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2007 2902 RMCG 32 02 00254 PDF
2007 2902 RMCG 32 02 00254 PDF
Vassallo, L.F., Aranda-Gómez, J.J. Solorio-Munguía, J.G., 2015, Hydrothermal alteration of volcanic rocks hosting the Late Jurassic-Early Cretaceous San Nicolás
VMS deposit, southern Zacatecas, Mexico: Revista Mexicana de Ciencias Geológicas, v. 32, núm. 2, p. 254-272.
formación de sericita, clorita y de minerales arcillosos. Posteriormente, are related with high-temperature magmatism within well-defined
una fuerte alteración cuarzo-pirita se relaciona con la mineralización. thermal corridors, as those described by Piercey (2011), associated
La zona alterada del bloque del piso de San Nicolás muestra cambios with extensional geodynamic settings in volcanogenic environments,
geoquímicos sistemáticos con una variación de la distancia a la proximi- Sillitoe, (1982). VMS deposits are determined by tectonic regime
dad a los cuerpos minerales. Esto incluye una disminución de Na y ele- change, evolution of the continental lithosphere composition, and
vación de Mg, S, Al, (AI=100*[MgO+K2O]/[MgO+K2O+Na2O+CaO]), irreversible transformations occurring in the Earth´s atmosphere,
CCPI(CCPI=100*[MgO+FeO]/[MgO+FeO+Na2O+K2O]), Mo, Bi y As. hydrosphere, and biosphere, Dergachev and Eremin, (2008).
Estas características geoquímicas pueden ser usadas en la exploración Hydrothermal alteration assemblages of VMS have been investi-
por sulfuros masivos (MVS) como guías hacia las menas, en la escala gated from mineralogical, textural, petrophysical, and chemical per-
de distrito y como vector discriminador de prospectos hidrotermales de spectives (e.g., Starostin, 1979, 1984; Franklin et al., 1981; Starostin and
sistemas diagenéticos alterados no prospectivos a escala regional. Dergachev, 1982; Lesher et al., 1986; Eastoe et al., 1987; Morton and
Franklin, 1987; Gemmell and Large, 1992; Large, 1992; Huston, 1993;
Palabras clave: México; alteración; rocas volcánicos del Jurásico; MVS. Khin et al., 1996; Paulick et al., 2001; Schardt et al., 2001; Solomon and
Gaspar, 2001; Starostin et al., 2002). Much of this research has con-
tributed to the knowledge of composition, mineralogical and chemical
INTRODUCTION zonation of footwall alteration systems below massive sulfide systems,
which are the sites of intense fluid-rock interaction in the upflow or
The western North American Cordillera hosts important gold- vent zone below the sea floor. Due to metamorphism, tectonic deforma-
bearing quartz veins, silver-bearing quartz veins, volcanogenic massive tion, and lack of access to alteration pipes, few studies have focused on
sulfide (VMS) deposits and Zn-Cu-Pb-Ag skarns systems including the stringer zones of VMS and their alteration assemblages (Lydon, 1988).
silver belt of central Mexico, the Mother Lode of southern California, San Nicolás is a Late Jurassic-Early Cretaceous, (Danielson, 2000,
and counterparts in British Columbia and southeastern Alaska, to the Iriondo et al 2003, Mortensen et al 2008), stratiform, polymetallic
Klondike district in central Yukon. All these veins, VMS and skarns massive sulfide deposit hosted within a felsic-basic lava-dominated
systems are structurally controlled by major fault zones or weakness sequence in southern Zacatecas, Mexico. The deposit has a total
zones, which are often reactivated terrane-bounding sutures that mineral resource of 99 Mt with 1.36 % Cu, 1.64 % Zn, 0.41 g/t Au and
formed in orogens built during accretion and subduction of terranes 24 g/t Ag, (Johnson et al., 2000). The San Nicolás ore consists of vari-
along the continental margin of North America, and in México along able proportions of pyrite, sphalerite, galena and chalcopyrite, with
the faults (Figure 1) related to the opening of the Gulf of México, (de gangue chlorite, tremolite, calcite, dolomite, barite, magnetite and
Cserna, 1976a, Pindell, 1985, Vélez, 1990, Vassallo, 2003, Vassallo et quartz. Massive and semi-massive sulfides occur in a single horizon
al., 2004, Piercey, 2011, Pindell et al., 2012). Mineralization ages span at the stratigraphic contact between rhyolite domes in the hanging-
mid-Jurassic to early Tertiary (Vassallo et al., 2000, 2004). The VMS wall and a volcano-sedimentary sequence dominated by mafic lavas
26°
Peñasquito
24°
Camino Rojo
16°
106° 104° 102° 100° 98° 96° 94°
0 400 800
800
kilometers
Figure 1. Ore deposits of Central Mexico. With Jurassic-Cretaceous faults modified after De Cserna (1976a), Vélez (1990), and others.
in the footwall. This rhyolite horizon is referred to the “San Nicolás ages for three concordant analyses (146.5±2.2 Ma) dated using
favorable unit” in this paper. Below the San Nicolás deposit there is U-Pb zircon methods (Mortensen et al.,2008). The upper La Virgen
a texturally, mineralogically and geochemically diverse strata-bound Formation comprises lithic sandstone and graywacke with some
alteration zone that extends across the controlling mineralization fault basaltic lava (Table 1) with a hornblende age of 117.94 Ma (Iriondo
zone into the footwall at least 200 m down, with gradational contacts et al., 2003), synvolcanic intrusions, and various volcaniclastic and
to the surrounding unaltered or weakly altered volcanic rocks. sedimentary rocks. Geochemical data suggests that the volcanic rocks
It has been recognized (Smirnov, 1944, 1963, 1968, 1976; Yakovlev, of the Chilitos Group were emplaced in an active continental margin
1959) that footwall alteration zones associated with volcanic massive (Schandl and Gorton, 2002). The Chilitos Group was wide folded and
sulfide (VMS) deposits may have a stratabound geometry or a took a tilted position during regional normal faulting in the Aptian.
