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HYPOGENE ALTERATION AND MINERALIZATION IN THE DOS POBRES PORPHYRY CU(-AU-MO) DEPOSIT, SAFFORD DISTRICT, ARIZONA: A - AND -RICH VARIANT OF ARIZONA PORPHYRY SYSTEMS

By Daniel Russin

______

A Thesis Submitted to the Faculty of the

DEPARTMENT OF GEOSCIENCES

In Partial Fulfillment of the Requirements For the Degree of

MASTER OF SCIENCE

In the Graduate College THE UNIVERSITY OF ARIZONA 2 0 0 8 2

STATEMENT BY THE AUTHOR

This thesis has been submitted in partial fulfillment of requirements for the Master of Science degree at The University of Arizona and is deposited in the Antevs Reading Room to be made available to borrowers, as are copies of regular theses and dissertations. Brief quotations from this manuscript are allowable without special permission, provided that accurate acknowledgment of the source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the Department of Geosciences when the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author.

Daniel Russin______(author’s signature) (date)

APPROVAL BY RESEARCH COMMITTEE

As members of the Research Committee, we recommend that this thesis be accepted as fulfilling the research requirement for the degree of Master of Science.

Mark D. Barton______Major Advisor (type name) (signature) (date)

Eric Seedorff______(type name) (signature) (date)

Jon Patchett______(type name) (signature) (date) 3

Hypogene alteration and mineralization in the Dos Pobres porphyry

Cu(-Au-Mo) deposit, Safford District, Arizona: A gold- and magnetite-

rich variant of Arizona porphyry copper systems.

Daniel Russin*

Mark D. Barton

Eric Seedorff

Center for Resources, Department of Geosciences, University of Arizona,

Tucson, Arizona 85721-0077

* E-mail: [email protected]

Abstract

The Dos Pobres Cu(-Au-Mo) deposit (211 million metric tonnes resource

0.73% Cu with up to 1 ppm Au) is located in the Safford district of southeastern Arizona and is one of several Au-bearing porphyry systems in Arizona. The deposit is centered on

Paleocene (57 Ma) monzodioritic porphyry dikes that intrude and alter Late

Cretaceous (67-73 Ma) basaltic andesites. The porphyry dikes locally contain igneous anhydrite. The volcanic rocks dip gently (10-15°) to the northeast; they and the ENE- trending porphyry dikes are cut by a NW-striking down-to-the-west normal fault that down-drops the southwestern portion of the Dos Pobres system by roughly 1 km. This study focuses on the characterization and distribution of veins, hydrothermal alteration, and below the base of , utilizing core logging and petrography 4 coupled with whole-rock geochemical and electron microprobe analyses, as well as U-Pb and Re-Os geochronology.

Hypogene veins at Dos Pobres are divided into groups based on their , textures, and alteration envelopes. Five early vein types have envelopes that are dominated by biotite and/or K-. These are: hairline biotite (biotite ± magnetite ± ); sugary quartz (quartz + K-feldspar ± sulfide (bornite  ) ± biotite ± anhydrite); comb quartz (inward-growing quartz + K-feldspar ± sulfide (bornite < chalcopyrite) ± biotite); complex biotite (biotite + K-feldspar + quartz + sulfide ( < bornite < chalcopyrite) ± anhydrite); and green mica veins (biotite + sericite + K-feldspar

± sulfide (bornite  chalcopyrite) ± anhydrite ± andalusite). Two types of veins with chlorite ± sericite envelopes are sulfide-sericite (sulfide (chalcopyrite > pyrite)

± quartz ± sericite ± chlorite ± anhydrite) and clotty sulfide-chlorite (quartz

± (chalcopyrite > pyrite) ± chlorite ± sericite ± anhydrite). These veins cut those with biotite and/or K-feldspar envelopes. Veins consisting of chlorite + +

+ quartz ± sulfide (pyrite > chalcopyrite) with chlorite + epidote + calcite envelopes are also common and cut those with chlorite ± sericite envelopes. veins without alteration envelopes cut all other vein types.

Potassic alteration assemblages with pervasive biotite ± K-feldspar ± magnetite comprise the best developed and earliest alteration suite. It is most intense in proximal locations where quartz + K-feldspar veins locally compose upwards of 30 vol percent of the rock. The intensity of this alteration diminishes outward and upward.

Scattered biotite + actinolite-hornblende + magnetite alteration is interpreted to represent 5 the fringes of pervasive potassic alteration. Hydrolytic alteration, characterized by sericite- and chlorite-rich replacement of and biotite is later and/or peripheral, partially overprinting potassic alteration. Propylitic alteration (chlorite

± epidote ± calcite) forms a weakly defined zone that overprints the earlier assemblages and shows a gradational boundary with unaltered host rock. Whole-rock geochemical analyses indicate that the Dos Pobres rocks have unextraordinary igneous compositions but that many of them have experienced significant metasomatic addition of

K2O, whereas hydrolytic alteration is quantitatively minor.

Hypogene sulfides are abundant and systematically distributed beneath the base of oxidation (depth ~350 m). Early bornite (± ± ) dominates the deep core of the deposit coincident with the most intense K-silicate alteration and quartz veins.

There is a transition from these through bornite-chalcopyrite assemblages into chalcopyrite-dominated veins. The chalcopyrite-bearing veins typically cut bornite-rich veins and surround the bornite-dominated core but are also associated with K-silicate alteration. Pyrite (± chalcopyrite)-bearing veins have hydrolytic envelopes and are most abundant in a ring-shaped zone surrounding the core. is rare but is most commonly associated with chalcopyrite in deep, flanking veins with associated hydrolytic alteration. Gold occurs as tiny (mostly <10 μm) grains of electrum (~10-15 wt % Ag) and in early bornite. is also present in early bornite, occurring as electrum, hessite, sylvanite, and a mineral (?). Silver also occurs as hessite and sparse argentiferous (up to ~2.5 wt % Ag) that commonly rim and crosscut all 6

Cu-Fe sulfides. bornite, chalcocite, and rare locally replace hypogene sulfides beneath the zone.

Dos Pobres is unusual among Arizona porphyry deposits in that it is relatively gold- and bornite-rich, and magnetite-bearing and is intimately associated with relatively mafic (quartz monzodiorite - low silica granodiorite) porphyry dikes. Conversely, it has considerably less pyrite and acid alteration than most other Arizona porphyry deposits.

These features are like those in many other Au-rich porphyry systems, and they have also stimulated comparisons with andesite-hosted -oxide(-Cu-Au) (IOCG) systems such as Candelaria.

At Dos Pobres, as in most Cu-Au-Mo porphyry deposits, Cu-Fe sulfides are deposited with voluminous early quartz veins, magnetite is widespread but minor in abundance, bornite is the dominant early ore mineral, deposition of pyrite postdates most deposition of Cu, and there is a close spatial and temporal association of mineralization with relatively mafic porphyry intrusions – all features consistent with introduction and cooling of magmatic fluids. These characteristics differ profoundly from andesite-hosted

IOCG deposits, which typically have abundant Fe- (tens of percent), REE enrichment, voluminous Na-Ca and/or K-Ca alteration, comparatively sparse quartz veins, and generally late copper mineralization.

Introduction

The Dos Pobres porphyry Cu(-Au-Mo) deposit is located in the North American

Laramide porphyry belt, which extends from western Mexico into Arizona and New 7

Mexico. This region is richly endowed with porphyry Cu-(Mo) deposits, yet Dos Pobres, one of at least four porphyry deposits in the Safford district (Langton and Williams,

1982), represents one of the few porphyry Cu(-Au-Mo) deposits, a distinctive family of porphyry deposits that are commonly associated with relatively mafic intrusive rocks

(Seedorff et al., 2005), that has been documented to date. The spatial and temporal association of Dos Pobres with comparatively Au-poor porphyry Cu-Mo deposits in the region and perhaps in the Safford district poses questions about comparisons between these systems and the processes that form them. Many hypotheses have been presented, including differences in composition and/or thickness of underlying crust (Hollister,

1975), differences in emplacement depth or wall-rock properties (Kesler, 1973), vertical zoning of Cu and Au coupled with different erosion levels (Titley, 1982), composition of mineralizing intrusions (Kesler, 1973; Sillitoe, 1979), and other complex magmatic geochemical factors (Sillitoe, 2000). As more of these deposits have been discovered and described, it is apparent that these systems show differences among themselves and that none of these hypotheses is sufficient – thus there is the need for continued systematic study of the deposits themselves and for their comparison with others.

This study, which was sponsored by Phelps Dodge Exploration (now Freeport-

McMoRan Copper and Gold), was undertaken with the twin goals of characterizing the mineralogy and distribution of precious metals in the hypogene mineralization and developing insight into the possible reasons for the unusual metal endowments in this atypically (for Arizona) Au-rich porphyry copper system. 8

Dos Pobres shows strong similarities to many other porphyry Cu(-Au-Mo) deposits worldwide, such as the predominance of early potassic (secondary biotite

± K-feldspar) alteration that carries most Cu and has associated precious metals (cf.

Gustafson and Hunt, 1975; Sillitoe, 1979; Seedorff et al., 2005), lack of well-developed quartz + sericite alteration (Sillitoe, 1979), and relatively low content. As the other deposits in the Safford district become more completely explored and described, the district may present an uncommon opportunity to compare and contrast different deposits that formed in identical host rocks and closely in time. The data presented in this study will add to the understanding of vein and alteration types and mineralization style present in Cu(-Au-Mo) deposits.

This study presents data on the host and intrusive rocks and their and U-Pb geochronology, alteration types and distribution, vein types (and their distribution, paragenetic sequence, and Re-Os geochronology), and sulfide mineralogy and distribution. Selected intervals of drill core were logged to enable the construction of an ENE-trending cross section through the deposit and a plan map on the 2,000 ft (600 m) level; selected samples from these intervals were made into polished thin sections.

These results compile to give a detailed picture that shows that Dos Pobres resembles aspects of other porphyry Cu-Au deposits worldwide, notably in the southwest Pacific, such as Grasberg, Papua, Indonesia, and Panguna, Bougainville, Papua New Guinea

(Rubin and Kyle, 1997; Fountain, 1972), Far Southeast, Philippines (Hedenquist et al.,

1998), and Goonumbla and Endeavour, New South Wales, Australia (Lickfold et al.,

2003; Wilson et al., 2003). 9

Location

Dos Pobres is located in southeastern Arizona ~50 km southwest of the Morenci district (Fig. 1A), near the boundary between the Basin and Range province of southern and western Arizona and the Colorado Plateau to the northeast. Dos Pobres is located in the Safford (Lone Star) district, which contains a NW-SE oriented group of porphyry deposits located northeast of the town of Safford, in the northwest-trending Gila Range

(Fig. 1B). Dos Pobres is situated at the northwestern end of the district; the other deposits include San Juan, Lone Star, and Sanchez, as well as several small prospects. The Lone

Star deposit is situated beneath the spine of the Gila Range, whereas Dos Pobres, San

Juan, and Sanchez crop out in the southwestern foothills.

Exploration and Development History

Copper mineralization in the Safford (Lone Star) district has been known for over one hundred years. The San Juan, Lone Star, and Sanchez deposits were claimed in the late 1800s, and some small-scale exploration and mining took place at these three deposits in the late 19th and early 20th centuries. By about 1920, exploration and production had largely ceased (Robinson and Cook, 1966).

Porphyry copper exploration of the district by many companies resumed in the late 1940s and was most active until the late 1960s. The Dos Pobres deposit was discovered by Phelps Dodge in 1958 (Langton and Williams, 1982). A project in the late

1970s to evaluate bulk underground mining of the deposit was abandoned due to geotechnical problems and other factors, such as copper price, water availability, and 10 project economics) (J. E. Gerwe, pers. comm., 2006). The Lone Star deposit, which was discovered by Bear Creek Mining Co. (a Kennecott subsidiary) in the mid-1950s and studied as a potential in situ leaching project (Robinson and Cook, 1966; Anonymous,

1973; D’Andrea et al., 1974), was acquired by Phelps Dodge in 1986. Drilling resumed at

Dos Pobres in early 1990, this time focused on the supergene mineralization; by 1991, a leachable resource was delineated. Phelps Dodge purchased the nearby San Juan deposit in 1992, in 1994 initiated permitting to put both Dos Pobres and San Juan into production as a single leach operation, and then in 1995 purchased the Sanchez deposit. Freeport

McMoRan acquired Phelps Dodge in 2007.

Production from the leachable part of the Dos Pobres deposit commenced in late

2007, and the combined Dos Pobres-San Juan leach operation at the end of 2007 carried a proven and probable ore reserve of 549 million metric tonnes at 0.36% Cu (weighted average of crushed and run-of-mine leach ore, FMI 2007 10-K Report). The sulfide portion of the Dos Pobres deposit contains 211 million metric tonnes of mineralized material at an average grade of 0.73% Cu (FMI 2007 10-K Report). There are no published figures for the sulfide portion of the San Juan deposit. FMI is actively exploring the Lone Star deposit and currently considers that the deposit contains 1,451 metric tonnes of leachable mineralized material at an average grade of 0.38% Cu (FMI

2007 10-K Report). FMI does not currently quote a size or grade of the sulfide portion of the Lone Star deposit, but Williams and Forrester (1995) published a sulfide resource of

~4,300 million metric tonnes at an average grade of 0.47% Cu. Sanchez contains 209 million metric tonnes of mineralized material at an average grade of 0.29% Cu (FMI 11

2007 10-K Report), and there are no published estimates regarding the sulfide portion of the deposit.

Previous Work

Published reports on the Safford district are few despite its long history of mineral exploration and its huge mineral resource. Robinson and Cook (1966) were the first to present a detailed study of the of the area; they focused on the Lone Star and San

Juan deposits and comparisons between them. Blake (1971) described the structure, alteration, and mineralization of the surface exposure of the San Juan deposit. Bolin

(1976) compared the major element whole-rock geochemistry of the Lone Star and San

Juan rock suites with several other barren and mineralized intrusive complexes in

Arizona. Dunn (1978) examined and interpreted the structure of the district. Langton and

Williams (1982) published the first description of the structure, alteration, and mineralization at the Dos Pobres deposit. Lang and Titley (1998) published major- and trace-element data as well as Sm-Nd and Rb-Sr isotopic data from Safford and other districts. Wilson (2004) mapped and interpreted different styles of leached capping present at Dos Pobres, concluding that the supergene zone may be the product of more than one cycle of weathering.

Synopsis of Safford District Ore Deposits

The Dos Pobres orebody is centered on a swarm of east-northeast-trending porphyry dikes of quartz monzodioritic composition and is broadly domal in form.

Bornite-chalcopyrite mineralization and biotitic alteration dominates the core of the 12 orebody, magnetite is widespread, and the overall deposit is relatively poor in molybdenum and rich in precious metals (Langton and Williams, 1982; this study).

Sericitic alteration is poorly developed and discontinuous in the sulfide zone and only somewhat better developed at higher levels, consistent with the relatively high oxide copper grades and moderate development of chalcocite enrichment (Langton and

Williams, 1982; Wilson, 2004; this study).

