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Magmatic anhydrite and calcite in the ore-forming quartz-monzodiorite magma at Santa Rita, New Mexico (USA): genetic constraints on porphyry-Cu mineralization
tat a,*, T. Pettke b, D. Dolejs c A. Aude
a

Institute of Mineralogy, Universita t Tu bingen, Wilhelmstrasse 56, Tu bingen D-72074, Germany b Isotope Geochemistry and Mineral Resources, ETH Zentrum, Zu rich 8092, Switzerland c Earth and Planetary Sciences, McGill University, Montreal, Quebec, Canada H3A 2A7 Received 13 November 2002; accepted 7 October 2003

Abstract A quartz-monzodioritic dike associated with the porphyry-Cu mineralized stock at Santa Rita, NM, has been studied to constrain physico-chemical factors ( P, T, fO2, and volatile content) responsible for mineralization. The dike contains a lowvariance mineral assemblage of amphibole, plagioclase (An30 50), quartz, biotite, sphene, magnetite, and apatite, plus anhydrite and calcite preserved as primary inclusions within the major phenocryst phases. Petrographic relationships demonstrate that anhydrite originally was abundant in the form of phenocrysts (1 2 vol.%), but later was replaced by either quartz or calcite. Hornblende plagioclase thermobarometry suggests that several magmas were involved in the formation of the quartzmonzodiorite, with one magma having ascended directly from z 14 km depth. Rapid magma ascent is supported by the presence of intact calcite inclusions within quartz phenocrysts. The assemblage quartz + sphene + magnetite + Mg-rich amphibole in the quartz-monzodiorite constrains magmatic oxygen fugacity at logfO2>NNO + 1, in agreement with the presence of magmatic anhydrite and a lack of magmatic sulfides. The same reasoning generally applies for rocks hosting porphyry-Cu deposits, seemingly speaking against a major role of magmatic sulfides in the formation of such mineralizations. There is increasing evidence, however, that magmatic sulfides play an important role in earlier stages of porphyry-Cu evolution, the record of which is often obliterated by later processes. D 2003 Elsevier B.V. All rights reserved.
Keywords: Magmatic; Anhydrite; Calcite; Sulfur; Porphyry copper

1. Introduction There is relatively little known about the role of sulfur in the formation of porphyry-Cu ( F Mo, Au)
* Corresponding author. Tel.: +49-7071-29-7890; fax: +497071-29-3060. E-mail address: andreas.audetat@uni-tuebingen.de tat). (A. Aude 0024-4937/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.lithos.2003.10.003

deposits, despite the fact that primary ore minerals are predominantly sulfides. Of particular interest is the question of whether the simultaneous enrichment of sulfur and metals is just accidental, or whether sulfur was actively involved in the metal enrichment process. Sulfur can be linked to ore-forming metals by various processes, including (i) preferential melting of a S- and Cu ( F Mo, Au)-bearing source; (ii) coupled assimilation of S and metals during magma ascent;

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(iii) sequestering of Cu, Mo, and Au in magmatic sulfides or immiscible sulfide melts; and (iv) simultaneous partitioning of sulfur and metals into exsolving aqueous fluids. Of these processes, the sequestering of Cu, Mo, and Au in magmatic sulfides or an immiscible sulfide melt has drawn particular attention in the past few years (Keith et al., 1991, 1997; Lynton et al., 1993; Cygan and Candela, 1995; Jugo et al., 1999; Larocque et al., 2000; Halter et al., 2002b) because it not only explains the close relationship between sulfur and metals, but also provides a viable mechanism for metal enrichment. It has been proposed that sulfide minerals or immiscible sulfide melts (in the following collectively called sulfides) could act as temporal storage medium for chalcophile ore metals like Cu and Au, thus preventing them to be incorporated at trace element levels within crystallizing minerals. Towards the end of crystallization, sulfides would get oxidized and release the metals together with sulfur to the exsolving aqueous fluids (Candela and Holland, 1986; Candela, 1989, 1992). Such a model is supported by experimental studies demonstrating that Cu and Au strongly partition into magmatic sulfide phases (Lynton et al., 1993; Cygan and Candela, 1995; Jugo et al., 1999), as well as by recent discoveries of primary sulfides in porphyryCu-related magmas (Keith et al., 1991, 1997; Halter et al., 2002b). Some observations, however, argue against a major role of sulfides in the formation of porphyry-Cu deposits. Most importantly, magmas spatially associated with porphyry-Cu mineralization are generally known to be oxidizing (e.g., Burnham and Ohmoto, 1980; Blevin and Chappell, 1992; Keith and Swan, 1995) and therefore should contain sulfates rather than sulfides. The studies of Dilles (1987) and Streck and Dilles (1998), for example, demonstrate that at Yerington, the magmas leading to porphyry-Cu mineralization were saturated in anhydrite during their whole evolution from quartz-monzodiorite to granite. Hence, it seems that the formation of magmatic sulfides (and their subsequent oxidation) is not a prerequisite for economic porphyry-Cu mineralization. The aim of this paper is to present a new example of an oxidized, porphyry-Cu-related magma (Santa Rita, NM, USA) and, in a second part, to discuss the controversy outlined above on a more general basis.

