
¼ 3KAlSi3 O8 þ 2CO2 ðgÞ þ 2H2 O
Similarly, the CO2 loss triggers a rapid crystallization of calcite, favoring
the formation of the tabular habit (e.g., André-Mayer et al., 2002):
2þ −
Ca þ 2HCO3 ¼ CaCO3 þ CO2 ðgÞ þ H2 O
Besides the above mineralogical criteria, which could not be
applied in low-CO2 systems, fluid inclusions can also provide evidence
120 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125
Fig. 3. Diagram showing four typical trends of distribution of fluid inclusion
populations, according to their temperature of homogenization (TH) and salinity (or
their ice-melting temperature, TM(ice)) (after Hedenquist and Henley, 1985; Wilkinson,
2001). (A) Boiling, in a volatile-free system; (B) dilution due to mixing with cold
groundwater; (C) boiling with effervescence, in a volatile-rich system; (D) cooling or
pressurization.
of boiling. The main criterion is the presence of clusters of fluid
inclusions that, belonging to a single paragenetic family, show variable
liquid-to-vapor ratios, reflecting the coexistence of vapor and liquid
(Fig. 2D; Bodnar et al., 1985; Haas, 1971; Van den Kerkhof and Hein,
2001). However, trapping of heterogeneous (vapor + liquid) fluids
seems to not occur extensively. Hence, Simmons and Christenson
(1994) found in an actively boiling geothermal system that only less
than 1% of the entrapped fluid inclusions were vapor-rich, despite the
vigorous generation of steam bubbles. Therefore, in many cases, boiling
can only be inferred from certain trends showed by fluid inclusion
populations in a plot of homogenization temperature (TH) ice-melting
temperature (TM; or alternatively the apparent salinity), in order that a
progressive increase in salinity (or decrease in TM) along with a TH
decrease reflects the partitioning of the non-volatile solutes into the
liquid phase during steam loss (Fig. 3; Wilkinson, 2001, and references
therein). Chlorine, which is the most important complexing ligand for
base metals and silver under a broad range of conditions (e.g., Ruaya and
Seward, 1986), has very low solubility in the vapor phase below ~370 °C
(e.g., Knight and Bodnar, 1989); thus, as steam is being produced during
boiling, chlorinity increases in the residual liquid phase (Henley et al.,
1984).
The residual liquid phase might cool during boiling due to the
adiabatic expansion, i.e. the total heat of the combined liquid and
vapor is constant (Henley et al., 1984). Since the adiabatic cooling of
the liquid eventually causes the cessation of boiling, the salinity
increase due to steam loss may not exceed 30% (Hedenquist and
Henley, 1985).
In order to ensure that, in any fluid inclusion microthermometry
study, a trend of increasing salinity with decreasing TH really reflects a
process of boiling, an enthalpy balance must be calculated (Hedenquist
and Henley, 1985). With this in mind, we developed a simple model
that, based on the mass and heat balance equations of Henley et al.
(1984), could be helpful for traditional fluid inclusion studies by
establishing the salinity–temperature possible paths during boiling of
a volatile-free, H2O–NaCl fluid. Additionally, starting from the
equations of Haas (1971) (and referenced therein), which relate the
fluid density and vapor pressure with salinity and temperature, we
propose a method for paleo-depth calculation, applicable to hydro-
thermal vein deposits that underwent boiling, which considers the
effect of steam in the hydrostatic pressure gradients.
The purpose and effectiveness of the proposed model is illustrated
with an example from the Bolaños Ag–Au–Pb–Zn epithermal deposit,
Western Mexico (Fig. 4), in which previous studies concluded that
Fig. 4. Simplified tectonic map of central and western Mexico, with the location of the
Bolaños Graben, which encloses the Bolaños Ag–Au–Pb–Zn Mining District (after
Ferrari et al., 2007). TMVB – Trans-Mexican Volcanic Belt (Miocene to Quaternary);
SMO – Sierra Madre Occidental silicic volcanic province (Late Cretaceous to Miocene).
boiling was a key factor in ore deposition (Aguirre-Díaz et al., submitted
for publication; Albinson and Rubio, 2001).
