Journal of Geochemical Exploration 89 (2006) 138 – 142

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Evolution of mineralizing fluids in the Zn–Pb–Cu(–Ag ± Au) skarn

and epithermal deposits of the world-class San Martín district,
Zacatecas, Mexico
Eduardo González-Partida, Antoni Camprubí ⁎
Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla,
Carretera 57 km. 15.5, 76023 Santiago de Querétaro, Qro., Mexico
Received 28 July 2005; accepted 30 November 2005
Available online 9 March 2006

Abstract

Mineralizing fluids at the San Martín skarn show an evolution characterized by prograde and retrograde associations. The
prograde mineral associations consist of (1) a massive garnet zone, (2) a tremolite ± garnet zone, and (3) a late association of quartz,
sphalerite, calcite and fluorite lining the vugs in the garnet zone. The fluids of the prograde associations exhibit decreasing
temperatures of homogenization (Th) and variable salinities. The fluids of the massive garnet zone have salinities of ∼36 wt.%
NaCl equiv. and Th of 645 to 570 °C, corresponding to pressures of ∼1055 bar. At the tremolite ± garnet zone, Th range from 438
to 354 °C. In the late association at the endoskarn, the following evolution can be drawn: (a) salinities of 50 to 42 wt.% NaCl
equiv., and Th of 455 to 346 °C in quartz, (b) salinities of ∼46 wt.% NaCl equiv., and Th of 415 to 410 °C in sphalerite, (c)
salinities of 50 to 37 wt.% NaCl equiv., and Th of 479 to 310 °C in calcite, (d) salinities of 33 to 28 wt.% NaCl equiv. and of 24 to
22 wt.% KCl in fluorite, and (e) two types of fluids with salinities of ∼2 and 39 wt.% NaCl equiv. and Th ∼344 and 300 °C,
respectively, in later saccharoidal quartz segregations. The retrograde mineral associations comprise pervasive propylitic alteration
to carbonization, and mantos with sulfides. Fluids in epidote have salinities of ∼7.6 wt.% NaCl equiv. and Th of 287 to 252 °C, and
in calcite have salinities of 9.2 to 1 wt.% NaCl equiv. and Th of 188 to 112 °C. Fluids in the sulfide assemblages in the mantos have
salinities of 8 to 3 wt.% NaCl equiv. and Th ∼300 °C, with corresponding pressures of ∼94 bar. Fluids in late epithermal veins
close to the intrusive body have salinities of 10 to 5 wt.% NaCl equiv. and Th of 275 to 200 °C, and distal veins show salinities of 2
to 1 wt.% NaCl equiv. and Th of ∼160 °C.
© 2006 Elsevier B.V. All rights reserved.

Keywords: San Martín; Mexico; Zn–Pb–Cu skarn; Epithermal veins; Mantos; Fluid inclusions

1. Introduction and enrichment zones occur in the deposits. These

The San Martín mining district is located west of the
Zacatecas state in central-north Mexico (Fig. 1) and
contains skarn and epithermal deposits associated with
the same suite of intrusions. Late supergene oxidation
⁎ Corresponding author.
E-mail address: camprubi@geociencias.unam.mx (A. Camprubí).
0375-6742/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2005.11.050
deposits, especially the veins and oxidation zones, were
mined by the Spaniards between the 15th and 18th
centuries with average mill-head grades of 450 ppm Ag
and 0.5 ppm Au. At present, large mantos are mined,
with average grades of 5% Zn, 1% Cu, 0.5% Pb, and
150 ppm Ag. Total ore reserves, including mined ores,
are estimated at over 100 Mt, thus indicating that San
Martín is a world-class mining district. Previous work in
 E. González-Partida, A. Camprubí / Journal of Geochemical Exploration 89 (2006) 138–142 139

the area comprised mineralogic, geochemical, and 2. Local geology

structural studies (Aranda-Gómez, 1978; Rubin and
Kyle, 1988; Starling et al., 1997), but little work has The study area is located in the Sierra Madre
been done on the fluid geochemistry of the skarn and Occidental, in the highlands of the state of Zacatecas,
epithermal deposits, which is the aim of this paper. Mexico. The local stratigraphy includes the prominent