Each of the other three deposits, Lone Star, San Juan, and Sanchez, is centered on near-vertical intrusions that are hosted by intermediate to mafic volcanic rocks, apparently localized along east-northeast trending faults or shear zones (Robinson and

Cook, 1966; Dunn, 1978; Dreier, 1994). The names used to classify the intrusions seem to imply that the compositions of stocks at certain deposits, such as Lone Star (Robinson and Cook, 1966), may be more silicic than at Dos Pobres, but Dunn (1978) noted that the main intrusions at each deposit “are nearly identical in composition and texture.” Several of the deposits contain crosscutting dikes, breccia pipes, and pebble dikes.

The three deposits other than Dos Pobres also have limited published information on their alteration-mineralization characteristics. Robinson and Cook (1966) describe a central area of intense sericitic alteration that is partially superimposed on a large area of biotitization. The only sulfides that Blake (1971) reported at the San Juan deposit are chalcopyrite and pyrite. At Lone Star, Robinson and Cook (1966) report that chalcopyrite is much more common than bornite, that magnetite is fairly common; and that molybdenite occurs in quartz veins and is more abundant in the deeper sulfide zones.

Maps of the distribution of Mo, Au, and Ag grades, presented by Langton and Williams 13

(1982) for Dos Pobres, have not been published for the other deposits. Moreover, the average grades of elements other than Cu have not been published for any deposit and may not be available considering that the development focus has been mostly on supergene mineralization.

It remains to be seen whether potential differences between deposits are within the range observed in other tonalitic-granodioritic porphyry Cu-(Au-Mo) deposits

(Seedorff et al., 2005), or whether some of the deposits may be gold-poor and related to more silicic intrusions, such as the quartz monzodioritic-granitic porphyry Cu-(Mo) deposits of the nearby Morenci district, which is permitted by the petrologic information presented below.

Geology

Stratigraphy

The known stratigraphy in the Safford district is composed entirely of Late

Cretaceous and younger volcanic and volcaniclastic rocks overlain by basin-filling sediments (Fig. 1B, C). The oldest rocks exposed are the Safford Volcanics (“older volcanics” of Robinson and Cook, 1966), which comprise >1,300 m of basaltic to dacitic volcanic and volcaniclastic rocks (Langton and Williams, 1982; Houser et al., 1985).

Near the Dos Pobres and San Juan deposits, these are dominantly basaltic

(trachy)andesites (see Fig. 2A below). Andesite hosting the Dos Pobres system has been dated at 73.3 ± 1.0 Ma (U-Pb, Appendix A), and stratigraphically higher andesite near 14

San Juan yielded 67.6 ± 1.4 Ma (Ar-Ar on hornblende, Houser et al., 1985). Their total thickness is unconstrained. The nearest Paleozoic rocks are ~25 km northwest of Dos

Pobres in the Gila Mountains; the nearest exposure of Precambrian rocks is ~50 kilometers to the southwest in the Pinaleño Mountains, a metamorphic core complex.

Xenoliths of presumably Precambrian schist, granite, and gneiss are present in the

Safford Volcanics. Quartzite xenoliths are also present, which resemble the Precambrian

Coronado Quartzite exposed near Morenci (Robinson and Cook, 1966).

Rock fragments in the andesites vary considerably in their appearance. Most fragments are andesitic in composition, with noticeable differences in color (shades of gray to black) and phenocryst size and abundance. Phenocryst contents in the Safford volcanics range from near zero to ~50 vol percent. They consist dominantly of

plagioclase (An20-An80, avg. An55) and range in size from <1 to 5 mm, with most between

1-3 mm. Hornblende or phenocrysts are common (up to ~5 vol %) with most 2 mm or less in length; near Dos Pobres shreddy biotite replaces most mafics. Magnetite is present as an accessory phase, usually containing <0.1 wt percent Ti. Individual units within the andesites differ greatly in the types, sizes, and abundances of fragments and phenocrysts present, but the units are intercalated and too altered to attempt correlation of units between drill holes.

Langton and Williams (1982) distinguish a younger, somewhat less altered sequence of andesitic agglomerates, flow breccias, and lithic tuffs that they term the

Baboon Volcanics. Freeport geologists believe that the Baboon andesites should be considered part of the Safford Volcanics, since they differ only in their alteration and may 15 interfinger with them (Bill Stavast, pers. comm., 2008). Dikes, sills, and plugs of hornblende andesite intrude both the Safford and Baboon volcanics and appear to be related to the extrusion of the Baboon sequence (Langton and Williams, 1982).

Regardless of affiliation, the older volcanic rocks are overlain by the Miocene-Pliocene

(?) Gila Volcanics, which consist of a bimodal sequence of basalts, tuffs, rhyolites, and agglomerates. The Gila Volcanics locally exceed 1 km in thickness and form the spine of the Gila Mountains. Middle Tertiary to Recent variably indurated gravels, finer-grained clastic rocks, and local evaporites fill valleys and partially cover the older units (Houser et al., 2004).

Intrusive Rocks

The largest known intrusive body in the Safford district is the Lone Star stock.

Numerous smaller intrusive bodies crop out in the district such as the San Juan stock and intrusive rocks near the Sanchez deposit.

The main intrusive phases known at Dos Pobres are Paleocene (57.1 Ma, U-Pb,

Appendix A) porphyries of quartz monzodioritic to low-silica granodioritic composition

(see Fig. 2E below). These occur as east-northeast trending dikes which, on the 2,000-ft level (~600 m a.s.l.), range from ~150-300 m in length and ~15-100 m in width (Fig.

1D); the ENE orientations are typical of Laramide-age intrusive in this region (Rehrig and Heidrick, 1972; Titley and Heidrick, 1982). The fresh rock (see Fig. 5A below) is medium gray in color with obvious plagioclase and biotite phenocrysts. Plagioclase

(An35-An60, avg. An40) is the most common phenocryst mineral; abundances range from 16

~20-50 vol percent. Crystal sizes range from <1 to about 10 mm, most commonly between 3 and 6 mm. Equant biotite phenocrysts are abundant, typically ranging from 2 to 5 mm, rarely up to 10 mm; abundances range from <1 to ~10 vol percent, but typically are ~5 vol percent. Hornblende phenocrysts (altered to biotite

± magnetite ± rutile) typically compose ~5 vol percent and are typically <5 mm in the long dimension. Quartz phenocrysts are generally absent, though they are locally present

(at ~5 vol %) and range from 3 to 6 mm. They are well rounded and partially resorbed.

The groundmass consists typically of fine, 0.05-0.1 mm plagioclase and biotite with quartz, K-feldspar, magnetite, sphene, and rare anhydrite. Anhydrite typically occurs as

<0.1 mm grains scattered in the groundmass; however, two larger (~1 cm) crystals also were noted (see Fig. 5B below). Magnetite is present as an igneous phase and very rarely shows evidence of exsolution; Ti contents are typically <0.1 wt percent. Chilled margins are locally observed at contacts with andesite.

Igneous Geochemistry

Appendix B summarizes whole-rock major- and trace-element data for Dos

Pobres. The compositions of various units are shown in Figures 2 and 3 below. The

Safford andesites are of continental affinity (Fig. 2B) and are metaluminous to weakly peraluminous (Fig. 2D). The freshest andesites cluster in the high-K calc-alkaline on

a K2O vs. SiO2 diagram (Fig 2C), but several lie in the shoshonite field due to

K2O metasomatism. IUGS and -normalized REE plots are shown in Figures 2E and 2F. The two freshest porphyry samples plot within the quartz monzodiorite field near 17 the boundary with granodiorite (Fig. 2E); the other four samples plot in the granite field

principally due to K2O metasomatism and quartz veining but with a possible contribution from original igneous variability. Similar trends representing addition of K-feldspar and quartz are visible in Fig. 2A, C, and D.

Several porphyry and andesite samples from Langton and Williams (1982) and

Lang and Titley (1998) are also plotted in Figures 2A, C, and E, as well as in Figure 4A below. The compositions of their samples plot with those analyzed in this study, with two exceptions: the “porphyry with secondary biotite” has an exceptionally low silica content for a porphyry (56 wt %) and based on the geochemistry is probably an intensely altered andesite; the “porphyry altered to quartz-sericite” has been subjected to more intense hydrolytic alteration than any samples collected during this study (see Fig. 4A below).

Analyses of Safford Volcanics provided by Blake (1971) and Bolin (1976) are similar to those plotted. Also plotted are compositions for the Lone Star stock, Lone Star porphyries, Baboon volcanics, and hornblende andesite dikes from Lang and Titley

(1998).

Chondrite-normalized REE patterns (Fig. 2F) of samples of the Safford Volcanics show a small positive Eu anomaly. The porphyries at Dos Pobres show more pronounced positive Eu anomalies; REE concentrations are reduced with increasing alteration intensity. Samples from the seemingly barren Lone Star stock and the porphyries from the

Lone Star deposit show slightly negative Eu anomalies (Lang and Titley, 1998). The

Baboon volcanics show a similar distribution pattern to the Safford Volcanics but with 18 slightly higher REE concentrations. The hornblende andesite dike material is similar to the Safford Volcanics.

Additionally, porphyries at Dos Pobres have a more primitive Nd signature (-3.2) than those at the Lone Star deposit (-8.7) and all other Laramide porphyries sampled by

Lang and Titley (1998).

Structure

The Safford district lies between the highly extended Pinaleño core complex to the southwest and the Mogollon Rim (the edge of the undeformed Colorado Plateau) to the northeast. The (Gila Volcanics in the Safford district are tilted

10-15° NE; the deposits and their host rocks are interpreted by previous workers to have experienced the same amount of tilting. Several sets of faults have been observed and documented in the Safford district. Langton and Williams (1982) describe a north-south trending fault set; they also mapped several low-angle faults near the Dos Pobres orebody but did not speculate on their significance. Structural maps published by Robinson and

Cook (1966) and Langton and Williams (1982) illustrate that all four deposits in this district are situated along ENE-trending shear zones. Robinson and Cook (1966) report that the shear zones at San Juan and Lone Star have uncertain displacements (possibly as much as 250 m combined) and dip vertically or steeply to the north. The shearing does not affect the Gila Volcanics. Langton and Williams (1982) also describe numerous faults that strike east-northeast. 19

The dominant structures in the district are the Butte and Red Dyke faults, which are normal faults that strike northwest and have down-to-the-southwest offset. Dunn

(1978) reports that the Butte fault has ~1,200 m of dip-slip displacement and an unspecified amount of left-lateral offset where it cuts the Dos Pobres system. Drilling data indicate that where the Butte fault cuts the southwestern portion of the Dos Pobres system, it juxtaposes barren Tertiary basaltic andesites and basalts in the hanging wall and mineralized andesites in the footwall from the surface down to a depth of at least 800 m (Dunn, 1978). Movement on these and other normal faults in the region has tilted the post-mineral volcanics 10-15° to the northeast, and this appears to be the total tilt in the district (Dunn, 1978). However, the intense deformation in the Pinaleño Mountains to the southwest coupled with the observations of low-angle faults in and near Dos Pobres suggests that the geologic setting may be more complicated than has been previously appreciated.

Alteration Types

Sulfide minerals, veins, and alteration envelopes are interrelated features. At Dos

Pobres, alteration occurs generally as envelopes on veins and veinlets which commonly partially coalesce but may be truly pervasive. Moreover, multiple vein types may contribute to a single alteration type. Sulfide minerals occur in both the vein fillings and the alteration envelopes. Here, we first describe the alteration types. Then we describe the veins separately, albeit linking their envelopes to the earlier description of alteration types. The veins also provide the best evidence for the relative ages of events 20

(paragenesis). We then describe the sulfide mineralogy, including the occurrence of precious metals. The sulfide mineralogy is organized by vein type, which in turn can be tied to alteration. Finally, we summarize the spatial distributions of veins and associated alteration and synthesize the temporal relationships.

There are several groups of alteration assemblages present at Dos Pobres. One of the goals of this study is to construct a map of the zoning of hydrothermal alteration around the porphyry dikes at Dos Pobres using observations from core logging and petrography. Alteration types and individual assemblages are summarized in Table 1.

Potassic Assemblages

Quartz + K-feldspar + Magnetite + Biotite Alteration

The earliest and most intense alteration observed occurs at the locus of intrusion and consists of quartz, K-feldspar, magnetite, and biotite (Table 1). In andesitic rocks, this alteration is typically texturally destructive, replacing the original rock with irregular masses of quartz, K-feldspar, and magnetite and lacing the rock with veins of identical mineralogy (see Fig. 5C below). The same alteration minerals are present in the porphyries, where igneous textures are typically preserved.

Biotite + K-feldspar + Magnetite Alteration

The dominant alteration assemblage at Dos Pobres consists of biotite, K-feldspar and magnetite (Fig. 3E, F, G, H, K, L, M). This type contains more biotite and less quartz, K-feldspar, and magnetite than the previous type; biotite is modally the most abundant mineral. Even in the most intense examples of this alteration type, magnetite 21 and K-feldspar form in mineral sites, as opposed to irregular masses, and igneous texture is preserved. This alteration is present with variable intensity in all logged intervals at

Dos Pobres, such that the effects of lower-temperature alteration types such as hydrolytic and propylitic (see descriptions below) are always superimposed this biotite-dominated alteration.

In andesite, this assemblage consists of biotite, magnetite, K-feldspar, quartz, rutile, and anhydrite. Mafic phenocrysts are completely replaced by biotite ± magnetite ± rutile. is uncommon; when present it occurs with biotite and magnetite in mafic sites. Plagioclase phenocrysts are partially to completely replaced by K-feldspar ± biotite

± magnetite. Where biotite and magnetite occur in plagioclase, they typically occur as tiny specks scattered throughout the phenocryst, but uncommonly biotite replaces selected zones that reflect original zoning in the plagioclase. Anhydrite is not abundant, but where present it occurs as tiny (0.1-0.5 mm) equant grains disseminated in the groundmass or with biotite and magnetite in mafic sites. The groundmass is flooded with biotite, and the rock thus appears dark gray to black in hand specimen (see Fig. 5F, L, M,

O below). Fragments in the andesites show marked differences in their susceptibility to alteration; they are typically less susceptible than the groundmass. Igneous magnetite may be rimmed with biotite. Hydrothermal magnetite is abundant (3-10 vol %) and contains up to 0.5 wt percent Ti, higher than typical igneous values (<0.1 wt %).

In the porphyries, K-feldspar dominates the potassic assemblage, commonly tingeing plagioclase phenocrysts pink and flooding the groundmass. Plagioclase phenocrysts are partly to completely replaced by K-feldspar but generally lack the 22 speckling of biotite and magnetite that is commonly present in the andesites. Magnetite is far less abundant than in the andesites (typically <5%). Some secondary biotite is present in the groundmass, and biotite phenocrysts may show thin rims of very fine (<20 μm) secondary biotite. In some areas, biotite alteration of porphyry is so intense that only the ghosts of biotite phenocrysts enable it to be distinguished from biotitized andesite

(Langton and Williams, 1982). Mafic phenocrysts are completely replaced by the same minerals as in the andesites. Anhydrite is more common than in the andesites, and occurs mainly as 0.1-0.5 mm grains scattered in the groundmass.