2. Methods
2.1. Boiling modeling
In the present model we make the assumption that fluids
undergoing boiling rise adiabatically, i.e. without a significant loss of
heat to the surrounding rocks, as would be expected in the epithermal
environment (b2 km depth; Simmons and Browne, 1997). Therefore,
a heat balance equation can be expressed as follows (Henley et al.,
1984):
HT = y ·HV + ð1–yÞ ·HL ð1Þ
where HT, HV and HL are the enthalpies for the reservoir (total), the
steam and the liquid water, respectively, and y is the steam fraction
(mass) separated during boiling. Thus, the steam fraction formed from
a rising fluid that starts boiling at a temperature Ti, over a given
temperature interval Ti–Tf, can be calculated considering the enthalpy
of vapor-saturated liquid water at Ti, when y is still 0, and for steam
and liquid water at Tf. Enthalpy data can be obtained from standard
steam tables for pure water such as those of Rogers and Mayhew
(1981), since the effect of salinity is very small (e.g., Wilkinson, 2001).
For modeling purposes, the tabulated enthalpy values were fitted to
polynomial regression functions of temperature (order 6; R2 ≥ 0.99).
The increase of salinity due to the partitioning of the non-volatile
solutes into the liquid phase during steam loss can be calculated from
Eq.(2).
−1
XF = XI · ð1–yÞ ð2Þ
where XI and XF are the salt concentrations (here NaCl) in molar units
in the initial and final (residual) liquids, respectively.
A program was written in FORTRAN code in order to model the
increase of salinity of the residual liquid during boiling, based on Eq.
(1), (2) and the enthalpy–temperature regression functions for steam
 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125 121

and vapor-saturated water. Running this program for a temperature Table 1

range between 375° and 100 °C (the approximate critical point and Thermal profile corresponding to the boiling path of a NaCl–H2O solution whose initial
temperature and salinity conditions (of 224 ° C and 7.60%, respectively) represent those of
the boiling point at 1 atm for pure water, respectively), with a step of the fluid inclusions hosted in sample AL-15 of the Bolaños Zn–Pb–Ag epithermal deposit
5 °C and at different values of XI (0.2, 0.4, 0.7, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, (Western Mexico). Density (L) column: density of the liquid phase. Density (L + V)
7.0, 8.0, 9.0, 10.0, 11.0, 13.0 and 15.0 wt.% NaCl), the diagram shown in column: combined density values of the coexisting vapor and liquid phases. Depth (A)
Fig. 6 was constructed. column: depth calculated considering a liquid column, without suspended vapor bubbles.
Depth (B) column: corrected depth values, calculated from the L + V combined density
Additionally, in order to model the temperature–salinity–pressure
values.
(–depth) relations of boiling fluids, the equations of Haas (1971) (and
referenced therein) were added into the FORTRAN code. These T Steam Salinity Pressure Steam Density Depth (m)
fraction volume (g/cm3)
equations consider a simple NaCl–H2O system, whose thermodynamic
properties approach those of natural solutions containing, besides Na, (°C) (mass (wt.%) (bar) (vol. %) (L) (L + V) (A) (B)
cations such as Ca and K. Hence, apparent salinity values, obtained by fraction)

fluid inclusion microthermometry and expressed in terms of NaCl wt.% 100 0.002 9.93 0.9 78.6 0.958 0.197 −1.2 0.0
equivalent, can be directly used. 102 0.002 9.89 1.0 76.8 0.957 0.213 −0.1 4.7
104 0.002 9.84 1.1 75.2 0.956 0.227 0.9 9.1
Density of the NaCl–H2O liquid phase (ρL), which depends on