Fig. 1. Above: Location and geological map of the San Martín district, Northern Zacatecas state, Mexico, modified from Rubin and Kyle (1988) and
Starling et al. (1997). Below: Geologic cross section featuring the main orebodies in the district, adapted from Starling et al. (1997). Key: SMO =
Sierra Madre Occidental, SMS = Sierra Madre del Sur, TMVB = Trans-Mexican Volcanic Belt.
140 E. González-Partida, A. Camprubí / Journal of Geochemical Exploration 89 (2006) 138–142

Fig. 2. Photomicrographs of (A) grossular–andradite crystals at the prograde garnet zone, with sphalerite and calcite crystals lining intercrystal vugs;
(B) late-epithermal veinlet with native silver and with earlier bornite, chalcopyrite, and sphalerite crystals; (C) deep retrograde metallic mineralization
with chalcopyrite, bornite, sphalerite, and bismuthinite; (D) liquid-rich fluid inclusions with halite and sylvite daughter crystals, in prograde
assemblages; (E) liquid-rich fluid inclusion with a halite daughter crystal, from prograde assemblages; (F and G) liquid- and vapor-rich fluid
inclusions, respectively, from late retrograde assemblages. Key: Ag = native silver, Bi = bismuthinite, Bn = bornite, Cc = calcite, Cpy = chalcopyrite,
Gr = garnet (grossular–andradite), Sp = sphalerite, L = liquid, V = vapor.

Cuesta del Cura Formation, of Lower Cretaceous age,
and Middle Eocene intrusive and volcanic rocks. The
Cuesta del Cura Formation consists of gray and black
micritic limestones, uniformly bedded and 5 to 40 cm
thick, and contains interbedded, 3 to 5 cm thick lutite
beds. An increasing content in lutites upwards in the
sedimentary series is characteristic of the contact
between the Cuesta del Cura and the overlying Indidura
formations. These strata were intruded by the Cerro de la
Gloria granitic stock which varies from a granite to
quartz monzonite with biotite + hornblende and pyrox-
ene. The granitic stock has yielded a K–Ar biotite age of
46.2 ± 1 Ma (Rubin and Kyle, 1988). The Cerro de la
Gloria stock developed endoskarn and exoskarn zones,
with an external aureole of pervasive carbonization that
extends over 1 km away from the contact between the
granitic stock and the Cretaceous carbonate rocks
(Fig. 1). Rhyolite flows from the Cerro Prieto effusive
center are found SE of the deposit and cover an area of
3.7 km2, with a maximum thickness between 250 and
300 m. These flows were deposited after skarn
formation.
According to Starling et al. (1997), the ore deposits
are associated with a ∼N–S extension event that
postdated the Laramidic compression and predated the
Basin-and-Range extension. The stock is controlled by
two WNW–ESE striking sinistral transtensional fault
zones in the pre-Laramide basement, located north and
south of the intrusion that were reactivated during the
Laramide orogeny. The main fault zones striking NW–
SE also control the location of late stage epithermal vein
deposits.
3. Ore deposits
The skarn system comprises four prograde zones
(Aranda-Gómez, 1978) from the granitic stock out-
wards: (1) garnet–clinopyroxene zone ± hedenbergite
zone, (2) tremolite–garnet–wollastonite zone, (3) trem-
olite–actinolite–marble zone, and (4) saccharoidal
quartz–potassium feldspar and stockwork zones. The
retrograde associations include: (1) propylitic alteration,
with epidote, vesuvianite, chlorite, calcite and minor
quartz, (2) silicification adjacent to epithermal veins,
and (3) calcite veinlets and pervasive carbonization,
with minor chalcedony, that represent the latest
hydrothermal event in the district. The deposition of
ore minerals occurred from the beginning of retrogra-
dation and continued with the formation of epithermal
veins.
Between mining levels 32 and 34, mantos up to 60 m
thick formed between the skarn and the host carbonate
rocks that extend from the skarn and lead into veins
upwards at about the height of level 16. Thus, the roots
of veins like Ibarra, Ramal Ibarra, and San Marcial are
actually replacement mantos formed initially in a skarn
environment (Fig. 1). Other vein systems are found at
greater distances from the granite stock, like the
 E. González-Partida, A. Camprubí / Journal of Geochemical Exploration 89 (2006) 138–142 141