2. The porphyry-Cu deposit at Santa Rita 2.1. Geological setting The porphyry-Cu deposit at Santa Rita (also called Chino Mine) in southwestern New Mexico belongs to a suite of approximately 50 other porphyry-type Cu deposits that formed between ca. 52 and 72 Ma during the so-called Laramide age in the American Southwest (Titley, 1993). These deposits represent one of the most significant metallogenic provinces on Earth. Their formation is linked to subduction of oceanic crust, as suggested by the following observations: (i) all deposits occur in a belt about 350 400 km landward of the reconstructed continental margin; (ii) the occurrences show a close spatial and temporal association with andesitic to dacitic, calc-alkaline volcanism; and (iii) there is evidence for compressive stress and uplift. Most deposits are associated with large ( z 2 km diameter), multiple intrusions ranging in composition from monzonite to granite, with usually only the most felsic members being spatially related to mineralization (Titley, 1993). Santa Rita is a classical quartz-monzodioritehosted ore deposit in which remnants of essentially the entire igneous sequence are exposed as either volcanic or intrusive rocks. An excellent summary of the geology of Santa Rita can be found in Rose and Baltosser (1966), whereas detailed geologic and petrographic descriptions are given by Jones et al. (1967). Igneous activity in the region began in the Late Cretaceous with the intrusion of dioritic to quartz-dioritic sills into a Precambrian basement overlain by a ca. 1-km-thick sequence of Paleozoic and Mesozoic sediments. Shortly afterwards, andesites and andesitic breccias erupted to the surface, whereas concomitant dioritic to gabbroic rocks formed at depth. This was followed by multiple intrusion of quartz-monzodioritic magma-forming dikes and the major stocks of Santa Rita and Hanover Fierro. The Santa Rita stock has been dated at 63 Ma (Paleocene) by the K Ar method on hydrothermally altered rock (Rose and Baltosser, 1966). Many quartz-monzodiorite dikes are apophyses of the larger quartz-monzodiorite intrusions, whereas others are younger and cut through them. Later generations of dikes are more siliceous and have compositions ranging from quartzmonzonite to quartz latite. Most of the mineralization

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occurred after the formation of quartz-monzodiorite dikes, and was contemporary with the emplacement of quartz-monzonite dikes (Rose and Baltosser, 1966). Between 1911 and 1966, about 250 million tons of copper ore were extracted from Santa Rita, with an average Cu content of 0.8 0.9 wt.% Cu (Rose and Baltosser, 1966). The mine is presently operating at an ore grade of 0.2 wt.% Cu and 0.02 wt.% Mo (Robert North, personal communication, 2000). 2.2. Methods To constrain the magmatic processes leading to copper mineralization at Santa Rita, we collected samples from quartz-monzodiorite stocks and dikes that were emplaced immediately before mineralization. Dikes appear more useful than stocks because they were quenched at a specific stage of crystallization, are less altered, and are less deformed. Samples described in this article were collected from one particular dike that crops out between the villages of Vanadium and Hanover, at coordinates 32j46.97VN/ 108j06.47VW along state road 356, ca. 4 km west of the southern pit of Santa Rita. This dike (in the following named SR8) belongs to a group of about 50 quartz-monzodiorite dikes extending north and west of the Santa Rita stock (Hernon et al., 1964). Based on their structural, mineralogical, and geochemical characteristics (average of three analyses: 63.4 wt.% SiO2; 16.1 wt.% Al2O3; 5.1 wt.% CaO; 4.4 wt.% FeOtot; 2.5 wt.% Na2O; 2.5 wt.% K2O; 2.0 wt.% MgO; 0.5 wt.% TiO2; 0.5 wt.% MnO), there is no doubt that these dikes are comagmatic with the mineralized intrusions at Santa Rita and Hanover Fierro (Jones et al., 1967). The collected rock samples were cut into 5- to 10mm-thick slices and examined with a binocular microscope. Well-preserved phenocrysts of quartz, sphene, and apatite were marked and cut out for thick-section preparation. From ca. 200 phenocrysts, so-called quick plates (i.e., nonpolished sections) were made, which were covered with immersion oil and studied with a standard petrographic microscope to recognize primary inclusion assemblages. The best 50 phenocrysts were polished on both sides and prepared for microanalysis. Unknown mineral inclusions were identified by Raman spectroscopy, using a Dilor XY Raman mi-