106 0.002 9.80 1.2 73.7 0.954 0.240 2.0 13.3
temperature and salinity, is calculated from (a) the specific volume of 108 0.002 9.76 1.3 72.2 0.953 0.252 3.0 17.2
H2O liquid at a given temperature (Smith and Keyes, 1934), and (b) 110 0.002 9.71 1.3 72.1 0.952 0.254 3.0 17.2
the apparent molal volume of NaCl in aqueous solution at a given 112 0.002 9.67 1.4 70.7 0.950 0.265 4.1 21.0
temperature and concentration (Haas, 1970). It is worth mentioning 114 0.002 9.63 1.5 69.4 0.949 0.277 5.1 24.6
116 0.002 9.59 1.6 68.0 0.948 0.288 6.2 28.1
that, for these calculations, we took into account the variation of 118 0.002 9.55 1.7 66.8 0.946 0.298 7.2 31.5
salinity with temperature obtained from the Eq. (1) and (2), in 120 0.002 9.51 1.9 64.4 0.945 0.318 9.3 37.9
contrast to Haas (1971), who used constant values of salinity. 122 0.002 9.47 2.0 63.3 0.943 0.326 10.4 40.9
The vapor pressure of the vapor-saturated NaCl–H2O fluid is 124 0.002 9.43 2.1 62.3 0.942 0.336 11.5 43.9
126 0.002 9.39 2.2 61.2 0.941 0.344 12.5 46.8
calculated, with the equation of Bain (1964) modified by Haas (1971),
128 0.002 9.35 2.4 59.2 0.939 0.360 14.6 52.5
as a function of temperature and salinity. Vapor pressure must be 130 0.002 9.31 2.5 58.3 0.938 0.368 15.7 55.2
equal to the hydrostatic pressure if the fluid undergoes “open” boiling, 132 0.002 9.28 2.7 56.5 0.936 0.382 17.9 60.5
that is, if fluid channels are continuous up to the surface (Haas, 1971). 134 0.002 9.24 2.9 54.9 0.935 0.394 20.0 65.6
Thus, depth can be calculated from Eq. (3). 136 0.002 9.20 3.0 54.1 0.933 0.401 21.1 68.1
138 0.002 9.17 3.2 52.6 0.932 0.412 23.2 73.0
p
140 0.002 9.13 3.4 51.1 0.930 0.424 25.4 77.7

∫ 1 142 0.002 9.10 3.6 49.8 0.928 0.434 27.5 82.3

h = 10 · dp ð3Þ 144 0.002 9.06 3.8 48.5 0.927 0.443 29.7 86.9
p0
ρ
146 0.002 9.03 4.0 47.3 0.925 0.452 31.8 91.3
148 0.002 8.99 4.2 46.2 0.924 0.460 34.0 95.7
where h is the depth, P and P0 are the values of hydrostatic pressure 150 0.002 8.96 4.5 44.5 0.922 0.473 37.2 102.1
152 0.002 8.92 4.7 43.5 0.920 0.479 39.4 106.3
(at a depth h below the water table) and atmospheric pressure at sea
154 0.002 8.89 5.0 42.1 0.919 0.490 42.7 112.4
level, respectively, and ρ is the density. For depth and thermal profiles 156 0.002 8.85 5.3 40.7 0.917 0.499 46.0 118.4
calculations, Haas (1971) took the liquid phase density, discarding the 158 0.002 8.82 5.5 39.9 0.915 0.505 48.1 122.4
lowering effect of steam bubbles on the hydrostatic pressure. 160 0.002 8.78 5.8 38.7 0.914 0.513 51.4 128.3
162 0.002 8.75 6.1 37.6 0.912 0.520 54.7 134.1
Alternatively, we propose to use a combined density (ρc) of the
164 0.002 8.71 6.5 36.2 0.910 0.530 59.1 141.7
coexisting vapor and liquid phases, which, approximating to zero the 166 0.002 8.68 6.8 35.2 0.909 0.536 62.4 147.3
value of steam density, can be calculated from Eq. (4). 168 0.002 8.64 7.1 34.3 0.907 0.542 65.7 152.8
170 0.002 8.61 7.5 33.1 0.905 0.549 70.1 160.1
−1 172 0.002 8.58 7.9 32.0 0.903 0.556 74.5 167.3
ρc = ð1–yÞ ·ρL · ðVL + VS Þ ð4Þ
174 0.002 8.54 8.2 31.3 0.901 0.560 77.9 172.7
176 0.002 8.51 8.6 30.3 0.900 0.565 82.3 179.8
where VL and VS are the volumes of liquid and steam per mass unit, 178 0.002 8.47 9.1 29.2 0.898 0.572 87.9 188.6
respectively. While VL can be directly calculated from ρL, VS was 180 0.002 8.43 9.5 28.3 0.896 0.576 92.3 195.5
182 0.002 8.40 9.9 27.6 0.894 0.580 96.8 202.4
approximated by means of the ideal gas law (at a given P and
184 0.002 8.36 10.4 26.6 0.892 0.585 102.4 211.0
temperature), in which the steam moles are stoichiometrically 186 0.002 8.33 10.9 25.8 0.890 0.590 108.0 219.5
