INTRODUCTION

Sulfur plays an essential role in the formation of many magmatic-hydrothermal ores, acting both as the agent to precipitate ore minerals and
as a primary ligand for transport of copper and gold in aqueous solutions to the site of ore deposition (Pokrovski et al., 2008). Many magmatic-
hydrothermal mineral deposits, including porphyry copper and high-sulfidation gold deposits, represent massive crustal sulfur anomalies and may
contain more than 1 Gt of sulfur (cf. Gustafson, 1979). Most researchers infer that sulfur in these deposits is derived via degassing of sulfur-rich
magma, although clear demonstration of close spatial and temporal links between sulfur-rich magmas and magmatic-hydrothermal ore deposits is
relatively rare in the literature (Deen et al., 1994; Audétat et al., 2004). Sulfate-rich and oxidized magmas can be recognized by the presence of
magmatic anhydrite as phenocrysts or in inclusions within silicate phenocrysts. Examples of anhydrite-bearing magmas of intermediate composition
have been documented among modern eruptions of Mount Pinatubo, El Chichon, Lascar, Nevado del Ruiz, and others (Luhr, 1990; Carroll and
Rutherford, 1987; Fournelle, 1990; Pallister et al., 1996; Matthews et al., 1999). Anhydrite has also been noted in ancient igneous rocks such as the
Eagle Mountain andesite in the San Juan volcanic field and Cajon Pass granites (Barth and Dorais, 2000; Parat et al., 2002). Magmatic anhydrite is
direct evidence of elevated sulfate content of magmas, but its presence is also dependent on the bulk composition, temperature, oxygen fugacity, and
total sulfur content of the parent magma.Sulfur is soluble as sulfate in oxidized dacitic magma at ~1000 ppm at 950 °C and at oxygen fugacity of
approximately NNO + 2 (Carroll and Rutherford, 1987), and in some eruptions, such as Pinatubo, there is also compelling evidence that additional
“excess” sulfur was present in a separate volatile phase and as anhydrite prior to eruption (Wallace and Gerlach, 1994).
This study presents data from Yanacocha, Peru, on anhydrite-bearing volcanic rocks. These rocks are genetically linked to large sulfur-rich
hydrothermal ore deposits that include nearsurface quartz-alunite-rich epi thermal gold deposits that rank among the largest in the world, and deeper
porphyry copper-gold deposits (Longo, 2005). The petrography and chemical composition of the anhydrite together with the petrology of the host
volcanic rocks can be used to demonstrate the existence of persistent sulfate-saturated conditions within a long-lived magma system, and serve as the
basis for estimating the magmatic contribution of sulfur to the mineral deposits.
THE YANACOCHA VOLCANICS
The Yanacocha district is located in the Andes of northern Peru in an area of relatively thick continental crust (~35 km) and long-lived
subduction-related arc magmatism. Volcanism began at ca. 20 Ma and focused in the Yanacocha vol canic center from 14.5 to 8.4 Ma where ~80
km3 of magma erupted in an area 20 km by 30 km (Longo, 2005). Compositions evolved from early pyroxene-bearing andesitic lavas through
hydrous hornblendebearing dacite ignimbrites, flow domes, lavas, and subvolcanic dikes, to late biotite-bearingdacite dikes and a rhyolite ignimbrite
(Longo, 2005). Hydrothermal alteration occurred in several well-dated pulses and locations, during the period from 13.6 to 8.2 Ma. Altered rock is
characterized by abundant alunite, pyro phyllite, and “vuggy silica” assemblages associated with “high-sulfidation ” epithermal gold-bearing ores
containing pyrite, covellite, and enargite. Hydrothermal contributions of gold and copper increased with time and peaked at the end of magmatism.
The Yana cocha mineral deposits include ~1500 t of gold in oxide ores averaging 0.5–1 g/t, with additional deeper sulfide resources containing gold
and >5 Mt of copper.
