2011 Society of Economic Geologists, Inc. Economic Geology, v. 106, pp.

13991424

Evidence for Magmatic-Hydrothermal Fluids and Ore-Forming Processes in Epithermal and Porphyry Deposits of the Baguio District, Philippines
DAVID R. COOKE,1, CARI L. DEYELL,1,* PATRICK J. WATERS,2 RENE I. GONZALES,2,** AND KHIN ZAW1
1 CODES

ARC Centre of Excellence in Ore Deposits, University of Tasmania, Private Bag 126, Hobart, Tasmania, 7001, Australia American Exploration Philippines Inc., 1101 Pearlbank Centre Building, 146 Valero Street, Salcedo Village, Makati City, Metro Manila, Philippines

2 Anglo

Abstract
The Baguio district contains a diverse array of epithermal, porphyry and skarn deposits, together with a large, broadly strata bound, advanced argillic lithocap. Magmatism, mineralization, and alteration occurred in response to subduction of the South China Sea plate and the Scarborough Ridge beneath northern Luzon over the past 3 m.y. Rapid uplift and exhumation resulted in epithermal veins overprinting several porphyry Cu-Au deposits. Most of the epithermal Au-Ag deposits of the Baguio district (including Antamok and Acupan, the two largest Au deposits) are intermediate sulfidation state quartz-carbonate-adularia-illite-base metal sulfide veins that contain electrum and minor Au-Ag tellurides. In contrast, high sulfidation mineralization at Kelly includes enargite, tennantite, electrum, and precious metal tellurides and is associated with advanced argillic alteration. Although the mineralizing fluids that formed the porphyry and epithermal deposits had distinct temperatures and salinities, stable and radiogenic data provide evidence for direct magmatic contributions into each deposit type. The epithermal mineralizing fluids were dilute (generally, <2 wt % NaCl equiv) and had moderate temperatures (<300C). Porphyry-style mineralization was associated with high temperature (300 to >600C) hypersaline brines (30 to >70 wt % NaCl equiv) and low-density vapor. Sulfur isotope compositions of sulfides in the porphyry, skarn and intermediate sulfidation epithermal veins of the southern and central Baguio district are mostly between +1 and +6 per mil, consistent with a predominance of H2S in the mineralizing fluids (i.e., reducing conditions). In contrast, sulfides from the high sulfidation, porphyry, and intermediate sulfidation deposits located adjacent to the Baguio lithocap mostly have negative sulfur isotope values (6.9 to +0.8), consistent with oxidizing (SO42-predominant) mineralizing fluids. Intermediate sulfidation epithermal veins at Acupan have crosscut a well-mineralized porphyry Cu-Au stockwork at Ampucao. The two deposits cannot be distinguished on the basis of radiometric age determinations (Ampucao: 0.51 0.26 Ma; Acupan: 0.65 0.07 Ma), and are interpreted to be cogenetic, with telescoping of the two environments caused by the rapid uplift and exhumation associated with ridge subduction. Measured 34Ssulfide (+1.1 to +6.6), 34Ssulfate (+10.4 to +31.8) values and initial strontium ratios of anhydrite (0.703780.70385) are consistent with identical and predominantly magmatic sources of these components for the Ampucao porphyry and Acupan epithermal veins. Helium isotopes provide further evidence of mantlederived components in the epithermal veins (R/Ra values of 6.0 and 6.7). Oxygen, deuterium, and carbon isotopes provide evidence for predominantly magmatic water at Ampucao and for hybrid magmatic-meteoric waters at Acupan that precipitated precious metals due to boiling. The proportion of magmatic water relative to meteoric water and precious metal grades both decreased with time during epithermal vein formation at Acupan. The common observation of cross-cutting relationships between porphyry and epithermal veins observed throughout the Baguio district imply that the evolution of porphyry-style to intermediate sulfidationstyle mineralization was a common phenomenon in this region, and contributed significantly to its rich metal endowment.

Introduction CLOSE SPATIAL and temporal relationships between porphyry and high sulfidation epithermal deposits have been demonstrated in several mineral districts (e.g., Mankayan, Philippines: Arribas et al., 1995; Hedenquist et al., 1998; Chang et al., 2011; Deyell and Hedenquist, 2011; Nevados del Famatina, Argentina: Losada-Calderon and McPhail, 1996; Pudack et al., 2009; Maricunga, Chile: Muntean and Einaudi, 2001). These geochronological, stable isotope, and fluid inclusion studies have provided compelling evidence for a genetic association between porphyry deposits, high sulfidation epithermal
Corresponding author: e-mail, d.cooke@utas.edu.au *Present address: Spectral International Inc., Arvada, Colorado. **Present address: PT. Sorikmas Mining, Jl. Torsiojo, Kotanopan, Mandailing Natal, North Sumatra, Indonesia.

Cu-Au-Ag mineralization, and zones of hypogene advanced argillic and silicic alteration (e.g., Sillitoe, 2010). In contrast, it can be difficult to demonstrate a genetic association between porphyry deposits and epithermal deposits dominated by quartz-carbonate-pyrite-illite-(adularia-sphalerite-galena) veins and breccias (aka carbonate-base metal sulfide veins: Corbett and Leach, 1998, or intermediate sulfidation veins: Hedenquist et al., 2000; Sillitoe and Hedenquist, 2003). The spatial association of these deposit types has been well-established in several districts, including Mankayan, Philippines (Sajona et al., 2002), Collahuasi, Chile (Masterman et al., 2005), and Rosia Montana, Romania (Wallier et al., 2006). Stable isotopic results give strong indications of magmatic contributions to the hydrothermal fluids forming epithermal mineralization in some districts (e.g., Rosia Montana: Wallier et al., 2006), but equivocal results in others (e.g., Victoria,

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COOKE ET AL.

Philippines: Sajona et al., 2002; Madjarova, Bulgaria: Rice et al., 2007; Cowal, Australia: Zukowski et al., submitted). The Baguio district, Philippines (Fig. 1), contains two giant and numerous smaller intermediate sulfidation state epithermal vein systems. Mineralized veins at the giant Antamok and Acupan deposits extend from surface to depths of almost a kilometer below surface (Sawkins et al., 1979; Cooke and Bloom, 1990; Cooke et al., 1996), and mining of these veins by Benguet Corporation produced more than 535 t Au during the 20th century (Waters et al., 2011). The district also contains porphyry Cu-Au deposits and prospects (e.g., Santo Tomas II, Ampucao, Nugget Hill), in addition to skarns (Thanksgiving, Mexico) and a high sulfidation state epithermal vein system (Kelly: Comsti et al., 1990; Aoki et al., 1993; Deyell and Cooke, 2003; Waters et al., 2011; Fig. 2). The porphyry deposits of the Baguio district were emplaced between 3 and 0.5 Ma, whereas epithermal veins appear to have formed in the last million years (Aoki et al., 1993; Imai, 2001; Waters et al., 2011; Table 1). This manuscript presents new stable and radiogenic isotopic data for epithermal and porphyry deposits of the Baguio district. These data are used to assess the relative importance of magmatic and meteoric components in the mineralizing fluids, evaluate likely depositional processes, and, in combination with new geochronological data from Waters et al.
118E 122E 126E

(2011), to establish whether the porphyry and intermediate sulfidation epithermal deposits are cogenetic. Geologic Setting of the Baguio District The geology of the Baguio district is described in Waters et al. (2011) and major tectonic elements of the Philippines are shown in Figure 1. Table 1 summarizes the characteristics of the main volcanosedimentary and intrusive rock units, and their distribution is shown on Figure 2. Key elements in the geologic evolution of the district are as follows: (1) sedimentation and volcanism in a submarine basin setting (Pugo Formation: Eocene-Oligocene); (2) shallow marine clastic and carbonate sedimentation and minor andesitic volcanism (ZigZag and Kennon Formations: late Oligocene-early to mid Miocene); (3) middle Miocene arc magmatism related to subduction of the South China Sea plate beneath northern Luzon along the Manila trench (Central Cordillera Diorite Complex; Hollings et al., 2011 a); (4) onset of mountain building uplift and terrestrial sedimentation (Klondyke Formation: middle to late Miocene); (5) commencement of subduction of the Scarborough ridge during the Pliocene, shallowing of subduction angle, transpressional displacement on the leftlateral Philippine fault system, rapid uplift and erosion, intrusion of mafic dikes, quartz diorite porphyries and dacite domes, diatreme volcanism, widespread Pliocene-Pleistocene porphyry and epithermal mineralization (Hollings et al., 2011b; Waters et al., 2011; Tables 1, 2). Mineral Deposits The mineral deposits of the Baguio district are described in Waters et al. (2011). Their characteristics are summarized in Table 2 and locations are shown on Figure 2. We provide detailed summaries of the Acupan and Kelly epithermal Au-Ag deposits and the Ampucao porphyry Cu-Au prospect, below, as most of our new analytical data are derived from these deposits. Acupan Pleistocene epithermal Au-Ag veins at the Acupan and Itogon mines (hereafter referred to collectively as Acupan) were described by Callow and Worley (1965), Sawkins et al. (1979), Cooke and Bloom (1990), Cooke et al. (1996) and Cooke and McPhail (2001). Acupan is the second-largest epithermal deposit in the Baguio district in terms of gold production (Table 2), and is also one of the largest epithermal vein systems in the world, in terms of contained gold (Hedenquist et al., 2000). Since the commencement of underground mining operations in 1931 until mine closure in 1993, the Acupan and Itogon mines exploited the western and eastern halves of the Acupan vein system (Fig. 3). More than 225 t Au was extracted during underground mining of the composite banded quartz-carbonate veins and hydrothermal breccias. In the late 1980s, average mining grades were approx. 6.1 g/t Au, with a cutoff grade of ~4.2 g/t (United Nations Development Programme-UNDP, 1987). A remaining bulk mining resource that contains about 99 t Au was defined by Placer Dome Inc. in the mid-1990s (Waters et al., 2011). The principal host rocks to mineralization at Acupan are the Virac granodiorite, Balatoc diatreme, and andesites of the ZigZag Formation (Fig. 3). The epithermal veins have intensely

nc h

Mankayan district
(3.5 - 1.4 Ma)
M an ila

Tr e

Phil

(3.1 - 0.5 Ma)

ippi

Baguio district

ne T renc

20N

Philippine Plate
16N

b Scar

orou e

gh

Ridg

Eurasian Plate
Sulu Trench

12N

8N

Philippine Fault

200 km

FIG. 1. Major tectonic elements of the Philippines. The locations of the Baguio and Mankayan districts in northern Luzon are highlighted by white diamonds. Active volcanoes are denoted by black triangles. The approximate position of the Scarborough Ridge has been interpreted from bathymetry data provided by the National Geophysical Data Centre (unpub. data, 2004). Active and inactive subduction zones are highlighted by black and whitefilled ticks, respectively. Diagram modified from Cooke et al. (2005). 0361-0128/98/000/000-00 $6.00

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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FIG. 2. Geology and mineral deposits of the Baguio district, Philippines (modified from Waters et al., 2011). 0361-0128/98/000/000-00 $6.00

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TABLE 1. Geology of the Baguio District with Geological Units Sorted by Formation Age (youngest at the top of the table)

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Unit Hartwell: dacite porphyry Ampucao: quartz diorite to quartz-phyric hornblende dacite porphyry Balatoc: polymict matrix-rich breccia (diatreme) and latestage Balatoc dacite porphyry Quartz diorite porphyry Santo Tomas II porphyry Cu-Au deposit Bumolo porphyry Cu-Au prospect Black Mountain porphyry Cu-Au deposits, Thanksgiving Au-base metal skarn, Mexico Cu-Au skarn Hosts high sulfidation state epithermal gold veins at Kelly Au-Ag mine Small diorite body at Baguio Gold correlated with Kelly diorite by Comsti et al (1990) Principal host to Baguio lithocap synchronous with Black Mountain porphyry complex? Kidao and Ubolan porphyry Cu-Au prospects Precursors to mineralization in the Baguio district Oldest known porphyry center in the district Kelly diorite dated at Tuding silica pit; the small diorite at Baguio Gold yielded a maximum K-Ar age of 2.3 Ma (Aoki et al., 1993) Malaterre (1989) reported an age of 3.57 Ma from andesite breccia; Maximum age only provided by pre-mineralization mafic dikes. Likely to be younger. Hornblende megacrysts up to 10 cm in diameter in individual dikes Some debate exists as to whether this is part of the Kennon Formation or a separate unit Hosts parts of Antamok and Baguio Gold veins May have originally hosted surface expression of epithermal mineralization at Acupan Skarn alteration and mineralization proximal to Pliocene intrusive complexes High energy depositional environmentdetritus generated by uplift and exhumation of the Luzon Central Cordillera Shallow marine settingshoaling of the Miocene arc? Most productive center of porphyry Cu-Au mineralization in the Baguio district Marginal clast-supported facies of Balatoc diatreme hosts significant Au mineralization at Acupan Late-stage Balatoc dacite pipe cuts epithermal veins Ampucao porphyry related to high grade porphyry Au-Cu mineralization at Ampucao Dacite intrusions have adakitic compositions de Guzman (pers. commun., 1986), Cooke and Bloom (1990), Defant and Drummond (1990), Waters et al. (2011), Hollings et al. (2011b)

Age

Lithofacies and contact relationships Association with mineralization Comments References

0361-0128/98/000/000-00 $6.00 Imai (2001), Waters et al. (2011) Callow (1967), Sweet et al. (2008), Waters et al. (2011) Comsti et al. (1990), Aoki et al. (1993) Quartz diorite porphyry, plagioclase hornblende andesite porphyry North-trending 1 km+ diameter microdiorite pluton Has intruded the Zigzag and Klondyke Formations COOKE ET AL. Terrestrial andesitic tuffaceous rocks, breccias and flows, intercalated with conglomerates and minor sandstones Hornblende diorite, quartz diorite porphyry Diabase, lamprophyre and appinite dike swarm Distinctive hornblende megacrysts Limestone Smith and Eddingfield (1911), De los Santos (1982), Malaterre (1989), Waters et al. (2011) Waters et al. (2011) UNDP (1987), Waters et al. (2011), Hollings et al. (2011b) Leith (1938), Malaterre (1989), Pea (1998), Waters et al. (2011) Durkee and Pederson (1961); UNDP (1987), Mitchell and Leach (1991), Pea (1998), Waters et al. (2011) Pena (1998), Waters et al. (2011) Conglomerates, grits, sandstones and mudstones with interbedded andesitic lavas, breccias and tuffaceous beds Grey biohermal limestone, calc-arenites, calc-rudites