deduced from the steam fraction, y. 188 0.002 8.29 11.4 25.0 0.888 0.593 113.7 227.9
Considering the P contribution and the ρc value for discrete 190 0.002 8.26 11.9 24.2 0.887 0.597 119.3 236.3
192 0.002 8.22 12.4 23.5 0.885 0.600 124.9 244.7
temperature steps, Eq. (3) was numerically integrated. An example of
194 0.002 8.18 13.0 22.7 0.883 0.603 131.7 254.6
a temperature–salinity–pressure–depth profile, calculated from 196 0.002 8.14 13.5 22.1 0.881 0.605 137.4 262.9
microthermometry data (TH and salinity) of a selected sample of the 198 0.002 8.11 14.1 21.4 0.879 0.608 144.2 272.8
Bolaños Ag–Au–Pb–Zn epithermal deposit, is shown in Table 1. 200 0.002 8.07 14.7 20.7 0.877 0.611 151.1 282.6
202 0.002 8.03 15.4 20.0 0.875 0.613 159.1 294.0
204 0.002 7.99 16.0 19.4 0.873 0.615 166.0 303.8
2.2. Sample selection and fluid inclusion microthermometry
206 0.002 7.96 16.7 18.8 0.871 0.617 174.0 315.1
208 0.002 7.92 17.4 18.2 0.868 0.618 182.0 326.5
A comprehensive fluid inclusion study of the Bolaños Ag–Au–Pb– 210 0.002 7.88 18.1 17.6 0.866 0.619 190.1 337.8
Zn epithermal deposit was performed by Aguirre-Díaz et al. 212 0.002 7.84 18.9 17.0 0.864 0.621 199.4 350.7
214 0.003 7.80 19.6 22.9 0.862 0.574 207.5 362.9
(submitted for publication). This study is based in a representative
216 0.003 7.76 20.4 22.3 0.860 0.576 216.8 376.8
sampling performed along 2200 m and down to 600 m deep in the El 218 0.003 7.72 21.2 21.6 0.858 0.578 226.1 390.6
Alacrán–San Francisco vein. Fluid inclusions of primary origin 220 0.003 7.68 22.1 21.0 0.856 0.580 236.6 406.1
(accordingly to the criteria of Roedder, 1984) were analyzed in 222 0.003 7.64 22.9 20.4 0.853 0.581 246.0 419.9
sphalerite, quartz and fluorite (Fig. 5). Those fluid inclusions where 224 0.003 7.60 23.8 19.8 0.851 0.583 256.6 435.3

leakage, decrepitation or other modifications were suspected were

rejected, following the recommendations of Bodnar et al. (1985) and
122 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125
Van den Kerkhof and Hein (2001). Primary fluid inclusions showed
regular morphology and were distributed following growth zones or
isolated. They ranged in size from 5 to 20 μm and were aqueous, mostly
with two phases (liquid and vapor, with no daughter minerals) at room
temperature, with bubbles representing ~10–15 vol.% in sphalerite, and
~15–30 vol.% in quartz and fluorite (Fig. 5). Heterogeneous trapping of
fluids due to boiling were reported in the shallowest levels of the deposit
(Aguirre-Díaz et al., submitted for publication).
At depths of 500 to 600 m below present surface (m bps), where
the highest Cu and Au grades are found, TH was of 240°–260 °C and
salinity averaged 2 wt.% NaCl eq., whereas in the upper 500 m, richer
in Ag, Pb, Zn and F, TH ranged between 121° and 230 °C, and salinity
between 4 and 11 wt.% NaCl eq. (Aguirre-Díaz et al., submitted for
publication).
Among the 53 samples analyzed by Aguirre-Díaz et al. (submitted
for publication, we selected four samples (BAL-16/200 m bps, AL-15/
440 m bps, AL-07/500 m bps, and AL-03/540 m bps) that showed a
clear trend of TH increase and salinity decrease with depth (trend
exemplified in Fig. 3A), thus avoiding samples which could record
mixing with cool and dilute (probably meteoric) fluids (trend
exemplified in Fig. 3B). None of these samples showed evidence of
heterogeneous trapping of fluids. In the selected samples, clathrates
were not observed during freezing experiments, indicating that CO2
contents were below 3.7 wt.% (Hedenquist and Henley, 1985). A
summary of fluid inclusion microthermometric data of the selected
samples is provided in Table 2.