The Yanacocha volcanics consist of crystalrich (30–60 vol%) medium-K andesite, dacite, and minor low-silica rhyolite, ranging from 58 to
71 wt% silica (100% volatile-free). Early andesitic lavas contain phenocrysts of augite, hypersthene, sparse hornblende, and accessory magnetite,
ilmenite and apatite (Fig. 1). These rocks are overlain by the hornblende-bearing Maqui-Maqui andesitic ignimbrite, followed by a sequence of
pyroxene-hornblende -bearing andesite lavas and domes (upper Yanacocha lavas). The hornblendepyroxene-biotite-bearing San Jose low-silica
dacite ignimbrite (11.5–11.2 Ma) overlies those units. The San Jose ignimbrite is associated with and postdated by a series of mineralogically similar
intrusions and domes (11.4–11.2 Ma). Dacite plugs and dikes (10.8–9.9 Ma) and a small-volume rhyolite ignimbrite (8.4 Ma) represent the only units
erupted after 11.4 Ma. The 11.4–8.4 Ma intrusions are also temporally associated with the majority of the gold and copper ores. These late dacites
contain hornblende, biotite, and sparse quartz as well as accessory magnetite and titanite (Fig. 1).
Two populations of Ca-amphibole are apparent (Longo, 2005; this study). Early andesites contain high-aluminum (high-Al) pargasitic
hastingsite (~12 wt% Al2O3), whereas the late dacite domes have only low-aluminum (low-Al) magnesiohornblende (~7–9 wt% Al2O3). The
Maqui-Maqui and San Jose ignimbrites contain both high- and low-Al amphiboles. High-Al amphiboles typically have a narrow rim of magnetite,
but range from the rim-free (lower San Jose ignimbrite) to 35 vol% rim (early andesite ). Applications of the Blundy and Holland (1990) plagioclase-
hornblende geothermometer and the Anderson and Smith (1995) hornblende geobarometer to plagioclase (~An30–40) and coexisting low-Al
amphibole suggest that these minerals equilibrated in the upper crust at ~800 °C and 150–200 MPa. Fe-Ti oxide compositions and the assemblage of
magnetite + titanite + quartz suggest that late dacite magmas were strongly oxidized (approximately NNO + 1.5 to NNO + 2; Wones, 1989).
High-Al amphibole apparently crystallized at higher temperature and pressure from a more mafic magma composition than dacite. High-Al
amphibole has a high Cr content (up to 0.8 wt%) and rare earth element (REE) contents 5%–10% of low-Al amphibole. The TiO2 (1.5–2.4 wt%)–
Al2O3 thermobarometer for basalts of Ernst and Liu (1998) yields estimated temperatures of 800–900 °C and pressures of 600–900 MPa, but Aliv =
1.7–2.0 yields higher temperature estimates of 930–1000 °C (Helz, 1973). The high-Al amphibole contains only anhydrite and apatite inclusions so
apparently did not crystallize from a melt containing either plagioclase or pyroxene. These relationships are consistent with the observation of
amphibole as the liquidus phase in hydrous magmas, for example at 900–950 °C at a water pressure of more than 2.5 kbar in experiments on Mount
Saint Helens dacite (cf. Rutherford et al., 1985). Thus, the high-Al amphiboles likely crystallized from hydrous andesite or basaltic melts at ~950 °C
in a mid-crustal magma conduit.
ANHYDRITE AT YANACOCHA
Anhydrite is ubiquitous as inclusions within amphibole and pyroxene phenocrysts throughout the Yanacocha volcanic sequence (Fig. 1) and
occurs in two distinct textural types. Anhydrite inclusions hosted by clinopyroxene in andesitic lavas and in San Jose dacitic domes occur as rela
tively large (20–200 μm diameter) crystalline inclusions that are rounded or equant and show typical anhydrite cleavage planes (Figs. 1 and 2A).
Anhydrite inclusions in pyroxene occur alongside, and are volumetrically subordinate to, inclusions of apatite, Fe-Ti oxides and plagio clase. Small
fluid (?) inclusions in anhydrite are indicated by dark trails parallel to cleavage planes (Fig. 2A). Anhydrite inclusions also occur in both high- and
low-Al amphibole populations in the San Jose ignimbrite (Fig. 1). In low-Al amphibole, anhydrite inclusions (10–60 μm diameter) are less common
but are similar in appearance to those that occur in clinopyroxene. High-Al amphiboles from the middle and upper San Jose ignimbrite also host
similar rounded anhydrite inclusions (10–40 μm diameter) with visible cleavage.