The intensity of this alteration varies, and the characteristics of biotite show these differences clearly. The grain size of secondary biotite in andesite tends to increase with increasing intensity; it is megascopically visible in the most intensely altered samples. In thin section, there are noticeable color differences in biotite; in intensely altered rocks, biotite is dark reddish brown, whereas in weakly altered rocks it assumes a tan or

greenish color. These color differences correlate with the TiO2 content of the biotite; as indicated by microprobe analyses, biotite from weakly altered rocks generally has

TiO2 contents between 1.5 and 3 wt percent, whereas igneous biotite and biotite from intensely altered rocks have TiO2 contents up to 4.5 wt percent (see Fig. 3B below).

Biotite + ± Magnetite Alteration

This uncommon mineral assemblage resembles biotite-dominated alteration in hand sample (see Fig. 5N below) but differs in thin section (see Fig. 5D below). Biotite and amphibole occur together in mafic sites whereas feldspars are partially replaced by

K-feldspar, biotite, and magnetite. The groundmass is typically clouded by very fine (<10 23

μm) magnetite grains though they are not always present. Exceptionally anorthitic

plagioclase (up to An95) is uncommonly present with this alteration; it is unknown if this plagioclase is igneous or hydrothermal.

Amphibole compositions obtained by electron microprobe are plotted in Fig. 3A below. Less silica in the tetrahedral site (lower TSi) indicates a higher crystallization temperature. Relict igneous hornblende is locally present at Dos Pobres, comprising the scattering of data in the magnesio-hornblende field. Hydrothermal hornblende plots in the actinolitic hornblende to actinolite fields with TSi values that indicate a lower crystallization temperature.

Hydrolytic Alteration

Hydrolytic alteration is spatially widespread but volumetrically minor in the sulfide portion of Dos Pobres. It is easily recognized in the porphyry dikes, where feldspars are destroyed by sericite and quartz and biotite (primary and secondary) is altered to sericite ± chlorite. In the andesites, chlorite is more abundant than in the porphyries; feldspars are altered to sericite, and biotite is altered to chlorite and/or sericite. -bearing minerals (sphene and/or rutile) are commonly present with chlorite and sericite after biotite; rutile predominates in more intense alteration whereas sphene is much more common in weakly altered areas. As a result, most Ti in porphyries is present as rutile, whereas in andesite a greater fraction is present as sphene. Hydrolytic alteration is easily recognized in the andesites where it is locally intense; however, weak hydrolytic alteration in andesitic rocks can be difficult to resolve because chlorite 24 commonly proxies for sericite in intermediate to mafic rocks (Seedorff et al., 2005).

Propylitic Alteration

In the andesites, abundant chlorite and epidote characterize this association (see

Fig. 5C, I below); in the logged intervals, this alteration is typically superimposed on biotitic alteration. Mafic sites are occupied by chlorite that may be accompanied by epidote, calcite, sphene, and/or rutile; these minerals have replaced earlier hydrothermal biotite and/or amphibole. Relict plagioclase phenocrysts and secondary K-feldspar may be partially altered to fine-grained epidote, chlorite, sericite, and/or clay. In some drill holes, texturally destructive patches of epidote ± chlorite ± magnetite are common (see

Fig. 5H below); this alteration may predate Cu mineralization (Langton and Williams,

1982). Sulfides are not typically associated with this alteration; where present, they consist dominantly of pyrite with traces of chalcopyrite.

Propylitic alteration is weak to absent in the porphyry dikes. Where it is present, it is most obviously manifested as the partial to complete replacement of igneous and hydrothermal biotite by chlorite accompanied by epidote, calcite, and/or sphene. In some samples, mafic minerals are replaced by apple-green intergrowths of epidote and calcite.

Epidote may attack feldspar (especially relict plagioclase phenocrysts), rarely causing a greenish tinge in hand sample. Feldspars also may be partially converted to clays. No epidote ± chlorite ± magnetite patches have been observed in the porphyry dikes. 25

Alteration Geochemistry

Selected whole-rock analyses (Appendix B) reported here and by Bolin (1976),

Langton and Williams (1982), and Lang and Titley (1998) parallel the mineralogical patterns. In silicate assemblages, addition of potassium and the correlated loss of and drives the compositions upward in Figures 2A and 2C and downward in Figure 2D. This common behavior is often misinterpreted as indicating particularly K-rich igneous compositions (cf. Jensen and Barton, 2000). Plotting the CaO

+ Na2O, K2O, and Al2O3 molar proportions on a ternary diagram (Fig. 4A) shows that the most samples have not been subjected to intense hydrolytic alteration, though “porphyry altered to quartz-sericite” and “biotitized core zone” andesite from Langton and Williams

(1982) clearly show alkali loss. Elemental gains and losses associated with hydrothermal alteration are shown in Figure 4B. Strong potassic alteration (quartz + K-feldspar + magnetite + biotite alteration as described above) results in increased Si and K (and possibly Fe) with corresponding decreases in Na, Ca, and Mg. Ore metals such as Cu, Au, and Ag are also enriched (as evidenced by core logging and petrography), though these increases are not quantifiable with data from this study.. This intense alteration removes rare-earth elements and results in concentrations as low as ~25-50% of their levels in less altered rocks (Fig. 2F). The most intense alteration results in significant iron addition

(Sample U-2, Fig 4B); most samples show little to no increase, indicating that their magnetite either is indigenous or formed from the oxidation of ferrous iron in the original mafic minerals. Andesite on the fringes of the deposit contains roughly 1.9%

K2O, whereas K2O concentrations in the core are nearly 4% (see Fig. 16.7, Langton and 26

Williams, 1982). While this is approximately 100% increase, it still represents a relatively modest addition of only 2%. This addition of K is offset by a roughly equivalent decrease in Na + Ca.

Less intense potassic alteration (biotite + K-feldspar + magnetite alteration) results in increased Si, K, Rb, and Ba but decreased Fe. Geochemical data also shows that biotitization does not necessarily correlate with strong potassium addition (Fig. 4B), because nearly all of the samples have several tens of percent biotite, yet most do not show pronounced addition of potassium.

Vein Types and Paragenesis

Hydrothermal veins at Dos Pobres are diverse. The observed veins have been divided into three groups based on the mineralogy of the veins and their associated alteration envelopes; some of these groups contain several subtypes. Crosscutting relationships have enabled the construction of a timeline of the relative ages of veins.

Vein types are summarized in Table 2.

Veins Associated with Potassic Alteration

The greatest number and diversity of veins are associated with potassic alteration.

They are most abundant proximal to the porphyry dikes but persist throughout the observed extent of the deposit. They are divided into the following seven types (Table 2). 27

Hairline biotite - The earliest observed veins are hairline ( 1 mm thick) biotite veins that are rare and typically contain small (<1 mm) clots of bornite, magnetite, and/or anhydrite. These veins are only observed in intensely altered andesite in the core of Dos

Pobres.

Sugary quartz – The most abundant early vein type at Dos Pobres consists of sugary-textured quartz with K-feldspar, bornite and chalcopyrite, magnetite, anhydrite, and biotite, with envelopes of K-feldspar that may also contain biotite, anhydrite, chalcopyrite, and/or bornite (Fig. 5D, E, G, H, O). The veins can be tens of centimeters in thickness but typically are < 1cm. These veins are a significant host of Cu and Au. They are abundant in the center of the deposit and gradually decrease in number and width with increasing distance.

Comb quartz - These veins are distinguished by inward-growing quartz crystals and centerlines of K-feldspar, chalcopyrite, bornite, and/or anhydrite (Fig. 5E). They may contain chalcopyrite, bornite, and/or minor molybdenite intergrown with the quartz; the veins are typically 1-10 mm in thickness. They commonly lack alteration halos, but where present they consist of K-feldspar. These veins can be difficult to distinguish from sugary quartz veins, and they are clearly cut by green mica veins. Their distribution is similar to that of sugary quartz veins.

Complex biotite - These are thin ( 5 mm) rare veins dominated by biotite. The vein fill consists of biotite, anhydrite, quartz, and K-feldspar. They have envelopes containing biotite, magnetite, quartz, and sulfides (chalcopyrite > pyrite > bornite) that are typically zoned from inner biotite + quartz + magnetite + sulfide to outer quartz 28 and alkali feldspar (Fig. 5F, M, L). These veins appear to cut sugary quartz veins, though documented crosscutting relationships are few. They are present throughout the deposit, but their scarcity makes their distribution and timing difficult to constrain.

Green mica - These are 1-5 mm thick veins containing biotite, sericite, bornite and chalcopyrite, andalusite, and K-feldspar with thick (3-20 mm), zoned alteration envelopes dominated by biotite (commonly replaced by chlorite) and sericite (Fig. 5G, I,

J). Monazite is uncommonly present as a trace constituent. Green mica veins are common throughout the deposit, persisting well outside the significant Cu mineralization.

Proximal examples are Cu-rich (bornite- and/or chalcopyrite-bearing) whereas distal veins are typically devoid of sulfides. They can be difficult to distinguish from complex biotite veins, especially in the porphyry dikes. These veins clearly cut sugary quartz and comb quartz veins.

Magnetite-dominated veins – These are deep veins that commonly contain chalcopyrite, with some examples also containing biotite and/or anhydrite. They locally have white envelopes consisting of quartz and alkali feldspar (Fig. 5K) but commonly do not have envelopes. Typical widths are 2-5 mm. These were observed cutting complex biotite veins, and they very commonly show evidence of superimposed low-temperature alteration, typically consisting of pyrite, chlorite, epidote, and zeolite minerals (Fig. 5L).

Magnetite-dominated veins were observed only in the andesites and are especially common in deep distal regions.

Molybdenite veins – These are rare planar veins continuous for several meters consisting of molybdenite and lesser quartz with no alteration envelopes. Typical widths 29 are  2 mm (Fig. 5M). They have been observed cutting sugary quartz, comb quartz, and complex biotite veins. Molybdenite from one of these veins yielded a Re-Os age of 60.9

± 0.3 Ma (Appendix A). They are quite rare, and thus their distribution is uncertain.

Veins Associated with Hydrolytic Alteration

Sulfide-sericite – Veins consisting of massive sulfide with strong sericite + chlorite alteration envelopes are the most common type associated with sericitic alteration (Fig. 5E, F, O). These veins typically are 2-5 mm thick. Chalcopyrite is the most common and minor bornite or pyrite is commonly present; bornite and pyrite have never been observed in equilibrium. Minor sericite and chlorite are commonly present in the vein fill, and molybdenite is typically a minor constituent.

Sericite and lesser chlorite dominate the envelopes, which are typically 3-5 times vein width. These commonly reopen sugary and comb quartz veins. Molybdenite from one of these veins yielded an age of 60.4±0.3 Ma (Appendix A). These veins are most common in a ring-shaped zone surrounding the core of the deposit and are rarely present in the deposit center or distally.

Clotty sulfide-chlorite – These are thin ( 2 mm) veins with clots of chlorite and sulfide (chalcopyrite and/or pyrite) and sericitic (sericite ± chlorite) envelopes. These may be thin equivalents of sulfide-sericite veins. These veins are common throughout the deposit and cut all potassic veins.

Anhydrite-dominated veins – These veins are rare and are dominated by anhydrite and quartz (Fig. 5K). Envelopes typically contain anhydrite, quartz, sericite, and chlorite; 30 these veins were only observed in andesite, and were only common in one drill hole in the north-central portion of the deposit.

Veins Associated with Low-Temperature Alteration

Chlorite-pyrite veins – These veins are planar, have sharp edges and even widths, and are dominated by chlorite with lesser pyrite (Fig. 5N). They are rare and have weakly defined actinolite-bearing envelopes. Their distribution and timing is difficult to constrain due to their rarity, but they likely represent a transition between hydrolytic and propylitic alteration types.

Propylitic veins - Veins containing quartz, chlorite, pyrite (locally chalcopyrite), epidote, and calcite are associated with propylitic alteration. These veins are common on the fringes of the deposit but rare in the higher-grade portions. These veins typically vary in thickness from 1-5 mm. They are mineralogically variable, but have distinctive white and green speckled envelopes that may be weakly zoned from inner quartz to outer chlorite (Fig. 5I, L). These also commonly reopen older veins.

Base-metal veins – Veins with Cu-Pb-Zn sulfides and no visible envelopes were observed in one location (from the central bornite-dominated zone). The veins are 2-3 mm wide and consist dominantly of calcite with, , chalcopyrite, galena, and pyrite.

Zeolite-dominated veins - The latest veins observed are dominated by various white to pink-orange zeolite minerals, which very commonly reopen, shatter, and cement earlier veins or fill jagged fractures (Fig. 5J, O), indicating formation in open space. 31

Many zeolite species are present, but stilbite-stellarite and heulandite are most common; calcite is variably present. Their thickness ranges from 1-10 mm. These veins are ubiquitous but their abundance varies widely, ranging from nearly zero locally to upwards of 10% in heavily fractured areas.

Mineralogy of Sulfides and Precious Metals

Sulfide minerals were observed and recorded during core logging and petrography, and precious metal minerals were observed and recorded using petrography and electron microprobe work involving mainly back-scattered electron (BSE) images and energy-dispersive X-ray spectroscopy (EDS). Langton and Williams (1982) reported

the presence of precious metals as hessite (Ag2Te) and sylvanite [(Au,Ag)2Te4] occurring within bornite grains. Descriptions of sulfides and precious metals observed in each vein type will be is followed by a synthesis of deposit-scale metal distributions

Potassic Veins

Based on observations during core logging and petrography, the group of veins that exhibit potassic alteration envelopes host most of the copper and practically all of the gold in Dos Pobres. The sulfides in these veins are dominated by bornite and chalcopyrite and have not been observed containing any cogenetic pyrite, although local sulfidation of bornite and chalcopyrite to pyrite is observed near later veins. In bornite-dominated veins, the grains commonly show chalcocite-digenite with an exsolution texture (Fig. 6A,

B, D, F). The majority of precious metals that were observed occur in bornite-dominated 32 veins, with or without this exsolution texture. They occur as hessite, sylvanite, electrum

(~85:15 Au:Ag), and possibly (AuTe2) embedded in bornite; most grains are

10 m in diameter (Fig. 6A, B). Bornite in some green mica veins contains wittichenite

(Cu3BiS3) within the exsolved chalcocite (Fig. 6D), and certain chalcopyrite grains rarely have associated (Ag2S). Galena (with up to ~20% Se) commonly forms in fractures and on grain boundaries of sulfides and may have associated hessite (Fig. 6E,

G). Sylvanite does not occur in this manner. In one sample, magnetite pseudomorphing specular hematite was observed intergrown with bornite-chalcocite (Fig 6F).