3. Application case: the Bolaños Ag–Au–Pb–Zn epithermal deposit
3.1. Geological setting and structure of the deposit
The Bolaños silver mining district, in Jalisco, dates back to the
Spanish colonial times and, despite its historical importance, only two
mines are active at present: Bolaños and San Martín de Bolaños. The
historical production until 1980 was 60 millions oz of silver (Lyons,
1988), and the mining rate in the last decade has been about 800 t/day
of ore, averaging between 300 and 350 g/t Ag, 0.6 g/t of Au, 1.5% Zn
and 0.8% Pb (Aguirre-Díaz et al., submitted for publication; Albinson
and Rubio, 2001).
Fig. 5. Photomicrograph of representative primary, liquid–vapor fluid inclusions, hosted in sphalerite (A), quartz (B) and fluorite (C and D) crystals associated to ores of the Bolaños
Ag–Au–Pb–Zn Mining District.
The mining district lies in the N–S trending Bolaños Graben, which
extends about 180 km long and 20–30 km wide in the southernmost
part of the Sierra Madre Occidental silicic volcanic province (Fig. 4).
According to Aguirre-Díaz (2008) this structure is a graben-type
caldera, whose formation is due to the overlapping of the Basin and
Range extensional province and the Sierra Madre Occidental,
particularly during Oligocene–Miocene times.
The Ag–Au–Pb–Zn mineralization of Bolaños consists in N–S
trending veins that mostly develop in normal faults of the graben-
caldera wall. To a lesser degree, it also occurs as silicic breccia pipes
associated to post-collapse rhyolitic domes (Aguirre-Díaz et al.,
submitted for publication). The ores mostly consists of galena and
sphalerite with subordinated argentite and Ag-sulfosalts, in a gangue
of fluorite and quartz (Aguirre-Díaz et al., submitted for publication;
Lyons, 1988).
Among the main ore occurrences, the El Alacrán–San Francisco
vein, in the northern part of the Bolaños Graben, extends along
2800 m in the direction 30° NE, at least down to 900 m bps, and is up
to 15 m thick. At the deepest portion of the vein (below ~ 500 m bps),
a copper-rich zone with high gold grades occurs beneath the lead- and
zinc-rich zone (Aguirre-Díaz et al., submitted for publication).
Albinson and Rubio (2001) and Aguirre-Díaz et al. (submitted for
publication) noticed the role of boiling in ore deposition in the upper,
lead- and zinc-rich zone, since they found, locally, evidence of
heterogeneous trapping of a two-phase fluid.
Following the classification criteria of Albinson et al. (2001), the
Bolaños deposits can be ascribed to the low-sulfidation epithermal
type with deep boiling and intermediate salinity fluids (Aguirre-Díaz
et al., submitted for publication). Among the most important deposits
in Mexico with similar characteristics are Fresnillo, Guanajuato,
Pachuca–Real del Monte and Tayoltita. According to Aguirre-Díaz
et al. (submitted for publication), the hydrothermal activity that
produced ore deposition in Bolaños was related to the last stage of
caldera volcanism (Early Miocene).
3.2. Boiling model
Microthermometry data of 108 fluid inclusions analyzed in the
four selected samples of the El Alacrán–San Francisco vein were
 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125
Table 2
Summary of microthermometric data of fluid inclusions of the Bolaños Ag–Au–Pb–Zn epithermal deposit (Western Mexico).
Sample Deptha Ore zone Host # TH (°C)
mineral
min.
BAL-16 200 Ag–Pb–Zn Sph 25 137
AL-15 440 Q 22 224
AL-07 500 Au (± Cu) Fl 28 234
AL-03 540 Fl 33 250
Key: TH = temperature of homogenization, TM(ice) = temperature of ice melting (freezing point depression).
# = number of analyzed inclusions, min. = minimum value; aver. = arithmetic mean; max. = maximum value.
Abbreviations: Fl – fluorite; Q – quartz; Sph – sphalerite.
a
Approximate; in m below present surface.