Ampucao-HartwellBalatoc cluster

Hartwell dacite: 1.09 0.10 Ma Ampucao porphyry: 0.51 0.26 Ma Balatoc dacite plug: 0.8 Ma (Defant and Drummond, 1990)

Santo Tomas IIBumolo-Clifton cluster

Santo Tomas II: 1.48 0.05 Ma; 1.47 0.05 Ma

Black Mountain Intrusive Complex

3.09 0.15 Ma to 2.81 0.24 Ma

Kelly diorite

3.1 1.1 Ma (Togashi, in Aoki et al., 1993) < 2.3 Ma at Baguio Gold (Aoki et al., 1993)

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Baguio Formation

3.594 0.070 Ma

Camp 4 Intrusive Complex

Pre-mineralization mafic dikes: 4.55 0.15 Ma; 4.028 0.074 Ma

Hornblende-phyric dike complex

Pliocene (4.56 0.28 Ma, 4.11 0.42 Ma, 4.03 0.14 Ma)

Mirador Limestone

Miocene-Pliocene (faunal age)

Klondyke Formation

Middle-late Miocene microfossil assemblages

Kennon Formation

Early-middle Miocene faunal ages

EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES The Virac granodiorite is the main Middle Miocene arc magmatism Shannon (1979), JICA host rock to epithermal veins at calc-alkaline intrusive suite (1983), Knittel and Defant Acupan characterized by low K and (1988), Cooke and Bloom Acupan epithermal veins pinch large ion lithophile abundances (1990), Cooke et al. out to the east in the Lucbuban The Virac granodiorite is a high (1996), Pea (1998), gabbro K calc-alkaline intrusion preWaters et al. (2011), Kelly diorite hosts vein mineralization viously thought to be Pliocene Hollings et al. (2011a) at Kelly in age Epithermal veins at Antamok pinch out to the east in the Antamok diorite Worley (1967), Pena (1970), Balce et al. (1980), Mitchell and Leach (1991), Cooke et al. (1996), Waters et al. (2011) Schaffer (1954), Balce et al. (1980), Pea (1998), Waters et al. (2011)

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Note: 40Ar39Ar age determinations from Waters et al. (2011), unless otherwise indicated

Middle miocene (Virac granodiorite; 20.23 0.38, 20.2 0.7 Ma; Lucbuban gabbro; 22.6 0.5 Ma)

Late Oligocene to middle Miocene faunal ages

Cretaceous to Eocene

developed sericitic (muscovite illite) alteration halos that pass outward to propylitic alteration assemblages. Five paragenetic stages have been defined in the crustiform banded veins: type A chalcedony (restricted to higher mine levels, commonly occurring as clasts in later-formed bands), marginal type B fine-grained gray quartz bands that contain abundant hydrothermal breccia textures, intermediate type C white quartz with moderately abundant hydrothermal breccias, central type D calcite with minor breccia textures, and barren late-stage type E anhydrite bands and veins (Cooke et al., 1996; Fig. 4). More than 1,000 fluid inclusions analyzed from two vein systems (381-No Name fault vein system and 209-Odd vein system) had homogenization temperatures between 300 and 200C, with a gradual decline in temperatures from type B to type D bands. Some anomalously high temperatures (>300C) were recorded, but these were attributed to mixed entrapment of liquid and vapor in boiling fluid inclusion populations. Calculated salinities were between 0.0 and 5.1 wt percent NaCl equiv, but mostly below 1 wt percent (Cooke and Bloom, 1990; Fig. 5). Over 440 veins have been mined underground. Most of the northeast-trending veins dip steeply to the southeast. A subordinate set of structures have easterly strikes and dip to the south (Fig. 3). High-grade ore shoots occur at the intersections of these two structural orientations. The veins are grouped into five main series. These are, from north to south, the 100, 200, 300, 400, and 500 series veins (Fig. 3). Both the direction and amount of displacement along these structures prior to epithermal mineralization is uncertain. Minor gouge is locally developed on the margins of some veins, suggesting minor postmineralization strike-slip movement. Displacements along the Star and Pine faults may be in excess of 150 m (Worley, 1967). Most of the veins are 0.5 to 1 m wide. The 364 vein has an average width of 4 m and attains a maximum of 12 m (Worley, 1967). The Acupan veins are exposed at surface, implying that the top of the deposit has been removed by erosion. The currently exposed vertical extent of vein mineralization is almost 1 km, considerably larger than many epithermal veins (cf. Cooke and Simmons, 2000; Simmons et al., 2005), and similar to the spectacular epithermal ore shoots at Pachuca Real-del Monte, in Mexico (Geyne et al., 1963). At the southern end of the Acupan mine, the 400 and 500 series epithermal veins have crosscut porphyry-style quartzmagnetite-chalcopyrite veins associated with the Ampucao porphyry Au-Cu prospect (Cooke and Bloom, 1990). The Acupan epithermal veins formed at 0.65 0.07 Ma, based on a K-Ar age determination from an illitic alteration halo to the 409 vein (Aoki et al., 1993). Ampucao The Ampucao porphyry Au-Cu prospect (also known as Acupan South) has been described by Cooke and Bloom (1990), Cooke (1991), and Waters et al. (2011). It was first discovered by underground drilling on the southern fringe of the Acupan mine (Figs. 3, 6). Subsequent field mapping by AngloAmerican in the late 1990s identified outcrops of potassic alteration and mineralizing intrusions. Porphyry-style mineralization is associated with the Ampucao porphyry complex, which comprises early- and intramineralization quartz diorite

References

TABLE 1. (Cont.)

Diorite, quartz diorite, granodiorite, gabbro, trondjhemite Has intruded the Zig-Zag and Pugo formations Unconformably overlain by the Klondyke Formation

Marine sedimentary rocks, minor basaltic to andesitic lavas and related breccias Unconformably overlain by the Klondyke Formation Zig-Zag Formation

Hosts porphyry and epithermal mineralization at several deposits, including Acupan and Antamok Limestone horizon hosts skarn mineralization at Thanksgiving Pugo Formation / Dalupirip Schist Basaltic and andesitic volcanic rocks, sandstones, argillites and cherts

Age

Lithofacies and contact relationships

Association with mineralization

Central Cordillera Diorite Complex (Agno Batholith)

Unit

Submarine basininterpreted to be the sedimentary cover to an ophiolite by Malaterre (1989)

Shallow marine settinglocal hematitic detritus may be of terrestrial origin

Comments

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TABLE 2. Mineral Deposits of the Baguio District Sorted by Approximate Age of Formation

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Deposit Intermediate sulfidation Estimated production of approximately 310 t Au; average grade ~ 4 g/t Au Strata-bound Wildcat Cu orebody had reserves of 0.65 Mt @ 3.7% Cu in 1971 Combined production of >225 t Au from 1931 to 1993, with a remaining bulk mineable resource ~99 t Au Average mining grade at Acupan of 6.1 g/t (4.2 g/t cutoff) during the 1980s; average grade at Itogon was 10 g/t during the same period Underground mining operation during the 1980s Two stages of mineralization: Stage I intermediate sulfidation state mineralization averaged 23 g/t Au (locally up to 10 g/t); stage II high sulfidation state mineralization typically had grades of up to 1117 g/t Au Two levels of underground production in the 1980s The upper drive at 920 m elevation had an average grade of 17 g/t Au, whereas the lower level had an average grade of 7 g/t Au The Little Corporal vein had grades of up to 29 g/t Au; 100 t/day of ore was produced from the Lonesome vein in the mid-1980s Underground mine active prior to World War II Low-grade (2.5 g/t Au) open cut and heap leach operation from 1984 to 1989 Camaso Vein had average grades of approximately 5 g/t Au Underground mine prior to World War II; reopened 19841987 Epsilon, Chi, and Bayating A + B veins averaged 613 g/t Au Drill hole intercept of 70 m @ 0.18% Cu, 0.95 g/t Au Underground mining started in 1957 Total ore reserves are estimated at 370 Mt with average grades of 0.3% Cu and 0.6 g/t Au No data available Average grades of 0.2% Cu and 0.5 g/t Au detected in early mineral quartz diorite porphyry Best intercepts: 37m of porphyry mineralization @ 0.11% Cu, 0.03 g/t Au; 3 m of skarn @ 0.14% Cu, 0.41 g/t Au Main (Kennon) orebody: pre-production reserve of 47 Mt ~ 0.38% Cu, 0.35 g/t Au, 0.01 % Mo Southeast orebodypre-production reserve of 15 Mt ~ 0.37% Cu, 0.26 g/t Au Production of 1.1 Mt ~12.8 g/t Au up to 1987; average grades of 3.8% Zn, 0.28% Cu, 36.9 g/t Ag, 5.7 g/t Au Surface rock chip assays of up to 0.97% Cu, 1.83 g/t Au Surface rock chip assays of up to 1.17% Cu, 4.58 g/t Au Rock chips from Kidao diorite average 0.27% Cu, 0.25 g/t Au, with local highs of 1.18% Cu, 0.64 g/t Au; Ubolan reported to be low grade Sawkins et al. (1979); UNDP (1987); Cooke and Bloom (1990); Cooke et al. (1996); Cooke and McPhail (2001); Waters et al. (2011) Comsti et al. (1990); Aoki et al. (1993); Deyell and Cooke (2003); Waters et al. (2011) Sawkins et al. (1979); Damasco, (1979); UNDP (1987); Waters et al. (2011)

Age

Mineralization style

Rock chip assays / grade and tonnage data

References

Antamok

Pleistocene ?

0361-0128/98/000/000-00 $6.00 Intermediate sulfidation High and intermediate sulfidation veins with advanced argillic alteration Intermediate sulfidation UNDP (1987); Mitchell and Leach (1991); Waters et al. (2011) UNDP (1987); Livingston (1939a, b); Mitchell and Leach (1991) UNDP (1987); Mitchell and Leach (1991); Waters et al. (2011) Waters et al. (2011) UNDP (1987); Waters et al. (2011) Cooke and Bloom (1990); Waters et al. (2011) Imai (2001); Waters et al. (2011) Intermediate sulfidation Intermediate sulfidation Intermediate sulfidation Intermediate sulfidation Cu-Au porphyry Cu-Au porphyry COOKE ET AL. Cu-Au porphyry Cu-Au porphyry Cu-Au skarn Cu-Au porphyry Imai (2001); Waters et al. (2011) Waters et al. (2011) Waters et al. (2011); Hollings et al. (2011b) Callow (1967); Bureau of Mines and Geosciences (1986); Sweet et al. (2008); Waters et al. (2011) Callow (1967); Bureau of Mines and Geosciences (1986); UNDP (1987); Waters et al. (2011) Waters et al. (2011) Waters et al. (2011) Waters et al. (2011) Au-Zn skarn (adjacent to Black Mountain porphyry) Cu-Au porphyry Cu-Au porphyry Cu-Au porphyry

Acupan-Itogon

K-Ar illite age: 0.65 0.07 Ma (Aoki et al., 1993)

Kelly-Baco

K-Ar illite maximum age: <0.6 Ma (Aoki et al., 1993)

Atok-Big Wedge

Pleistocene?

Baguio Gold

Pleistocene?

Cal Horr

Pleistocene?

Chico Mine

Pleistocene?

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Sierra Oro

Pleistocene?

Ampucao

0.51 0.26 Ma

Santo Tomas II

1.48 0.05 Ma; 1.47 0.05 Ma

Clifton

K-Ar age: 1.7 0.6 Ma (Imai; 2001)

Bumolo

2.06 0.70 Ma

Mexico

3.09 0.15 Ma to 2.90 0.15 Ma

Black Mountain (Kennon and Southeast)

3.09 0.15 Ma to 2.81 0.24 Ma

Thanksgiving

~ 3 Ma?

Chico prospect

Pliocene?

Nugget Hill

Pliocene?

Camp 4 (Kidao and Ubolan)

<4.028 0.074 Ma

Note: 40Ar-39Ar age determinations from Waters et al. (2011), unless otherwise stated

EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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Acupan
3000 W 16000 S 1500 W ZERO 1500 E

Itogon
3000 E

LEGEND
Andesite dikes Collapse breccia Balatoc diatreme
v

B Vein

36 Shaft
90

Ve in

20500 S

V ine

ein

237

n Lode Vei
286 364 Vein
No

Shaft

Vein
au lt

21

0V

ein

F me Na

k Haw

eye

F ault

22000 S
ein 403 V

381

Vei

23500 S

422 Vein

Fr

rt

Ve 412

Fa

og

in
Vein

Cu

Fog Shaft

ult

Ve in

25000 S

501

Acupan

FIG. 3. Geology of the Acupan intermediate sulfidation epithermal vein system, as exposed on underground mine level 1500. Also shown is the location of the Balatoc diatreme and the property boundary between the Acupan and Itogon mines (modified after Cooke et al., 1996).

porphyries and a late-mineralization dacite porphyry with adakitic affinities (Waters et al., 2011). A40Ar-39Ar age determination of 0.51 0.26 Ma has been obtained from the Ampucao porphyry complex, making it the youngest known porphyry deposit in the Baguio district (Waters et al., 2011). Figure 6 shows the geology and assay data from discovery drill hole 741-1FJ. One-meter composite samples mostly assayed between 0.2 and 5 g/t Au, although free gold was only observed from one vein intersection in the ~300 m long drill hole (de Guzman, pers. commun., 1986; Cooke and Bloom,

Sericite-altered wallrocks

B B

C B D E
~1 m

C D

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19000 S

99

in Ve

Go

17500 S

St

ar

Fa

ul t lde n te Ga

Fa

ul t

(dacite plug, young plug)

Hartwell plug Ampucao dacite Virac granodiorite

14 in Ve

v v

Lucbuban gabbro Klondkye Formation

364 V

ein

Zig-Zag Formation

Structures
410 Vein

Lithological boundary (definite) Lithological boundary (inferred)

Fault / vein

Sample locations
0 500 m

209Odd Vein System

Itogon

381 VeinNo Name Fault Vein System

1990). Average grades in the bottom 70 m of this drill hole were ~0.18% Cu and 0.95 g/t Au. Potassic alteration has produced a secondary biotite-magnetite-quartz-anhydrite assemblage in the andesites of the Zig-Zag Formation, and orthoclase-quartz-anhydrite assemblages in the Ampucao porphyry complex and Virac granodiorite (Cooke and Bloom, 1990). Intermediate argillic and phyllic alteration assemblages overprinted the early-formed potassic assemblages. Early quartz-magnetite-anhydrite-chalcopyrite veins were deposited from high temperature (300C

FIG. 4. Schematic space-time diagram for mineralization hosted by composite banded epithermal veins at Acupan (modified after Cooke et al., 1996). The granodiorite and andesite wallrocks are typically altered to quartz-sericite-pyrite (K-mica) assemblages adjacent to the veins. Earliestformed gray quartz-cemented breccia bands (type B) occur on the margins of the crustiform banded veins, and contain high grade gold-silver mineralization and abundant altered wallrock clasts. Locally brecciated bands dominated by coarse-grained white quartz (type C) are typically the most abundant component of the veins volumetrically, and contain some high-grade Au-Ag mineralization, particularly near contacts with type B bands. Central cavities of the composite veins have typically been infilled by calcite (type D) and/or anhydrite (type E). Anhydrite only occurs in the epithermal veins at depth in the southern part of the deposit. Type A chalcedony occurs as clasts (A) within type B and C bands at high elevations within the mine. Chalcedony is only a minor clast component within the breccia veins, which are dominated by clasts of locally-derived sericite-altered wallrocks and earlierformed vein material. Gold occurs primarily in type B and C bands.