Hydrolytic Veins

Drill core observations show that these veins also host considerable Cu, largely as chalcopyrite (Table 2), but microprobe study indicates that these veins contain very little

Au. Silver is present as evidenced by galena and minor hessite commonly present on the edges of grains and in fractures. Although bornite does uncommonly occur in certain hydrolytic veins, no precious metals were found in the bornite contained in these veins, in contrast to bornite contained in veins that exhibit potassic envelopes. Microprobe observations indicate that chalcopyrite in some sulfide-sericite veins may have rare tiny (<10 μm) inclusions of unidentified Sn- or Zn-bearing non- sulfide minerals.

Low-Temperature Veins

Propylitic veins were observed in drill core to be only a minor host of Cu, which occurs only as chalcopyrite and typically subordinate to pyrite. Microprobe analyses 33 shows that these veins do not carry gold, though galena and minor hessite are commonly found on grain boundaries and in fractures, as in other vein types. Base-metal veins contain Cu, Pb, and Zn, but no precious metals were observed.

Spatial Distribution of Alteration-Mineralization Features

Alteration and Vein Distribution

Distribution of alteration is shown in Fig. 7A and B. Potassic alteration is overwhelmingly dominant, with propylitic alteration increasing distally. Potassic alteration is locally overprinted by discontinuous patches of hydrolytic alteration; this alteration type may be limited to vein envelopes. Biotite + amphibole alteration is uncommonly present in outlying holes. The intensity of K-silicate alteration decreases with distance from the locus of intrusion. Moderate to weak K-silicate alteration is present in andesite for considerable distances (> 1,000 m), persisting far outside the limits of significant known Cu mineralization. A small amount of biotite-cemented breccia was observed at one location; the matrix consists of biotite, bornite, quartz, and , and the clasts are andesite fragments altered to quartz + biotite.

Many of the vein types were not distinguished at the outset of core logging; some were distinguished only after subsequent petrography; and certain types occur only sparsely. Although qualitative observations on distribution and abundance have been noted in the descriptions above (e.g., more abundant in proximal than distal locations, etc.), estimates of abundance either are not available for most vein types or cannot be 34 confidently contoured in plan or cross section with the data gathered in this study.

However, semi-quantitative estimates of the abundance of quartz veins (combining sugary and comb quartz veins) are shown in Figures 7 E and F. Quartz veins are most abundant (~25 vol %) in the strong quartz + K-feldspar + magnetite + biotite alteration zone in the core of the deposit. Their abundance decreases rapidly to <10% but remains above 1% for several hundred meters.

Sulfide and Metal Zoning

The distribution of the dominant sulfide minerals is shown in Figures 7 C and D.

Bornite content increases with depth and proximity to the deposit center, thus bornite- dominated veins form an inverted cone-shaped zone. Chalcopyrite content increases outward, forming a zone of chalcopyrite-dominated veins that surrounds the bornite core and gradually yields to pyrite. Veins with potassic (K-feldspar ± biotite) envelopes host early Cu mineralization (primarily bornite + chalcopyrite), and veins with sericite ± chlorite envelopes dominate late mineralization (chalcopyrite ± bornite or pyrite). Copper grade contours (from Langton and Williams, 1982) are shown in Fig. 1D above; they reach a maximum of approximately 2% Cu.

The highest molybdenum concentrations (~0.01 % MoS2) occur in a ring-shaped zone that broadly coincides with the greatest intensity of hydrolytic alteration, with

Cu:Mo ratios ranging from >1000:1 in the Mo-poor core to ~35:1 in the areas with more abundant sericitic veinlets (Fig. 16.6 of Langton and Williams, 1982). 35

Most precious metals at Dos Pobres are embedded in bornite grains, with textures suggesting having been exsolution at high temperatures from a solid solution; therefore, grades of Au and Ag are highest in the bornite-dominated core (Figs. 16.9 and 16.10 of

Langton and Williams, 1982). They are observed in most types of “potassic” veins

(excluding magnetite-dominated and molybdenite veins), but sugary quartz veins are the dominant host due to their greater abundance. Gold content is highest in the core of the deposit and decreases outward; silver follows the same distribution and Ag:Au ratios range from ~10:1 in the Au-rich core to >100:1 in the fringes (Figs. 16.9 and 16.10,

Langton and Williams, 1982). Aside from occurrences related to potassic veins, silver occurs on the edges of and in fractures in sulfide grains, perhaps deposited via adsorption under hypogene conditions (e.g., Simon et al., 2000). The occurrence of precious metals mainly within bornite and as small grains is metallurgically favorable because most would report to the concentrate rather than be lost to the tailings.

Supergene Features

The Dos Pobres system has been thoroughly oxidized and partially leached to a depth of ~350 m (Langton and Williams, 1982; Wilson, 2004). Wilson (2004) reports that the leached capping at Dos Pobres is dominated by hematite; this is interpreted to be a result of oxidation of iron-bearing mafic minerals in addition to hypogene metal sulfides.

Oxide copper minerals (neotocite [tenorite?], cuprite, and chrysocolla) are visible in the center of the surface exposure but chalcocite is uncommon. Goethite-dominated capping occurs in areas where oxidation of mafic minerals was minor; this capping style is 36 interpreted to represent oxidation of hypogene sulfide minerals only (Wilson, 2004). Due to the low pyrite:(chalcopyrite + bornite) ratio of the and pH buffering capacity of the wall rocks at Dos Pobres, mobilization of copper was limited. In the mixed oxide- sulfide zone, native copper, chalcocite, and covellite are abundant (Langton and

Williams, 1982).

At the deeper levels examined in this study, supergene bornite and chalcocite commonly partially replace hypogene sulfide grains, typically as thin rims near zones of fracturing. Supergene bornite has only been observed replacing chalcopyrite; supergene chalcocite replaces bornite and chalcopyrite. In local areas of heavy fracturing, sulfides may be completely oxidized. Covellite is typically absent but is locally abundant in the mixed oxide-sulfide zone and is associated with rare hawleyite

(CdS) (Fig. 6H).

Fluid Inclusion Observations

The petrographic characteristics of fluid inclusions were observed, but no heating or freezing experiments were conducted. Diverse fluid inclusion types occur in hydrothermal quartz as summarized in Table 3. Most inclusions are small ( 10 m).

Many are interpreted to be of secondary origin by the criteria of Roedder (1984), but a significant fraction of equant (commonly exhibiting negative crystal forms) lack obvious secondary characteristics and are irregularly scattered in unstrained quartz. An aqueous liquid, lesser vapor, and – typically – one or more daughter minerals fill the inclusions.

Daughter minerals include equant salts (most commonly a single cubic crystal = halite) 37 and lesser opaque (triangles = chalcopyrite, red equant = hematite) and elongate birefringent minerals.

Inclusions in early proximal veins associated with intense potassic alteration contain abundant daughter minerals, including halite and other phases. The abundance of opaque and birefringent daughter minerals decreases rapidly with distance from the bornite-rich core of the deposit and in time, as inferred from paragenesis of vein types.

Halite-bearing inclusions are common in later and more distal veins such as those with sericitic envelopes, but inclusions in propylitic (late and typically distal) veins have no daughter minerals. Opaque minerals and elongate birefringent daughter minerals are associated with the quartz-bearing potassic vein types (sugary quartz, comb quartz, complex biotite). Quartz veins associated with sericitic alteration have more abundant liquid-vapor inclusions, but halite and opaque-bearing inclusions are rarely present and may indicate that the quartz containing those inclusions formed as part of an earlier vein assemblage. Quartz in propylitic veins contains only liquid-vapor inclusions, many of which have larger bubbles than those observed in other veins.

Time-Space Evolution

The porphyry dikes are sufficiently similar in appearance and composition that the number of distinct intrusions is uncertain. The U-Pb ages are well within error (57.2 ±

0.9, 57.2 ± 1.2, 57.0 ± 1.1 Ma; Appendix A), but several factors point to more than one intrusive event. The variable abundance of embayed quartz phenocrysts, the marked differences in alteration intensity between dikes, and the observation of sugary quartz 38 veins truncated at contacts all require multiple intrusive events. The facts that no truncated veins of other types were observed and that no reversals in offsetting vein relationships (in the sense of Seedorff and Einaudi, 2004) were noted imply that the intrusions were emplaced in fairly rapid succession, before lower-temperature assemblages (e.g. quartz + sericite + chlorite + pyrite ± chalcopyrite) became stable. The vein types observed thus appear to represent a single overall thermal event. With the rare exception of sugary quartz veins truncated at intrusive contacts, there is no evidence of hydrothermal reversals (multiple events with similar features).

The paragenesis of the ore mineralogy is also typical of many gold-bearing porphyry copper deposits (Sillitoe, 2000). During early potassic alteration, bornite and precious metals have a direct correlation (indicating deposition by the same fluid).

Chalcopyrite dominates the later moderate-temperature assemblages, which contain the highest concentrations of molybdenum but have very low concentrations of precious metals.

The ages of the porphyry dikes and andesites are well within the expected ranges for this region. The difference between the ages of the porphyry dikes (~57.1 Ma) and the host andesite (67 - 73 Ma) demonstrates that they are not coeval, as others have suggested

(Dunn, 1978; Langton and Williams, 1982). The Re-Os age of molybdenite mineralization (60.4 ± 0.3 and 60.9 ± 0.3 Ma) is enigmatic, being older than the porphyry dikes (~57 Ma). This is probably a result of disturbance in the Re-Os isotopic system.

This is not the only deposit in which molybdenite Re-Os geochronology has yielded ages that are significantly older than those obtained by other methods (cf. Raul-Condestable, 39

Peru; De Haller et al., 2006). The two Re-Os dates overlap within error, even though their concentrations differ by nearly a factor of 10 (Appendix A).

The presence of possible anhydrite phenocrysts in the porphyry dikes is important, since their presence indicates that the had a high oxidation state. While hardly common, anhydrite phenocrysts have been reported from a few other deposits, including Santa Rita, New Mexico (Audétat et al., 2004) and Endeavour (Lickfold et al., 2003).

A schematic cross section through the core of the deposit is shown in Figure 8 showing the time-space evolution of Dos Pobres. In panel A, porphyry dikes were emplaced, causing intense potassic alteration and the formation of sugary quartz veins. In panel B, the continued emplacement of dikes caused the continuation of sugary quartz vein formation, along with weaker widespread potassic alteration and the formation of the other potassic vein types. In panel C, as temperature drops, hydrolytic alteration is superimposed on the earlier potassic. Later propylitic alteration weakly overprints the entire system. Panel D shows the deposit in its current state, after faulting, tilting, weathering, and erosion.

Discussion

Comparison of Alteration, Veins, and Ore Mineralogy

A distinctive K-rich, acid-poor alteration package has long been recognized as a feature of many gold-rich porphyry deposits (Hollister, 1975; Sillitoe, 1979). Most have a 40 potassic (K-feldspar + quartz ± biotite) core, which grades outward into a propylitic halo.

Intense quartz + K-feldspar alteration similar to that present at Dos Pobres is reported from the cores of many other deposits (Sillitoe, 1979), as is widespread biotitization of mafic minerals (Seedorff et al., 2005). Propylitic alteration with similar features to that at

Dos Pobres has been described from many other deposits. Biotite-amphibole alteration like that described here has not been distinguished in other deposits. It may represent a transition between potassic and propylitic alteration, since it shows some features common to both. The high TSi content of the in this alteration requires a low temperature of formation.

All of the vein types described in this study are similar to reports from other deposits. Hairline biotite and sugary quartz veins represent the early vein stages at most porphyry copper deposits (Seedorff et al., 2005). Comb quartz veins are similar to “B” veins at El Salvador (Gustafson and Hunt, 1975), though at Dos Pobres they can be difficult to distinguish from sugary quartz veins and could be combined into one category

(cf. “AB” veins of Clode et al., 1999, at Batu Hijau, Indonesia.) Veins similar to complex biotite veins have been reported from several deposits, such as Butte, Montana (“EDM” veins of Meyer, 1965; Brimhall, 1977), El Salvador, Chile (“C” veins of Gustafson and

Quiroga, 1995), and Los Pelambres, Chile (“type 4” veins of Atkinson et al., 1996). Green mica veins have been described from other deposits, such as Butte

(Brimhall, 1977), El Salvador (“EB” veins of Gustafson and Quiroga, 1995), and Los

Pelambres (Atkinson et al., 1996). Magnetite veins have been reported at several deposits, notably Park Premier, Utah (John, 1989), and Island Copper, British Columbia 41

(Arancibia and Clark, 1996). These veins are interpreted to be of late magmatic age, but magnetite veins at Dos Pobres clearly formed later. Veins with sericitic and propylitic envelopes at Dos Pobres are unremarkable, displaying features observed at many other deposits. Zeolite veins are common in deposits that occur in mafic host rocks (Seedorff et al. 2005).

This diversity of vein types is probably not abnormal. Unfortunately, thorough descriptions of veins and their relative ages are lacking in many deposits, with many authors opting instead to group veins into broad categories that fail to capture critical differences. Comprehensive descriptions of veins and their associated alteration envelopes are necessary if one seeks to learn about the changes in hydrothermal fluid chemistry with time. For example, rarely described vein types such as green mica veins and complex biotite veins can contain mineral assemblages that provide constraints on fluid chemistry. At Dos Pobres, the assemblage K-feldspar + biotite + andalusite + muscovite in green mica veins constrains temperature to near

600°C.

Ore mineralogy in Dos Pobres is also typical of Au-rich porphyry deposits. Gold is always associated with potassic alteration, as described in many deposits (cf. Gustafson and Hunt, 1975; Cuddy and Kesler, 1982; Langton and Williams, 1982; Gustafson and

Quiroga, 1995, Sillitoe, 2000), and gold and copper contents vary sympathetically (cf.

Sillitoe, 1979). Electrum is the dominant gold mineral, and it is always associated with bornite. The abundance of precious metal tellurides is unusual, but there are other documented examples of this style of mineralization, such as Granisle and Bell, British 42

Columbia, Canada (Cuddy and Kesler, 1982), Almalyk, Pakistan (Shayakubov et al., 1999), Bingham, Utah (Redmond and Einaudi, 2000), Goonumbla, New South

Wales, Australia (Heithersay and Walshe, 1995), and numerous other deposits for which mineralogic studies have been conducted on concentrates (Tarkian and Stribrny, 1999).

Minerals containing other uncommon elements, such as the Bi and Sn that were noted in this study of Dos Pobres, are common in the base-metal lode environment of porphyry systems (e.g., Meyer et al., 1968; Einaudi, 1982; Takagi and Brimhall, 1999), but trace occurrences of such phases occasionally are reported from porphyry deposits worldwide that lack advanced argillic alteration (e.g., Tarkian and Stribrny, 1999; Redmond and

Einaudi, 2000).These rare occurrences are of geochemical curiosity but generally have little practical (e.g., metallurgical) consequence.

Although Dos Pobres is the best documented Cu-(Au-Mo) porphyry deposit in

Arizona, there are some Arizona deposits with which it shares some characteristics. The

Ajo deposit has a strongly biotitized core with bornite-chalcopyrite mineralization

(Gilluly, 1946; Dixon, 1966), with a reported mill production of 399 million metric tonnes at 0.80 percent Cu, 0.005 percent Mo, and 0.34 g/t Au (Long, 1995). However, extremely coarse-grained (~1 cm) hydrothermal biotite is present in the core of the Ajo deposit, whereas the coarsest hydrothermal biotite at Dos Pobres is barely megascopic.