croprobe with a resolution of 1800 lines/mm, a focal length of 500 mm, and a Peltier-cooled CCD detector with 1024 elements. Electron microprobe (EMP) analyses of apatite, anhydrite, and amphibole phenocrysts were performed on a Cameca SX50, using 15 kV acceleration voltage, 20 nA sample current, a fixed beam of 5 Am diameter, and peak counting times between 20 and 100 s. Quantitative analysis of selected minerals and inclusions was performed by EMP and laser ablation inductively coupled plasma mass spectrometry (LAICP-MS). The latter method has the advantage that it allows analysis of samples that became heterogeneous after entrapment (e.g., feldspars, Fe Ti oxides, sulfides, melts, and fluid inclusions) without the prerequisite of prior homogenization. The main disadvantage of LA-ICP-MS is that it produces relative element abundances only, which need to be transformed into absolute values by means of an internal standard tat et al., 2000; Halter et (Gu nther et al., 1998; Aude al., 2002a). The LA-ICP-MS system used in this study is composed of a 193-nm excimer laser (Lambda Physik, Germany), special energy homogenization optics (Microlas, Germany), and an Elan 6100 quadrupole mass spectrometer (Perkin Elmer, Canada). Technical details can be found in Gu nther et al. (1997, 1998), Gu nther and Heinrich (1999a,b), and Halter et al. (2002a). 2.3. Results 2.3.1. General petrology Hand specimens collected from quartz-monzodiorite dike SR8 appear dark-green and contain phenocrysts of white plagioclase (f 20 vol.%), amphibole (f 5 vol.%), biotite (f 5 vol.%), and quartz (f 2 vol.%) disseminated in a fine-grained matrix of the same minerals plus alkali feldspar. The rock also contains 1 2 vol.% lath-shaped cavities filled with an orange powder (Fig. 1a and b), which seem to represent former anhydrite phenocrysts (see below). Other minor phenocryst phases include apatite, sphene, and magnetite. Phenocrystic orthoclase was probably present as well (see Jones et al., 1967), but could not be recognized in SR8 due to the strong alteration of the feldspar crystals. Jones et al. (1967) determined the anorthite content of unaltered plagioclase phenocrysts in several quartz-monzodior-

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Fig. 1. (a) Photograph of a quartz-monzodiorite sample taken from dike SR8 at Santa Rita. The circle marks a lath-shaped cavity filled with orange-brown powder, which we interpret to represent a decomposed anhydrite phenocryst. (b) Digitally enhanced picture of the same view area, with the orange-brown shades replaced by dark color. Based on such pictures the total volume of former anhydrite phenocrysts in this rock was estimated at 1 2 vol.%. (c) Photomicrograph of an apatite phenocryst containing primary inclusions of anhydrite, magnetite, and amphibole (doubly polished thick section viewed in transmitted light). (d) Schematic view of petrographic relationships observed between apatite, anhydrite, and orange-brown powder. The upper part shows an apatite phenocryst with inclusions of anhydrite arranged along an early growth zone. One inclusion is intersected by a crack and filled with the same orange-brown powder as that present in the cavities. The latter often contain apatite crystals within and attached to them, suggesting a preferential intergrowth between apatite and anhydrite.

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ite dikes at An30 An50, whereas our LA-ICP-MS analyses of five plagioclase inclusions in quartz phenocrysts reveal a more narrow composition of An32 An42. The characteristics of each phenocryst phase and contained primary inclusions are summarized in Table 1, together with the method of inclusion analysis. A primary inclusion origin was inferred if the following criteria were fulfilled: (i) occurrence along a defined growth zone, (ii) complete enclosure within the host crystal, and (iii) no intersection by any visible crack or fluid inclusion trail. All minerals except calcite and ilmenite occur both as a phenocryst phase as well as inclusions within other minerals, suggesting that the assemblage plagioTable 1 Phenocryst phases and their inclusions in granodiorite sample SR8 Phenocryst Appearance Abundance (vol.%) 2

clase + amphibole + quartz + biotite + magnetite + sphene + apatite + anhydrite F K-feldspar was in stable equilibrium at the time of dike emplacement. An example of coeval inclusions of magnetite, amphibole, and anhydrite trapped within a single apatite phenocryst is shown in Fig. 1c. 2.3.2. Anhydrite The following petrographic observations suggest that the 1 2 vol.% cavities in SR8 represent decomposed anhydrite phenocrysts: (1) anhydrite occurs as primary inclusions within apatite (demonstrating that the melt was actually anhydrite-saturated; Fig. 1c); (2) cracked anhydrite inclusions within apa-

Maximum size (mm) 5

Contains inclusions of Plagioclase Apatite Hornblende Sphene Opaque Calcite Melt inclusions Zircon Anhydrite Magnetite Sphene Hornblende Biotite Melt inclusions Apatite Zircon Ilmenite Magnetite Melt inclusions Anhydrite Sphene Magnetite Melt inclusions Apatite Plagioclase Apatite Hornblende Apatite

Analyzed by LAa x x x x EMPb Ramanc x x

Quartz

Mostly euhedral; some grains embayed

x x x x x x x x x x x x x x x x x x x x

Apatite

Euhedral prisms

<1

Sphene

Euhedral crystals containing numerous inclusions

<1

Hornblende

Dark-green prismatic grains

x x

Plagioclase Anhydrite Biotite Magnetite K-feldspar

a b

Strongly altered; some grains rounded Decomposed to an orange-brown powder Totally altered Some grains embayed (Presence inferred only)

20 12 5 <1 ?

10 5 4 1 ?

LA-ICP-MS analysis. Electron microprobe analysis. c Identification by Raman spectroscopy.