discordant, pipelike shape. A comparative study of Australian VMS The area probably represents the northeastern part of a large NW-SE
(Large, 1992) and VMS in Russia and Kazakhstan (Yakovlev, 1959; trending overthrust structure, and in some places the Chilitos Group
Smirnov, 1976; Smirnov and Gorzhevskii, 1978; Starostin, 1984), overthrusts the Lower Cretaceous limestone of the Proaño Group
showed that most deposits have stratabound and semiconformable (Trejo, 2001), as seen in the Town of Fresnillo (de Cserna, 1976b). The
footwall alteration zones. Well-defined, pipelike alteration zones, such regional metamorphic grade increases from sub-greenschist in the
as those associated with Precambrian deposits of Noranda-Canada, eastern part to greenschist in the western part of the Zacatecas state
(Sangster, 1972; Barrett and MacLean, 1994; Shriver and MacLean, (Vassallo and Solorio-Munguia, 2005).
1993), Paleozoic deposits of Rudnii Altai (Yakovlev, 1959; Smirnov, In early Tertiary, the Saucito and Peñón Blanco plutons were
1976; Smirnov and Gorzhevskii, 1978) and Tertiary Kuroko deposits, emplaced (Aranda et al., 2007), which postdates the end of Laramide
(Ohmoto and Skinner, 1983; Shikazono et al., 2008), are common deformation (Aranda et al., 2007; Vassallo et al., 2008). Its porphy-
worldwide. ritic texture, with beta quartz pseudomorphs and euhedral sanidine
The study of stratabound alteration zones is relevant for base phenocrysts suggests a shallow subvolcanic intrusion. The absence of
metal exploration and for research in rock-water interaction processes. penetrative fabrics associated with folding and/or shearing indicates
Because of their large extent below the deposit, stratabound alteration a post-tectonic emplacement. A 40Ar/39Ar age of 49.5 Ma constrains
zones provide better exploration criteria than the spatially confined the end of Laramide deformation in this area (Aranda et al., 2007).
alteration pipes. However, in contrast to pipelike alteration zones, Tertiary rhyolitic rocks from 32 to 27 Ma cover the mining district.
stratabound footwall alteration zones typically lack clear boundaries Samples MC-14, 15, 20, 33 and P5-95 (Table 1) provide several ages
of mineralogical zoning that increases the difficulty for massive sulfide for the known volcanic episode at Pinos, Zacatecas, 20 km east of San
exploration. Nicólas, (Aranda et al., 2007).
Careful examination of geological, petrographical, and geochemical A later phase of Miocene extensional faulting is associated with the
data is required to discriminate the large-scale alteration zones gener- NE-SW faults structures that formed large grabens and cut the VMS
ated by general mineralizing hydrothermal activity from alteration deposits and Eocene clastic units (Figure 3).
related to syn-volcanic seafloor alteration processes.
This paper provides a regional geological appraisal and a detailed
description of alteration observed at San Nicolás ore deposit, includ- GEOLOGICAL SETTING OF THE SAN NICOLÁS
ing textural, mineralogical and geochemical characteristics. Several ORE DEPOSIT
geochemical features like CCPI, AI, Na2O, show systematic variations
with increased proximity to the massive stratabound sulfide deposits. San Nicolás ore deposit is the largest known VMS deposit in central
Mexico. The San Nicolás mining district contains several stratiform,
mound or lense-shape orebodies, which extend over an area of more
REGIONAL GEOLOGY than 500 km2, at the middle of the Chilitos Group. The San Nicolás
deposit and its host-rock succession are examined here in 5 drill core-
The San Nicolás deposit is located in a NW-SE-trending belt based cross sections through the deposit (Figures 3 and 4).
of deformed Jurassic-Cretaceous marine sedimentary and volcanic A model for the paleofacies architecture of the host-rock suc-
rocks defined in this paper as the Chilitos Group in the central part of cession is reconstructed based on structural-volcanic analysis. The
Mexico (Figure 2). The lower unit of this group was defined first by de San Nicolás deposit formed on a paleochannel or graben produced
Cserna (1976a) as Chilitos Formation. Discontinuous outcrops over by Jurassic-Cretaceous growing longevity faults, that act as feeders
a distance of more than 300 km (Zacatecas to Guanajuato) expose a of marine bimodal-felsic volcanic rocks as Kuroko type deposits of
grossly conformable stratigraphic succession, up to 1.5 km thick, with Piercey, (2011), one of them La Panza fault is the principal control of
gentle folding and NW 45° axis orientation. The group was intruded the mineralization (Figures 4, 5). This geologic setting is analogous
by Jurassic to early Tertiary plutons (El Saucito, Peñon Blanco and to the environment of the modern PACMANUS hydrothermal field,
Comanja type plutons). Mesozoic rocks are for the most part covered Manus Basin, Papua New Guinea, (Binns and Scott, 1993), and oth-
by the Tertiary rhyolitic La Bufa Formation and others minor volcanics ers described by Schulz, (2012). Lydon, (2010) also recognized the
by semiconsolidated alluvium. important role that have the synsedimentary faulting and the growing
The Chilitos Group was divided into three conformable formations longevity faults that control the mineralization also in Sedex (VMS
(Vassallo, 2012). At the base is the Arroyo Chilitos Formation, (de variant) deposits at B.C. Canada.