Sericite-altered wallrocks

~1 km

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1600

COOKE ET AL.
1600

Type B
1400

Type C
white quartz

Type D
calcite
1400

gray quartz

1200

1200

Elevation (m)

Elevation (m)

1000

1000

800

800

600

600

400

400

200 100 200 300 400 100 200 300 400 100 200 300 400

200 500

Homogenization temperature

( C)

FIG. 5. Fluid inclusion homogenization temperatures for type B, C, and D bands from the 381-No Name fault system at Acupan, plotted with respect to elevation (modified after Cooke and Bloom, 1990). Symbols: white diamonds = vapor-rich twophase fluid inclusions that homogenize to vapor, gray circles = liquid-rich two-phase fluid inclusions that homogenize to liquid, black squares = liquid-rich, three-phase fluid inclusions that homogenize to liquid and that contain an insoluble non-ionic daughter mineral. Also shown are boiling point-depth curves for pure H2O liquid (after Haas, 1971) that have been fitted to the data sets visually in order to estimate paleodepths below surface (Cooke and Bloom, 1990). The gradual decrease in temperatures with elevation is consistent with boiling-induced cooling of the mineralizing fluids. The decrease in paleodepths is consistent with landsurface degredation during evolution of the hydrothermal system (Cooke and Bloom, 1990). Anomalously high temperatures (above 300C) were obtained from samples that contain both liquid-rich and gas-rich fluid inclusions, and are interpreted to be spurious data, caused by mixed entrapment of water and steam during boiling (Cooke and Bloom, 1990).

Cu ( %)

0.4

0.2

0
Fog Shaft

L-2300

Au ( g/t)

9695

15 10

9695 2

9695 3 9695 4

9695

5 0

9695

5 6 9695 7 9695 9

9696

2 9696

Ampucao dacite Virac granodiorite Zig-Zag Formation Stable isotope sample location
FIG. 6. Drill hole log and assay results for diamond drill hole 741-1FJ, modified after Cooke and Bloom (1990). Also shown are stable isotope sample locations from the Ampucao porphyry deposit. Drill hole 741-1FJ was collared at Fog Shaft on the 2300L of the underground mine at Acupan, and was drilled at an angle of 15 due south of Fog Shaft, where it intersected the Ampucao porphyry system. The last 70 m of the drill hole had an average grade of 0.95 g/t Au and 0.17 wt percent Cu. 0361-0128/98/000/000-00 $6.00

50 m

1406

9696

L-2600

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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to >600C) hypersaline (30 to > 70 wt % NaCl equiv) magmatic-hydrothermal brines and low density vapors (Cooke and Bloom, 1990). Later stage phyllic alteration and related quartzpyrite veins formed from low salinity, moderate temperature fluids (12 wt % NaCl equiv; 260345C; Cooke and Bloom, 1990). Kelly The Kelly-Baco gold deposit (hereafter referred to as Kelly) was described by Comsti et al. (1990), Aoki et al. (1993), and Deyell and Cooke (2003). Kelly is located in the northern part of the Baguio district, immediately to the east of, and 200 to 300 m below the Baguio lithocap, a large, strata-bound domain of silicic and advanced argillic alteration that crops out at high elevations on the eastern side of Baguio city (Waters et al., 2011; Fig. 2). Kelly is atypical of the Baguio epithermal veins, in that it contains tennantite, enargite, and bornite mineralization, and hypogene advanced argillic alteration assemblages (pyrophyllite-diaspore-alunite; Comsti et al., 1990; Aoki et al., 1993), in addition to intermediate sulfidation illite + base metal calcite veins that are more typical of the Baguio district. The deposit is distinguished by the presence of high sulfidation state sulfides (e.g., enargite, tennantite; Fig. 7A) and the presence of tellurium-rich minerals (calaverite and goldfieldite; Fig. 7B). An average grade of 4 g/t was reported by Mitchell and Leach (1991) for Kelly, although resource figures are not available. Hypogene advanced argillic alteration (pyrophyllite-illite) along the Kelly vein has an approximate age of <0.6 Ma, whereas alunite from the nearby Baguio lithocap has been dated at 1.4 0.3 to 0.9 0.1 Ma (Aoki et al., 1993). Mineralization at Kelly occurs in steeply north-dipping, east-striking quartz veins hosted by the Oligocene-Miocene Zig-Zag Formation and Pliocene Kelly diorite (K-Ar age of 3.1 1.1 Ma; Aoki et al., 1993; Table 1). The major vein systems include the Kelly, Bungalow, Kelly 35 south split, Maptung, Comasom, Frank, Lost Herd, and Dapung veins (Comsti et al., 1990). These veins are oriented orthogonal to the major northeast- and northwest-trending vein systems at Acupan, Baguio Gold, and Antamok (Fig. 2). Comsti et al. (1990) noted that the Kelly veins had cut relict biotite and actinolite alteration at surface in the southern (Baco) area of the Kelly vein system, and also on level 170 of the Kelly mine, which suggests that an as-yet undiscovered porphyry system may be located nearby. Fluid and Mineral Chemistry Stable and radiogenic isotope data can be used to trace fluid sources in hydrothermal ore deposits, and to help constrain likely ore-forming processes. We have used a variety of isotopic techniques in order to assess fluid compositions, depositional processes, and genetic relationships between the porphyry and epithermal styles of mineralization. Sulfur isotopes We have completed detailed sulfur isotope studies of the Acupan, Ampucao, and Kelly deposits, and reconnaissance surveys of other systems in the Baguio district. Imai (2001) undertook sulfur isotope analyses of porphyry-style mineralization from Santo Tomas II, and his data are used for comparative purposes.
0361-0128/98/000/000-00 $6.00

calav qz gf

Au

cp

0.1 mm

B
qz tn

en

cp

0.25 mm

FIG. 7. Reflected light photomicrographs of high sulfidation state mineralization from the Kelly gold mine. (A) Native gold (Au) associated with calaverite (calav) and surrounded by goldfieldite (gf) and chalcopyrite (cp). (B) Enargite (en) overgrown by tennantite (tn) and chalcopyrite (cp), infilling void space between quartz crystals (qz).

Sulfur isotope data for sulfides from Acupan, Ampucao, and Kelly were determined at the University of Tasmania, by use of both conventional and laser ablation sulfur isotope techniques. Powdered mineral separates (~30 mg) were analyzed according to Robinson and Kusakabe (1975) with measurements performed on a VG Sira Series II mass spectrometer. Laser analyses on doubly polished mineral chips were completed using a Quantronix model 117 Nd:YAG laser coupled with a VG Sira Series II mass spectrometer using the technique of Huston et al. (1995). Conventional sulfate analyses were completed on ~100 mg powdered mineral separates, according to the methods of Fritz et al. (1974), on the VG Sira Series II mass spectrometer. The results are expressed in standard per mil () notation relative to the Canyon Diablo Troilite (CDT). Internal standards used are homogeneous galena samples from Broken Hill (34S = 3.2) and Rosebery (34S = 12.4), and barite from Madame Howard (34S = 31.2) and Tasul I (34S = 20.9), together with an SO2 reference gas (34S CDT).

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COOKE ET AL.

Approximately 8 to 10 samples were analyzed per day, together with one standard. Analytical uncertainties for sulfide analyses are estimated at 0.1 per mil and for sulfate analyses at 0.4 per mil. Acupan: Sulfur isotope samples were selected from several of the major epithermal veins, primarily the 381 vein-No Name fault (NNF) and the 209-Odd vein systems (Fig. 3; Table 3). Samples include sulfides from type B, C, and D bands (Fig. 4) and type E vein anhydrite and selenite. A chalcopyrite clast was analyzed from the Balatoc diatreme. All results are listed in Table 3 and are summarized in Figure 8A. The 34S values of 23 pyrite and 4 sphalerite grains from Acupan range from +1.1 to +5.9 per mil with a median value of +3.2 per mil. Sulfates from type E bands (16 anhydrite and 2 selenite analyses) have 34S values ranging from +13.4 to

+31.8 per mil, with most data between +14 and +18 per mil and a median value of +15.9 per mil. The median 34S values for pyrite from individual paragenetic stages are constant (type B: 3.1, type C: 3.2, type D: 3.1) and are lower than the median value for pyrite from the altered wall rocks (4.9). Sphalerite has lower median 34S values than pyrite for each paragenetic stage analyzed (type B: 2.8, type C: 1.0). The chalcopyrite clast from the Balatoc diatreme yielded a distinctive 34S value of 1.4 per mil. The 34S values of pyrite and sphalerite from type C and D bands in the 381 vein NNF vein system increase with increasing elevation (Fig. 9A). No such trend was observed for type C samples collected at lower elevations from the 20-Odd vein system (Fig. 9A), or from type E anhydrite from either vein system (Fig. 9B). The lowest 34Ssulfide values from the

TABLE 3. Sulfur Isotope Data as Per Mil Values Relative to CDT for Samples of Epithermal Vein and Breccia-Hosted Mineralization from the Acupan Deposit Sample no. 96811 96635 96664* 96713 96649 96782 96866 96664* 96664 96664* 96939 96887 96892 96877 96697 96642 96616 96877 96877 96797 96730 96894 96800 97062 96726 96731 96801 96876 96802 96805 96745 96914 96677 96666 96732 96664* 96664* 96646 96664* 96744 Host rock Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Virac Balatoc Virac Virac Virac Virac Virac Virac Virac Zig-Zag Virac Virac Virac Virac Virac Virac Virac Virac Vein / breccia 403 vein 381 vein 381 vein No name fault No name fault 403/Hawkeye 381 vein 381 vein 381 vein 381 vein Odd vein 210 vein 210 vein No name fault No name fault 403 vein 381 vein No name fault No name fault No name fault No name fault 210 vein No name fault GW#5 No name fault No name fault No name fault No name fault No name fault No name fault No name fault 209 vein No name fault 381 vein No name fault 381 vein 381 vein No name fault 381 vein No name fault Mine easting 2000 W 2664 W 3045 W 2460 W 2062 W 167 W 3012 W 3045 W 3045 W 3045 W 2041 W 1730 W 1695 W 1871 W 2185 W 1028 W 2341 W 1871 W 1871 W 1870 W 2140 W 1695 W 1943 W 2538 W 2140 W 1943 W 1871 W 1923 W 2090 W 2200 W 2590 W 2485 W 3308 W 2140 W 3045 W 3045 W 1984 W 3045 W 2200 W Mine northing 22700 S 22594 S 23210 S 22800 S 22620 S 21687S 23249 S 23210 S 23210 S 23210 S 21071 S 21150 S 21035 S 22762 S 22637 S 22118 S 22143 S 22762 S 22762 S 22000 S 22830 S 21035 S 22935 S 23000 S 22830 S 22935 S 22762 S 22935 S 22945 S 22960 S 21150 S 22887 S 23292 S 22830 S 23210 S 23210 S 22576 S 23210 S 22960 S Elevation1 (m) 1371.6 980.9 819.0 766.8 801.1 862.8 760.8 819.0 819.0 819.0 461.0 495.7 450.9 672.9 762.8 801.1 1072.3 672.9 672.9 618.0 709.5 450.9 633.9 528.9 709.5 709.5 633.9 672.9 620.0 629.9 661.0 572.2 833.0 801.1 709.5 819.0 819.0 801.1 819.0 661.0 Stage B: gray qz B: gray qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz C: white qz D: calcite D: calcite D: calcite D: calcite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite E: anhydrite Sericite alt Sericite alt Sericite alt Sericite alt Ser-chl alt 34Spy () 1.9 4.4 2.2 2.3 2.8 3.1 3.1 3.2 3.7 3.8 3.9 4.5 4.8 1.2 2.8 3.4 5.2 34Ssp () 34San () 34Ssel ()

3.1 2.6 1.0 1.1 13.4 13.8 14.0 14.1 14.2 15.2 15.3 15.5 15.6 16.1 16.2 16.6 16.6 16.9 17.6 17.8 18.3 31.8

3.5

4.3 4.9 5.1 5.9 2.8

Notes: Vein stages defined by Cooke et al. (1996) are illustrated schematically in Figure 4. Abbreviations: 403/Hawkeye = intersection of 403 vein and Hawkeye fault; alt = alteration, an = anhydrite, Balatoc = Balatoc diatreme, GW#3 = GW breccia-hosted orebody no. 3, GW#5 = GW breccia-hosted orebody no. 5, py = pyrite, qz = quartz, sel = selenite, ser-chl = sericite-chlorite, sp = sphalerite, ZigZag = Zig-Zag Formation 1 Elevation relative to sea level *indicates sample analyzed by laser ablation 0361-0128/98/000/000-00 $6.00

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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B: pyrite C: pyrite C: sphalerite D: pyrite D: sphalerite E: pyrite
209 - Odd Vein

10

Elevation (m)

A: Acupan
8 6 4 2 0 -10 10 0 10

1400
bx clast: pyrite B: pyrite ser alt: pyrite C: pyrite C: sphalerite D: pyrite D: sphalerite E: pyrite E: anhydrite E: selenite

1200 1000 800 600 400 0

A
in - No Name F ault

381 V e

20
I: chalcopyrite I: anhydrite

30

1400

S (, CDT)
34

B: Ampucao
8 6 4 2 0 -10 12 10 8 6 4 2 0 -10 20 0 10 0 10

IIA: chalcopyrite IIA: pyrite IIA: anhydrite IIB: pyrite IIB: anhydrite ser-chl alt: py

Elevation (m)

1200 1000 800 600

E: anhydrite E: selenite

400 12

14

16

18

20

20

30
pyrite chalcopyrite enargite tennantite

34S (, CDT)
FIG. 9. Relationships between 34S values (, CDT) of epithermal vein samples and elevation at the Acupan gold mine. All data listed in Table 3. (A) 34Ssulfide values for samples of type B (pyrite), C (pyrite and sphalerite), D (pyrite and sphalerite) and E (pyrite) vein material from the 381 vein-No Name fault vein system, and from the 209-Odd vein system, plotted against elevation. Note that pyrite samples from altered wall rocks have not been plotted on this diagram, in order to highlight the positive correlation between 34S values and elevation for type C and D sulfides in the 381 vein-No Name fault vein system. (B) 34Ssulfate values for samples of type E (anhydrite) and selenite from the Acupan epithermal veins plotted against elevation.