Additionally, magnetite at Ajo is seemingly less common than at Dos Pobres. Gold also has been produced from the Bisbee deposits and the Courtland-Gleeson mining district

(Lang et al., 2001; Stegen et al., 2005), but only from carbonate replacement bodies peripheral to the porphyry deposits themselves. 43

Comparison with Porphyry Cu-Mo systems

The porphyry Cu-Mo class includes most of the world’s largest known deposits, such as , Chile, Morenci, Arizona, and Resolution, Arizona, as well as many of the smaller porphyry deposits in southwestern North America (Seedorff et al., 2005). They are most commonly associated with quartz monzodioritic to granitic intrusions. Chalcopyrite is the most common copper mineral (bornite is absent in some districts), and hydrolytic alteration is typically intense and voluminous. Molybdenum is much more abundant in these deposits, and precious metals (especially gold) are much less abundant than in Cu-(Au-Mo) deposits.

Since the recognition of the geologically real difference between Mo- and Au-rich porphyry copper deposits (Kesler, 1973), there have been many hypotheses concerning the differences in the origins of the two deposit types. The observation that porphyry deposits formed in island arc environments tend to be Au-rich while deposits formed in continental arcs are typically Mo-rich was made early in the discussion (Kesler, 1973).

This observation led to the hypothesis that the composition of the crust through which the traveled and in which they are emplaced influences the abundance of these metals. As noted by Gustafson (1978) and others, many deposits (including Dos Pobres) do not follow this trend, and this idea was dismissed by Sillitoe (1979). Emplacement depth and wall-rock permeability were also hypothesized to have some effect (Kesler,

1973), though these have also since been ruled out. Titley (1982) proposed that the two deposit types simply represent different levels of exposure in broadly similar systems, but this view has also been dismissed based on greater vertical exposure at many deposits of 44 both types (Sillitoe, 2000). Composition of the mineralizing intrusions is important

(Seedorff et al., 2005), but observations of closely associated compositionally identical plutons with different styles of mineralization (i.e., Saindak, Pakistan; Sillitoe, 1979), as well as substantial compositional overlap between classes (Fig. 8C, Seedorff et al., 2005) imply that this is not the sole factor. In light of all of these observations, composition coupled with complex geochemical processes during the production, emplacement, and crystallization of the productive magmas (as suggested by Sillitoe,

2000) appear to control the style of mineralization.

While little is known about the sulfide portions of Lone Star, San Juan, and

Sanchez, what information is available suggests that there may be significant differences between them and Dos Pobres. Thus as the Safford district is further explored, it may present an uncommon opportunity to study the relationships between Cu-Au and Cu-Mo porphyry systems. All four deposits certainly formed in a continental arc environment, and there is no evidence to suggest that the deposits were emplaced or are exposed at significantly different levels. Geochronologic and field evidence suggest that the deposits all were emplaced within a few million years of each other, attesting that the source magmas traveled through the same underlying crust and likely have a shared origin.

Similarly, we can rule out the possibility of influence from wall-rock chemistry or permeability since the Safford Volcanics host all four deposits. However, further speculation is impractical until more information becomes available.

There are also other variables to consider. An injection of mafic magma into a silicic magma chamber may affect the type of mineralization formed, such as at Bingham 45

(Keith et al., 1997). Many volcanic arcs show evolution from mafic to felsic over time, and produce different mineralization types at different stages (Barton, 1990; 1996); this factor may be particularly important, since Dos Pobres is slightly older than the other deposits in the Safford district (M. D. Barton, unpub. data). The more primitive Nd value for the Dos Pobres porphyry relative to the porphyries at the Lone Star deposit also is interesting (Lang and Titley, 1998). It seems that some fundamental change may have taken place in the Safford district, in which the magmas changed from the more primitive type present at Dos Pobres to the more evolved type seen in the other deposits.

Comparison with Fe-oxide(-Cu-Au) Systems

Selected shared features between Au-rich porphyry systems and andesite-hosted iron-oxide(-Cu-Au) (IOCG) systems, such as Candelaria, Chile, have stimulated comparisons (e.g., Ryan et al., 1995; Barton and Johnson, 2000). Indeed, the abundance of magnetite in many Au-bearing porphyry deposits coupled with scattered reports of sodic- and potassic-calcic alteration (e.g., Dilles et al., 1995; Lang et al., 1995) has led some to speculate a genetic link between this deposit type and IOCG deposits (Marschik and Fontboté, 2001). However, the differences between the two deposit types are more significant than their similarities. By definition, porphyry deposits show a clear genetic relationship with intrusive rocks, whereas the link between magmatism and IOCG deposition is not fully understood. IOCG deposits typically have extensive sodic- and/or potassic-calcic alteration, whereas such alteration in porphyry deposits (such as Dos

Pobres) is commonly absent and limited in scope where present. IOCG deposits 46 commonly are enriched in , , and REE, while Dos Pobres shows no such enrichment. Quartz veins are abundant in nearly all porphyry deposits, whereas hydrothermal quartz in IOCG deposits is comparatively sparse. Most IOCG deposits contain several tens of percent iron oxide, but magnetite content in porphyry deposits rarely reaches 10%. In light of these observations, the resemblance between Cu-Au-Mo porphyry deposits and IOCG deposits appears to be only superficial.

Conclusions

Dos Pobres is a typical Cu(-Au-Mo) deposit. Its alteration assemblages and mineralization styles are typical of the deposit type, as outlined by Sillitoe (2000). The ore deposit was formed by the devolatilization of porphyry dikes and the subsequent cooling of those magmatic fluids, resulting in deposition of voluminous quartz veins and

Cu-Fe sulfide minerals. We expect that as more deposits are discovered and described, the characteristics of Dos Pobres will closely resemble many more Cu-Au-Mo deposits worldwide.

Acknowledgments

This work was undertaken as the senior author’s Masters Thesis at the University of Arizona guided by committee members Mark Barton, Eric Seedorff, and Jon Patchett.

Primary funding for this project and permission to publish this report were provided by

Phelps Dodge, now a part of Freeport-McMoRan Copper and Gold, Inc., and are gratefully acknowledged. Related work was funded through NSF grant EAR 02-30091, 47 the U.S. Geological Survey Porphyry Copper Life Cycle Project, and the University of

Arizona-U.S.G.S Center for Mineral Resources. We thank Jeff Gerwe, Ralph Stegen, and

Bill Stavast for providing access to drill core and relevant data as well as support and ideas throughout the process; we also appreciate their reviews of this manuscript.

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Figure Captions

Fig. 1: Location maps. (A) Arizona, showing location of the Safford mining district. (B) Enlargement of the Safford mining district (modified from Langton and Williams, 1982). The town of Safford is 13 km SSW of Dos Pobres. (C) Surface map of Dos Pobres (modified from Langton and Williams, 1982). (D) 2000 ft (600 m) level map of Dos Pobres showing grade contours from Langton and Williams (1982).

Fig. 2: Rock geochemical plots. Triangles are Safford andesites, circles are porphyries. Gray symbols represent intense alteration; black symbols are data from Langton and Williams (1982) or Lang and Titley (1998). (A) Total alkali vs. silica plot, showing fields of Le Maitre et al., (1989) and approximate composition of Safford andesites before the intrusion of the porphyry. (B) La/Yb vs. Sc/Ni andesite discrimination plot showing Safford andesites and classification fields of Bailey (1981). (C) K2O vs. silica plot showing alteration type paths and fields of Rickwood (1989). (D) A/(N+K) vs. A/(C+N+K) plot. (E) IUGS diagram showing normative compositions of Safford rocks and fields of Streckheisen (1974). The gray shaded area in the lower right is the basalt/andesite field. (F) Chondrite-normalized REE plots of Safford district rocks, using the normalization of Anders and Grevesse (1989).

Fig. 3: Mineral composition plots. (A) Amphibole compositions, showing fields from Leake (1978). Higher tetrahedral silicon (TSi) indicates lower crystallization temperature. Samples with lower TSi may be relict igneous hornblende. (B) Biotite compositions, markers corresponding to the alteration packages with which the samples are associated.

Fig. 4: Alteration geochemical plots: (A) Al2O3-Na2O+CaO-K2O ternary plot (molar proportions) showing ‘fresh’ rock compositions (gray oval). Inset shows alteration type paths. (B) Spider diagram showing the effect of alteration on chemical components in the porphyry dikes. Samples are normalized to

Al2O3 in the least-altered porphyry. Samples U-2 and U-3 have intense potassic alteration; the other Dos Pobres samples have weak-moderate potassic alteration. One sample is “porphyry altered to quartz-sericite” from Langton and Williams (1982), which shows hydrolytic alteration superimposed on potassic.

Fig. 5: Photos of rocks, veins, and age relationships. Scale bar is 1 cm except where noted. Vein and envelope terminology is: vein mineral(s)//envelope mineral(s); i.e. a quartz + bornite vein with a biotite envelope is qtz-bn// bio. (A) Least altered porphyry, with weak biotitic and later weak chl + ep ± cal alteration. Mafic minerals are converted to biotite (some to chl + ep) and feldspars are partially altered to sericite+clay. (B) Porphyry showing weak hydrolytic alteration and a possible anhydrite phenocryst. (C) Intense qtz + kfs + mt alteration in andesite. Groundmass is replaced by irregular masses of K-feldspar and magnetite which are cut by sugary quartz (qtz-kfs- mt//-) veins. (D) Photomicrograph (crossed polarizers) of biotite-amphibole-magnetite alteration developed in amygdaloidal (?) andesite. “Amygdule” is filled with biotite and amphibole and cut by a sugary quartz (qtz-anh// bio) vein; the groundmass is darkened by fine magnetite. (E) Sugary quartz (qtz-bn//kfs) veins developed in porphyry cut by a comb quartz (qtz-cpy-anh-bn//-) vein, which is in turn cut by a sulfide-sericite (cpy-ser- bn//ser+chl) vein. (F) Complex biotite (bio-qtz-mt-kfs-bn-cpy-cal-zeol//bio-qtz-kfs) vein cut by a sulfide sericite (cpy-ser-chl-anh//ser-chl) vein that has reopened a sugary quartz (qtz+bn//bio) vein in andesite. (G) Green mica (bio-ser-cpy-bn-mt//bio-ser-kfs) vein cutting a sugary quartz (qtz-kfs-bn-bio//-) vein in fragmental andesite. (H) Propylitic alteration in andesite, with patches of intense epidote alteration. A narrow sugary quartz veinlet (qtz//bio) is reopened by zeolites. (I) Green mica (?) (chl[after bio?]-cpy-ser//ser) vein cut by propylitic (cpy-qtz-cal-chl- zeol//qtz-chl-ep-ser) vein in andesite. (J) Green mica (?) (bio-cpy-kfs//bio) vein cut by numerous zeolite veins in andesite. (K) Anhydrite-dominated (anh-qtz-cpy) vein with zoned (inner qtz, outer chl) envelope cuts (cross cutting 58 relationship not shown) a magnetite-dominated (mt-anh-cpy-bio//qtz) vein in andesite. (L) Complex biotite (bio- kfs-qtz-cpy-cal-chl[after bio]//bio-qtz) vein cut by a magnetite-dominated (mt-cpy-qtz-zeol-cal//qtz) vein in andesite. A propylitic (cpy-qtz-chl-ep//qtz-chl-ser) vein is shown in the corner of the sample. (M) Molybenite (moly-qtz//-) vein cuts complex biotite (qtz-bio-cal-kfs-cpy-bn//qtz-bio) and comb quartz (qtz-cpy-kfs//-) veins in andesite. (N) Chlorite-pyrite (chl-pyr-qtz//bio-amph) vein cuts quartz veinlets in andesite with biotite + amphibole + magnetite alteration. (O) Complex cross cutting relationship in andesite with a sulfide-sericite (cpy-moly//?) vein that has reopened a sugary quartz (qtz-bn//-) vein, and has been reopened by zeolites which fracture and embed fragments of the earlier veins. Amph = amphibole, anh = anhydrite, bio = biotite, bn = bornite, cal = calcite, chl = chlorite, cpy = chalcopyrite, ep = epidote, kfs = K-feldspar, mt = magnetite, moly = molybdenite, pyr = pyrite, qtz = quartz, ser = sericite, zeol = zeolite minerals.

Fig. 6: Ore photos: (A) and (B) Bornite (Bn) with bluish gray exsolved chalcocite (Cc) and native gold (Au). (C)

Bornite with gold and sylvanite (Sylv, [Au,Ag]2Te4). (D) Bornite with chalcocite and wittichenite (Cu3BiS3). (E) Hessite (Hess, Ag2Te) and galena (Gal) deposited on the edge of chalcopyrite (Cpy). (F) Bornite with chalcocite and associated magnetite (Mt) pseudomorph after hematite (Hm). (G) Back-scattered electron (BSE) image of galena and hessite deposited along a grain boundary between bornite and chalcopyrite. (H) BSE image of chalcocite and covellite (Cov) with associated hawleyite (CdS).

Fig. 7: Plan maps and cross sections. Gray bars in cross sections are logged intervals, vertical scale is elevation in feet. (A) and (B) Plan map and cross section showing dominant alteration type. (C) and (D) Plan map and cross section showing dominant sulfide mineral. (E) and (F) Plan map and cross section showing quartz vein abundance.

Fig. 8: Cartoon cross section showing formation of hydrothermal features and subsequent faulting and tilting at Dos Pobres. (A) Intrusion of early porphyry dikes into andesite and development of intense potassic alteration. (B) Intrusion of later dikes and widespread weaker potassic alteration. (C) Formation of weak hydrolytic (sericitic) and propylitic alteration. (D) Faulting, tilting, weathering, and erosion.