plotted in Fig. 6, showing that the deeper the sample was taken, the
higher TH and the lower salinity (apparent) values were found. Thus,
the overall range of variation of TH and salinity is constrained between
sample BAL-16 (taken from 200 m bps), with TH of 137º–157 °C and
salinity of 9.2–10.9 wt.% NaCl eq., and sample AL-03 (taken from
540 m bps), with TH of 250°–279 ° C and salinity of 2.4–3.1 wt.% NaCl
eq. The general distribution of fluid inclusions in this plot follows a
trend typical of boiling (Fig. 3A), with a progressive increase in salinity
along with a TH decrease owing to the partitioning of salts into the
liquid phase during steam loss. However, according to the modeled
salinity–temperature paths, only the fluid evolution between samples
AL-15 (440 m bps) and BAL-16 (200 m bps) can be satisfactorily
explained by boiling; in other words, the mineralizing fluids should
have underwent boiling from depths not greater than 440 m bps. In
contrast, the fluid variations from the deepest samples (AL-03,
540 m bps; AL-07, 500 m bps) to AL-15 (440 m bps) cannot be
explained in terms of boiling, because the increase of salinity is
much greater than the expected considering solely the steam fraction
lost for the corresponding temperature drop. Individually, samples
AL-15 and AL-03 seem to show a dilution trend (exemplified in
Fig. 3B), probably reflecting intermittent, minor ingress of colder
fluids into the hydrothermal system.
According to what has been stated above, a temperature–salinity–
pressure–depth boiling profile was calculated from starting temper-
ature and salinity conditions yield by sample AL-15 (224 °C and
Fig. 6. Diagram showing the feasible salinity–temperature boiling paths (arrows),
modeled for the epithermal environment conditions using the mass and enthalpy
balance equations of Henley et al. (1984). Individual fluid inclusions analyzed in four
samples representative of the Alacrán–San Francisco vein of the Bolaños deposit have
been plotted by their ice-melting TM(ice) and homogenization temperatures (the
approximate depth below present surface of samples is: BAL-16, 180 m; AL-15, 420 m;
AL-07, 480 m; AL-03, 520 m). The differences of temperature and salinity between
samples AL-15 to BAL-16 is congruent with a boiling path of a rising fluid. On the other
hand, the fluid temperature and salinity variations from the deepest samples (AL-03
and AL-07) to AL-15 cannot be explained in terms of boiling, but they could reflect
pulses of high temperature and salinity.
123
TM(ice) (°C) Salinity
(wt.% NaCl eq.)
aver. max. min. aver. max. min. aver. max.
144 157 −7.3 −6.9 −6.0 9.2 10.4 10.9
232 241 −6.0 −5.3 −4.8 7.6 8.3 9.2
244 259 −4.8 −3.8 −2.0 3.4 6.1 7.6
262 279 −1.8 −1.5 −1.4 2.4 2.6 3.1
7.6 wt.%). These conditions correspond to the fluid inclusion with the
lowest TH, which was selected to avoid any effect on the TH due to any
vapor that may have been trapped, to some degree, if the inclusions
formed under boiling conditions (Taguchi and Hayashi, 1982). The
complete profile, with a temperature step of 2 °C, is presented in
Table 1, and the corresponding curves for salinity, density and
pressure are shown in Fig. 7. Additionally, the calculated thermal
profiles are plotted in Fig. 8.
Salinity shows an almost linear negative correlation (R2 = 0.999)
with respect to temperature; so that for the TH range of sample BAL-16
(137° to 157 °C), the expected salinity averages 9.0 wt.% and, if the
fluid will eventually reach the surface, salinity would attain 9.9 wt.%.
On the other hand, the vapor pressure vs. temperature curve fits a
polynomial (2°) curve with a positive correlation (R2 = 0.999).
The resulting temperature–depth profile (Fig. 8) was constructed
in two ways: (a) considering a liquid column without suspended
vapor bubbles, only taking into consideration the temperature
decrease and the corresponding increase of salinity, and (b)
calculating the effect of steam bubbles on fluid density and therefore
on the hydrostatic pressure. The calculated depth for sample AL-15,
which marks the beginning of boiling for the rising fluid, is of 256 m
considering a liquid column and of 435 m considering the effect of
suspended bubbles, being the last value much closer to the sampling
depth (440 m bps).
4. Suitability of the model and concluding remarks
The proposed model for salinity–temperature evolution, as plotted
in Fig. 6, permits to confirm or discard if a fossil hydrothermal system
underwent boiling, simply by comparison between the modeled
boiling paths and the trend of distribution of fluid inclusions from an
ensemble of samples taken at different depths of a vein.