Cserna, 1976b), which consists of dominantly basaltic to andesitic sills The footwall alteration zone at San Nicolás is laterally continuous
and lavas, similar to those described at Guanajuato, (Vassallo, 1988a, along the strike extent of the deposit and extends for at least 200 m
1988b; Vassallo et al., 1989, Freydier et al., 1997, 2000, Vassallo and into the hosting volcanic rocks. Nevertheless, Larson (1984) found in
Reyes-Salas, 2007, Aranda-Gómez et al., 2012). the footwall andesitic rocks at Bruce VMS deposit, Arizona, that the
The overlying San Nicolás Formation mainly consists of rhyolitic alteration zone extends for at least 400 m away from the ore lenses.
lavas, synvolcanic intrusions and volcaniclastic rocks. The crystalliza- Contacts with the surrounding unaltered basalts are gradational.
tion age of a rhyolite sample is given by the total range of 206Pb/238U Moderately altered rhyolite represents the bulk of the footwall altera-
FRESNILLO
FRESNILLO
23°00´
SALINAS HIDALGO
SAN NICOLÁS
Quaternary sediments
22°30´
Miocene sediments
Oligocene rhyolites
Oligocene andesites
REAL DE ANGELES
Paleocene sediments
Ks-Ti granites
PINOS
K limestones and sediments.
22°15´
Js-Ki volcano-sedimentary rocks
Ore deposits
103° 00´ 102° 45´ 102° 30´ 102° 15´ 102° 00´ 101° 45´ 101° ´30 101° 15´
257
Hydrothermal alteration of the San Nicolás VMS deposit, Zacatecas, Mexico
Vassallo et al.
Table 1. Age Determinations of rocks. Modified after Aranda-Gómez et al, barite with disseminated sulfides represent peripheral, low-temperature
(2007). zones of the hydrothermal system (Huston and Large, 1987).
The structural geology of the San Nicolás area was examined in
Sample Material %K 40
Ar* %Ar* Age (Ma) 2s
detail by Johnson et al. (2000) and Vassallo (2003). Two generations
MC-14 San 6.205 7.677 81 32.32 3.1 of faults have been recognized. A NW-trending pattern of faults of
6.191 7.710 72 Jurassic-Cretaceous age cut the footwall rhyolite rocks into an apparent
8.404 78 hanging wall position (Figure 3). NW trending faults structures have
7.620 87 been recognized at San Nicolás, for example the so called La Panza
P5-95 wr 5.070 0.583 94.8 30 3.0
Jurassic-Cretaceous growing fault, (Figures 5, and 6) after Johnson
0.585 0.585 95.1
et al., (2000). The San Nicolás mining district is cut by a second NE–
striking group of normal faults (Miocene Basin and Range structures
MC-15 San 8.660 9.450 91 28.67 1.80 of Vassallo, 2003; Figure 3).
8.446 9.783 88
K-Ar Data
9.270 81
9.904 88 ALTERATION FACIES AND GEOMETRY OF THE
MC-33 San 4.864 6.414 76 28.7 1.4 ALTERATION ZONE AT SAN NICOLÁS
4.682 6.225 64
5.456 78 Alteration at the San Nicolás deposit is mineralogically and textur-
ally diverse and several alteration facies have been defined here on the
MC-20 San 6.185 6.567 77 27.28 1.2
basis of dominant mineral assemblages and alteration intensity with
6.265 6.660 72
variable proportions of quartz, muscovite, chlorite, epidote, tremolite,
6.677 66
calcite, K-feldspar, and pyrite, (Figures 6, 7). Alteration facies is a
6.691 68
strictly descriptive term as proposed by Riverin and Hodgson (1980),
Age method Age (Ma) and Vassallo (2003). In this paper alteration facies refers to rocks with
Ar/39Ar Data
To Zacatecas
200000E
198000E
Q
49
Q
S. CORAZÓN
# SCORPIÓN
To San Lu
is Potosí
#
Q
2506000N
DESQUITE NORTH
#
#DESQUITE
Q Q
2504000N
#
TEPOZÁN
TEPOZÁN SW
# #
LA VIRGEN
Q
Q Q
Q
2502000N
QUATERNARY
#SAL-132 LOW ZONE Q
TERTIARY
Quaternary cover undivided.
##
Q Cherts, sediments and tuffs.
XLT
SAN NICOLÁS LOW
2500000N ZINC ZONE XLT Diorites,mafic flows.
SW SECTION MVS Hornblende basalts. (117.94 M).
JURASSIC ORE CONTROLLING MVS Porphyritic basalts.
STRUCTURES MVT Mafic flows, sediments.
Rhyolite flows and felsic intrusions
Q RFD (VMS related) (146.5 M).
3
MIOCENE BASIN AND RANGE MVT Porphyritic mafic flows and tuffs.
STRUCTURES
QRY Quartz rhyolites (148.9 M).
# Ore Deposits or prospects.
194000E
3 Roads.
Figure 3 . Geological map of the San Nicolás area. Modified after Johnson et al. (2000).
5. Disseminated tremolite and patchy carbonate-tremolite-chlorite rics. This facies is dominantly siliceous with 5 to 20 % (modal) pyrite
(Ab-calc-ep) alteration facies (Figure 7) exist sporadically in the foot- in disseminated grains and irregular veins. The total phyllosilicate
wall alteration zone, generally in the top of the rhyolite lava and in content is <20 % and proportions of muscovite, chlorite and biotite
association with the tectonic breccias of the San Nicolás sulfide SW are variable (Figure 8).
lenses (Figures 6, 7). Herrmann and Hill (2001) interpreted this type
of alteration facies as representing metamorphosed hydrothermal
carbonate-chlorite-quartz alteration facies. GEOCHEMISTRY OF ALTERATION FACIES
6. Intense, quartz-pyrite (silica alteration and cpy-py stringers) al-
teration facies, (Figure 7) develop stratiform bands around the massive This section examines the major and trace element compositions
sulfides and discordant zones within the footwall, that are interpreted of the variably altered volcanics for San Nicolás deposit. Representative
as the main fluid pathways during mineralizing hydrothermal activ- analyses of least altered footwall rhyolite, quartz-eye porphyry, hang-
ity. Apart from relict, partly recrystallized quartz phenocrysts, the ing wall dacite and the principal alteration facies are presented in
quartz-pyrite alteration facies retains no primary mineralogy or fab- Table A1 (in the electronic supplement).