C: Kelly

20

30
chalcopyrite cp bornite cp pyrite anhydrite gypsum

D: Santo 15 Tomas II (Imai, 2001)

10 5 0 -10

10

20

30
PCD sulfides HS sulfides IS sulfides skarn sulfides PCD sulfates IS sulfates

35 E: All Baguio 30 data 25 20 15 10 5 0 -10 0

10

20

30

34S (, CDT)
FIG. 8. Histograms showing range of sulfur isotope data (, CDT) for ore deposits of the Baguio district. (A) Acupan intermediate sulfidation epithermal deposit (Table 3). (B) Ampucao porphyry Cu-Au prospect (Table 4). (C) Kelly high sulfidation epithermal deposit (Table 5). (D) Santo Tomas II porphyry Cu-Au deposit (data from Imai, 2001; includes mixtures of chalcopyritebornite and chalcopyritepyrite). (E) Compilation of all data from the Baguio district (Tables 36; Imai, 2001). Abbreviations: bx clast = chalcopyrite clast from Balatoc diatreme, cp = chalcopyrite, HS = high sulfidation deposit, IS = intermediate sulfidation deposit, PCD = porphyry Cu deposit, py = pyrite, ser alt = sericite alteration, ser-chl alt = sericite-chlorite alteration. 0361-0128/98/000/000-00 $6.00

381 vein-NNF vein system were from the NNF, 403 vein and the margin of the Hartwell Plug (Fig. 10). Ampucao: Chalcopyrite, pyrite, and anhydrite were analyzed from porphyry-style quartzmagnetite-sulfide and anhydrite-chlorite-sulfide veins from the Ampucao porphyry Cu-Au prospect. The samples were collected from drill hole 741-1FJ, on the southern margin of the Acupan mine (Figs. 3, 6). All results are listed in Table 4 and are illustrated on Figure 8B. The 34S values of 19 pyrite and 5 chalcopyrite grains from Ampucao range from +2.3 to +6.6 per mil, with a median value of +4.0 per mil. These results are similar to 34S values of pyrite from the Acupan veins (Figs. 8A, B, 11). Six anhydrite samples collected over a 140-m downhole interval at Ampucao yielded 34S values from +10.4 to +19.2 per mil and a median of +14.5 per mil (Table 4; Fig. 8B), similar to most of the anhydrite data obtained from a much broader sampling area at Acupan (Table 3). Kelly: Sulfur isotope data for the Kelly deposit were first reported by Deyell and Cooke (2003). All sulfide 34S values are compiled in Table 5, which includes data for pyrite, chalcopyrite, enargite, and tennantite. Sulfide 34S values range from 3.2 to +0.8 per mil (n = 24; Figs. 8C, 11) and are lower than values obtained from the Acupan and Ampucao sulfides. Aoki et al. (1993) analyzed four alunite samples from the nearby Baguio lithocap, obtaining 34S values from +15 to +24 per mil. Other deposits and prospects: Reconnaissance sulfur isotope analyses of sulfides from other deposits and prospects in the Baguio district were completed in order to examine the

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3000 W 0 20500 S
e Pin

COOKE ET AL.
1500 W ZERO

250 m
in Ve

237

Vei

n Lode

Shaft

21

in Ve

286 364 Vein

N

Vein
au lt

eF am oN

e 403 V

in

Hartwell plug Virac granodiorite

Zig-Zag Formation

Sulfur isotope sample

(circle size corresponds 34 to S values)

Structures
Lithological boundary

Fault / vein

FIG. 10. Spatial distribution of 34S data (, CDT) obtained from pyrite samples from the Acupan epithermal vein system with respect to the local host rocks. Data are grouped according to the host vein and are projected onto the 1500L geologic map modified from Cooke et al. (1996). Circle size corresponds to 34Spyrite value (small circle = low 34Spyrite). All 34S data are listed in Table 3.

TABLE 4. Sulfur Isotope Data as Per Mil Values Relative to CDT for Samples of Porphyry-Style Mineralization from the Ampucao Porphyry Cu-Au Prospect Sample no. 96954 96955 96955 96962 96954 96954 96954 96954 96955 96955 96955 96957 96959 96956B 96956B 96956B 96956B 96956B 96956C 96953 96962 96962 96964 96964 96964 96964 96964 96959 96954 Host rock Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Ampucao dacite Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Ampucao dacite Ampucao dacite Ampucao dacite Ampucao dacite Ampucao dacite Ampucao dacite Ampucao dacite Zig-Zag Formation Zig-Zag Formation Drill hole depth (m) 132.0 147.5 147.5 252.0 132.0 132.0 132.0 132.0 147.5 147.5 147.5 152.5 179.5 152.5 152.5 152.5 152.5 152.5 152.5 120.0 252.0 252.0 270.5 270.5 270.5 270.5 270.5 179.5 132.0 Mine easting 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W 1660 W Mine northing 24640 S 24690 S 24690 S 25023 S 24640 S 24640 S 24640 S 24640 S 24690 S 24690 S 24690 S 24706 S 24792 S 24706 S 24706 S 24706 S 24706 S 24706 S 24706 S 24602 S 25023 S 25023 S 25082 S 25082 S 25082 S 25082 S 25082 S 24792 S 24640 S Elevation1 (m) 673.3 669.5 669.5 641.1 673.3 673.3 673.3 673.3 669.5 669.5 669.5 668.2 660.9 668.2 668.2 668.2 668.2 668.2 668.2 676.6 641.1 641.1 636.1 636.1 636.1 636.1 636.1 660.9 673.3 Vein stage I I I I IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIa IIb IIb IIb IIb IIb IIb IIb IIb IIc ser-chl alt 34Spy ()
34S cp

Fr

V 412

og

ein

422 Vein

Ve i

23500 S

Cu rt

22000 S

n Vei 381

Fa

keye Haw Fault

variability of sulfur isotope signatures as a function of spatial location and mineralization style. Samples were selected from a range of porphyry prospects, epithermal veins, skarn mineralization, and one massive sulfide occurrence (Wildcat; Table 6). The sulfur isotope data compiled in Figure 8 and Tables 3 to 6 show that there are two distinct modes of 34S values for sulfides from the Baguio district (7 to +1 and +1 to +6). The sulfide isotope compositions appear to be influenced by geographic location, specifically with regards proximity to the Baguio lithocap. Most of the intermediate sulfidation epithermal veins from the central, eastern, and southern Baguio district, distal to the lithocap, have 34S values of +2 to +6 per mil. In contrast, 34S values obtained from the intermediate sulfidation veins at Baguio Gold, located proximal to the northern end of the Baguio lithocap (Fig. 2), have 34S values of 6.8 to +0.5 per mil, and two sulfide samples from intermediate sulfidation veins at Chico mines have 34S values of 2.9 and 2.8 per mil. These results are comparable to the data from the Kelly high sulfidation veins, which are also located adjacent to the lithocap (Fig. 2). The porphyry deposits from the central and southern Baguio district mostly have sulfides with 34S values between +4 and +6 per mil. This includes the sulfides analyzed by Imai (2001) from the Santo Tomas II porphyry deposit, which have similar sulfur isotope values to the Ampucao porphyry samples (compare Fig. 8B and D). Lower 34S values were obtained

ult

() 6.6 2.5 4.1 3.4

34S an ()

3.9 4.8 4.9 10.4 2.3 2.9 3.4 19.2 12.9 4.2 4.5 5.0 5.9 4.8 16.7 16.0 2.8 5.7 3.4 3.8 4.0 5.3 5.6 3.3 2.7

Note: All samples were collected from drill hole 741-1FJ (locations shown on Figure 6). Vein stages defined by Cooke and Bloom (1990) Abbreviations: an = anhydrite, cp = chalcopyrite, py = pyrite, ser-chl alt = sericite-chlorite alteration 1 Elevation relative to sea level 0361-0128/98/000/000-00 $6.00

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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HS epithermal

Baguio district

IS epithermal (Acupan) IS epithermal (others) Porphyry (Ampucao) Porphyry (others) Skarn

Mankayan district

Porphyry HS epithermal IS epithermal -12 -10 -8 -6 -4 -2 0 2 4 6 8

34S ()
FIG. 11. Comparison of sulfur isotope ranges (, CDT) for sulfides from the Baguio and Mankayan districts. Baguio district high sulfidation (HS) epithermal data are from the Kelly deposit (Table 5). Intermediate sulfidation (IS) epithermal includes data from the Acupan deposit (Table 3) and other IS deposits and prospects in the district (Table 6). Porphyry data includes results from Ampucao (Table 4), Santo Tomas II (Imai, 2001) and other prospects from this study (Table 6). Skarn data are compiled from all samples in this study (Table 6). Mankayan district data taken from the Far Southeast porphyry Cu-Au deposit (Imai, 2000; Hedenquist and Sasaki, unpub. data), Lepanto high sulfidation Cu-Au deposit (Hedenquist and Garcia, 1990; Hedenquist and Mancano, unpub. data; Hedenquist and Sasaki, unpub. data) and Victoria intermediate sulfidation Au-Ag deposit (Sajona et al., 2002).

from porphyry-style mineralization at Black Mountain (1.5 and +0.8; Table 6), located at the southern end of the Baguio lithocap (Fig. 2).
TABLE 5. Sulfur Isotope Data as Per Mil Values Relative to CDT for Sulfides and Sulfosalts Collected from Underground Exposures and Surface Outcrops at Kelly (data originally reported by Deyell and Cooke, 2003) Sample no. B-11 B-18 B-14a B-17 B-18 B-20a B-6a KR-4a B-4 B-2 KR-1 KR-2 B-2 B-2 KR-2 B-8 B-8a KR-6a B-15a B-7b KR-3 B-13 B-12a KR-6b Mine Kelly Kelly Kelly Kelly Kelly Kelly Kelly Baco Baco Baco Kelly Baco Baco Baco Baco Kelly Kelly Baco Kelly Kelly Baco Kelly Kelly Baco Vein Kelly vein Kelly vein K 35 SS vein Kelly vein Kelly vein Kelly vein K 35 SS vein K 35 SS vein Kelly vein K 35 SS vein Pines vein Frank vein K 35 SS vein K 35 SS vein Frank vein K 35 SS vein K 35 SS vein K 35 SS vein K 35 SS vein K 35 SS vein Pines vein K 35 SS vein Kelly vein K 35 SS vein Mine level 170 45 45 45 45 45 270 45 100 170 45 100 170 170 100 170 170 170 100 270 45 45 Surface 170 34Spy 34Scp 34Sen 34Stn () () () () 3.2 2.6 2.2 2.1 1.7 1. 1.3 1.3 1.0 0.9 0.8 0.7 0.6 0.6 0.6 0.4 0.4 0.2 0.1 0.2 0.2 0.6 0.7 0.8

Skarn sulfides have 34S values that range from +1.0 to +4.6 per mil. They overlap with the porphyry and intermediate sulfidation epithermal data from the central and southern Baguio district (Figs. 8, 11; Table 6). Strontium isotopes The results of strontium isotope analyses of five anhydrite vein and breccia samples from the Acupan epithermal and Ampucao porphyry deposits are listed in Table 7. Analyses were conducted at La Trobe University by Roland Maas. Samples were hand-drilled, yielding powders that were then leached in cold 1M HCl, with the resulting supernatant solution extracted. The residue was washed with water once, and then leached and partially dissolved in 5M HCl. The HCl was then evaporated, and the residue picked up in 1M HCl and centrifuged. Part of each solution was loaded as phosphate onto single Ta filaments and analyzed in static multicollection mode on a Finnigan-MAT 262 mass spectrometer. Mass fractionation was corrected by normalizing to 86Sr/88Sr = 0.1194. The initial strontium isotopic compositions of anhydrite from Acupan and Ampucao range between 0.70378 and 0.70385, and are essentially indistinguishable within analytical error (Fig. 12; Table 7). Oxygen-deuterium isotopes We analyzed the oxygen isotope values of quartz (n = 31) and chalcedony (n = 1) from crustiform banded veins at Acupan, and also quartz veins from the Ampucao porphyry prospect (n = 4). Quartz was separated by handpicking of crushed samples, and the purity of mineral separates was assessed by optical examination to be greater than 95 percent. Quartz was sonically cleaned in a water bath and then baked

Abbreviations: cp = chalcopyrite, en = enargite, K = Kelly, py = pyrite, SS = south split, tn = tennantite 0361-0128/98/000/000-00 $6.00

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COOKE ET AL. TABLE 6. Sulfur Isotope Data as Per Mil Values Relative to CDT for Sulfides Collected from Mines and Prospects Around the Baguio District

Sample no. 804971 804962 804969 804970 804968 811643 811645 804965 804964 804966 804967 811549 811548 804961 806119 806121 806122b 806122a 806117a 806116 806118a 806118b 806117b 806113b 806113a 806112b 806115b 806112a 806113c 806115a 811642b 811641a 811641b 811642a

Deposit type IS IS IS IS IS PCD PCD PCD PCD IS IS PCD PCD Skarn Skarn Skarn Skarn Skarn PCD PCD PCD PCD PCD IS IS IS IS IS IS IS Skarn Skarn Skarn Skarn