Figure 1 59 60

Figure 2 61

Figure 3 62 63

Figure 4 64

Figure 5 65

Figure 6 66

Figure 7 67

Figure 8 68

Table 1: Summary of Alteration Assemblages in Porphyry Dikes and Andesites Typ Feldspar Mafic Associated vein e Host Groundmass sites sites types (see Table 2) Assemblage Potassic associations qtz, kfs, mt, Andesite kfs bio, mt Quartz + K-feldspar bio + Magnetite ± Biotite Sugary Quartz qtz, kfs, mt, (intense) Porphyry kfs bio, mt bio shreddy kfs, bio, Hairline Biotite, Andesite bio (high kfs, bio, mt mt Sugary Quartz, Biotite + K-feldspar + Ti) ± Mt Comb Quartz, Magnetite (intense) shreddy Magnetite-Dominated qtz, kfs, mt, Porphyry kfs bio (high (?), Anhydrite- bio, anh Ti) ± Mt Dominated (?) shreddy Andesite ± kfs bio (low bio, mt Sugary Quartz, Biotite + K-feldspar + Ti), mt Comb Quartz, Green Magnetite (weak) shreddy Mica, Complex Porphyry ± kfs bio (low bio Biotite Ti), mt act, bio kfs ± mt, Andesite (low Ti), mt, bio bio Biotite + Amphibole + mt Magnetite-dominated Magnetite (?), Chlorite-Pyrite (?) Porphyry - - - Hydrolytic associations

Andesite ser ± chl ser ± chl ser, chl Sericite-Chlorite (intense) Porphyry ser ser ± chl ser Sulfide-Sericite, Clotty Sulfide- Chlorite, Base Metal Andesite ser ± chl chl ± ser chl Sericite-Chlorite (weak) Porphyry ser chl ± ser ser ± chl

Propylitic association chl, ep, ± ep, chl, Andesite sph, cal chl, ep cal, clay [bio] Propylitic (intense) chl, ep, ± ep, chl, Porphyry sph, cal chl, ep cal, clay [bio] Propylitic, Zeolite chl, ep, ± ep, chl, Andesite sph, cal chl, ep cal, clay [bio] Propylitic (weak) chl, ep, ± ep, chl, Porphyry sph, cal chl, ep cal, clay [bio] 69

Table 3: Summary of Fluid InclusionTable 2:Observations Summary of Dos Pobres Vein Types Minerals present Abundance Abundance in EnvironmentVein type L-V Vein Fill L-V-H Envelope L-V-H-Opdescription Complex Comments Cu Mo Deposit Observed Timing Relationships PotassicQuartz veins Common Common Common Common Inclusions with daughter Hairline Biotite biotite ± quartz ± bornite ±magnetite biotite Very thin ( 1 mm), brown to black, appearing as dark lines along hairline fractures T - T Cut by all other veins; intrusive assoc-iated with secondary minerals usually have contacts not observed. strongSugary KQuartz alterationquartz + K-feldspar + Cu-Fe-sulfide ± K-feldspar ± quartz ± biotite ± anhydrite [ Sugary-textured quartz-K-feldspar veins with disseminatednegative bornite, minor crystal biotite and forms anhydrite, and CT A Cut hairline and complex biotite veins, magnetite ± anhydrite ± biotite ± ± chlorite ± sericite] rare chalcopyrite. Envelopes most commonly consist of K-feldspar, though biotite and/or K-feldspar cut by all other veins; occasionally molybdenite [ ± chlorite ± sericite ± envelopes may be present in andesitic host rocks. Several observed examples are cut by breccias truncated at intrusive contacts. Quartz veinssphene ± rutile] Common Commonand Rare porphyry. Similar to "A"Rare veins of Gustafson and Hunt Same(1975). as above; associated with secondary inclusions in distal veins Comb Quartz quartz + K-feldspar + Cu-Fe-sulfide ± K-feldspar ± quartz ± biotite ± anhydrite [ Dominated by inward-growing quartz with scattered sulfides, K-feldspar, and biotite. They show CT C Cut hairline and complex biotite veins weak K alterationbiotite ± anhydrite ± molybdenite[± ± chlorite ± sericite] poorly- to well-defined centerlines of K-feldspar, chalcopyrite,have and/orfewer bornite. daughter If present, envelopes and sugary quartz veins, commonly chlorite ± sericite ± calcite ] are similar to 2b veins but not as intense. K-feldspar envelopes in andesitic host rocks are easily reopened by green mica and sulfide- overlooked in hand sample but distinctive when stained. Similar tominerals "B" veins of Gustafson and Hunt sericite veins. Cut intrusive contacts Quartz veins Common Common Very(1975) Rare Very Rare Some inclusions with where observed.

associatedComplex Biotite wbiotiteith + quartz + Cu-Fe-sulfideprimary ± K- andbiotite + Cu-Fe-sulfide + quartz ± Very thin veins dominated by biotite with envelopesdaughter zoned from inner biotite-quartz-sulfideminerals may with minor A- R Cut sugary quartz veins; intrusive feldspar ± anhydrite [ ± chlorite ± sericite] magnetite [ ± chlorite ± sericite] secondary chlorite-sericite to outer quartz. Possibly similar to "C" veins of Gustafson and Quiroga contacts not observed. sericitic alteration secondary (1995) or "type 4" veins of Atkinson et al. (1996). be related to earlier Green Mica biotite + muscovite + Cu-Fe-sulfide + K- biotite + muscovite + K-feldspar + Cu-Fe- Thin (<5mm) mineralogically complex veins with lumpy irregular envelopesevents zoned from inner biotite R- C Cut sugary quartz and comb quartz feldspar ± anhydrite ± andalusite [ + sulfide ± anhydrite [ + chlorite + rutile + (usually replaced by chlorite, rutile, and titanite), sericite, and K-feldspar to outer K-feldspar. Sulfides veins; cut intrusive contacts (one Quartz veinschlorite + rutile ± titaniteCommon ± epidote] titanite ± epidote]Absent Absentare commonly scattered throughout Absent the envelope. Possibly Only similar L-V to "green inclusion mica" veins of Brimhall example). associated with primary and (1977). observed; these are late Magnetite-Dominated magnetite ± pyrite ± chalcopyrite ± quartz quartz ± alkali feldspar Wavy to planar veins up to 1 cm thick, dominated by large magnetite grains with other minerals R- R Cut complex biotite veins (one propylitic± anhydrite ± actinolitesecondary, ± epidote ± interstitial. Common in deep distal zones and mostly distal veins example), cut by anhydrite-dominated alterationchlorite some have veins (one example). Molybdenite molybdenite ± quartz none Thin (<2 mm) planar veins that are continuous for several meters. Common in deep flanking zones. - A T Cut complex biotite, sugary quartz, large bubbles and comb quartz veins ComplexHydrolytic inclusions contain elongate birefringent daughter minerals Sulfide-Sericite Cu-Fe-sulfide ± quartz ± sericite ± sericite ± chlorite ± Cu-Fe-sulfide ± quartz Typically consist of massive chalcopyrite, commonly reopening or filling residual open spaces in AR A Cut all potassic veins; relationships (anhydrite?) chlorite ± anhydrite ± molybdenite earlier veins. Envelopes consist of coarse sericite and chlorite, in rare cases zoned from chlorite with other sericite-chlorite veins are L = liquid, V = vapor, H = halite, Op = opaques inner to sericite (±K-feldspar) fringes. Similar to "D" veins of Gustafson and Hunt (1975). uncertain. Cut all intrusive contacts. Clotty Sulfide-Chlorite quartz + Cu-Fe-sulfide + chlorite ± sericite sericite + quartz ± Cu-Fe-sulfide ± chlorite Most commonly occur as thin (<3mm) quartz veins with clots of sulfides and chlorite, with envelope C- C Same as above ± anhydrite width approximately 3 times vein width.

Anhydrite-Dominated anhydrite + quartz + chalcopyrite quartz + anhydrite + sericite + chlorite Planar veins of variable width with distinctive envelopes zoned from inner quartz to outer chlorite- T- T Cut magnetite-dominated veins (one sphene example)

Low-Temperature Chlorite-Pyrite chlorite + pyrite ± quartz ± sericite chlorite + actinolite Thin (<3 mm), planar, straight-sided veins dominated by chlorite with quartz and intermittent pyrite T- T Cut sugary quartz veins (one and actinolite envelopes. example), cut by propylitic veins (one example)

Propylitic quartz + Cu-Fe-sulfide + chlorite ± calcite quartz + chlorite + epidote ± titanite ± Quite variable in appearance, speckled green and white envelope can be confused with that of other R- C Cut all veins except zeolite. Not ± epidote ± zeolites ± amphibole albite ± K-feldspar types. Commonly observed reopening earlier veins, leading to complex relationships. observed in porphyry dikes.

Base Metal calcite + sphalerite + chalcopyrite + sericite + chlorite Very rare veins with Zn-Pb-Cu mineralization and intense sericitic envelopes. C - T Cut sugary quartz veins galena + pyrite + sericite

Zeolite-Dominated stellarite ± heulandite ± phillipsite ± stilbite fine-grained zeolites, clays Occur as both planar and irregular veins, very commonly reopening earlier veins of all types. -- C Cut all veins wherever present. ± laumontite ± gonnardite(?) ± analcime ± Stellarite, heulandite, and phillipsite are common. Envelopes are rare; where present they consist of calcite clays and very fine zeolites. Commonly reopen, shatter, and cement earlier veins, hence appearing to be Cu-Mo bearing.

Estimation of overall vein abundance (VA), and Cu and Mo abundance in each vein type: A = abundant, C = common, R = rare, T = trace, - = not present 70 Appendix A: Geochronology

U-Pb analyses were performed at the Arizona LaserChron Center, using a Multicollector Inductively Coupled Plasma Mass Spectrometer (GVI Isoprobe) coupled to a 193 nm Excimer laser ablation system (New Wave Instruments and Lambda Physik). Re-Os analyses were performed by Fernando Barra at the University of Arizona.

Table A1: Summary of Geochronology

Sample Method Age (Ma) Description/Comments Number

Andesite, weak-moderate biotite alteration with partial propylitic S-2 U-Pb (zircon) 73.3+1.0/-0.72 overprint. Age based on 8 usable zircons.

Porphyry, bornite-chalcopyrite S-5 U-Pb (zircon) 57.0±1.1 mineralization with sugary quartz+K- feldspar veins. Porphyry, intense quartz + K- S-7 U-Pb (zircon) 57.2±1.2 feldspar + magnetite alteration

Porphyry, feldspars altered to clay, S-16 U-Pb (zircon) 57.7±0.65 zeolite veins common

~0.5 cm pyrite-molybdenite vein Re-Os RL-2 60.4±0.3 cutting across core; paragenetic (molybdenite) relationships unknown 2 mm molybdenite-quartz vein, observed cutting sugary quartz, Re-Os S-10 60.9±0.3 comb quartz, and complex biotite (molybdenite) veins (Fig. 5M). 71

83

81

79

77

AGE 75

73

71 S-2 AGE = 73.4 +2.6/-1.7 Ma 69 (2

67 Fig. A1: Individual laser spots for sample S-2.

Fig. A2: Individual laser spots for sample S-5. 72

68

64

60 AGE 56

52 S-7 AGE = 57.2±1.2 Ma Mean = 57.2±0.7 48 MSWD = 2.3 ) (2

44 Fig. A3: Individual laser spots for sample S-7. 73

63

61

59

AGE 57

55

S-16 AGE = 57.2±0.9 Ma 53 Mean = 57.19±0.44 MSWD = 1.00 ) (2 51

49 Fig. A4: Individual laser spots for sample S-16. 74

0.24 1300

0.20 1100

0.16 900 U 238

Pb/ 0.12 700 206 data-point error ellipses are 68.3% conf

0.08 500

Intercepts at 300 60±2 & 1238±89 Ma 0.04 MSWD = 0.41 100

0.00 01234 207Pb/235U Fig. A5: Concordia plot for sample S-16 showing zircon inheritance.

Table A2: Analytical results from Re-Os geochronology. Total Re 187 Re 187 Os Age Error (Ma) Sample No. Weight (g) (ppm) (ppm) (ppb) (Ma) (2 sigma) S-10 2017 0.065 900.1 565.9 574.7 60.9 0.3 RL-2 2016 0.053 118.4 74.5 75 60.4 0.3 RL-2 2016 0.054 120.1 75.5 75.9 60.3 0.3 75 76 Appendix B: Whole-Rock Geochemistry

Table B1: Descriptions of Samples for Whole-Rock Geochemistry Name Rock Type Alteration RL-2 1997-1998.5 andesite weak potassic RL-5 2033-2035 andesite weak potassic RL-6 2028-2030 andesite weak potassic RL-8 2054 andesite weak potassic RL-9 2014-2016 andesite weak potassic RL-10 1613-1615 andesite biotite-amphibole RL-10 2033-2035 andesite weak potassic RL-14 2075-2077 andesite biotite-amphibole S-2 1245-1246 andesite weak potassic S-9 2113-2114 andesite weak potassic S-13 2022.5-2023.5 andesite weak potassic S-14 1966-1968 andesite weak potassic S-15 2133.5-2135 andesite weak potassic S-17A 2066-2069 andesite strong potassic S-18 1996.5-1997.5 andesite weak potassic S-19 2041-2042.3 andesite weak potassic U-1 495-496 andesite weak potassic RL-1 2033-2034 porphyry weak potassic RL-26 2015.5-2017.5 porphyry weak potassic S-8 1764-1765 porphyry weak potassic S-8 2064-2065.5 porphyry very weak potassic U-2 467-469 porphyry strong potassic U-3 481-482 porphyry strong potassic 77 Table B2: Whole-rock geochemical analyses Sample #RL-2 RL-5 RL-6 RL-8 RL-9 RL-10 ARL-10 B Rock type andesite andesite andesite andesite andesite andesite andesite

SiO2 (wt%) 59.61 53.81 55.56 56.49 54.71 52.34 58.84

Al2O3 (wt%) 18.82 18.15 17.9 19.34 18.85 17.75 17.64

Fe2O3 (wt%) 5.72 9.14 7.24 7.19 8.36 9.45 6.24 MnO (wt%) 0.05 0.06 0.04 0.04 0.05 0.05 0.04 MgO (wt%) 1.7 2.89 1.95 2.4 2.45 3.14 2.26 CaO (wt%) 5.07 6.44 6.22 5.69 6.22 5.12 4.34

Na2O (wt%) 3.76 2.92 3.18 4.04 3.85 3.4 3.27

K2O (wt%) 2.7 2.13 2.14 1.86 1.73 1.56 2.98

TiO2 (wt%) 0.597 0.917 0.877 0.777 1.058 0.777 0.832

P2O5 (wt%) 0.28 0.35 0.35 0.23 0.41 0.18 0.3 LOI (wt%) 1.5 2.39 3.45 1.14 2.3 4.84 3 Total (wt%) 99.8 99.19 98.9 99.19 99.98 98.6 99.73