EARLY CRETACEOUS
Mafic Flows Volcaniclastic sediments and tuffs (TUF)
TUF-50 TUF
The unit comprises mafic flows, fine to coarse grained volcaniclastic rocks,
and minor siliceous sediments, greywackes. 50 meters.
Figure 4. Stratigraphic columm VMS San Nicolás. Modified after Johnson et al. (2000).
Methods from Johnson et al. (2000) and quartz-eye porphyry (Mortensen et al.,
Whole-rock chemical analyses were obtained from 100 samples 2008). These analyses were performed at the ACME Laboratory using
of altered footwall volcanics and hanging wall rhyolites (Table A1). a combination of ICP-OES for major elements, XRF on pressed powder
Crushed samples of drill core (quarter core splits, 10 cm long) were pellets for Zr and Ba, and atomic absorption spectroscopy (AAS) for Cu,
pulverized in a tungsten carbide mill. Major elements were measured Pb and Zn. Furthermore, supplementary analyses of altered volcanic
by X-ray fluorescence spectrometry (XRF) on fused discs and pressed rocks in diamond drill holes (DDH) SN-25, SN-35-37 and SN-40-41,
powder pellets at the ACME Laboratory in Vancouver, Canada. (Table A1) were analyzed by ICP-OES for major elements, ICP-MS
Concentrations of the trace elements (Ag, Bi, Cd, Sb, Cs, Tl, and U) and INAA for trace elements, XRF on pressed powder pellets for Zr,
were determined by ICP-MS, (0.5 gm sample leached with 3 ml 2-2-2 AAS for Cu, Pb, and Zn, and Leco (infrared spectrophotometry) for S.
HCl-HNO3-H2O at 95 oC for one hour, diluted to 10 ml), REE by LiBO2
fusion, ICP/MS finished, at the same laboratory. Major element geochemistry
Additional data were compiled from previous studies. These The altered mafic rocks show large variations in the concentra-
included analyses of carbonate-tremolite-chlorite alteration facies tions of Na, Ca, Mg and Fe (Figure 7, Table A1, DDH SN-25, samples
2000 m.
Faults
1900 m.
Drills SAL-25
GEOLOGY
1800 m. Tertiary Volcanics
Mafic Flows-Volcaniclastic sediments and tuffs (TUF)
Mafic Flows and Breccias (XLT)
1700 m. Mafic Flows and Sediments (MVS)
Rhyolite Flow-Dome (RFD)
Massive Sulfide (MS)
Mafic Volcanics (MVT)
1600 m.
Quartz Feldspar rhyolite (QRY)
Ore-Brecias
Graphitic Mudstones (Gsed)
1500 m.
Figure 5. Cross section (SW-NE), showing the ore body and the growing fault La Panza at San Nicolás.
BSN-28-31). Least altered mafic rocks are within Mg and Fe average the ore body), which is related to a combination of carbonate (dolo-
and contain between 3 and 8 wt % Na2O+CaO, which is within the mite) and chlorite (Figures 9, 10). Samples of quartz-eye porphry have
range typical for fresh modern mafic volcanics. Increasing alteration MgO+Fe2O3 values mainly between 6 and 10 wt % and their Na2O+CaO
is coupled with a gradual decrease in Na2O and CaO, culminating content ranges between <1 and 4 wt %, (BSN-05-43) overlapping with
in intensely altered basalts having Na2O+CaO values < 1.04 wt % least altered, weakly altered, and moderately altered footwall rhyolite.
(sample BSN-45). This trend is indicative of plagioclase destruction The alteration facies of the San Nicolás deposit can be geochemical-
and formation of muscovite (sericitization). Intense pyritic alteration ly distinguished in one diagram, which utilizes two multielement ratios
facies is characterized by high MgO+FeO values, commonly between to monitor relative changes in the concentrations of MgO, FeO, K2O,
3 and 20 wt % (up to 36 wt %, sample BSN-24), due to the abundance Na2O and CaO (the alteration boxplot; Large et al., 2001; Figures 9, 10).
of pyrite and chlorite. The calcareous alteration facies show extreme The alteration index (AI = 100*[MgO+K2O]/[MgO+K2O+Na2O+CaO];
CaO and MgO enrichment (samples BSN-11-12, BSN-76-81, above Ishikawa et al., 1976) quantifies Ca and Na depletion and enrich-
? ? ? ? ?
+100 m. Graphitic mudstones (Gsed) F. Zacatecas
Legend Rhyolites and tuffs (Tcg) Mafic flows and sediments (MVS) Graphitic mudstones (Gsed)
Mafic flows volcaniclastic sediments Rhyolite flow-dome (RFD) Massive sulfide (MS)
and tuffs (TUF)
Mafic volcanics (MVT) High alteration zone
Mafic flows and breccias (XLT)
Figure 6. Model for the volcanic structure of the San Nicolás host-rock succession. Cross section SW-NE.
Unaltered
2000 m.
SAL-25 Ab-calc-ep
1500 m.
0 100 m Faults
Drill hole
Figure 7. Alteration facies at the San Nicolás deposit. Cross section SW-NE.
ment relative to Mg and K. The AI increases as a result of plagio- with the least and weakly altered footwall rhyolites and mottled altera-
clase destruction or chlorite, muscovite, and K feldspar formation. tion facies (Figure 10).