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tat et al. / Lithos 72 (2004) 147161 A. Aude Table 2 Electron microprobe analyses of apatite and anhydrite in SR8 P2O5 Apatite Phenocryst M; spot 1 (core) Phenocryst M; spot 2 Phenocryst M; spot 3 Phenocryst M; spot 4 Phenocryst M; spot 5 (rim) Phenocryst N Phenocryst F Phenocryst C Phenocryst K Phenocryst I; core Inclusion in quartz Inclusion in sphene 1 Inclusion in sphene 2 Anhydrite Anhydrite inclusion in crystal M Anhydrite inclusion in crystal N 40.99 41.07 41.47 40.92 41.11 41.44 41.85 42.25 41.87 42.34 41.93 40.81 41.50 SO3 CaO Na2O F Cl Total 98.69 98.72 99.56 98.85 99.01

tite are replaced by the same orange-brown powder as that present in the cavities (i.e., Fig. 1d); (3) anhydrite is unstable in most groundwaters (explaining its decomposition); (4) the cavities show the typical lathshaped outline of anhydrite crystals; and (5) there is a close spatial relationship between apatite crystals and cavities (Fig. 1d), suggesting anhydrite apatite intergrowths similar to those described from Mt. Pinatubo (Baker and Rutherford, 1996; Pallister et al., 1997). Xray diffraction (XRD) analysis of the orange-brown powder revealed that it consists essentially of microcrystalline quartz. In two samples from other quartzmonzodiorite dikes in the area, however, both the cavities in the matrix and opened anhydrite inclusions within apatite phenocrysts are filled with calcite. The latter contain ca. 20% void space, which corresponds 2 to the reduction in mineral volume if every SO4 2 anion of the former anhydrite is replaced by CO3 . In view of this evidence, we regard it as certain that the 1 2 vol.% cavities in SR8 represent former anhydrite phenocrysts. Assuming a density of 2.9 g/cm3 for the anhydrite and 2.7 g/cm3 for the quartz-monzodiorite, this amount of anhydrite phenocrysts translates into a magma sulfur content of 2500 5000 ppm S. Despite careful examination, we could not find any traces of magmatic sulfides in SR8, neither as inclusions within phenocryst phases, nor as oxidized remains in the matrix (i.e., Larocque et al., 2000). Most of the sulfur present in this magma was therefore dissolved as sulfate, suggesting high fO2. High magmatic oxygen fugacities are suggested also by the assemblage quartz + magnetite + sphene + Mg-rich hornblende (Wones, 1989), which requires a minimum of log fO2 z NNO + 1 at the reconstructed crystallization temperature of 770 F 50 jC (see below). 2.3.3. Apatite Electron microprobe analyses of six apatite phenocrysts and three apatite inclusions in sphene and quartz are listed in Table 2. Due to the potential use of apatite as a tool for monitoring magmatic sulfur contents (e.g., Streck and Dilles, 1998; Parat et al., 2002), we focus this discussion on their SO3 content. Sulfur incorporation in apatite is possible through several substitution mechanisms, which are coupled such that S c [Si-REE3 + + Na] (Streck and Dilles, 1998). Dsulfur, apatite/melt, therefore, not only depends on melt temperature and oxygen fugacity (Baker and

0.20 54.04 0.12 0.18 53.97 0.11 0.14 54.39 0.10 0.17 54.28 0.10 0.24 54.17 0.09 0.18 0.16 0.15 0.13 0.20 54.01 54.33 53.58 54.54 54.27 0.08 0.08 0.06 0.11 0.12

2.04 1.31 2.11 1.27 2.20 1.27 2.10 1.28 2.11 1.30 2.39 2.12 2.59 2.37 2.45

1.38 99.48 1.30 99.84 1.25 99.89 1.14 100.16 1.30 100.68 99.83 99.16 99.79

0.35 53.91 0.13 0.52 54.08 0.21 0.31 54.30 0.17

2.06 1.45 2.16 1.39 2.11 1.40

0.18 56.39 41.40 0.01

0.00 0.01

97.99

0.11 56.69 41.84 0.03

0.00 0.00

98.68

All values are in weight percent.

Rutherford, 1996; Peng et al., 1997), but also on melt chemistry. Crystallization conditions of apatite in dike SR8 are approximated by a laboratory experiment of anhydrite-saturated Pinatubo dacite at 760 jC, 2200 bar, and MNO-buffered oxygen fugacity (run H12 of Baker and Rutherford, 1996; MNO buffer equals to NNO + 3). In this experiment, Dsulfur, apatite/melt was determined at about 9. Using this distribution coefficient and a sulfur content of 520 2080 ppm S in apatite of SR8, the sulfur concentration in the coexisting melt is calculated at 60 230 ppm. This value is in agreement with experimentally determined sulfur solubilities in anhydrite-saturated magmas (Carroll and Rutherford, 1987; Luhr, 1990; Baker and Rutherford, 1996). A major implication of the