Location Antamok (Wildcat orebody) Antamok (440 vein) Baguio Gold (Lonesome vein) Baguio Gold (Lonesome vein) Baguio Gold (Lonesome vein) Black Mountain Black Mountain Camp 4 Camp 4 Chico mines Chico mines Chico prospect Chico prospect Mexico Mexico Mexico Mexico Mexico Nugget Hill Nugget Hill Nugget Hill Nugget Hill Nugget Hill Sierra Oro Sierra Oro Sierra Oro Sierra Oro Sierra Oro Sierra Oro Sierra Oro Thanksgiving Thanksgiving Thanksgiving Thanksgiving

Easting (UTM) 249774 249398 249111 249111 249111 243826 245591 246823 247061 246346 246346 247216 247054 244956 243091 243023 242964 242964 246441 246439 246441 246441 246441 246275 246275 246205 246331 246205 246275 246331 244513 244513 244513 244513

Northing (UTM) 1814310 1815114 1816010 1816010 1816010 1809792 1808396 1805641 1805645 1813120 1813120 1811963 1811778 1813536 1809000 1809080 1809038 1809038 1809771 1809835 1809771 1809771 1809771 1809277 1809277 1809249 1809306 1809249 1809277 1809306 1810000 1810000 1810000 1810000

34Spy () 2.5 1.5 6.8 5.5 0.5

34Scp ()

34Ssp ()

34Sgl ()

1.5 0.8 0.7 2.2 2.9 2.8 1.0 2.9 1.9 3.2 3.4 3.7 3.8 2.0 2.2 3.3 3.3 5.0 0.1 1.0 1.1 1.5 2.4 3.5 3.5 1.0 1.9 3.9 4.6

Notes: Deposit locations are shown on Figure 2; deposit descriptions are provided in Table 2 Abbreviations: cp = chalcopyrite, gl = galena, IS = intermediate sulfidation deposit, PCD = porphyry Cu deposit, py = pyrite, sp = sphalerite

in an oven for 12 h at 100C. A total of 26 samples were analyzed at the University of Tasmania, where oxygen was extracted from quartz and chalcedony by reaction for 12 h with BrF5 at 520C in evacuated nickel reaction vessels (Clayton and Mayeda, 1963). The liberated oxygen was converted to

CO2 when the gas was reacted with heated graphite (Taylor and Epstein, 1962). Isotope ratios were measured using the VG Micromass 602D mass spectrometer in the Central Science Laboratory. One internal standard, UT quartz, was run with every five quartz samples, and was calibrated against the

TABLE 7. Strontium Isotope Data for Anhydrite from the Acupan Epithermal Gold Mine and the Ampucao Porphyry Cu-Au Prospect Mine easting 2590 W 1695 W Mine northing 21150 S 21035 S Elevation1 (m) 572.2 450.9

Sample no. 96914 96894 97062 (leachate) 97062 96956C 96957

Location Acupan: 209 Vein Acupan: 210 Vein Acupan: GW#5 orebody Acupan: GW#5 orebody Ampucao Ampucao

Host rock Zig-Zag Formation Virac granodiorite Balatoc diatreme Balatoc diatreme Zig-Zag Formation Zig-Zag Formation

87Sr/86Sr

Error (2 sigma mean) 0.000017 0.000018 0.000013 0.000016 0.000018 0.000018

1640 W 1660 W

24601 S 24706 S

668.2 664.2

0.70378 0.70384 0.70380 0.70385 0.70380 0.70382

Notes: The isotopic compositions of Sr standards used in this study are as follows: SRM987: 0.71023 4, BCR-1: 0.70500 4, BHVO-1: 0.70348 5, seawater: 0.70916 2; all errors reported are external reproducibilities at 2 population; note that during sample preparation, sample 97062 dissolved more rapidly that the other four samples in the 1M HCl leach, and there was very little undissolved material left after that stage; consequently, two aliquots of this sample were analyzed: the first aliquot analyzed (97062 leachate) was the 1M HCl leachate, and the second aliquot was the 5M HCl digest after the mild HCl leach had been removed 1 Elevation relative to sea level 0361-0128/98/000/000-00 $6.00

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Sub-crustal magmas

Crustally contaminated magmas

Acupan Ampucao Philippines & PNG Mt Polley, BC Seawater North Parkes, NSW Cadia, NSW Central & Northern Chile Bajo de la Alumbrera Laurani SW Arizona 0.703 0.704 0.705 0.706 0.707 0.708 0.709 0.710 0.711

Initial Sr
FIG. 12. Strontium isotope results for anhydrite from Acupan and Ampucao (Table 7), compared to Sr isotope analyses of intrusions from calc-alkalic porphyries from island arc and continental arc settings (data from Sillitoe, 1987), and from alkalic porphyries at Mt. Polley, British Columbia (data from Pass et al., submitted), Cadia and North Parkes, Australia (data from Cooke et al., 2007).

international isotope standard NBS-28, which was run occasionally. Duplicate analyses showed a precision of 0.2 per mil. An additional six quartz samples were analyzed at Monash University, where isotopic ratios were measured on a Finnigan MAT Delta-E mass spectrometer, and ClF3 used as the oxidizing reagent. A single 18O analysis of the NBS-28 quartz standard during the sample run at Monash University yielded a value of 9.59 per mil; the accepted value is 9.62 per mil. 18O values of water in equilibrium with quartz were calculated using the fractionation curve of Matsuhisa et al. (1979) combined with fluid inclusion homogenization temperatures from Cooke and Bloom (1990). All 18O values are reported in standard per mil notation relative to V-SMOW. The results of our silicate oxygen isotope analyses are listed in Table 8 and illustrated on Figures 13 and 14. The range of 18O values from Acupan are as follows: type A (chalcedony): 6.4 per mil (n = 1); type B (gray quartz): 6.3 to 10.6 per mil (n = 7); type C (white quartz): 1.7 to 10.7 per mil (n = 24). The analyzed 18O values of quartz veins from Ampucao are: stage I: 8.2 and 9.0 per mil (n = 2); stage IIa: 8.1 and 9.5 per mil (n = 2). Previous oxygen-deuterium isotope studies in the Baguio district focused primarily on determining the isotopic compositions of modern geothermal waters (Sawkins et al., 1979; Japan International Cooperation Agency-JICA, 1984; Table 9). The waters were found to have values that range from 11.5 to 2.2 per mil (18O) and 75 to 55.4 per mil (D). They plot on or close to the meteoric water line (Fig. 15). Six oxygen and four deuterium isotopic analyses of type C white quartz from the Acupan and Antamok epithermal vein systems were completed by Sawkins et al. (1979; Table 9; Fig. 15). They found that the ore-forming solutions at both deposits could contain no more than a few percent by volume of
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magmatic water, with meteoric waters predominant in both systems. Sawkins et al. (1979) also analyzed five altered whole-rock samples from the Baguio district (Table 9). They found that 18O depletion in the altered rock samples had been caused by partial isotopic equilibration with meteoric waters. Carbon-oxygen isotopes We analyzed C-O isotope values from 15 calcite samples from Acupan. These are the first C-O isotope data obtained for any epithermal veins of the Baguio district. All calcite samples were hand drilled to yield ~10 mg of fine powders. CO2 was liberated by reaction with H3PO4 at 25C (Walters et al., 1972; Swart et al., 1991) and analyzed using the method of McCrea (1950). All 18O values are reported in standard per mil () notation relative to SMOW, and 13C values are reported relative to the Cretaceous Peedee Belemnite (PDB). The 18O and 13O values of water in equilibrium with calcite have been calculated using the fractionation equations derived by Field and Fiferak (1985) from the data of Friedman and ONeil (1977), combined with fluid inclusion homogenization temperatures from Cooke and Bloom (1990). Analytical uncertainties for both 18O and 13C are estimated at 0.03 per mil. Approximately 8 to 10 samples were analyzed per day, together with one internal standard (ANUM1: 13C = 1.45; 18C = 5.90). The 18Ocalcite values range from 0.8 to 11.1 per mil, whereas 13Ccalcite values range from 8.5 to 3.6 per mil (Figs. 13, 16; Table 8). Helium isotopes Two fluid inclusion samples from Acupan and Antamok that had previously been analyzed for their deuterium isotope compositions by Sawkins et al. (1979) were subjected to helium isotope analyses by Stuart Simmons (pers. commun.,

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COOKE ET AL. TABLE 8. Oxygen Isotope Analyses, as Per Mil Values Relative to VSMOW, of Type B and C Quartz, Type D Calcite, and Type A Chalcedony from the Acupan Epithermal Vein System, and Stage I and IIa Quartz from the Ampucao Porphyry Deposit (also listed are carbon isotope analyses of type D calcite, as per mil values relative to PDB, from Acupan)

Sample no.

Host vein / Rock

Mine easting

Mine northing

Elevation1 (m) Ampucao

Vein stage

Temperature (C)

18Omineral ()

18Owater ()

13CPDB ()

96959M 96951M 96956BM 96969M

Zig-Zag Formation Zig-Zag Formation Zig-Zag Formation Ampucao dacite

1640 W 1640 W 1640 W 1640 W

24792 S 24389 S 24601 S 24792 S

660 687 668 632 Acupan

Stage I quartz Stage I quartz Stage IIa quartz Stage IIa quartz

515 511 513 499

8.2 9.0 8.1 9.5

5.6 6.3 5.5 6.7

96817 96811 96711 96616 96796 96630 96756 96814 96732 96926 96753 96635 96896 96942 96882 96913 96931 96679 96737 96807M 96724 96807M,D 96864 96947 96836 96782 96664 97105 96608 96802 96713 96649 96808 96642 96920 96912 96942 96775 96674 96814 96646 96926 96711 96814D 96724 96616 96737

Santoy vein 403 vein 381 vein 381 vein 409 vein 381 vein 403-Hawkeye vein Santoy vein No Name fault Odd vein 403 vein 381 vein 209 vein Odd vein 210 vein 209 vein Odd vein No Name fault No Name fault No Name fault No Name fault No Name fault 381 vein 206 vein Taka hanging wall split 403-Hawkeye vein 381 vein Taka HWS 381 vein No Name fault No Name fault No Name fault 418 vein 403 vein 209 vein 209 vein Odd vein 409 vein No Name fault Santoy vein No Name fault Odd vein 381 vein Santoy vein No Name fault 381 vein No Name fault

3440 E 2000 W 1564 W 2341 W 785 W 2727 W 2004 W 3220 E 2140 W 2805 W 2736 W 2664 W 2960 W 2316 W 1780 W 2965 W 2304 W 2460 W 1590 W 2859 W 2497 W 2859 W 3012 W 180 W 1250 E 167 W 3045 W 1686 E 2468 W 1923 W 2460 W 2062 W 1500 W 1028 W 3269 W 3125 W 2316 W 936 E 2272 W 3220 E 1984 W 2805 W 1564 W 3220 E 2497 W 2341 W 1590 W

19460 S 22700 S 22220 S 22143 S 22285 S 22569 S 21687 S 19633 S 22830 S 21310 S 22834 S 22594 S 21295 S 21169 S 21165 S 21260 S 21158 S 22484 S 22580 S 23198 S 22801 S 23198 S 23249 S 20420 S 20735 S 21687 S 23210 S 20371 S 22381 S 22935 S 22800 S 22620 S 22000 S 22118 S 21311 S 21300 S 21169 S 21416 S 22652 S 19633 S 22576 S 21310 S 22220 S 19633 S 22801 S 22143 S 22580 S

1033.9 1371.6 754.9 1072.3 709.5 1016.7 916.8 1033.9 709.5 528.9 916.8 980.9 620 461 489.4 572.2 502 862.8 709.5 711 746.9 711 761 450.9 1061.6 862.8 819 1184 1028.5 620 766.8 801.1 1341.1 801.1 537.1 572.2 461 980.9 858.6 1033.9 801.1 528.9 754.9 1033.9 746.9 1072.3 709.5

A: chalcedony B: gray quartz B: gray quartz B: gray quartz B: gray quartz B: gray quartz B: gray quartz B: gray quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz C: white quartz D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite D: calcite

220* 250* 268 300 300* 273 279 270* 216 231 212 228 256 276 269 262 279 209 248 281 277 281 291 265 220* 264 237 270 217 293 245 289 140* 147 251 257 264 166 225 160* 233 238 247 160* 240* 140* 223

6.4 7.7 7.2 6.3 6.6 8.1 9.4 10.6 1.7 2.0 4.4 4.5 3.2 2.6 3.1 3.4 2.8 6.3 4.3 4.0 3.6 4.3 3.4 4.7 7.4 5.9 8.2 6.8 9.6 6.4 9.4 10.7 1.0 4.0 0.8 0.0 0.3 4.6 1.7 5.3 1.5 2.1 2.0 7.0 4.4 11.1 6.2

4.0 1.2 0.9 0.6 0.3 0.2 1.7 2.6 12.4 7.8 6.5 5.5 5.4 5.2 5.0 5.0 4.9 4.8 4.7 4.2 4.1 3.9 3.8 3.5 3.0 2.4 1.3 1.2 1.0 0.7 0.3 3.4 12.4 8.9 8.1 7.0 7.0 6.9 6.6 6.6 6.5 5.7 5.4 4.9 3.3 2.3 2.2

7.8 6.6 8.1 8.2 8.5 6.6 7.9 5.8 7.5 8.0 6.8 3.6 6.3 7.5 5.5

1 Elevation relative to sea level *Temperature estimated from boiling-point depth curve on Figure 5 (no fluid inclusion data available); all other temperatures are average homogenization temperatures calculated for each sample from the fluid inclusion data of Cooke and Bloom (1990); 18Owater values were calculated using the fractionation equations of Matsuhisa et al. (1979) M Samples analyzed at Monash University; all other samples analyzed at the University of Tasmania D Duplicate analysis

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8 7 6 5 4 3 2 1 0 -4 -2 0
18