In contrast, relative K depletion due to K-feldspar alteration or
Ca enrichment associated with carbonate alteration results in low AI Immobile trace element ratios— constraints on primary geochemistry
values. On the other hand, the carbonate-chlorite-pyrite index CCPI Geochemical discriminant diagrams are relatively common for
=100*[MgO+FeO]/[MgO+FeO+Na2O+K2O]; measures total alkali mafic volcanic rocks (Pearce and Cann, 1973; Winchester and Floyd,
depletion relative to Mg and Fe enrichment associated with chlorite 1977, and Wood, 1980). Discriminant diagrams are commonly (al-
and pyrite formation and dolomite- and/or ankerite-rich carbonate though not exclusively) based on elements that are considered to be
precipitation. A combination of both indices in the boxplot (Figure 10) immobile under most geologic conditions. These include selected
enables discrimination of the main alteration assemblages and separates major, trace, and rare earth elements. Some well-known discriminant
unaltered or weakly altered samples, representing background compo- diagrams use absolute concentrations of element pairs such as Zr-Y, Nb-
sitions, from samples with hydrothermal alteration (Large et al., 2001). Y, Zr-Nb, Zr-Ti, Th-Ta, Th-Yb, Th-Hf, and La-Yb, whereas others use
Least altered footwall volcanic rocks have AI values between 28 element ratios. Because the behavior of some elements is comparable
and 36 and CCPI values between 44 and 64 (Figure 10), reflecting (i.e., Zr and Hf, Nb and Ta, Y and Yb), these elements are commonly
relatively high, primary concentrations of alkalis and low Fe and Mg used on diagrams, depending on the preferred analytical technique. In
concentrations (samples BSN- 26-27-28). order to avoid common geochemical problems associated with mass
In contrast, intensely altered, pyrite-rich rhyolites plot in the up- loss and mass gain caused by extensive hydrothermal alteration of the
per right-hand corner of the boxplot (AI: >90, CCPI: 50–95). BSN-29 host volcanic rocks around VMS deposits, the diagrams presented are
(CCPI=80, from 35 m to ore body), BSN-15 (CCPI=81.8 from 100 based on element ratios, rather than on element concentrations (Gorton
mto the ore), BSN-77 (CCPI=75.6 from 80 m to the ore), and BSN-48 and Schandl, 2000, Schandl and Gorton, 2002).
(CCPI=78.8 from 83 m to ore body). The large range of CCPI is related A Zr/TiO2-Nb/Y discrimination diagram (Figure 11) shows that
to variations in the proportions of chlorite, biotite and muscovite. immobile element data are consistent with the classification of volcanic
The mottled alteration facies has intermediate AI and CCPI rocks of San Nicolás (Winchester and Floyd, 1977). Hanging wall ore-
values, partly overlapping the fields for the least altered rhyolite and related rhyolite flow-dome (RFD) plots in the field for rhyolite despite
pyrite-rich alteration facies. Samples of the carbonate alteration fa- the extensive modifications of bulk-rock composition due to alteration.
cies plot along the upper boundary of the diagram (CCPI >90) and This suggests that rhyolite was a typical acid rock essentially homoge-
the large spread in AI values reflects variations in the proportions of neous in primary composition prior to hydrothermal alteration. The
carbonate, chlorite, and tremolite. Samples of the quartz-K feldspar immobile element signature of hanging-wall dacite is similar to ratios
alteration facies overlap with samples of the mottled alteration fa- of fresh volcanics of dacitic and rhyodacitic composition. Samples of
cies and define a trend toward the composition of K feldspar. Most quartz-eye porphyry also plot in the field for dacite and rhyodacite
samples of the hanging-wall dacite and a few samples of weakly al- because of their lower Zr/TiO2 ratios compared to footwall rhyolite.
tered footwall rhyolite have low AI values (<20), which is consistent Samples of footwall strong chl-py-ser K-feldspar plot in the field for
with albite alteration. Samples of quartz-eye porphyry show a wide basaltic and andesite-basaltic rocks because of their lower Zr/TiO2
distribution in the alteration box-plot, with data points overlapping ratios compared to hanging-wall weak chl-ser mafic rocks.
a) b)
5 6
c) d)
75a 75b
e) f)
10 11
Figure 8a. Textures of volcanics at the San Nicolás deposit. Altered mafic volcanic rocks. a) BSN-05- depth 526 m (MVT), py, sericite, calcite, chlorite; b) BSN-6-
depth 501 m (MVT), py, sericite, calcite, chlorite; c) BSN-75 a- depth 414 m (MVT), py, sericite, chlorite; d) BSN- 75 b- depth 414 m (MVT), py, sericite, chlorite.
BSN-10- depth 412 m (MVT), py, chlorite, sericite; f) BSN-11- depth 217 m (MVS), py, sericite, qtz, chlorite. (continues).
Base metals and mobile trace elements hanging wall mafic volcanics (samples BSN-26-31) to some samples of
Concentrations of Cu, Pb, Zn, Ba, Rb, Sr, Tl, As, Bi, and Mo were moderately to intensely altered footwall mafic volcanics (samples BSN-
plotted against Na2O, because Na depletion is an indicator of increased 41-45) may be related to the formation of muscovite and K feldspar
alteration intensity in the footwall alteration zone, whereas albite- replacing primary plagioclase with Ba and Rb for K. Thus, muscovite-
altered hanging-wall dacite has high Na2O values (Figures 12, 13). poor samples of the intense quartz-pyrite-ser alteration facies (Figure
The base metal contents of samples from the footwall alteration zone 7, Table A1) have low Ba and Rb concentrations. Extremely low values
vary substantially and intensely altered rhyolite often has one order for Ba and Rb occur in several Na-rich samples of the hanging wall
of magnitude higher Cu, Zn, and Pb concentrations than least altered rhyolite where albitization of feldspar led to concurrent K, Ba and
rhyolite, hanging-wall dacite, and quartz-eye porphyry (Figures 12, 13). Rb depletion. Samples of cabonate alteration facies are barium-rich
However, there is overlap and no clear correlation between alteration (commonly about 1 wt %), which is related to the occurrence of barite.