In contrast, high-Al amphibole phenocrysts that lack Fe oxide rims from the lower San Jose ignimbrite (sample RC6; Longo, 2005) host
populations of unusual wormy and amoeboidalshaped anhydrite inclusions (referred to as “wormy”). These range from ~5 to 100 μm long and occur
in much higher proportions (up to ~10 vol%; Fig. 2B) than equant inclusions described above. Wormy inclusions are also distinctive because they do
not follow amphibole cleavage planes or growth zones (Fig. 2B), they contact rare high-sulfate apatite (0.24–1.2 wt% SO3; ~5–10 μm diameter) also
included in amphibole, and they commonly contain a few percent “bubble-shaped” features (Fig. 2C).
ANHYDRITE COMPOSITIONS
 The major and trace element compositions of anhydrite inclusions from Yanacocha were determined using electron microprobe and laser
ablation ICP-MS at Oregon State University (Table DR1 in the GSA Data Repository1). We also report data from other magmatic and
hydrothermally formed anhydrite: (1) phenocrysts and inclusions hosted by amphibole from Pinatubo, Philippines (from the June 15, 1991, eruption),
(2) phenocrysts from the Bolulu dacite dike, Julcani, Peru, (3) high-temperature hydrothermal porphyry Cu-Mo ores from Butte, Montana; El
Salvador, Chile; and Ajo, Arizona (Fig. 3).
The SrO and FeO contents of magmatic and hydrothermal anhydrites vary greatly (Fig. 3A). The SrO content of magmatic anhydrite is
typically high but ranges from <0.1 to 1.8 wt% in all samples, and from 0.4 to 0.8 wt% at Yanacocha. The FeO content of Yanacocha anhydrite
included in amphibole and pyroxene is elevated relative to both hydrothermal anhydrite and phenocrysts from Julcani, Pinatubo, and El Chichon. In
addition, anhydrite inclusions within amphibole from both Pinatubo and the San Juan volcanic field (Fig. 3A) (Parat et al., 2002) have similar
elevated FeO contents. We interpret that the elevated FeO is not a primary igneous feature but rather is the product of subsolidus diffusion of Fe from
the host amphibole and pyroxene into anhydrite.
The REE contents of anhydrite are also variable but display consistent differences between magmatic anhydrites from different settings.
Yanacocha and Pinatubo anhydrites have similar primitive mantle–normalized patterns with light REEs (LREEs) enriched by a factor of ~100
compared to heavy REEs (Fig. 3B). Julcani anhydrite phenocrysts display similar patterns, but REE abundances are ~20% lower. Yanacocha,
Pinatubo, and Julcani also have no Eu anomaly, although El Chichon anhydrite (Luhr, 1990) displays a marked positive Eu anomaly. In contrast,
high-temperature (~500–600 °C) hydrothermal anhydrites from Butte and El Salvador have flatter REE patterns with lesser enrichment of LREEs.
Ajo pegmatitic hydrothermal anhydrite has a pattern similar to magmatic anhydrite but with slightly higher REEs. Ajo and Butte samples also have a
negative Eu anomaly, whereas the El Salvador sample displays a slight positive Eu anomaly.
DISCUSSION AND CONCLUSIONS
Significance of Magmatic Anhydrite
The Yanacocha anhydrite occurrences provide compelling evidence for persistent sulfate-saturated conditions within a long-lived
intermediate magma system that spanned a sixmillion-year period. Texturally and compositionally, the Yanacocha anhydrites are magmatic in origin:
Anhydrite occurs as inclusions within igneous phenocrysts and has REE patterns consistent with crystallization in equilibrium with the host andesitic
to dacitic melts and unlike hydrothermal anhydrite. Moreover, the Yanacocha magmas are associated with large hydrothermal Cu and Au mineral
deposits and provide a direct link between high magmatic sulfate contents and sulfur-rich hydrothermal mineralization.
We suggest that sulfate saturation in intermediate magmatic systems may be more common than currently realized. The presence of
inclusions of anhydrite in silicate phenocrysts may represent a robust method for tracking anhydrite saturation in magmas and provide a means to
evaluate the potential of hydrous magmas for producing sulfur-rich hydrothermal ore deposits. The presence of high-sulfur apatite coexisting with
anhydrite at Yanacocha also supports the use of apatite composition as a monitor of high magmatic sulfur content (Streck and Dilles, 1998).