1989; Table 9). These samples yielded R/Ra values of 6.7 and 6.0 respectively, where R is the 3He/4He ratio of the inclusion fluid and Ra is the atmospheric ratio of 3He/4He. The high R/Ra values provide evidence for mantle-derived magmatic helium with minimal crustal contamination in the epithermal fluids of the Baguio district (Simmons et al., 1987). Discussion Baguio contains all of the classic elements of a porphyry-related mineral district (cf. Sillitoe, 1989, 2010), with several porphyry Cu-Au and intermediate sulfidation epithermal AuAg deposits, two skarn deposits, one high sulfidation epithermal Au-Ag deposit, and a large, broadly strata-bound lithocap (Waters et al., 2011). Magmatism and hydrothermal activity occurred episodically in the Baguio district over the past 3 m.y., based on the geochronological data of Aoki et al. (1993), Imai (2001), and Waters et al. (2011). Our new stable and radiogenic isotopic data now provide an opportunity to assess genetic relationships between the porphyry and epithermal deposits, particularly at Acupan and Ampucao. However, given that most of our isotopic data come from the Acupan epithermal Au-Ag veins, we can first use this more detailed data set to assess likely epithermal ore-forming processes, before moving on to the bigger picture and assessing possible links between deposit styles. Isotopic modeling of epithermal ore-forming processes Mineral deposition in intermediate sulfidation epithermal environments can result from a range of processes, including decompressional boiling, gas condensation, fluid mixing, water-rock interaction, and conductive cooling (Cooke and Simmons, 2000). Each process produces distinctive mineral assemblages, but only the first three are likely to be important for gold deposition (Henley, 1984; Drummond and Ohmoto, 1985; Reed and Spycher, 1985; Spycher and Reed, 1989; Seward, 1989; Cooke and McPhail, 2001; Rae et al., 2011). Detailed geochemical modeling of epithermal ore formation for the Acupan vein system was undertaken by Cooke and McPhail (2001). They concluded that boiling was the predominant ore-forming mechanism, but that certain mineral assemblages were better explained by the processes of fluid mixing, gas condensation or water-rock interaction. Stable isotope analyses of quartz and calcite have the potential to discriminate between cooling, boiling, and mixinginduced mineral deposition in the epithermal environment. In general, the temperature-dependent fractionation between quartz and water (Truesdell et al., 1977; Larson and Taylor, 1987) results in isotopically heavier quartz being precipitated at lower temperatures. Boiling aqueous solutions will preferentially fractionate 18O into the residual liquid phase (Truesdell et al., 1977; Lynch et al., 1990; Bowers, 1991), and any quartz precipitated from a boiling solution should therefore be enriched in 18O compared to quartz deposited by conductive cooling from non-boiling waters. Open-system boiling of a fluid ascending along an open conduit should result in a systematic and distinctive increase in 18O isotope values with respect to elevation for minerals precipitated from that boiling solution. Fluid mixing with cool near-surface groundwaters also has the potential to cause gold precipitation in the epithermal environment (e.g., Spycher

10

12

14

Omineral (, VSMOW)
Acupan Type A
chalcedony clasts

Acupan Type D
calcite bands

Acupan Type B
gray quartz bands

Ampucao Stage I
quartz veins

Acupan Type C
white quartz bands

Ampucao Stage IIa

quartz veins

FIG. 13. Histogram showing all measured 18Omineral values (, VSMOW) measured from stage I and IIa quartz veins from Ampucao and type A, B, C, and D gangue minerals from Acupan. All data listed in Table 8.

1400

A
Stage I Stage IIa Type A Type B Type C Type D

Elevation (m)

1200 1000 800 600 400

-12 1400

-8

18Omineral (, VSMOW)
B

-4

12

Elevation (m )

1200 1000 800 600 400 -12 -8 -4 0 4 8 12

18Owater (, VSMOW )
FIG. 14. Plots of (A) measured 18Omineral values (, VSMOW) versus sample elevation, and (B) calculated 18Owater values versus sample elevation for quartz vein samples from Ampucao (stages I and IIa) and quartz-calcite vein samples and chalcedony breccia clasts from Acupan (types A, B, C, and D). All data listed in Table 8. Note that for samples listed in Table 8 that lack fluid inclusion data, depositional temperatures have been estimated from the boiling point-depth curves on Figure 5. Type A = chalcedony, type B = gray quartz, type C = white quartz, type D = calcite. 0361-0128/98/000/000-00 $6.00

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COOKE ET AL. TABLE 9. Oxygen and Deuterium Data, as Per Mil Values Relative to VSMOW, from Sawkins et al. (1979) and JICA (1984), for Whole-Rock Samples, Quartz Veins, Fluid Inclusions and Geothermal Waters from the Baguio District

Sample no. 76B1 76B3 76B4 76B5 76B11 76B12 76B14 76B15 76B26 76B27 DA IT1 IT2 KL AS PU LA1 LA2 BA1 BA2 DAST PRE 75B25 75B88 75B43 75B35 75B23 75B22 76B16 76B21 76B22 75B1 76B2 76B17

Material Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Geothermal water Pyroxene andesite Balatoc diatreme Volcaniclastic conglomerate Hornblende diorite Graywacke C: white quartz C: white quartz C: white quartz C: white quartz qz C: white quartz C: white quartz C: white quartz

Location Acupan Acupan Acupan Itogon Antamok Antamok Antamok Acupan Acupan Dalupirip Itogon town Itogon town Klondyke Asin Pugo Laboy Laboy Acupan Acupan East of Dalupirip Baguio Acupan

Mine level 3150 2600 2600 1850 1850 1550 3150 1500

Elevation1 (m) 451 618 618 surface

Temperature (C) 63.7 46.1 46.1 87.9 51.7 40.6 46.1 61.1 20 42.5 89.5 62.2 49.5 73.8 36.3 47.5 47.5 81 62.1

18Omineral ()

18Owater () 8.12 6.54 10.71 10.45 2.17 5.82 10.23 9.3 8.12 11.48 9.8 9.8 9.6 9.2 8.5 8.1 10.1 10.5 7.7 7.6 10.1 9.9 1.6 2.6 4.2 4.6 2.4 3.55 6.2 4 0.85 3.25 3.3

D () 65 57 71 71 67 61 58 66 68 75 67.1 67.2 67.6 64.9 59.9 55.4 69.2 70.7 62.3 62.5 71 66.9

R/Ra

Reference 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 1 1, 3 1 1 1, 3

3300 3150

451 981 surface surface surface surface surface surface surface surface ~4002 451 surface surface

Antamok Antamok Antamok Acupan Acupan Acupan

400 700 700 2450 3300 661 ~4002

261 251.5 313.5 278 272.5

5.3 3.2 4.4 6.1 5.0 5.2

79 82 72 76

6.0 6.7

Notes: Helium isotope ratios from Simmons (unpub. data) for inclusion fluids; location of prospects and deposits shown on Figure 2; references: 1 = Sawkins et al. (1979), 2 = JICA (1984), 3 = Simmons (unpub. data) 1 Elevation relative to sea level 2 Precise elevation uncertain

and Reed, 1989; Cooke and McPhail, 2001), and could result in shifts towards more negative 18Owater values, if the local meteoric groundwaters have lower 18O values than the ascending hydrothermal fluids. The 18Omineral and calculated 18Owater values from Acupan broadly increase with elevation (Fig. 14), consistent with epithermal quartz and calcite deposition from lower temperature fluids at higher elevations. We have undertaken isotopic modeling of 18O values for quartz and calcite from Acupan in order to further evaluate the relative importance of different types of ore-forming processes in the Acupan epithermal veins. Cooke and McPhail (2001) calculated the proportions of water and vapor produced during incremental open system boiling of an Acupan-type water (5C steps) using CHILLER (Reed and Spycher, 1985; Spycher and Reed, 1989). These proportions were used to calculate the theoretical isotopic compositions of quartz and calcite produced by incremental (5C) open-system boiling from 300 to 100C (Fig. 17). Average 18O values of mineralizing fluids were assumed to be -0.5 per mil for type B quartz, 4.0 per
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mil for type C quartz and 6.5 per mil for type D calcite (Table 8; Figs. 16, 18). The theoretical 18Omineral values compositions of quartz and calcite precipitated by cooling, boiling and mixing from 300 to 100C have been plotted on Figure 19A-C as a function of elevation using paleowater table elevations inferred for type B, C, and D mineralization from Figure 5. Also plotted are the measured 18O isotope compositions of type B and C quartz and type D calcite (Fig. 19 A, B, and C, respectively). The measured 13C and 18O values of type D calcites mostly vary systematically and are consistent with deposition from a cooling hydrothermal fluid with a constant isotope value (13CH2CO3 = 7.0; 18Owater = 6.1; Fig. 16). However, spatial variations of 18Ocalcite values are not as systematic, with a broad scatter in data between 700 and 1,000 m (Fig. 19C) corresponding to locations where high grade ore shoots occur and where empirical evidence for boiling has been detected from fluid inclusion petrography (observations of coexisting primary liquid- and vapor-rich fluid inclusions in growth zones; Cooke and Bloom, 1990) and textural studies

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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0
M et

at

er

-20

eo

ric

Volcanic vapors

D (, VSMOW)

White Island

Felsic magmas

-40 -60 -80

Broadlands-Ohaaki McLaughlin Antamok-Acupan Great Valley sequences

AntamokAcupan

-100 -120 -140 -20

Comstock

BroadlandsOhaaki Comstock McLaughlin Tayoltita

-15

-10

-5
18

10

15

20

O (, VSMOW)
FIG. 15. Plot of 18O vs. D (, VSMOW) for mineralizing waters and modern geothermal waters of deposits of the Baguio district (modified after Cooke and Simmons, 2000). Baguio district data from Sawkins et al. (1979) are listed in Table 9. The range of compositions of water discharged from high temperature fumaroles on andesitic volcanoes is outlined by the box labeled volcanic vapors (Giggenbach, 1992), and the range of compositions of water dissolved in felsic melts is outlined by the box labeled felsic magmas (Taylor, 1992). Other data sources from Cooke and Simmons (2000).

(presence of bladed calcite; Cooke et al., 1996). Cooling-induced spatial variations in 18O values have also been detected from type B and C quartz bands at Acupan, but with considerable scatter in calculated 18Owater values at higher elevations (Fig. 19A, B). Conductive cooling could explain some of the quartz isotopic data, but this mechanism is not a viable alternative for calcite deposition due to calcites retrograde solubility (Rimstidt, 1997). Conductive cooling is sluggish and will only occur in areas of low flow rates and intimate fluid-rock contacts

(Drummond and Ohmoto, 1985). It is therefore considered unlikely to have been important for quartz or calcite vein formation at Acupan. The principal cooling mechanism responsible for calcite deposition at Acupan is likely to have been boiling, based on the common observed occurrence of bladed calcite. However, the scatter in 18Ocalcite values at higher elevations (Fig. 19C) may imply that mixing with local
300

Cooling mechanisms
(a) multistage boiling (300 100C) (b) conductive cooling (300 100C) (c) mix 250 C chloride water with 20C cold water ( 18O = -10)

D pe Ty O

Temperature ( C)

18

13Ccalcite (, PDB)

-2 -4 -6 -8 -10 -8 -6 -4 -2 0 2 4 6 8 10 12
250C 35 300C 0C 40 0 C

250

ter wa

e lcit c a -6.5

100C

150C
200C

200
il Bo A:

Ty p
18

O
w

B
=

at er

qu
-0

150
C :M ix

.5

ar

tz
A: Bo il

C: x Mi

B:

Co

B: ol

Co

18Ocalcite (, VSMOW)
FIG. 16. Plot of measured 18Ocalcite (, VSMOW) and 13Ccalcite values (, PDB) from type D calcite bands at Acupan. All data listed in Table 8. Also shown is the theoretical compositions of calcite precipitated from a H2CO3-predominant cooling water with a bulk isotopic composition of 6.5 (18O) and 7.0 (13C), calculated using the fractionation equations derived by Field and Fiferak (1985) from the data of Friedman and ONeil (1977). The calcite data from Acupan are broadly coincident with the theoretical cooling trend, indicating that calcite deposition could have occurred from a cooling, predominantly meteoric, water over a temperature range of approximately 300 to 150C. 0361-0128/98/000/000-00 $6.00

100 -2 0 2 4 6 8

ol

10 12 14 16 18 20 22

18Omineral (, VSMOW)
FIG. 17. Calculated isotopic compositions of modeled fluids for conductive cooling, boiling, and fluid mixing simulations, plotted as a function of temperature. Irrespective of the depositional process (boiling, cooling, or mixing), the 18O isotope compositions of quartz and calcite are predicted to increase with decreasing temperature. Initial 18Owater compositions are assumed to be 0.5 per mil (type B) and 6.5 per mil (type D). Calculations of cooling, boiling, and mixing increments are based on the numerical simulations of Cooke and McPhail (2001).

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1418
3 2 1 0 -14 -12 -10 -8 4 3 2 1 0 -14 -12 -10 -8 6 5 4 3 2 1 0 -14 -12 -10 -8 4 3 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6 -6 -4 -2 0 2 4 6

COOKE ET AL.

Stage II Stage I
8

groundwaters occurred intermittently during vein formation. This would help to explain the observed occurrence of coarse rhombohedral calcite crystals in some type D bands, and could also help to explain the unusual transition at Acupan from alkaline pH conditions at low elevations associated with quartz-adularia-carbonate gangue to weakly acidic pH conditions at high elevations associated with quartz-muscovitepyrite alteration that was highlighted by Cooke and McPhail
1400

IIIb: Mix
I: Cool
275C 300C

Elevation (m)

Type A (chalcedony)

Type B (gray quartz)

A: Type B gray quartz

Owater = -0.5
18

200C

1200 1000 800 600 400 -2 1400

il Bo II: IIIa: Mix

250C

Type C (white quartz)

8
150C

10
IIIb: Mix

12

B: Type C white quartz

Owater = -4.0
18

Elevation (m)

1200 1000

200C 200C

150C

I: Cool

II:
250C 275C

Bo

il
150C

IIIa: Mix

800 600 400 -2 1400 0 2

10

12

Elevation (m)

2 1 0 -14 -12 -10 -8 -6 -4 -2

Type D (calcite)

18 C: Type D calcite Owater = -6.5

1200 1000 800 600 400 -2 0 2 4

I: Cool
250C

ix IIIb: M
200C 200C

150C 150C 100C

100C

II: Boil

IIIa: Mix

100C

6 5 4 3 2 1 0

10

12

Modern thermal waters

18Omineral (, VSMOW )
FIG. 19. Acupan epithermal veins: measured 18Oquartz values (, VSMOW) from (A) type B and (B) type C bands, and (C) 18Ocalcite values from type D bands, plotted as a function of elevation. Also shown are curves illustrating the calculated 18Omineral values for quartz (panels A and B) and calcite (panel C) that would be precipitated from the boiling, cooling and mixing conditions outlined in Figure 17, assuming initial 18Owater values of (A) 0.5, (B) -4.0 and (A) 6.5 per mil. Modeling conditions: curves show calculated 18Omineral values for quartz or calcite precipitated from waters that undergo (I) conductive cooling from 300 to 100C; (II) isoenthalpic boiling from 300 to 100C, and (III) cooling to 250C and then mixing with a shallow, cool (20C) meteoric groundwater that has an estimated 18Owater value of 10 per mil. Two extreme end-members are shown for case III. In the first (IIIa), mixing occurs entirely at the elevation where the two waters first meet. In the second, (IIIb) mixing occurs incrementally up to the elevations that correspond to the estimated depth of the paleowatertable for each vein stage as estimated from Figure 5. Calculations of cooling, boiling, and mixing increments are based on the numerical simulations of Cooke and McPhail (2001). For the white quartz data (B), excursions to high 18Oquartz values at high elevations can be explained by mixing with meteoric groundwaters, whereas type C bands precipitated in the deeper mine levels have compositions consistent with deposition from boiling hydrothermal fluids. Most of the calcite data (C) are consistent with deposition from a boiling hydrothermal fluid (consistent with the occurrence of bladed calcite textures). Excursions away from the boiling curve may be explained by subsurface fluid mixing with cool meteoric groundwaters.