intensity and base metal concentrations. The somewhat erratic variations in Sr concentrations are probably
Variations in Ba, Rb and Sr contents and in the Rb/Sr ratio are related to occurrences of epidote and calcite where Sr replaces Ca.
probably controlled by differences in mineralogical composition The concentrations of Tl, As, Bi and Mo (Figure 13, Table A2 in
(Figures 12, 13). The increase in Ba and Rb from the least altered the electronic supplement) are close to or below the detection limit for
g) h)
12 13
i) j)
14 15
k) l)
B01 B02
Figure 8 (cont.). Textures of volcanics at the San Nicolás deposit; g) BSN-12- depth 188 m (MVS), plagioclase, sericite, chlorite; h) BSN-13- depth 164 m (MVS), py,
sericite, calcite, chlorite; i) BSN-14 - depth 145 m Mafic flows (XLT), py, calcite, sericite, chlorite; j) BSN-15- depth 125 m Mafic flows, volcaniclastic sediments and
tuffs (TUF), Basalt with low alteration, qtz, calcite, k) B01- superficial sample, greywackes (TUF) with: py, chlorite, sericite; l) B02 - superficial sample, sandstone
(TUF) with: py, sericite, qtz, chlorite.
most samples with Na2O values higher than approximately 1 wt %. In altered hanging wall rhyolite ~220 m over the San Nicolás Formation.
contrast, samples of altered rhyolite, with Na2O <2 wt % show a large Drill hole SAL-35 (100 m to the south-west of the section in figures 3, 5)
range of variation of As with maximum values typically 10 to 15 times cuts 245 m of several zones of quartz-pyrite alteration facies. This drill
higher than in least altered rhyolite. hole starts in no altered basalts and ends with quartz-K feldspar altera-
tion facies ~40 m stratigraphically below the San Nicolás Formation.
Drill hole SAL-25 was selected to examine the geochemistry of a thick
GEOCHEMICAL INDICATORS OF PROXIMITY TO THE SAN lava unit directly overlying the massive sulfides in San Nicolás deposit.
NICOLÁS DEPOSIT
Footwall halo
Representative drill holes from San Nicolás deposit were selected to
illustrate the relationship between geochemical changes and proximity Major elements and alteration indexes
to the massive sulfide lenses. The orientation of these drill holes with The data from drill hole SAL-25 illustrate the geochemical vari-
regard to the San Nicolás Formation (rhyolite flow-dome, RFD in ability of the San Nicolás alteration zone in the hanging wall (samples
Figure 4) is variable. (Figure 7). Drill hole SAL-25 was collared in no BSN-41-45), which is characterized by elevated values for MgO, S,
40 values just below the San Nicolás Formation (203 m depth) is correlated
with a tremolite and barite-rich sample of strong chl-py-ser-K-feldspar
30 Chloritization, alteration facies. The pattern for S drops from 2.61 wt % to almost zero,
Pyritization although most samples have concentrations <1 wt % and one zone of
chl-py-ser-K-feldspar alteration facies has exceptionally high S values
MgO+FeO
Base metals
AI, and CCPI in San Nicolás due to the abundance of chlorite-rich Concentrations of base metals in altered rhyolite show erratic vari-
quartz-pyrite alteration facies. ations with comparable ranges in San Nicolás. Although values higher
In drill hole SAL-25, the vertical concentration of Na2O decreases than background are predominant, numerous samples show base metal
toward the San Nicolás Formation and values <1 wt % are common concentrations within the range of the least altered rhyolite. There
in the upper part of the mottled alteration facies between 384 to 420 are no consistent trends in the base metal data that could be used as
m (Table A1, Figure 14). The concentration of MgO increases from a guide to the massive sulfides in San Nicolás. Consequently, analyses
regional background levels (2-3 wt %) to values around 9.82 wt % of Cu, Pb, and Zn have a low potential as vectors to ore (Figure 14).
in the central part of the alteration zone. Alteration index and CCPI
values are close to values typical (35-64) for the least altered rhyolite Trace elements
in the lower part of the mottled alteration facies but increase toward In general, concentrations of Ba show consistent changes with
the San Nicolás Formation sulfides (203 m depth) (45–80). Sulfur distance from the San Nicolás favorable unit, and increases with CCPI
concentrations are high (2.61 %) at the quartz-pyrite alteration facies values. Ba-rich samples in the vicinity of massive sulfides are poten-
just below the massive ore body (384 m), and low (0.03 wt %) over tially useful as mine-scale exploration vectors and correlate with local
the sulfides (203 m). occurrences of barite. In San Nicolás the chlorite-rich quartz-pyrite
In drill hole SAL-25, Na2O values are below 1.62 wt % for most alteration facies are marked by strong depletion in Ba. A general
samples and AI values >61.4 predominate (Figures 6, 14). A drop in AI increase in the Rb/Sr ratio can be observed in all the ore body of San
dolomite ankerite
100
epidote chlorite
Strong carbonate alteration
calcite pyrite
Least 45
80 altered 29 41
box 31 30
andesite/basalt
26
CCP 60 Least
altered Intense pyritic
alteration
box
CCP Index
28
dacite 44
40 27 Hydrothermal
Least alteration
altered Background
box
rhyolite 42 sericite
20
43
albite
0
K-feldspar
0 20 40 60 80 100
Alteration Index AI
Figure 10. The alteration facies at San Nicolás, DDH (diamond drill hole) SAL-25 (samples 45-41 under ore; 31-26 above ore, arrows are from bottom to surface),
with alteration facies box-plot (Large et al., 2001). Stars represent other drill samples. (see Table A1 in the electronic supplement).
100000
(ppm)
Comendite 10000
100 pantellerite
Phonolite
Cu 1000
Rhyolite 100
Trachyte
0.1
Rhyodacite/dacite 10
Zr/TiO2
1 2 3 4
Na2O %
Trachyteandesite
100000
Andesite (ppm)
Basanite
nephelinite 10000
0.01
Alkali basalt
Andesite Basalt
Pb 1000
0.01 0.1 1 10 10
1 2 3 4
Nb/Y Na2O %
Figure 11. Immobile element data are consistent with the field classification of 100000
(ppm)
volcanics at San Nicolás and are not influenced by alteration.