Esmeralda, Pollo–Pollito, Noria de Pantaleón, Refugio,

Extensión Ibarra, Estructuras E–W, Estructura NW, and
San Antonio–Belén veins. The manto-rooted veins have
strong bottom to top metal zonations, being (1) rich in
Cu ± Zn ± Bi in their deep portions (Fig. 2C), (2) rich in
Ag–Au–Pb–Zn in intermediate portions (Fig. 2B), and
(3) rich in Hg–Sb in shallow portions. There are also
later Au-rich veins with quartz and Fe–Mn oxides.

4. Fluid inclusions

4.1. Prograde fluids

Fluid inclusions suitable for microthermometry from

prograde zones were found in garnet, tremolite,
sphalerite, fluorite, quartz, and calcite. Sphalerite,
calcite and fluorite are interstitial to garnet crystals
(Fig. 2A). All the fluid inclusions in these minerals
contained halite as a daughter mineral (Fig. 2E) and
some also have sylvite (Fig. 2D). The fluid inclusions
are mostly 10 to 30 μm in size. Salinities of fluid
inclusions with daughter minerals are calculated using
the temperatures of solubilization of these minerals. In
the garnet + hedenbergite zone, inclusion fluids are
L + V + SNaCl, and fluid inclusions in garnet have
temperatures of homogenization (Th) that range from
645 to 570 °C, and salinities that range from 36 to 34 wt.
% NaCl equiv. Trapping pressures under lithostatic
conditions are estimated at ∼1052 bar. Fluid inclusions
in sphalerite have Th that range from 415 to 410 °C and
salinities around 46 wt.% NaCl equiv. Fluid inclusions
in calcite have Th that range from 479 to 310 °C and Fig. 3. Above: Th versus salinity diagram showing the average values
salinities that range from 50 to 37 wt.% NaCl equiv. for the analyzed samples, grouped according to the main mineral
associations. Below: Correlation diagram between temperature and
Fluid inclusions in fluorite have salinities that range
depth of mineralizing fluids in the San Martín district, as derived from
from 33 to 28 wt.% NaCl equiv. and from 24 to 22 wt.% the present fluid inclusion study, showing the phase relations in the
KCl; no Th values were obtained in fluorite because the system water–NaCl, at lithostatic pressure, and key isosalinity lines
inclusions decrepitated above 350 °C. Fluid inclusions (30, 50 and 70 wt.% NaCl equiv), adapted from Fournier (1999). It
in quartz have Th from 455 to 346 °C and salinities that includes the envelopes of the data drawn from fluid inclusions in this
study. Key: L = liquid, S = solid (halite), V = vapor.
range from 50 to 42 wt.% NaCl equiv.
In the tremolite ± garnet ± calcite zone fluids are
L + V + SNaCl, and fluid inclusions in tremolite have late quartz of this association have a bimodal distribu-
Th from 438 to 354 °C and salinities from 46 to 45 wt.% tion between a relatively high temperature and low
NaCl equiv. Only the saccharoidal quartz exhibits salinity fluid (from 358 to 359 °C, and from 3 to 2 wt.%
evidence for boiling, with L + V + SNaCl, V ± L, and NaCl equiv.) and a relatively low temperature and high
L + V fluid inclusions within the same fluid inclusion salinity fluid (from 320 to 288 °C, and from 39 wt.%
assemblages (Fig. 2F and G), with average Th ∼479 °C, NaCl equiv.).
and the highest salinities of the deposit, from 37 to
50 wt.% NaCl equiv. This zone is considered to be 4.2. Retrograde fluids
transitional between the prograde and retrograde
assemblages, and boiling may be the result of a switch In sulfide-bearing mantos, between mining levels 22
in the pressure regime, from lithostatic to hydrostatic and 34, fluid inclusions in sphalerite and quartz have Th