Au (ppb) 8 50 32 7 < 5 11 20 Ag (ppm) 0.5 1.7 2.5 0.5 < 0.5 1 1 As (ppm)< 2< 2< 2< 2< 2< 2< 2 Ba (ppm) 561 290 392 296 228 184 722 Be (ppm)1111111 Bi (ppm)< 2< 2< 2< 2< 2< 2< 2 Br (ppm)< 1< 1< 1< 1< 1< 1< 1 Cd (ppm) < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Co (ppm)12181813172932 Cr (ppm) 4 19 6 4 7 7 < 1 Cs (ppm) 2 2.4 1.9 3.1 2.2 5.2 2.5 Cu (ppm) 2090 2620 5750 799 585 1610 1950 Hf (ppm) 1.1 1.4 1.7 1.9 1.9 0.9 1.9 Hg (ppm)< 1< 1< 1< 1< 1< 1< 1 Ir (ppb)< 5< 5< 5< 5< 5< 5< 5 Mo (ppm)2521304 92316 Ni (ppm) 2 15 6 3 6 8 6 Pb (ppm) 5 < 5 8 < 5 12 13 73 Rb (ppm)60708080504090 S (wt%) 0.345 0.132 1.72 0.093 1.14 3.95 0.793 Sb (ppm) < 0.2 < 0.2 < 0.2 0.5 < 0.2 0.3 < 0.2 Sc (ppm) 5.1 15.4 8 6.8 9.2 8.7 9.3 Se (ppm)< 3< 3< 3< 3< 3< 3< 3 Sr (ppm) 651 746 672 790 780 764 610 Ta (ppm)< 1< 1< 1< 1< 1< 12 Th (ppm) 1.5 1.1 1.2 2.1 1.4 1.7 2.8 U (ppm) 0.8 0.6 < 0.5 0.6 0.7 1.2 1 78 V (ppm) 85 214 121 106 143 125 131 W (ppm) 4 < 3 3 < 3 < 3 4 5 Y (ppm)1513141215918 Zn (ppm)50836446314644 Zr (ppm) 78 67 71 101 78 65 106 La (ppm) 10.2 10 10.1 12.1 8.9 10 13.7 Ce (ppm)19192022201925 Nd (ppm)9 81211131010 Sm (ppm) 2.5 2.5 2.5 2.7 2.6 2.3 3.2 Eu (ppm) 1.1 0.9 1.1 1.1 1.1 0.8 1.2 Tb (ppm) < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Yb (ppm) 1.5 1.3 1.5 1.3 1.6 0.9 1.8 Lu (ppm) 0.23 0.19 0.22 0.2 0.24 0.13 0.26 79 Table B2 (continued) Sample #RL-14 S-2 S-9 S-13 S-14 S-15 S-17A Rock type andesite andesite andesite andesite andesite andesite andesite

SiO2 (wt%) 52.51 54.57 54.52 55.38 50.92 53.12 53.14

Al2O3 (wt%) 17.89 18.82 17.78 18.55 17.45 18.4 17.96

Fe2O3 (wt%) 10.55 8.06 8.68 6.47 11.28 8.6 8.4 MnO (wt%) 0.06 0.03 0.05 0.04 0.06 0.06 0.04 MgO (wt%) 3.53 3.71 4.19 2.39 4.02 4.38 4.98 CaO (wt%) 7.32 4.17 5.38 5.34 7.21 6.1 2.86

Na2O (wt%) 2.6 3.29 2.97 3.01 2.51 2.46 2.73

K2O (wt%) 1.73 2.67 2.57 2.36 2.31 2.8 5.35

TiO2 (wt%) 1.003 0.833 0.927 0.981 1.1 0.971 1.024

P2O5 (wt%) 0.3 0.22 0.29 0.31 0.42 0.37 0.31 LOI (wt%) 1.49 3 2.25 4.23 1.93 2.21 2.5 Total (wt%) 98.98 99.38 99.61 99.05 99.22 99.47 99.31

Au (ppb) < 5 37 91 9 < 5 14 13 Ag (ppm) 0.9 1.4 1.7 1.7 0.9 1.3 1.8 As (ppm)< 2< 2< 2< 2< 2< 2< 2 Ba (ppm) 164 169 209 323 180 217 1500 Be (ppm)2111111 Bi (ppm)< 2< 2< 2< 2< 2< 2< 2 Br (ppm)< 11< 1< 1< 1< 1< 1 Cd (ppm) < 0.5 0.6 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Co (ppm)25162127212826 Cr (ppm) 15 7 31 < 1 20 19 19 Cs (ppm) 3.6 2.5 2.7 4.2 4.8 3.1 6.6 Cu (ppm) 1530 3470 2610 3860 1710 2790 5180 Hf (ppm) 1.4 1.8 1.3 1.9 1.8 1.6 1.6 Hg (ppm)< 1< 11< 1< 1< 1< 1 Ir (ppb)< 5< 5< 5< 5< 5< 5< 5 Mo (ppm)710614401521 Ni (ppm) 15 8 19 3 18 13 20 Pb (ppm)< 59< 5< 5< 5< 5< 5 Rb (ppm) 60 90 40 100 100 70 160 S (wt%) 0.2 0.391 0.11 0.55 0.895 0.362 0.551 Sb (ppm)< 0.2< 0.2< 0.2< 0.2< 0.2< 0.2< 0.2 Sc (ppm) 17.3 9.9 18.8 8.2 18.5 17.2 16.9 Se (ppm)< 3< 3< 3< 3< 3< 3< 3 Sr (ppm) 485 629 551 681 475 824 810 Ta (ppm) < 1 1 < 1 1 < 1 < 1 < 1 Th (ppm) 1.3 2 1.4 1.8 2.2 1.6 1.3 U (ppm) < 0.5 < 0.5 < 0.5 < 0.5 1.1 < 0.5 < 0.5 80 V (ppm) 223 138 249 133 212 212 230 W (ppm) < 3 7 < 3 5 7 < 3 < 3 Y (ppm)12121216141211 Zn (ppm)49497626508143 Zr (ppm)69775582906666 La (ppm) 7.4 11.7 8.8 11.9 10.5 10 7.8 Ce (ppm)13221624211817 Nd (ppm) 7 12 9 14 12 10 6 Sm (ppm) 2.2 2.6 2.4 3 2.8 2.6 2.3 Eu (ppm) 0.8 0.9 0.9 1.2 1 0.9 0.9 Tb (ppm) < 0.5 < 0.5 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Yb (ppm) 1.2 1.2 1.1 1.7 1.5 1.4 1.2 Lu (ppm) 0.18 0.17 0.2 0.27 0.23 0.23 0.2 Table B2 (continued) Sample S-18 S-19 U-1 RL-1 RL-26 S-8 AS-8 B Rock type andesite andesite andesite porphyry porphyry porphyry porphyry

SiO2 (wt%) 53.08 53.58 66.46 66.31 59.88 63.73

Al2O3 (wt%) 55.26 17.92 17.4 15.79 14.78 16.71 16.15

Fe2O3 (wt%) 17.79 9.04 8.52 3.2 3.5 5.41 4.01 MnO (wt%) 8.38 0.06 0.05 0.04 0.04 0.04 0.03 MgO (wt%) 3.7 4.7 4.47 1.78 2.36 4.2 2.37 CaO (wt%) 5.67 5.76 4.01 2.45 2.23 3.48 3.58

Na2O (wt%) 2.66 2.66 3.29 3.38 2.55 3.72 3.81

K2O (wt%) 2.69 2.81 3.38 4.65 4.57 2.11 3.17

TiO2 (wt%) 1.008 1.023 1.005 0.479 0.547 0.783 0.579

P2O5 (wt%) 0.31 0.32 0.28 0.13 0.14 0.19 0.16 LOI (wt%) 1.71 2.14 2.48 1.9 2.44 3.96 2.48 Total (wt%) 99.22 99.51 98.47 100.3 99.47 100.5 100.1

Au (ppb) 101 58 131 14 165 35 117 Ag (ppm) 3.6 1.7 6.2 1.2 3.4 < 0.5 2.3 As (ppm)< 2< 2< 2< 2< 2< 2< 2 Ba (ppm) 367 229 323 848 775 417 678 Be (ppm)1111< 121 Bi (ppm) < 2 < 2 11 < 2 3 < 2 < 2 Br (ppm)< 1< 1< 1< 1< 1< 1< 1 Cd (ppm) < 0.5 0.6 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Co (ppm)2224228 9139 Cr (ppm)13161614273624 Cs (ppm) 3.3 4.7 3.5 1 1.7 2.9 1.2 Cu (ppm) 7100 2580 9210 2250 5750 285 4520 Hf (ppm) 1.2 1.6 1 2.2 2.5 2.2 2.4 Hg (ppm)< 1< 1< 1< 1< 1< 1< 1 81 Ir (ppb)< 5< 5< 5< 5< 5< 5< 5 Mo (ppm) 35 16 34 7 15 3 2 Ni (ppm)15171714162517 Pb (ppm) < 5 < 5 < 5 7 16 < 5 7 Rb (ppm) 100 110 110 80 110 60 80 S (wt%) 0.452 0.148 0.541 0.228 0.45 0.019 0.6 Sb (ppm) < 0.2 < 0.2 < 0.2 0.3 0.2 < 0.2 < 0.2 Sc (ppm) 16.8 16 17.1 5 6.1 12.3 6.9 Se (ppm)< 3< 3< 3< 3< 3< 3< 3 Sr (ppm) 715 499 559 732 394 543 576 Ta (ppm)< 1< 1< 1< 12< 1< 1 Th (ppm) 1.2 1.5 0.9 6.1 5.3 4.1 5.1 U (ppm) 0.7 < 0.5 < 0.5 2.5 0.8 < 0.5 0.7 V (ppm) 221 240 254 73 69 144 90 W (ppm) < 3 3 5 < 3 7 < 3 < 3 Y (ppm)1212125 9107 Zn (ppm)58597760686746 Zr (ppm) 64 80 50 102 82 89 98 La (ppm) 8.7 10.5 9.2 10.2 12.7 14.9 13.9 Ce (ppm)17211918232926 Nd (ppm)8889101210 Sm (ppm) 2.4 2.7 2.5 1.5 2.1 2.8 2.3 Eu (ppm) 0.9 1 0.9 0.6 0.7 0.9 0.8 Tb (ppm) < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Yb (ppm) 1.4 1.2 1.3 0.4 0.7 1 0.8 Lu (ppm) 0.22 0.22 0.19 0.1 0.1 0.16 0.12 Table B2 (continued) Sample U-2 U-3 Rock type porphyry porphyry

SiO2 (wt%) 69.9 77.06

Al2O3 (wt%) 10.57 9.02

Fe2O3 (wt%) 7.27 2.63 MnO (wt%) 0.04 0.02 MgO (wt%) 1.98 1.12 CaO (wt%) 1.55 0.9

Na2O (wt%) 1.75 0.83

K2O (wt%) 4.07 5.37

TiO2 (wt%) 0.509 0.329

P2O5 (wt%) 0.13 0.08 LOI (wt%) 1.22 1.2 Total (wt%) 98.99 98.56

Au (ppb) 133 307 82 Ag (ppm) 2.1 8.6 As (ppm) < 2 < 2 Ba (ppm) 625 712 Be (ppm) < 1 < 1 Bi (ppm) < 2 30 Br (ppm) < 1 < 1 Cd (ppm) < 0.5 < 0.5 Co (ppm) 12 7 Cr (ppm) 15 18 Cs (ppm) 1.7 1.2 Cu (ppm) 3430 11500 Hf (ppm) 1.1 1.5 Hg (ppm) < 1 < 1 Ir (ppb) < 5 < 5 Mo (ppm) 4 33 Ni (ppm) 15 10 Pb (ppm) 7 12 Rb (ppm) 70 90 S (wt%) 0.19 0.703 Sb (ppm) 0.5 0.8 Sc (ppm) 8.4 4 Se (ppm) < 3 5 Sr (ppm) 190 173 Ta (ppm) < 1 < 1 Th (ppm) 1.6 3.1 U (ppm) < 0.5 < 0.5 V (ppm) 132 65 W (ppm) < 3 4 Y (ppm) 3 1 Zn (ppm) 63 49 Zr (ppm) 41 57 La (ppm) 3.9 3.7 Ce (ppm) 8 7 Nd (ppm) < 5 < 5 Sm (ppm) 0.8 0.6 Eu (ppm) 0.3 0.4 Tb (ppm) < 0.5 < 0.5 Yb (ppm) 0.3 0.2 Lu (ppm) 0.07 0.06

Appendix C: Microprobe Analyses 83 Electron microprobe analyses were performed at the University of Arizona.

Table C1: Feldspar analyses

RL-2 RL-2 RL-2 RL-2 RL-4 RL-4 RL-4 RL-4 RL-4 RL-4 Sample # 1982 1982 1982 1982 2117.5 2117.5 2117.5 2117.5 2117.5 2117.5 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 6.99 4.35 8.47 10.11 10.12 10.33 8.96 8.23 5.69 7.10

K2O 0.12 0.10 0.34 0.15 0.17 0.10 0.28 0.14 0.19 0.13

SiO2 60.93 52.90 61.97 66.57 65.20 65.36 62.02 60.47 54.53 57.32

Al2O3 24.87 29.96 24.04 21.10 22.42 21.94 24.20 25.46 29.21 27.48 CaO 7.55 12.06 4.77 1.51 2.64 2.65 4.85 6.36 10.67 8.70

TiO2 0.02 0.02 0.00 0.01 0.01 0.00 0.01 0.01 0.05 0.06 FeO 0.15 0.16 0.00 0.09 0.03 0.05 0.05 0.40 0.32 0.18 MnO 0.00 0.03 0.00 0.01 0.04 0.00 BaO 0.00 0.00 0.00 0.08 0.13 0.06 0.12 0.01 0.12 0.11 Total 100.62 99.56 99.60 99.62 100.72 100.54 100.50 101.08 100.83 101.08

Or 0.01 0.01 0.03 0.01 0.01 0.01 0.02 0.01 0.01 0.01 An 0.51 0.72 0.34 0.12 0.20 0.20 0.34 0.42 0.64 0.54 Ab 0.49 0.27 0.63 0.86 0.79 0.79 0.64 0.57 0.35 0.45

RL-4 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 2117.5 1610 1610 1610 1610 1610 1610 1610 1610 1610 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 4.15 8.87 6.22 8.93 9.63 4.06 8.68 7.23 5.60 8.81

K2O 0.10 0.14 0.10 0.14 0.18 0.22 0.08 0.08 0.08 0.10

SiO2 51.74 58.95 54.60 61.46 62.43 60.33 60.01 57.70 53.75 60.24

Al2O3 31.20 25.88 28.34 24.07 23.19 25.11 24.31 26.81 29.09 25.10 CaO 13.26 6.78 10.30 4.82 4.15 5.72 5.57 7.99 10.99 5.88

TiO2 0.06 0.04 0.07 0.00 0.01 0.03 0.06 0.03 0.03 0.01 FeO 0.33 0.43 0.00 0.19 0.27 0.15 0.21 0.25 0.90 0.14 84 MnO 0.00 0.00 0.00 0.02 0.00 0.00 0.02 0.00 0.00 0.03 BaO 0.05 0.00 0.07 0.00 0.01 0.01 0.03 0.03 0.00 0.00 Total 100.90 101.10 99.70 99.62 99.88 95.63 98.97 100.14 100.44 100.32

Or 0.01 0.01 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.01 An 0.75 0.42 0.61 0.34 0.29 0.56 0.38 0.51 0.65 0.39 Ab 0.24 0.57 0.38 0.65 0.70 0.41 0.61 0.48 0.34 0.60

Table C1 (continued)

RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1610 1610 1610 1836.5 1836.5 1836.5 1836.5 1836.5 1836.5 1836.5 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 8.02 8.35 8.57 3.89 7.68 5.88 5.80 11.34 8.57 8.83

K2O 0.13 0.12 0.14 0.34 0.12 0.09 0.16 0.48 0.15 0.23

SiO2 59.11 59.69 59.16 50.90 59.91 66.63 55.00 66.09 60.39 61.11

Al2O3 25.72 24.97 22.74 33.48 25.45 20.75 27.26 21.60 25.34 24.70 CaO 6.48 5.82 4.48 7.57 6.48 5.89 7.82 1.13 6.17 5.57