-14 -12 -10 -8

-6

-4

-2

18Owater (, VSMOW )
FIG. 18. Histograms showing calculated 18Owater values (, VSMOW) for veins from Ampucao and Acupan. All data are listed in Table 8. (A) Ampucao porphyry-style quartz veins: stage I (black bars), stage IIa (pattern fill). (B) Acupan epithermal veins: early-stage type A chalcedony (stippled bar) and type B gray quartz (gray bars). (C) Acupan epithermal veins: main-stage type C white quartz. (D) Acupan epithermal veins: late-stage type D calcite. (E) Compositions of modern geothermal waters from the Baguio district (Table 9), shown for comparative purposes. Note that Ampucao quartz has values consistent with magmatic water compositions. At Acupan, calculated 18Owater values are highest for the gold-rich type B gray quartz bands that occur on the vein margins (Fig. 4). Calculated 18Owater values decrease to near-meteoric values in the central type D calcite bands, indicating an increase in the proportion of meteoric to magmatic water with time, and/or decreasing amounts of isotopic exchange between meteoric waters and igneous wall rocks. 0361-0128/98/000/000-00 $6.00

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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(2001). Excursions above the theoretical boiling-related 18Oquartz values for type B and C bands could also be explained by intermittent fluid mixing, in a similar fashion to type D calcite. Fluid mixing with cool meteoric groundwater is therefore inferred to have occurred in the upper levels of the Acupan vein system, causing the broad scatter in isotopic data at higher mine levels (Fig. 19C). We speculate that mixing may have occurred due to episodic descent of the paleogroundwater table, possibly in response to periods of very heavy rainfall that can occur in a monsoonal climate, as is the case in the modern-day setting of the Baguio district. Sulfur isotope geothermometry and bulk sulfur isotopic compositions Epithermal mineralizing fluids at Acupan were dilute (generally < 2 wt % NaCl equiv) and had moderate temperatures (< 300C; Fig. 5), whereas porphyry-style mineralization at Ampucao was associated with high temperature (300 to >600C) hypersaline brines (30 to >70 wt % NaCl equiv) and low-density vapor (Cooke and Bloom, 1990). In order to further constrain the temperatures of ore formation at these two deposits, sulfur isotope thermometry was attempted for mineral pairs using the fractionation equations of Ohmoto and Rye (1979). The 34S values from sulfate-sulfide pairs are used to help constrain the oxidation state and bulk sulfur compositions (i.e., 34S values) of the mineralizing fluids. Two sulfide-sulfate pairs analyzed from stage IIa veins at Ampucao yielded sulfur isotope thermometry results of 860 and 530C. These results could be explained by equilibrium precipitation of anhydrite and pyrite from a fluid with a 34S 2 value of ~5 per mil and a H2S(aq)/SO4 (aq) ratio of about 10 (i.e., reducing conditions). Analysis of primary brine inclusions from one of these samples yielded an average homogenization temperature of 450C, although the overall temperature range recorded by the individual inclusions was large (400 to > 600C; Cooke and Bloom, 1990). Isotopic disequilibrium is suspected, and so the results of this attempt to constrain the temperature and bulk sulfur isotopic composition of the Ampucao mineralizing fluids must be treated with caution. Four pyritesphalerite pairs from Acupan yielded temperatures from 96 to 192C, with an outlier at >800C. Some of these results are consistent with the fluid inclusion data of Cooke and Bloom (1990; Fig. 5), whereas others are not. One pyrite-anhydrite pair analyzed from a type E anhydrite band at Acupan yielded a sulfur isotopic temperature of 480C, much higher than the fluid inclusion temperatures recorded from these epithermal veins (Cooke and Bloom, 1990; Fig. 5). The isotopic compositions of the coexisting pyrite and anhydrite could be explained by co-deposition from a fluid with a similar 34S value to that estimated for Ampucao (~5), 2 but with a less reducing composition (H2S(aq)/SO4 (aq) ~ 5). However, this result is equivocal due to suspected isotopic disequilibrium, as implied by the discrepancies between temperature estimates by fluid inclusion and sulfur isotopic analyses. More detailed analyses and microsampling of coexisting sulfate and sulfide grains are required to better constrain the bulk sulfur isotope compositions of mineralizing fluids at Acupan and Ampucao. The absence of coexisting sulfide-sulfate mineral pairs at Santo Tomas II and Kelly prevents the bulk sulfur values of
0361-0128/98/000/000-00 $6.00

the magma and mineralizing fluids being determined directly. The 34S must be between the 34S value of the sulfates and sulfides, i.e., between +4 and +13 per mil at Santo Tomas II (Imai, 2001), and between +0.8 and +15 per mil at Kelly, assuming that the alunite from the nearby lithocap is representative of Kelly sulfate. Enrichment in 34S for porphyry deposits and related magmas is common in the western Luzon arc (Imai et al., 1996; Imai, 2000, 2001) and elsewhere (Arribas, 1995), and 34S estimates of +5 per mil for the Baguio district probably implies contamination of magmatic sulfur by sedimentary sulfate, possibly due to assimilation (Ohmoto and Rye, 1979). Isotopic tracing Our radiogenic isotope analyses provide evidence for mantle-derived magmatic components in the mineralizing fluids that formed the porphyry and epithermal deposits of the Baguio district. Early anhydrite veins from the Ampucao porphyry Cu-Au deposit and late anhydrite veins from the Acupan epithermal Au-Ag deposit have identical initial strontium ratios (0.703780.70385; Table 7). The data overlap with the main range of initial strontium ratios for Pliocene and Pleistocene igneous rocks from the Baguio district (0.70366 0.70388; Hollings et al., 2011b) and are well within the broader range of data reported for the Philippines by McDermott and Hawkesworth (1991; 0.703560.70476). The anhydrite initial Sr data also overlap with results obtained from porphyry deposits that formed in oceanic island arc terrains elsewhere (Fig. 12). The initial Sr ratios of anhydrite from Acupan and Ampucao are consistent with a primitive mantle-derived magmatic Sr source for both deposits, and preclude any significant crustal contamination of Sr during anhydrite deposition (Fig. 12). Similarly, the helium isotopic compositions of fluid inclusions from Acupan and Antamok are indicative of a mantle-derived (magmatic) noble gas component in the epithermal mineralizing fluids, and preclude the possibility of contamination by atmospheric He during hydrothermal activity (Table 9; Simmons et al., 1987). The oxygen and deuterium isotopic data listed in Tables 8 and 9 provide evidence for the following: (1) a predominance of magmatic water in the Ampucao porphyry system, (2) involvement of both magmatic and meteoric water in the Acupan epithermal veins, and (3) a predominance of meteoric water in the present-day geothermal systems of the Baguio district. The calculated 18O values of water that precipitated stage I and IIa quartz veins from Ampucao are +5.6 to +6.3 per mil and +5.5 to +6.7 per mil, respectively (Fig. 18A; Table 8). These are the highest 18Owater values detected from the Baguio district, and are consistent with a predominance of magmatic water at Ampucao. Calculated isotope values of hydrothermal fluids for the major vein stages at Acupan are: type B gray quartz-18Owater from 1.2 to +2.6 per mil (median = 0.3; Fig. 18B); type C white quartz 18Owater from 12.4 to +3.4 per mil (median = 4.2; Fig. 18C); type D calcite-18Owater from 12.4 to 2.2 per mil (median = 6.6; Fig. 18D; Tables 8, 9). There is a notable decrease in 18Owater values with time at Acupan (Fig. 18). The early-formed gray quartz bands (Fig. 4) have the highest 18Owater values, whereas the central type D calcite bands (Fig. 18D) have 18Owater values similar to the modern-day

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COOKE ET AL.

meteoric geothermal waters (Fig. 18E). This is interpreted to indicate a significant magmatic component in the mineralizing waters during the deposition of gold-rich type B mineralization, and a progressively smaller magmatic component and increasing meteoric component during deposition of goldrich type C and gold-poor type D bands. Alternatively, it could be argued that the waters that precipitated type B gray quartz underwent the greatest amount of isotopic exchange with the surrounding igneous wall rocks, shifting their 18O values away from meteoric compositions. Mantling of the major banded veins by early-formed quartz could then have isolated late-stage waters from the surrounding wallrocks, allowing preservation of near-meteoric 18O values in the central calcite bands. However, this alternative model does not adequately explain the mantle-derived radiogenic isotopic compositions of Sr and He obtained from the epithermal veins, and so our preferred model is for a significant magmatic water component in the earliest-formed epithermal veins at Acupan. Based on gold, silver and tellurium solubility relationships, Cooke and McPhail (2001) argued that the presence of tellurides at Acupan indicates direct input of magmatic H2Te(g), and a magmatic source of gold and silver remains the simplest explanation for the huge endowment of these metals in the Acupan vein system, with boiling the principal ore-forming mechanism. Our carbon isotope analyses of calcite from Acupan cannot discriminate between a magmatic or atmospheric source of carbon. The 18O and 13C values for type D calcite plot on a theoretical cooling curve for a H2CO3-predominant hydrothermal water with a 13C value of 6.5 per mil (Fig. 16), meaning that the carbon could be sourced from atmospheric or magmatic CO2 (Field and Fifarek, 1985). The calculated 18O value of 7.0 per mil for this cooling array is consistent with a predominance of meteoric water during calcite deposition. A predominance of magmatic sulfur (i.e., values near 0; Ohmoto and Rye, 1979; Field and Fifarek, 1985) is evident from our sulfur isotope dataset (Tables 36), but individual deposits appear to have been associated either with oxidized (SO42-predominant) or reduced (H2S-predominant) hydrothermal fluids. Predominantly negative 34Ssulfide values (6.8 to +0.8) were obtained from sulfides and sulfosalts from epithermal and porphyry deposits located adjacent to the Baguio lithocap, specifically Kelly, Baguio Gold, Black Mountain and Chico prospect (Figs. 2, 8C, E; Tables 5, 6). The sulfur isotopic compositions obtained from these deposits are consistent with sulfide deposition from an oxidized (sulfate-predominant) magmatic fluid (cf. Rye, 1993; Wilson et al., 2007; Wolfe and Cooke, 2011). Their 34S values are similar to the isotopic compositions of sulfides and sulfosalts from the Lepanto high sulfidation epithermal Cu-Au and Far Southeast porphyry Cu-Au deposits in the nearby Mankayan district (Fig. 11), where detailed investigations have demonstrated a genetic link between the Mankayan lithocap, Lepanto high sulfidation Cu-Au deposit and Far Southeast porphyry Cu-Au deposit (Arribas et al., 1995; Hedenquist et al., 1998; Imai, 2000; Chang et al., 2011; Deyell and Hedenquist, 2011). Evidence for reduced magmatic-hydrothermal fluids comes from the 34S values of sulfides from Acupan, Ampucao and Santo Tomas II. Their 34S values range from +1.1 to +6.6 per mil, with one exceptiona chalcopyrite clast from
0361-0128/98/000/000-00 $6.00

the Balatoc diatreme that yielded a value of -1.4 per mil (Fig. 8A, B, D; Tables 3, 4; Imai, 2001). The more limited 34S datasets obtained from Nugget Hill, Sierra Oro, Chico Mine, Camp 4, and Antamok overlap with this restricted range of positive 34Ssulfide values, with the exception of a chalcopyrite grain from the Wildcat Cu replacement orebody at Antamok that yielded a value of 2.5 per mil, and a chalcopyrite vein from Camp 4 (0.7; Table 6). The 34S values obtained from sulfate minerals from Acupan, Ampucao, and Santo Tomas II range from +13.4 to +18.3 per mil, apart from one outlier of +31.8 per mil (Tables 3, 4; Imai, 2001). The sulfur isotope results from these porphyry and epithermal deposits are consistent with a common, homogenized sulfur source that was predominantly magmatic with a 34S value of ~5 per mil, and mineralizing fluids that were most likely reduced (H2S-predominant with H2S(aq)/SO42(aq) ~ 5 to 10; cf. Rye, 1993; Wilson et al., 2007). The 34Ssulfide values obtained from skarns of the Baguio district are similar, ranging from +1.0 to +4.6 per mil (Table 6; Fig. 8E). It appears likely that reduced (H2S-predominant) magmatic-hydrothermal fluids prevailed in the porphyry, epithermal, and skarn deposits of the central and southern Baguio district. Genetic links between deposit styles Absolute age determinations imply that the Acupan epithermal veins (0.65 0.07 Ma; Aoki et al., 1993) are the same age as the Ampucao porphyry deposit within analytical error (0.51 0.26 Ma; Waters et al., 2011), although crosscutting relationships show that the porphyry vein stockwork formed first (Cooke and Bloom, 1990; Cooke, 1991; Fig. 20A). The oxygen isotope data from Ampucao and Acupan shows an evolution from magmatic to meteoric water-dominated fluid compositions with time (Fig. 18). The sulfur isotope compositions of sulfides and sulfates from both deposits are similar (Fig. 8A, B) and the strontium isotope compositions of early porphyry and late epithermal anhydrite are identical within analytical error (Table 7). All of these features are consistent with a genetic link between these two deposits. We therefore conclude that the Acupan veins are a late-stage manifestation of hydrothermal activity associated with the Ampucao porphyry deposit, with rapid uplift and exhumation promoting telescoping of the epithermal veins into the early-formed porphyry stockwork (Fig. 20A). Evidence for uplift rates of ~1 km per million years were obtained from fluid inclusion studies (Cooke and Bloom, 1990; Fig. 5), and this rapid uplift resulted in superposition of the shallow-crustal epithermal environment into the earlier-formed, deeper-level porphyry system. The Kelly high sulfidation epithermal veins (illite K-Ar <0.6 Ma; Aoki et al., 1993) are apparently younger than the Baguio lithocap (alunite K-Ar ages of 1.4 to 0.9 Ma; Aoki et al., 1993), implying that there were at least two major phases of acidic magmatic-hydrothermal fluid activity in the northern parts of the Baguio district (Fig. 20B). These episodes of intensely acidic hydrothermal alteration and mineralization were associated with oxidized magmatic-hydrothermal fluids, which precipitated sulfides with negative 34S values that are distinct from the sulfides associated with the porphyry, epithermal, and skarn deposits of the southern and central Baguio district. This suggests that the high sulfidation state veins at

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EPITHERMAL AND PORPHYRY DEPOSITS OF THE BAGUIO DISTRICT, PHILIPPINES

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Kelly are likely to have formed proximal to a very young, and therefore possibly more deeply buried, magmatic-hydrothermal (porphyry?) center in the northern part of the Baguio district (Fig. 20B). Detailed geochronological investigations are required to establish whether there are genetic links between Kelly and the nearby Antamok, Baguio Gold, or Atok-Big Wedge intermediate sulfidation vein systems. The fluid source(s) for the Baguio lithocap remains unknown. Potential candidates include the Nugget Hill and Chico porphyry prospects, for which no age determinations are currently available, or another, as yet undiscovered, porphyry center located somewhere beneath or to one side of the lithocap (Fig. 20B).