10000
Ba
Nicolás; however, there is considerable scattering and overlapping
1000
with the range for the least altered rhyolite. Just below the San Nicolás
favorable unit, the Rb/Sr ratio decreases dramatically to the presence
of disseminated tremolite alteration facies. The concentrations of Mo, 100
Bi, and As are typically less than 1 ppm in the least altered footwall
rhyolite. In contrast, altered footwall rhyolites often contain several to 10
1 2 3 4
>10 ppm of these elements. In San Nicolás, the concentrations of these Na2O %
elements vary erratically and a correlation with distance from ore is
100000
not apparent. In the west part of San Nicolás, elevated values of Mo (ppm)
and As (>10 ppm) are restricted to the quartz-pyrite alteration facies
immediately below massive sulfides. In general, Tl concentrations 10000
are close to, or below, the detection limit (<0.5 ppm) for all samples
Zn
regardless of alteration facies. However, elevated Tl values (>3 ppm)
1000
occur in samples just at the begining of the San Nicolás favorable unit
in drill hole SAL-25 (from 210 to 380 m, Figure 14).
Barium concentrations are strongly controlled by mineralogy of 100
30
4 25
3 20
Rb As 15
2
10
1 5
0 0
0 1 2 3 4 0 1 2 3 4
Na2O Na2O
30
4
20
3
Mo
Sr
2
10
1
0 0
0 1 2 3 4 0 1 2 3 4
Na2O Na2O
5
4 4
3
3
Rb/Sr Bi
2 3
1 1
0 00
0 1 2 3 4 1 2 3 4
Na2O Na2O
30
3000
20
2000
Tl
Ba
10 1000
0 0
0 1 2 3 4 1 2 3 4
0
Na2O Na2O
Figure 13. Variation diagrams for SAL-25 DDH showing the variability of trace element concentrations in hanging-wall rhyolite and quartz-eye porphyry (Rb, Sr,
Rb/Sr, Tl, As, Mo, Bi and Ba ppm vs. Na2O %).
extremely sulfur-poor with values generally below the detection limit Carbonate alteration
(<0.01 wt %). This enrichment in S, Zn, Pb and Bi may be related to The origin of the carbonate alteration has been examined in detail
localized late activity of the San Nicolás hydrothermal system. by Herrmann and Hill (2001) at the Thalanga deposit, Australia, who
concluded that carbonate-tremolite-chlorite alteration facies represents
the metamorphic equivalent of intense chlorite-calcite ± dolomite
DISCUSSION alteration, which occurred in footwall rocks close to the sea floor by a
process involving mixing of hydrothermal fluids and seawater.
Hydrothermal alteration of the volcanic rocks The abundance of the carbonate-tremolite-chlorite alteration facies
The San Nicolás alteration zone consists of six alteration facies with in central San Nicolás suggests that the volcaniclastic units and the fault
a distinctive mineralogical and geochemical characteristics. Based on pathway (Figures 5, 10) provided favorable conditions for mixing of
geological, mineralogical and geochemical data, a conceptual model upwelling hydrothermal fluids with ambient seawater.
for the evolution of the San Nicolás hydrothermal system is presented Hydrothermal carbonate alteration is common in VMS deposits
(Figure 7). Although a temporal evolution of the hydrothermal system and has been described from several deposits in Tasmania, such as
is suggested, other alteration processes may have occurred concurrently Rosebery deposit, (Lees et al., 1990); Hercules deposit, (Zaw and
in different parts of the system. Large, 1992); Hellyer deposit, (Gemmell and Large, 1992), in VMS
russian districts (Smirnov, 1968, 1976; Smirnov and Gorzhevskii, 1978; probably led to changes in the location of quartz-K feldspar alteration
Starostin, 1984), in Chisel Lake, Canada, (Galley et al., 1993), and in and, overprinting with the mottled alteration facies.
Kuroko, Japan (Shikazono et al., 1998). It has also been observed in
modern, submarine hydrothermal systems Middle Valley, northern Mineralizing alteration
Juan de Fuca Ridge, (Goodfellow et al., 1993). In general, oxidizing The fault zone of the quartz-pyrite alteration facies is interpreted
conditions and low temperatures (<200 °C) are inferred for carbonate to represent the principal pathways of hydrothermal fluids during
alteration. By analogy, carbonate alteration at San Nicolás is interpreted mineralizing hydrothermal activity (Figures 5, 6). This interpretation
to represent a relatively low temperature process, which occurred at an is supported by the high abundance of disseminated pyrite and pyrite
early stage during the development of the San Nicolás hydrothermal veins, the substantially elevated concentrations of S, base metals, and
system (Figures 7, and 10). trace elements, such as As, Mo, and Bi, and the observed connection
between massive sulfides and quartz-pyrite alteration facies. However,
Phyllosilicate-dominated alteration the mechanism that controlled discharge of hydrothermal fluids at
Feldspar-destructive, muscovite-chlorite-biotite-rich mottled San Nicolás is the growing faults systems. Synvolcanic faults have
(strong chl-py-ser K-feldspar) alteration facies, (Figure 7). The bulk been recognized (Vassallo, 2003), and a comparison of volcanic facies
of the footwall alteration zone consists of the mottled facies, which architecture and the distribution of alteration facies showed that intense
shows destruction of primary feldspars, formation of hydrothermal hydrothermal fluid flow was controlled by Jurassic faulting and in
phyllosilicates, and precipitation of disseminated pyrite. In comparison part by lithofacies. The mineralizing event was between 148.9 Ma and
mineral assemblages in modern submarine hydrothermal systems 146.5 Ma, whereas all the volcanic process involved lasted from
with sulfide mineralization on the seafloor suggests that hydrothermal 148.9 Ma to 117.94 Ma, about 31 Ma (Figure 4).