conditions. As a result of boiling, fluid inclusion data in around 300 °C, salinities that range from 8 to 3 wt.%
142 E. González-Partida, A. Camprubí / Journal of Geochemical Exploration 89 (2006) 138–142
NaCl equiv., and corresponding pressures under hydro-
static conditions of ∼94 bar. In more shallow levels,
between levels 16 and 12, proximal epithermal veins are
rooted in mantos and exhibit 275 to 200 °C isotherms in
their upper portions. The salinities of inclusion fluids
vary from 10 to 5 wt.% NaCl equiv. in their deep
portions, to 5–3 wt.% NaCl equiv. upwards. Distal
veins, in contrast, have Th from 160 to 112 °C and
salinities of 2 to 1 wt.% NaCl equiv. In the Noria de
Pantaleón epithermal Au vein, south of the Cerro de la
Gloria stock, fluid inclusions in quartz and calcite have
Th from 225 to 135 °C and salinities of 10 to 0.2 wt.%
NaCl equiv. Fluid inclusions in epidote from the
propylitic alteration have Th from 287 to 252 °C and
salinities around 7.6 wt.% NaCl equiv. North of the
district, we carried out a systematic sampling of the
pervasive carbonization zone close to the Cerro
Papantón. Fluid inclusions in calcite from that zone
have Th from 188 to 112 °C and salinities that range
from 9.2 to 1 wt.% NaCl equiv. that positively correlate
and thus indicate fluid mixing in this system, possibly to
the downfall of carbonic fluids as hydrothermal activity
waned.
5. Conclusions
The skarn deposits of the San Martín district in
Zacatecas exhibit a “classical” evolution of mineralizing
fluids (Fig. 3), from
(1) high-salinity (∼40 to 50 wt.% NaCl equiv.) and
high-temperature (b ∼650 °C) magmatic fluids
during the prograde stage to
(2) moderate-salinity (∼10 wt.% NaCl equiv.) and
lower-temperature (∼300 °C) magmatic and
meteoric fluids, at the beginning of the retrograde
stage, to
(3) moderate- to low-salinity (9 to 1 wt.% NaCl
equiv.) and moderate- to low-temperature
(b 290 °C) fluids, during the retrograde stage,
probably involving an increasing amount of
meteoric and formation waters that had interacted
at depth or shallower levels.
Using the structural, mineralogical, and fluid inclu-
sion data (temperature, pressure, and salinity), these
deposits can be classified as proximal to proximal–distal
(Einaudi et al., 1981; Einaudi and Burt, 1982; Sillitoe,
1995), evolving from a deep to a shallow skarn under
lithostatic conditions, and to proximal and distal
epithermal deposits under hydrostatic conditions, prob-
ably of both intermediate and low sulfidation types. The
evolution of inclusion fluids traces a decompression
path from lithostatic to hydrostatic conditions (Fig. 3):
(1) fluid inclusions from the prograde skarn zone have a
minimum pressure of 1055 bars, (2) fluid inclusions
from saccharoidal quartz and stockwork zones have a
minimum pressure of 800 bars, (3) the transition from
the saccharoidal quartz zone and the manto ores is
marked by an average pressure of ∼400 bars, coinciding
with the ductile–brittle and lithostatic–hydrostatic
transitions, and (4) carbonization and late Au epithermal
veins formed from 200 to 72 bars.
Acknowledgements
This work was partially funded with the Conacyt
research project 46473. Special thanks to Industrial
Minera México S.A. de C.V. and the staff at San Martín
for their assistance. We also gratefully acknowledge the
critical reviews of Daniel Kontak and an anonymous
referee.
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