Carroll and Rutherford (1987), Baker and Rutherford (1996), and Jugo et al. (2005) have shown that for sulfate-bearing oxidized magmas (>
NNO + 1) the solubility of sulfur increases with temperature and the iron content of the magma. Yanacocha and other anhydrite-bearing magmas are
strongly oxidized ( f O2 ≈ NNO + 1 to NNO + 2) and water-rich dacites andesites (cf. Baker and Rutherford, 1996). Pre-eruptive magmatic
conditions for Yanacocha, El Chichon, and Pinatubo are all ~800 °C and ~200 MPa, with the Julcani dacite possibly extending up to 900 °C. At these
temperatures and compositions, the magmas would dissolve <200 ppm sulfur as sulfate, and additional sulfur could only be stored as anhydrite
crystals or as a separate volatile phase. In contrast, anhydrite-bearing Yanacocha high-Al amphibole crystallized at ~950 °C at a significant depth
(~20–30 km) and was likely derived from a more mafic magma emplaced into the base of the upper crustal dacite magma chamber. Assuming an
andesitic composition, such a magma would have a sulfur solubility of ~1000 ppm (Luhr, 1990; Baker and Rutherford, 1996). This anhydrite-
saturated andesitic magma may have supplied much of the sulfur to the upper crustal dacite magma, with the result that the latter was also sulfate-
saturated (Fig. 4).
 Magmatic Sulfur Budget and Ore Formation
We can also estimate a minimum magmatic contribution of sulfur to Yanacocha hydrothermal fluids, assuming sulfur is quantitatively
degassed from subvolcanic intrusions. Using an intrusion to extrusion ratio of 5:1 and ~80 km3 of extrusions, we estimate an intrusive volume of
~400 km3 (1100 Gt at ρ = 2.75 g/cm3). An average minimum concentration of 1000 ppm sulfur results in an estimate of ~1100 Mt of sulfur mainly
degassed as SO2 over the six-millionyear period of magmatism. The giant Yanacocha mineral deposits lie within large volumes of rock (>4 km3)
that are intensely hydrothermally altered by sulfate-rich and low-pH fluid to rock rich in alunite (up to 50 vol%) and pyrite (1–5 vol%). A minimum
estimate for the total amount of hydrothermal sulfur added as alunite and sulfides is 200 Mt (Table DR2). Our magmatic sulfur estimate is
approximately five times greater than this amount and shows that the magmatic system is easily capable of providing all the hydrothermal sulfur
present in known Yanacocha deposits. Most hydrothermally mineralized rocks at Yanacocha formed relatively late (ca. 11.2–8.4 Ma), which suggests
either more efficient hydrothermal precipitation at this stage or a temporal increase in the amounts of magmatic sulfur. We conclude that unusually
sulfur-rich magmas at Yanacocha were able to supply the observed hydrothermal sulfur, and speculate that such magmas are required to form large
magmatichydrothermal ore deposits.
Sulfate Melt as a Sulfur Source?
Finally, our study provides textural evidence for the presence of an immiscible CaSO4-rich melt that coexists with silicate melt and could be a
source of sulfur in magmatic systems. Wormy anhydrite inclusions containing vapor “bubbles” are observed in high-Al amphiboles and contrast with
rounded and equant anhydrite that we interpret to have been trapped as solids in low-Al amphibole and pyroxene. Such unusual wormy textures have
not been reported before for anhydrite inclusions, and we suggest that they may result from trapping a CaSO4-rich liquid. Jugo et al. (2005) found
sulfate blebs in run products from experiments involving oxidized basalt with 1.5 ± 0.2 wt% dissolved sulfur at 1300 °C and 1 GPa, and suggested
that they were derived from melt rather than the expected solid anhydrite (melting point 1450 °C). Additionally, recent experiments on sulfur-rich
phonolites at 920 °C produced an immiscible sulfateand chloride-dominated and water-bearing melt or fluid (J.D. Webster, 2008, personal commun.).