phyllosilicates included sericite, chlorite and clay minerals, such as illite The quartz-pyrite alteration facies also exists as stratiform zones
and smectite (Binns and Scott, 1993). The muscovite-chlorite-biotite immediately below the massive sulfides. These probably formed as a
mineral assemblages observed in mottled alteration facies represent result of lateral flow of hydrothermal fluids below the paleo-seafloor.
the metamorphic equivalents of these hydrothermal phyllosilicates. This process appears to have been particularly important in southern
The textural diversity of the mottled alteration facies and the part of San Nicolás where the stratiform ore zone is up to 50 m thick
abundance of apparent clastic textures indicate that multistage alteration (Figures 5, 6).
processes were common. These processes may have been related to In contrast to the quartz-pyrite alteration facies, which is ubiqui-
variations in fluid composition, temperature and changing water/rock tous below the lowest San Nicolás sulfide lenses, the chlorite-pyrite
ratios. The continuous lateral extent of the mottled alteration facies alteration facies is restricted to a narrow zone underlying massive
suggests that upwelling of hydrothermal fluids was diffuse (Figure 8). sulfides in San Nicolás (Figures 5, 6). This alteration facies (samples
The mottled alteration facies has been intersected by drill holes BSN-07-08) is distinctive in having the highest enrichment in Mg,
down to a stratigraphic depth of at least 150 m below the San Nicolás Fe, and substantial depletion of SiO2. Possibly, a relatively short lived
favorable unit (Figure 10); however, its full extent into the footwall is episode of hydrothermal alteration characterized by Mg-rich, Si-poor
unknown. Broad, feldspar-destructive alteration zones of similar lateral fluids forming zones of chlorite-pyrite alteration facies occurred in up-
dimensions as at San Nicolás have been recognized below Mesozoic per San Nicolás. Subsequently, the conditions of alteration and/or the
VMS deposits in the Francisco I. Madero district, in central Zacatecas, composition of the hydrothermal fluid may have changed promoting
(Vassallo, 1995). These can be traced for up to 300 m into the footwall quartz-pyrite alteration.
stratigraphy where they become narrower and more confined. Hence,
the apparently stratabound footwall alteration zone at San Nicolás Geochemical proximity indicators to the
may represent the upper part of a similarly broad, transgressive zone San Nicolás deposit
of hydrothermal fluid upflow. The footwall geochemical halo of the San Nicolás deposit can be
Quartz-K feldspar alteration facies type has rarely been reported devided into an outer and an inner zone (Figures 5, 6). Furthermore,
from alteration zones associated with VMS deposits. Nevertheless, a small hanging wall halo was locally developed. Notwithstanding the
K feldspar has been observed in the outer parts of alteration mineralogical and geochemical variability of altered rhyolite there are
systems associated with the Kuroko deposits in Japan (Shirozo, several geochemical features that distinguish hydrothermally altered
1974, Shikazono et al. 2008) and the Que River deposit, Tasmania, rhyolite from the surrounding, least altered volcanic rocks and are
Australia, (McGoldrick and Large, 1992). At Que River, K feldspar is therefore important for the recognition of ancient, mineralizing hydro-
associated with silicification and Au-rich mineralization, interpreted thermal systems in felsic volcanic successions. These include elevated
to have formed by mixing of ore fluids of moderate temperature MgO, S, AI, CCPI, Rb/Sr, Mo, Bi and As, and depletion of Na2O.
(200–250 °C) and seawater. Some geochemical parameters show well-constrained correlations
By analogy with these studies and based on the observation that with proximity to ore at San Nicolás. For example, the CCPI values
quartz-K feldspar alteration facies is restricted to the outer (cooler?) increase steadily from background values from 25 to values >90 just
parts of the San Nicolás hydrothermal system, it is inferred that this type below the San Nicolás favorable unit in San Nicolás. High values of
of alteration took place under relatively low temperature conditions Tl, Ba, S, AI, CCPI, Rb/Sr, Mo, or As indicate immediate proximity to
and low water/rock ratios. The formation of K feldspar rather than ore defining the inner footwall halo (Table A1, A2).
sericite suggests that the pH of the hydrothermal fluids increased Alteration of the hanging-wall volcaniclastic rocks is generally
from acidic in the central parts of the hydrothermal alteration system characterized by weak alteration facies, which formed as a result of
to near-neutral on its fringes. background alteration processes unrelated to the mineralizing hy-
It is inferred that mixing of hydrothermal fluids with seawater at drothermal system. Nevertheless, rare minor geochemical anomalies
the margin of the hydrothermal system could have caused simultane- (elevated S, Zn, Pb, and Bi) in basalt 50 m above the massive sulfides
ous cooling and neutralization of the fluid, resulting in the formation suggest that some late-stage hydrothermal activity was locally ongoing
of the quartz-K feldspar alteration facies. Variations in the influx rate, at the time of basalts emplacement in lower Cretaceous, or when the
temperature, composition, and pathways of the hydrothermal fluids faults were still moving during Cretaceous time (Figure 14).
100
150
200
250
300
350
400
450
500
150
200 1707
2176
926
250 729
558
300
350
400
450
Figure 14. Geologic logs and geochemical data for SAL-25 DDH through the hanging wall and footwall alteration zone in San Nicolás. The orebody is between
204 and 383 m deep, a vertical distance of 179 m.
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GSA, Section - 108th Annual Meeting (29-31-March-2012), Paper No.
25-2, 44(3), 48 <http://gsa.confex.com/gsa/2012CD/finalprogram/ Manuscript received: August 6, 2014
abstract_201603.htm>. Corrected manuscript received: April 13, 2015
Manuscript accepted: April 27, 2015