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discussion above is that the amount of sulfur stored in the melt of SR8 was negligibly small compared to the 2500 5000 ppm S present in the form of anhydrite phenocrysts. 2.3.4. Amphibole Electron microprobe and LA-ICP-MS analyses of amphiboles are listed in Table 3 and summarized in Fig. 2. A plot of Al2O3 vs. FeO reveals three compositionally distinct groups (Fig. 2a). One comprises amphibole inclusions within apatite, whereas the other two comprise amphibole phenocrysts and a single quartz-hosted amphibole inclusion. The composition of amphibole preserved as inclusions and phenocrysts can be used to constrain P T conditions of amphibole crystallization by means of Al-in-hornblende barometry and hornblende plagioclase thermometry. Fig. 2b summarizes the results of calculations performed with a spreadsheet kindly provided by J.L. Anderson. The thermometry part in this spreadsheet is based on the reaction edenite + albite = richterite + anorthite, as described in Holland and Blundy (1994). A problem arises from the fact that the plagioclase phenocrysts in SR8 are zoned, which renders it impossible to assign a particular plagioclase composition to a specific amphibole composition. Hence, for the calculation of data points in Fig. 2b, we used an average plagioclase composition of An40 and added error bars displaying the change in temperature (and corresponding effect on pressure) when the plagioclase

composition is varied from An30 to An50 (cf. Jones et al., 1967). Calculated temperatures are the same (within error) for all three amphibole populations analyzed, suggesting crystallization temperatures of 770 F 50 jC. The Al-in-hornblende barometer applies to lowvariance granitic rocks containing an equilibrium assemblage of seven solid phases (quartz, K-feldspar, An25 35 plagioclase, biotite, hornblende, sphene, and Fe Ti oxides) in the presence of melt and a free vapor phase. Originally formulated by Hammarstrom and Zen (1986) and Hollister et al. (1987), the barometer has been extended by Anderson and Smith (1995) to include a temperature correction. The latter authors recommend that the barometer be used only for hornblendes with Fetot/(Fetot + Mg) < 0.65, which is fulfilled for all amphiboles analyzed from SR8 (their ratio ranging from 0.17 to 0.45). However, the conditions of: (i) plagioclase composition of An25 35 , (ii) coexistence with K-feldspar, and (iii) coexistence with a vapor phase may not always have been fulfilled. The effect of neglecting these criteria is not well known, but a test on SR8-similar experimental run products of Mt. Pinatubo dacite with the assemblage hornblende + magnetite + plagioclase (An40) + ilmenite Fanhydrite (i.e., An-content too high, K-feldspar missing, and partly vapor-undersaturated) yielded Al-in-hornblende pressures that reproduced the run conditions to within F 0.5 kbar (runs 58 and 67 of Scaillet and Evans, 1999). An empirical error bar of F 0.5 kbar has therefore been added to the data points in Fig. 2b.

Table 3 Electron microprobe and LA-ICP-MS analyses of hornblende in SR8 (all values in wt.%) Hornblende sample Phenocryst P; core Phenocryst P; middle Phenocryst P; rim Phenocryst F; core Phenocryst G; core Phenocryst G; rim Phenocryst F; core Inclusion in quartz Inclusion in apatite Q Inclusion in apatite J Inclusion in apatite K SiO2 TiO2 Al2O3 FeOtot MgO MnO CaO Na2O K2O Total T P T P T P (An30) (An30) (An40) (An40) (An50) (An50) 47.5 48.4 48.1 45.1 44.4 44.7 46.0 48.5 44.6 44.3 44.4 1.2 1.2 1.3 1.8 1.2 1.7 1.4 1.1 1.4 1.5 1.6 7.4 6.8 7.1 12.0 13.2 12.4 13.4 7.0 9.5 9.6 10.0 14.4 14.2 14.3 6.9 7.9 7.2 6.3 14.4 16.7 16.5 17.1 14.0 14.3 14.1 18.2 17.0 17.8 17.0 14.2 11.8 11.8 11.7 0.5 0.5 0.5 0.1 0.1 0.1 0.1 0.6 0.5 0.5 0.5 11.5 11.7 11.7 11.3 11.5 11.5 11.1 11.5 11.5 11.6 11.5 1.4 1.3 1.3 2.8 2.6 2.7 2.8 1.4 1.7 1.7 1.9 0.7 0.6 0.6 0.7 0.9 0.8 0.9 0.7 1.0 1.1 1.1 98.6 98.8 99.0 98.9 98.7 98.8 99.0 99.3 98.8 98.6 99.8 742 732 732 760 733 749 725 733 758 763 772 2.2 1.9 2.1 5.0 6.4 5.5 6.6 2.0 3.5 3.5 3.5 769 760 760 784 756 772 748 760 784 789 799 1.7 1.4 1.7 4.4 5.9 5.0 6.1 1.6 3.0 2.9 2.9 817 808 807 825 794 812 788 809 829 834 844 0.6 0.4 0.7 3.2 4.9 3.9 5.1 0.5 1.8 1.7 1.6

Thermobarometric results based on three different plagioclase compositions are shown on the right.