A
S

Acupan IS epithermal veins

0.65 0.07 Ma 34Ssulfides = +1.1 to +5.9
v v v

N
v v v v v v v v
o o

Ampucao porphyry
0.56 0.21 Ma 34Ssulfides = +2.3 to +6.6

Balatoc diatreme

not to scale

> 0.8 Ma 34Schalcopyrite = -1.4

Chico IS epithermal veins

unknown age 34 Ssulfides = -2.9 to -2.8

Kelly HS epithermal veins

< 0.6 Ma 34 Ssulfides = 3.2 to +0.8

Conclusions The porphyry, epithermal, and skarn deposits of the Baguio district formed over the past 3 m.y. when dioritic to dacitic magmas intruded the shallow crust in response to ridge subduction beneath northern Luzon. This geodynamic setting triggered shallow crustal hydrous magmatism, promoted rapid uplift and erosion, and juxtaposed porphyry, skarn, high and intermediate sulfidation deposit styles. Individual deposit types and locations were influenced by local structural, stratigraphic, magmatic and hydrothermal phenomena. Magmatic fluid sources were fundamental to ore formation. The strongest isotopic evidence for direct magmatic contributions to the mineralizing fluids are provided by the 18O values of quartz from Ampucao (Fig. 18A; Table 8), 34S values and initial strontium ratios of anhydrite from Ampucao and Acupan (Figs. 8A, B, 12), 34S values of sulfides and sulfosalts (Fig. 8) and helium isotope compositions of fluid inclusions from Acupan and Antamok (Table 9). The oxygen isotope data collected for quartz and calcite samples from the Acupan veins (Fig. 18A-D), combined with the oxygen and hydrogen isotope data of Sawkins et al. (1979; Fig. 15) and JICA (1983; Fig. 18E), and fluid inclusion data of Cooke and Bloom (1990) suggest epithermal vein deposition from boiling hybrid magmatic-meteoric waters, with the magmatic component decreasing to minimal amounts in later, weakly mineralized vein stages (Fig. 18). Isotope values of quartz and calcite vary markedly in the upper mine levels at Acupan, possibly indicating some fluid mixing with cool meteoric groundwaters. The Baguio district has been underexplored for bulk tonnage porphyry Cu-Au-style targets, despite almost a century of underground mining of high-grade epithermal Au-Ag

Thanksgiving skarn ( ~3 Ma?) 34 Ssulfides = +1.0 to +4.6

SSW

o o o o o o o o o o o o o o o oo o o ? o? o o

o o o o o o o o

Black Mt porphyry
3.09 0.15 Ma 34 Ssulfides = -1.5 to +0.8

Chico porphyry

Baguio Gold

unknown age IS epithermal veins 34 Ssulfides = +1.0 to +2.9 unknown age 34 Ssulfides = -6.8 to +0.5

Nugget Hill porphyry

unknown age 34Ssulfides = +2.0 to +5.0

not to scale diorite porphyry potassic alteration pyrite halo propylitic alteration skarn

LEGEND
High sulfidation vein
(advanced argillic halo)

Intermediate sulfidation vein

(illite alteration halo)

Balatoc diatreme
(> 0.8 Ma)

o o o o o

Baguio lithocap
(1.4 to 0.9 Ma)

0361-0128/98/000/000-00 $6.00

v v v

NNE
?o ?

FIG. 20. Schematic cross sections through the Baguio district showing key spatial relationships between ore deposits, prospects and alteration zones, together with geochronological data and 34Ssulfide values. Note that these sections are schematic cartoonsthey are not drawn precisely to scale, and include speculative elements indicated by ? symbols. (A) N-S section (~2.5 km long) through the Acupan intermediate sulfidation epithermal veins, Balatoc diatreme, and Ampucao porphyry. Potassic alteration (biotite-magnetite-quartz-chalcopyrite-anhydrite and orthoclase-quartz-chalcopyrite-anhydrite assemblages) occurs around the Ampucao intrusive complex and also in the deeper levels of the Acupan mine adjacent to the Balatoc diatreme. The intermediate sulfidation veins dip towards the Ampucao porphyry, and have cut the porphyry and diatreme, but cannot be discriminated from the porphyry using radiometric age determinations. (B) NNE-SSW section between Baguio Gold and Black Mountain (~ 8 km long), with the Kelly high sulfidation veins, Chico porphyry, Chico intermediate sulfidation veins, and Nugget Hill porphyry projected onto the section from locations up to 1 to 2 km to the east. Mineralization in the Baguio district commenced with the formation of the Black Mountain porphyry Cu-Au deposit and Thanksgiving skarn at about 3 Ma, and continued intermittently through to <0.6 Ma with the formation of the Kelly high sulfidation veins. The 1.4 to 0.9 Ma Baguio lithocap is a single contiguous body of advanced argillic and silicic alteration up to 7.5 km long and 4 km wide that has a crescent-shaped outcrop pattern (Fig. 2). It is shown here in section as two discrete bodies because the cross section only passes through the southern and northeastern edges of the lithocap. The fluid source(s) for the Baguio lithocap remain unknown, but based on the outcrop patterns in Figure 3, we speculate that Nugget Hill may have been a source for the southern part of the lithocap, and that one or more asyet undiscovered porphyries may have been the source(s) of fluids for the lithocap, and also for the high and intermediate sulfidation state epithermal veins at the northern end. Abbreviations: HS = high sulfidation, IS = intermediate sulfidation.

v vv

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COOKE ET AL. Bureau of Mines and Geosciences, 1986, Geology and mineral resources of the Philippines. Volume 2. Mineral resources: Metro Manila, Philippines, Bureau of Mines and Geosciences, Ministry of Natural Resources, 446 p. Callow, K.J., 1967, The geology of the Thanksgiving mine, Baguio district, Mountain Province, Philippines: ECONOMIC GEOLOGY, v. 62, p. 472481. Callow, K.J., and Worley, B.W., Jr., 1965, The occurrence of telluride minerals at the Acupan gold mine, Mountain Province, Philippines: ECONOMIC GEOLOGY, v. 60, p. 251268. Chang, Z., Hedenquist, J.W., White, N.C., Cooke, D.R., Roach, M., Deyell, C.L., Garcia, Jr., J., Gemmell, J.B., McKnight, S., and Cuison A.L., 2011, Exploration tools for linked porphyry and epithermal deposits: Example from the Mankayan intrusion-centered Cu-Au district, Luzon, Philippines: ECONOMIC GEOLOGY, v. 106, p. 13651398. Clayton, R.N., and Mayeda, T.K., 1963, The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis: Geochimica et Cosmochimica Acta, v. 27, p. 4352. Comsti, M.E.C., Villones, R.I., de Jesus, C.V., Natividad, A.R., Rollan, L.A., and Duroy, A.C., 1990, Mineralization at the Kelly gold mine, Baguio district, Philippines: fluid-inclusion and wall-rock alteration studies: Journal of Geochemical Exploration, v. 35, p. 297340. Cooke, D.R., 1991, Styles and controls of mineralization, Acupan gold mine, Baguio district, Philippines: Unpublished Ph.D. thesis, Clayton, Victoria, Monash University, 396 p. Cooke, D.R., and Bloom, M.S., 1990, Epithermal and subjacent porphyry mineralization, Acupan, Baguio district, Philippines: A fluid inclusion and paragenetic study: Journal of Geochemical Exploration, v. 35, p. 297340. Cooke, D.R., and McPhail, D.C., 2001, Epithermal Au-Ag-Te mineralization, Acupan, Baguio district, Philippines: numerical simulations of mineral deposition, ECONOMIC GEOLOGY, v. 96, p. 109131. Cooke, D.R. and Simmons, S.F., 2000, Characteristics and genesis of epithermal gold deposits: Reviews in Economic Geology, v. 13, p. 221244. Cooke, D.R., Hollings, P., and Walshe, J.L., 2005, Giant porphyry deposits: Characteristics, distribution and tectonic controls: ECONOMIC GEOLOGY, v. 100, p. 801818. Cooke, D.R., McPhail, D.C., and Bloom, M.S., 1996, Epithermal gold mineralization, Acupan, Baguio district, Philippines: geology, mineralization, alteration and the thermochemical environment of ore deposition: ECONOMIC GEOLOGY, v. 91, p. 243272. Cooke, D.R., Wilson, A.J., House, M.J., Wolfe, R.C., Walshe, J.L., Lickfold, V., and Crawford, A.J., 2007, Alkalic porphyry Au-Cu and associated mineral deposits of the Ordovician to Early Silurian Macquarie Arc, New South Wales: Australian Journal of Earth Sciences, v. 54, p. 445463. Corbett, G.J., and Leach, T.M., 1998, Southwest Pacific rim gold-copper systems: Structure, alteration and mineralisation: Society of Economic Geologists Special Publication no. 6, 236 p. Damasco, F.V., 1979, Geology of the Wildcat copper deposit in the Antamok mine of Benguet Consolidated, Inc.: Journal of the Geological Society of the Philippines, v. 33, p. 116. De los Santos, R.B., 1982, Geology of the Southwestern Baguio district: Bureau of Mines and Geosciences, Metro Manila, Philippines, Technical Information Series, Geology, v. 53, 17 p. Defant, M.J. and Drummond, M.S. 1990, Derivation of some modern arc magmas by melting of young subducted lithosphere: Nature, v. 347, p. 662665. Deyell, C.L., and Cooke, D.R., 2003, Mineralogical and isotopic evidence for the genesis of the Kelly gold-silver deposit, Baguio district, Philippines: Diverse mineral assemblages in a hybrid epithermal system, in Eliopoulos, D., et al., Mineral Exploration and Sustainable DevelopmentProceedings of the Seventh Biennial SGA Meeting: Millpress, Rotterdam, v. 1, p. 469472. Deyell, C.L., and Hedenquist, J.W., 2011, Trace element geochemistry of enargite in the Mankayan district, Philippines: ECONOMIC GEOLOGY, v. 106, p. 14651478. Drummond, S.E., and Ohmoto, H., 1985, Chemical evolution and mineral deposition in boiling hydrothermal system: ECONOMIC GEOLOGY, v. 80, p. 126147. Durkee, E.F., and Pederson, S.L., 1961, Geology of Northern Luzon, Philippines: Bulletin of the American Association of Petroleum Geologists, v. 45, p. 137168. Field, C.W., and Fifarek, R.H., 1985, Light stable-isotope systematics in the epithermal environment: Reviews in Economic Geology, v. 2, p. 99128. Friedman, I., and ONeil, J.R., 1977, Data of geochemistry. Compilation of stable isotope fractionation factors of geochemical interest: U.S. Geological Survey Professional Paper 440-KK, p. 112.

veins. This may relate in part to a lack of appreciation of the potential links between porphyry deposits and intermediate sulfidation state veins, despite the best efforts of Sillitoe (1989, 2010) and others to promote this potential genetic relationship. We believe that several porphyry-style targets in the Baguio district currently warrant drill testing. They include the Ampucao, Chico, and Nugget Hill prospects, where significant rock chip and drill core assay results indicate the potential for discovery of high-grade Cu-Au resources (Table 2; Waters et al., 2011). The high sulfidation-state mineralization at Kelly is a favorable sign of a magmatic-hydrothermal (porphyry?) fluid source nearby, with supporting evidence provided by the early biotite and actinolite alteration that has been cut by the high sulfidation veins (Comsti et al., 1990). The geology and sulfur isotope data of Kelly compares favorably with the Lepanto deposit in the Mankayan district (Fig. 11), where deep drilling resulted in the discovery of the Far Southeast porphyry deposit (Hedenquist et al., 1998; Chang et al., 2011). High temperature quartz-magnetite-sulfide veins are cut by intermediate sulfidation calcite-quartz veins at the Baguio Gold deposit, similar to the observed crosscutting relationships between Acupan and Ampucao, and again suggesting proximity to a porphyry-style centre. We believe that the Wildcat massive chalcopyrite replacement-style orebody, which is cut by the Antamok intermediate sulfidation veins, probably lies close to a magmatic-hydrothermal source, given the high copper grades of 1.4 to 3.7 wt percent that were mined from Wildcat during the 1970s (Damasco, 1979; Table 2). All of these empirical observations imply that one or more buried porphyry-style Cu-Au deposits remain to be discovered in the Baguio district. Acknowledgments We thank Christine Cook and Mike Power for their assistance in performing C-O and S isotope analyses. Ian Cartwright is thanked for undertaking O isotope analyses, and Roland Mass for Sr isotope analyses. Stuart Simmons is thanked for providing access to his unpublished helium isotope data. Mike Baker and Norman Tamayo are thanked for assistance with figure preparation. The manuscript was improved markedly by the thoughtful reviews of Antonio Arribas, Kevin Faure, Stuart Simmons, and Pete Hollings. CODES is the Australian Research Councils Centre for Excellence in Ore Deposits.
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