We selected the Bolaños Ag–Au–Pb–Zn epithermal deposit to test
the suitability of the model, since previous works (Albinson and Rubio
Ramos Albinson and Rubio, 2001; Aguirre-Díaz et al., submitted for
publication) pointed out the prevalence of boiling during the active
life of this hydrothermal mineralization. The fluid evolution drawn by
the distribution of fluid inclusion data of Bolaños revealed that rising
mineralizing fluids should have undergone boiling, but from (present)
depths not exceeding 440 m bps (Fig. 6). Conversely, below this level
fluid evolution cannot be explained in terms of boiling and probably
accounts for the episodic injection of brines. In principle, this fact
would modify the previous deposit model for the Bolaños deposit,
which was apparently consistent with the “deep-vein with boiling”
type of Albinson et al. (2001). According to these authors, this
category, which would include many of the major epithermal deposits
in Mexico (e.g., Fresnillo, Guanajuato, Pachuca–Real del Monte and
Tayoltita), is characterized by having boiling stages at depths of
~1000 m or more and at temperatures of ~300 °C. However, our
results cast doubt on boiling having occurred at depths greater than
500 m, which must be taken into account for exploration purposes.
124 C. Canet et al. / Journal of Geochemical Exploration 110 (2011) 118–125
Fig. 7. Evolution curves for salinity, density of the liquid phase and pressure, calculated
for a boiling path between the fluid conditions represented by samples (A) AL-15 and
(B) BAL-16 (temperature from 224° to 137 ° C, salinity from 7.6 to 9.2%), from the
Alacrán–San Francisco vein of the Bolaños deposit.
Once identified by the above procedure a sample representative of
the beginning of boiling (or of the deepest level of the vein in which
boiling occurred), temperature–depth profiles can be calculated
taking as starting conditions the TH and apparent salinity values
obtained by fluid inclusion microthermometry in such sample
(Table 2). In this case, TH of liquid-rich inclusions can be taken as
the real temperature of the fluid (trapping temperature, Tt), since we
have confirmed that boiling occurred during fluid inclusion entrap-
ment (e.g. Wilkinson, 2001; Fig. 1). The resulting thermal profiles
allow to establish paleo-depths (under the water table when the
hydrothermal system was active) for the studied deposit (Table 1,
Fig. 8). In this study, we have shown that for paleo-depth calculation it is
necessary to consider the drop in fluid density that is caused by steam
bubbles. Neglecting this effect may lead to serious underestimations of
depth (of ~40–50% for fluid temperatures of 200° to 225 ° C; Table 1,
Fig. 8).
A difference between sampling depth (below the present surface)
and paleo-depth calculated by the proposed method could indicate
the level of erosion that has affected the deposit. In the case of
Bolaños, the calculated paleo-depth for the level in which boiling
started is very similar to the sampling (present) depth, thus indicating
that only the shallowest parts of the hydrothermal system may have
been eroded. This agrees with the relatively young, Early Miocene-age
of the Bolaños deposit (~75% of the epithermal deposits in Mexico are
Fig. 8. Boling-point curves corresponding to a rising hydrothermal fluid whose
temperature and salinity conditions evolve from those represented by AL-15 to BAL-16
samples (224° to 137 ° C, and 7.6 to 9.2%, respectively), of the Alacrán–San Francisco
vein of the Bolaños deposit. Both curves (A and B) were constructed taking into
consideration a progressive increase of salinity due to the steam loss during boiling, but,
in curve (A), depth was calculated considering a liquid column, without suspended
vapor bubbles, whereas in curve (B) the effect of vapor bubbles on fluid density and
therefore on the hydrostatic pressure were considered (Table 2). The parallel changes
in salinity, density and pressure are shown in Fig. 7. The calculated depth for sample AL-
15 is of 256 m considering curve (A) and of 435 m considering curve (B), being the last
value much closer to the sampling depth (440 m bps). Thus, neglecting the effect of
bubbles in fluid density may lead an underestimation of depth of ~ 40%.
Eocene–Oligocene; Camprubí and Albinson, 2006), and with the fact
that the host rocks of the mineralization are rhyolitic lavas and
breccias, very resistant to erosion.
Acknowledgements
Fluid inclusion microthermometry analyses were carried out in
Centro de Geociencias, UNAM. Graciela Herrera Zamarrón is thanked
for her assistance in the mathematical aspects included in this work.
Alfons M. Van den Kerkhof, Maria Luce Frezzotti and Pura Alfonso are
thanked for their helpful comments and suggestions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
doi:10.1016/j.gexplo.2011.04.005.
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