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them ascended directly from z 14 km depth without residing for an extended period of time at lower pressure. 2.3.5. Magmatic calcite Several quartz phenocrysts host small inclusions of calcite (Fig. 3). The following observations support a primary (i.e., magmatic) origin of this calcite: (i) the inclusions are not intersected by any cracks or fluid inclusion trails; (ii) they occur as single crystals (which would not be the case if they were secondary fillings or replacements); and (iii) there is no calcite present in the altered groundmass. Primary calcite is very rare in siliceous magmas, and its crystallization from granitic melts has been experimentally constrained to pressures above 3 kbar (Swanson, 1979). The stability of calcite in silicate melts is limited by the equilibrium: calciteCaCO3 quartzSiO2 wollastoniteCaSiO3 CO2
Fig. 2. (a) Composition of five amphibole phenocrysts and four amphibole inclusions in apatite and quartz, plotted in a diagram according to Leake et al. (1997). Some data points are hornblendes sensu strictu, while others are edenites, pargasites, and hastingites. (b) Reconstructed P T conditions of amphibole crystallization, based on Al-in-hornblende barometry and plagioclase hornblende thermometry. The uncertainty in temperature arises from the compositional range of coexisting plagioclase, whereas the uncertainty in pressure accounts for the fact that not all phases required for the application of the barometer may have been coexisting. Also included is the stability field of magmatic calcite and the reaction curve (calcite + quartz X wollastonite + CO2) in the presence of a pure CO2 fluid (see text for further explanations).

The results suggest that the amphibole phenocrysts originate from different depths, with one group having crystallized at pressures of more than 5 kbar and one at a pressure of less than 2 kbar (cor-responding to 14 and 6 km, respectively). Notably, core rim variations within individual phenocrysts are much smaller than variations between them, which is difficult to explain by ascent of a single magma batch (in this case, rims of high-pressure phenocrysts should display the same chemistry as low-pressure phenocrysts). This suggests that several magmas were involved in the generation of SR8 and that one of

which is divariant in the presence of H2O in a coexisting fluid phase. The stability field of calcite in granitic magmas is limited by the granite solidus and the strongly pressure-dependent position of reaction (1) above (Fig. 4a). The lowest pressure at which melt + calcite can coexist is at 3.8 kbar, with an aCO2 of 0.2 in the coexisting fluid phase (Fig. 4b). Hence, the presence of primary calcite in quartz phenocrysts of SR8 suggests that these quartz crystals formed at z 3.8 kbar (translating into a depth of z 10.8 km based on an average crustal rock density of 2.85 g/ cm3), and that the melt contained appreciable amounts of dissolved CO2. Additional information can be derived from the fact that the calcite inclusions are still intact and show no reaction with the host quartz (the Raman spectrum in Fig. 3b shows no signs of the prominent wollastonite bands at 971 and 636 cm 1). Once incorporated within another mineral, the pressure in the calcite inclusion is determined by the relative volume change occurring during decompression and cooling. The compressibilities of quartz and calcite are 25 10 6 and 13.5 10 6 MPa 1, respectively, whereas the thermal expansion coefficients are 44 10 6 and 28.5 10 6 K 1, respectively (Gottschalk, 1997).

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Fig. 3. (a) Photomicrograph of a quartz phenocryst with inclusions of magmatic calcite (transmitted light). (b) Raman spectra obtained from the same calcite aggregate, showing the typical wavelength shifts produced by calcite.

Therefore, isobaric magma cooling leads to an increase of pressure within the calcite inclusion, whereas isothermal magma decompression causes the pressure to drop rapidly to nearly zero. In the latter case, calcite starts to react with the host quartz to produce wollastonite + CO2 (i.e., reaction (1) is driven to the right), until the pressure required for calcite stability is reached (e.g., 3 kbar at aH2O = 0 and 770 jC in Fig. 4b). Thus, if nearly isothermal (770 F 50 jC) decompression from greater than 5 kbar to less than 2 kbar (as suggested by hornblende plagioclase ther-

mobarometry) was followed by a prolonged residence time of the magma at lower pressure, it would have resulted in partial reaction of the calcite to wollastonite and a buildup of 1 kbar overpressure within the inclusions. Such a high overpressure in inclusions of >50 Am size inevitably would have resulted in inclusion decrepitation (Roedder, 1984). Calcite inclusions in the quartz phenocrysts of SR8, however, are still intact and show no signs of partial reaction to wollastonite, suggesting that they are preserved in a metastable equilibrium. This requires rapid ascent of

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2.4. Summary of results for Santa Rita We have shown that the premineralization quartzmonzodioritic magma at Santa Rita contained 1 2 vol.% anhydrite phenocrysts, which were decomposed to an orange-brown powder. This amount of anhydrite translates into a minimum content of 2500 5000 ppm S in the magma, making it one of the most sulfur-rich magmas ever recorded. In comparison, the sulfur-rich magmas erupted from n contained 1000 4000 Mt. Pinatubo and El Chicho and 5000 ppm S, respectively (Baker and Rutherford, 1996). Magmatic oxygen fugacity was high ( z NNO + 1), as shown by the assemblage quartz + magnetite + sphene + Mg-rich amphibole and the absence of sulfides. The results of plagioclase hornblende thermometry and Al-in-hornblende barometry suggest that at least two magma batches were involved in the generation of SR8, one of which has ascended directly from z 14 km depth. Rapid ascent of one magma batch is suggested also by the metastable presence of calcite inclusions within quartz phenocrysts.

3. Relation to other calc-alkaline magmas 3.1. Sulfur speciation Sulfur speciation in silicate melts and associated stability of sulfides vs. sulfates strongly depends on the oxidation state of the magma. Relatively reduced magmas (logfO2 < NNO + 0.5) are characterized by the predominance of S2 and become saturated with sulfides (pyrrhotite or immiscible sulfide melts), whereas oxidized magmas (logfO2>NNO + 0.5) contain mainly sulfate (SO4)2 and precipitate anhydrite (Whitney and Stormer, 1983; Carroll and Rutherford, 1987; Luhr, 1990; Baker and Rutherford, 1996; Ducea et al., 1999). The transition from S2 predominance to 2 SO4 predominance (both at the 90% level) occurs between logfO2 = NNO 1 and NNO + 1.5, independent of melt chemistry and absolute values of P and T (Matthews et al., 1999). At a given pressure and temperature, sulfur solubility in dacitic melts displays a minimum at around log f O 2 = NNO 0.5 and increases towards both lower and higher oxygen fugacities (Carroll and Rutherford, 1988).

Fig. 4. (a) T XCO2 diagram showing the position of the granite solidus and the reaction (calcite + quartz X wollastonite + CO2) at pressures of 2, 5, and 10 kbar. The stability field of magmatic calcite at 10 kbar is indicated by light gray shading, whereas the corresponding field at 5 kbar is shown in dark gray. At 2 kbar, the granite solidus and the calcite wollastonite reaction curve do not intersect, precluding crystallization of magmatic calcite. (b) P T stability field of magmatic calcite. The minimum is located at 3.8 kbar and XCO2 c 0.2 in the coexisting fluid. Data source: Jacobs and Kerrick (1981), Ebadi and Johannes (1991), and Holland and Powell (1998).

some quartz phenocrysts from z 10.8 km depth, in agreement with the findings from hornblende thermobarometry.

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3.2. Oxidation state The oxidation state of natural silicic magmas can be constrained from mineral equilibria between ferromagnesian silicates and oxides (Wones, 1981; Ghiorso and Sack, 1991; Frost and Lindsley, 1992; Xirouchakis et al., 2001). Felsic (i.e., quartz-saturated) magmas display a systematic relationship between the oxygen fugacity and the ferromagnesian silicate phases present, suggesting that fO2 was actually buffered by mafic minerals in these magmas (Carmichael, 1967, 1991). Their oxygen fugacity was found to increase from olivine-bearing magmas (logfO2= NNO 3 to NNO 1) over orthopyroxene-bearing magmas ( Fbiotite, amphibole, cummingtonite; logfO2 = NNO 0.5 to NNO + 1) to biotite F amphibole F sphene-bearing magmas (logfO2 = NNO + 1 to NNO + 2.5; olivine and orthopyroxene absent). The T fO2 field of orthopyroxene vs. biotite + amphibole-bearing magmas is shown in Fig. 5. Intermediate-to-felsic rocks hosting porphyry-Cu deposits are characterized by the occurrence of amphibole F biotite (e.g., Lowell, 1974; Gustafson and Hunt, 1975). They thus belong to the most oxidized group with an oxygen fugacity of logfO2 = NNO + 1 to NNO + 2.5, in which the majority

of sulfur occur as sulfate. The same applies to coarsergrained intrusions cropping out in the vicinity of (or below) the porphyry stocks, which are characterized by the assemblage amphibole + magnetite + sphene (Keith and Swan, 1995; MacMillan and Panteleyev, 1995) and may represent the source of the mineralizing fluids. Hence, porphyry-Cu-related magmas seem to be too oxidized that magmatic sulfides could have played a major role in the mineralization process. The following arguments, however, suggest that this may be a rash conclusion. Firstly, one has to bear in mind that the change from oxidized to reduced sulfur does not occur instantaneously, but follows approximately a function (2 ) of the form: log[XSO4 /XS(2 )] = 1.02 DNNO 0.45, where Xi is the mole fraction of species i and DNNO is the deviation of fO2 (in log units) from the NiNiO buffer (Wallace and Carmichael, 1994). It implies that two log units above NNO, there are still 2.5% of the total sulfur present as sulfide. This amount is certainly negligible in terms of sulfur budget, but it can be dramatic with respect to the budget of chalcophile elements with high sulfide/silicate melt partition coefficients such as copper and gold (DCu, pyrrhotite/silicate melt and DAu, sulfide melt/silicate melt are on the order of 2.6 103 and 5.7 103, respectively; Jugo et al., 1999). Secondly, there is increasing evidence for the presence of magmatic sulfides in earlier stages of porphyry-Cu evolution, as revealed by recent discoveries in the Bingham and Tintic mining districts, at Mt. Pinatubo and at Alumbrera (Pallister et al., 1997; Imai et al., 1997; Keith et al., 1997; Hattori, 1997; Hattori and Keith, 2001; Maughan et al., 2002; Halter et al., 2002b). 3.3. Significance of contributions by mafic magmas At Mt. Pinatubo, it could be shown that the sulfur-rich eruptions between June 7 and June 15 in 1991 were triggered by intrusion of hot, basaltic magma into a relatively cool, dacitic magma chamber that was highly oxidized (logfO2 = NNO + 3) and saturated with anhydrite (Hattori, 1993, 1997; Kress, 1997; Pallister et al., 1997). The intruding basaltic magma contained globules of an immiscible sulfide melt, and it has been proposed that the sulfur-rich nature of the Mt. Pinatubo volcanic system ulti-

Fig. 5. Oxygen fugacity of natural silicic magmas as a function of their ferromagnesian mineral assemblage (data from Carmichael, 1991). Also shown is the boundary between SO2 and S2 4 predominance of dissolved sulfur (after Carroll and Rutherford, 1988), and the reconstructed crystallization conditions of sulfur-rich n (EC), as magmas erupted from Mt. Pinatubo (Pin) and El Chicho summarized in Baker and Rutherford (1996).

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mately stems from interaction with these mafic melts (Hattori, 1993, 1997; Kress, 1997; Pallister et al., 1997). Evidence for mixing between mafic and silicic magmas has been reported also from the Bingham and Tintic mining districts (Keith et al., 1997; Hattori and Keith, 2001; Maughan et al., 2002). Magmatic sulfides are present mainly in intermediate magma compositions, but they are conspicuously absent in the most mafic member. The presence of magmatic barite inclusions in olivine phenocrysts from the most mafic unit at Bingham suggests that this magma was oxidized and contained high amounts of dissolved sulfur (Keith, personal communication, 2003). Most recently, magmatic sulfides have been den scribed from intermediate intrusions in the Farallo Negro Volcanic Complex (Halter et al., 2002b). The fact that the Cu/Au ratio in the magmatic sulfides closely matches the Cu/Au ratio of the bulk ore at Alumbrera suggests that magmatic sulfides form an important part of the metal enrichment process. In contrast to the previous two localities, closed-system magma fractionation, rather than magma mixing, has been invoked to explain the compositional evolution n Negro Volcanic Complex (Halter et al., of the Farallo 2002b). It should be noted that in the case of magma mixing, the record of an involvement of mafic magmas is likely to become obscured. The only evidence for the former presence of mafic magmas may be found in a mafic enclave, in the trace element signature of the whole rock, or in the occurrence of inversely zoned phenocrysts. In the case of Santa Rita, magma mixing is indicated by the presence of compositionally diverse amphibole phenocrysts and intact calcite inclusions within quartz phenocrysts. In fact, the presence of compositionally variable amphibole phenocrysts seems to be a characteristic feature of porphyry-Curelated rocks in general and has even been proposed as a criterion to distinguish barren from mineralized systems (Mason, 1978; Mason and McDonald, 1978; Hendry et al., 1985).

was highly enriched in sulfur. Magmatic oxygen fugacity is constrained by the coexistence of quartz + amphibole + biotite + sphene (suggesting a logfO2 zNNO +1; Wones, 1989; Carmichael, 1991), and by the absence of magmatic sulfides. The sulfur content of the magma was on the order of 2500 5000 ppm S, as suggested by the former presence of 1 2 vol.% anhydrite phenocrysts. Similarly high sulfur contents were observed in the magmas erupn (e.g., Luhr, ted from Mt. Pinatubo and El Chicho 1990; Baker and Rutherford, 1996). The presence of compositionally diverse amphibole phenocrysts without markedly zoned intermediate members indicates that several magmas were involved in the formation of the quartz-monzodiorite. Al-in-hornblende barometry as well as magmatic calcite inclusions within quartz phenocrysts suggest that one of these magmas ascended directly from z 14 km depth. A comparison with other porphyry-type Cu deposits reveals that most of them are associated with oxidized intrusions in which the dominant sulfur species was sulfate. It might be premature, however, to conclude that magmatic sulfides were not important in these systems. Firstly, even small amounts of magmatic sulfides can dominate the budget of chalcophile elements, and, secondly, there is increasing evidence from both active and fossil porphyry-Cu systems that magmatic sulfides are present at stages where mafic melts interact with the oxidized magmas. Future studies will show whether such an interaction is a common feature of volcano-plutonic complexes hosting porphyry-Cu ore deposits.

Acknowledgements We like to thank Bob Bodnar (Virginia Tech, USA) and the Swiss National Science Foundation for financing this study. We are grateful also to Luca Fedele and Gretchen Benedix for help with the electron microprobe, and to Jing Leng for performing the Raman analyses. The paper improved significantly through discussions with Werner Halter and thorough reviews by Jeff Keith and Fleurice Parat. Additional thanks go to Bob North for guiding the senior author in the Santa Rita mine, and to Lawford Anderson for

4. Conclusions The premineralization quartz-monzodioritic magma at Santa Rita had a high oxygen fugacity and

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providing a spreadsheet for hornblende plagioclase thermobarometry. References

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