TiO2 0.03 0.00 0.03 0.26 0.02 0.02 0.03 0.01 0.00 0.00 FeO 0.18 0.05 0.28 0.54 0.05 0.12 0.25 0.10 0.06 0.05 MnO 0.04 0.03 0.00 0.03 0.01 0.01 0.00 0.04 0.01 0.03 BaO 0.05 0.00 0.00 0.00 0.02 0.00 0.00 0.03 0.03 0.00 Total 99.76 99.04 95.40 97.00 99.74 99.38 96.33 100.82 100.71 100.52

Or 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.04 0.01 0.02 An 0.43 0.40 0.33 0.63 0.44 0.49 0.56 0.08 0.40 0.37 Ab 0.56 0.59 0.66 0.34 0.55 0.50 0.43 0.87 0.58 0.61

RL-10 RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 Sample # 2140.7 2140.7 2140.7 1985 1985 1985 1985 1985 1985 1985 85 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 9.17 4.91 4.99 4.98 5.63 1.33 1.14 2.09 1.30 1.67

K2O 0.27 0.20 0.20 0.10 0.13 0.07 0.02 0.03 0.03 0.02

SiO2 62.41 54.06 51.27 53.65 54.58 46.53 44.83 47.19 45.52 46.68

Al2O3 24.10 29.33 28.16 29.82 29.25 33.30 35.99 33.81 35.43 34.40 CaO 4.90 11.06 10.96 11.21 11.12 17.37 18.51 16.66 18.30 16.85

TiO2 0.00 0.05 0.04 0.00 0.00 0.02 0.02 0.02 0.01 0.00 FeO 0.11 0.50 0.73 0.21 0.58 0.74 0.50 0.82 0.50 0.60 MnO 0.03 0.03 0.00 0.01 0.00 0.01 0.00 BaO 0.00 0.11 0.10 0.04 0.00 0.11 0.00 0.18 0.00 0.06 Total 100.95 100.22 96.46 100.06 101.32 99.48 101.02 100.80 101.11 100.29

Or 0.02 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.00 An 0.33 0.67 0.67 0.68 0.65 0.92 0.94 0.88 0.93 0.91 Ab 0.65 0.31 0.32 0.31 0.34 0.07 0.06 0.12 0.07 0.09

Table C1 (continued)

RL-14 RL-26 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 Sample # 1985 2001 1182.5 1182.5 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 6.42 9.96 6.53 6.74 6.14 4.65 5.92 9.40 10.76 5.42

K2O 0.10 0.15 0.12 0.15 0.26 0.23 0.13 0.13 0.25 0.11

SiO2 56.64 65.83 57.17 56.75 53.89 51.89 55.29 62.39 64.04 52.06

Al2O3 27.87 22.44 27.03 27.53 28.13 30.61 29.10 24.17 22.05 29.82 CaO 9.28 2.58 8.87 9.04 9.67 12.40 9.99 4.55 2.25 11.26

TiO2 0.04 0.00 0.02 0.02 0.02 0.02 0.00 0.03 0.01 0.01 FeO 0.80 0.05 0.32 0.43 0.58 0.31 0.29 0.16 0.06 0.15 MnO 0.02 0.00 0.01 0.00 0.00 0.01 0.03 0.02 0.00 BaO 0.00 0.00 0.08 0.00 0.03 0.12 0.00 0.00 0.21 0.03 Total 101.19 101.02 100.14 100.68 98.73 100.25 100.73 100.86 99.65 98.87 86

Or 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.01 0.02 0.01 An 0.58 0.20 0.56 0.56 0.59 0.71 0.61 0.31 0.16 0.66 Ab 0.41 0.79 0.43 0.43 0.39 0.28 0.38 0.67 0.82 0.33

S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 Sample # 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 2085.4 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 5.60 5.29 6.31 5.52 9.18 10.16 5.84 6.11 9.55 4.55

K2O 0.08 0.16 0.19 0.11 0.34 0.12 0.11 0.15 0.11 0.16

SiO2 53.26 52.96 55.81 54.25 61.99 63.28 54.42 54.47 62.65 52.64

Al2O3 29.08 29.40 28.70 29.44 23.57 23.25 29.57 29.06 23.77 30.82 CaO 10.78 11.25 9.82 10.89 4.37 3.73 10.75 10.44 4.28 12.29

TiO2 0.01 0.00 0.00 0.04 0.03 0.02 0.02 0.03 0.02 0.02 FeO 0.19 0.19 0.19 0.40 0.06 0.02 0.15 0.25 0.11 0.23 MnO 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 BaO 0.00 0.00 0.04 0.05 0.01 0.00 0.00 0.08 0.02 0.00 Total 99.02 99.28 101.06 100.71 99.55 100.58 100.87 100.57 100.51 100.72

Or 0.01 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.01 0.01 An 0.65 0.66 0.59 0.65 0.31 0.26 0.63 0.62 0.30 0.71 Ab 0.35 0.32 0.39 0.34 0.67 0.73 0.36 0.37 0.69 0.27

Table C1 (continued)

S-2 S-2 S-2 S-5 S-5 S-5 S-5 S-5 S-5 S-7 Sample # 2085.4 2085.4 2085.4 2003 2003 2003 2003 2003 2003 1537 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag. 87

Na2O 7.95 10.21 6.69 7.59 8.61 8.85 8.11 5.60 7.90 4.13

K2O 0.29 0.20 0.17 0.26 0.27 0.18 0.24 0.18 0.18 0.06

SiO2 57.24 63.44 55.16 59.92 60.90 60.91 61.41 54.90 58.78 51.80

Al2O3 26.16 23.01 28.65 24.43 24.32 25.06 24.66 28.25 26.04 30.99 CaO 7.33 3.41 9.72 5.33 5.07 5.74 5.25 9.79 6.92 12.73

TiO2 0.01 0.00 0.00 0.01 0.00 0.01 0.01 0.08 0.00 0.02 FeO 0.29 0.06 0.28 0.28 0.18 0.15 0.19 0.59 0.97 0.18 MnO 0.02 0.04 0.05 0.00 0.00 0.00 0.04 0.00 0.00 0.02 BaO 0.02 0.00 0.03 0.00 0.01 0.00 0.00 0.00 0.00 0.08 Total 99.31 100.36 100.76 97.81 99.35 100.90 99.91 99.40 100.80 100.02

Or 0.02 0.02 0.01 0.02 0.02 0.01 0.02 0.01 0.01 0.00 An 0.46 0.24 0.58 0.39 0.35 0.38 0.38 0.62 0.45 0.74 Ab 0.52 0.74 0.41 0.58 0.62 0.61 0.60 0.37 0.53 0.25

S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 Sample # 1537 1537 1537 1537 1537 1537 1537 1537 1537 1537 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 4.70 4.45 9.49 4.49 5.92 5.21 4.53 5.66 5.58 5.89

K2O 0.09 0.11 0.25 0.19 0.20 0.12 0.12 0.23 0.16 0.25

SiO2 52.09 51.86 64.73 52.96 55.47 53.95 52.61 54.13 54.65 53.62

Al2O3 30.75 30.72 23.47 30.73 28.59 29.22 30.64 29.30 29.19 29.25 CaO 12.44 12.51 3.64 12.03 10.08 10.86 12.14 10.83 10.47 10.80

TiO2 0.03 0.03 0.01 0.03 0.02 0.00 0.01 0.03 0.01 0.00 FeO 0.23 0.20 0.27 0.17 0.43 0.39 0.32 0.21 0.17 0.49 MnO 0.00 0.02 0.00 0.00 0.01 0.03 0.01 0.01 0.01 0.04 BaO 0.07 0.00 0.00 0.00 0.04 0.06 0.09 0.00 0.05 0.00 Total 100.40 99.91 101.87 100.61 100.76 99.86 100.47 100.42 100.29 100.34

Or 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.02 0.01 0.02 88 An 0.71 0.72 0.26 0.71 0.61 0.66 0.72 0.64 0.64 0.63 Ab 0.28 0.27 0.71 0.28 0.37 0.33 0.28 0.35 0.35 0.36

Table C1 (continued)

S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-10 Sample # 1537 1537 1537 1537 1537 1537 1537 1537 1537 2121.5 mineral plag. plag. plag. plag. plag. plag. plag. plag. plag. plag.

Na2O 5.20 7.81 9.90 7.40 8.84 6.83 6.54 6.28 5.43 8.41

K2O 0.16 0.24 0.35 2.05 0.27 0.12 0.15 0.13 0.10 0.23

SiO2 53.10 59.53 63.72 64.99 63.41 57.48 55.38 55.04 54.32 62.73

Al2O3 30.90 25.55 23.05 21.84 23.17 28.17 28.34 28.68 29.66 24.78 CaO 11.73 6.71 3.74 2.02 3.92 9.24 9.74 10.01 10.81 5.41

TiO2 0.01 0.02 0.01 0.00 0.01 0.00 0.01 0.02 0.01 0.01 FeO 0.22 0.25 0.28 0.35 0.29 0.13 0.20 0.25 0.21 0.26 MnO 0.04 0.01 0.00 0.05 0.02 0.00 0.00 0.01 0.02 BaO 0.04 0.00 0.09 0.24 0.10 0.02 0.10 0.00 0.00 0.01 Total 101.41 100.13 101.15 98.95 100.03 101.99 100.47 100.43 100.56 101.85

Or 0.01 0.02 0.03 0.20 0.02 0.01 0.01 0.01 0.01 0.02 An 0.68 0.44 0.26 0.17 0.29 0.56 0.58 0.60 0.65 0.38 Ab 0.31 0.54 0.71 0.64 0.68 0.43 0.41 0.39 0.34 0.61

S-10 S-15 S-15 S-16 S-16 S-16 RL-2 RL-2 RL-2 RL-2 Sample # 2121.5 2041 2041 2056 2056 2056 1982 1982 1982 1982 mineral plag. plag. plag. plag. plag. plag. K-feld. K-feld. K-feld. K-feld.

Na2O 7.60 3.70 1.11 11.08 8.99 9.42 0.89 0.91 0.51 0.28

K2O 0.17 0.06 0.09 0.02 0.37 0.48 12.97 14.33 15.40 10.22 89

SiO2 53.21 49.70 45.31 64.93 62.36 62.58 39.61 65.15 56.83 47.51

Al2O3 24.70 32.45 35.63 21.90 23.90 23.87 13.00 19.16 17.44 30.89 CaO 7.08 14.65 18.26 2.37 4.63 2.45 0.06 0.06 0.00 0.00

TiO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.21 FeO 0.56 0.12 0.23 0.04 0.12 0.08 0.00 0.06 0.06 4.17 MnO 0.00 0.04 0.00 BaO 0.11 0.01 0.00 0.16 0.13 0.03 0.43 0.36 0.78 0.03 Total 93.43 100.69 100.63 100.51 100.56 98.93 66.96 100.04 91.02 93.33

Or 0.01 0.00 0.01 0.00 0.03 0.04 0.94 0.94 0.97 0.98 An 0.47 0.79 0.94 0.17 0.32 0.19 0.00 0.00 0.00 0.00 Ab 0.52 0.21 0.06 0.83 0.65 0.76 0.06 0.05 0.03 0.02

Table C1 (continued)

RL-2 RL-4 RL-4 RL-4 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1982 2117.5 2117.5 2117.5 1836.5 1836.5 1836.5 1836.5 1836.5 1836.5 mineral K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld.

Na2O 0.86 0.55 0.04 2.19 0.40 0.34 5.17 0.56 0.27 0.56

K2O 15.15 15.25 16.23 10.87 16.04 16.49 7.66 15.79 15.93 15.81

SiO2 63.39 64.50 64.99 62.55 63.99 63.80 64.26 63.91 63.67 63.09

Al2O3 18.63 19.25 18.87 20.33 18.97 18.71 20.59 18.73 18.60 19.52 CaO 0.00 0.10 0.00 1.01 0.00 0.00 1.09 0.00 0.03 0.00

TiO2 0.00 0.02 0.00 0.07 0.00 0.00 0.02 0.01 0.00 0.00 FeO 0.00 0.02 0.09 0.03 0.00 0.01 0.27 0.01 0.01 0.34 MnO 0.06 0.00 0.00 0.04 0.01 0.00 0.02 0.00 0.00 BaO 0.28 0.09 0.07 2.47 0.01 0.03 0.16 0.16 0.23 0.05 Total 98.31 99.85 100.30 99.51 99.46 99.39 99.21 99.19 98.76 99.38 90 Or 0.95 0.96 1.00 0.79 0.98 0.98 0.58 0.97 0.98 0.97 An 0.00 0.01 0.00 0.06 0.00 0.00 0.07 0.00 0.00 0.00 Ab 0.05 0.03 0.00 0.14 0.02 0.02 0.35 0.03 0.01 0.03

RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 RL-14 RL-26 RL-26 S-2 Sample # 2140.7 2140.7 1985 1985 1985 1985 1985 2001 2001 2085.4 mineral K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld.

Na2O 0.22 0.42 0.11 0.09 0.32 0.50 0.07 0.50 0.47 0.50

K2O 15.97 15.92 10.71 10.74 16.13 14.87 10.49 12.93 15.70 15.76

SiO2 67.00 65.35 46.31 46.88 63.41 62.53 47.23 41.57 64.57 60.51

Al2O3 19.43 19.05 34.96 36.99 18.40 19.37 35.01 12.18 18.84 18.50 CaO 0.05 0.02 1.09 0.21 0.78 0.09 0.21 0.00 0.00 0.21

TiO2 0.00 0.00 0.01 0.02 0.02 0.08 0.00 0.00 0.04 0.00 FeO 0.05 0.01 2.10 1.02 0.51 0.19 2.30 0.02 0.05 0.10 MnO 0.01 0.00 0.00 0.00 0.00 0.00 BaO 0.16 0.00 0.00 0.00 0.03 2.58 0.00 0.21 0.27 0.51 Total 102.88 100.78 95.31 95.95 99.63 100.22 95.30 67.41 99.93 96.09

Or 0.99 0.98 0.91 0.98 0.94 0.97 0.98 0.97 0.97 0.96 An 0.00 0.00 0.08 0.02 0.04 0.01 0.02 0.00 0.00 0.01 Ab 0.01 0.02 0.01 0.01 0.02 0.03 0.01 0.03 0.03 0.03

Table C1 (continued)

S-2 S-2 S-2 S-2 S-5 S-7 S-7 S-7 S-7 S-7 Sample # 2085.4 2085.4 2085.4 2085.4 2003 1537 1537 1537 1537 1537 mineral K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld.

Na2O 1.03 0.59 0.75 0.86 1.27 1.06 0.77 0.91 1.08 1.57 91

K2O 15.44 15.34 15.14 15.15 7.85 15.43 14.94 15.48 15.36 13.92

SiO2 63.06 62.64 63.76 63.52 62.07 64.42 62.23 63.98 64.02 64.37

Al2O3 19.08 19.23 18.88 18.97 23.04 18.93 18.16 18.83 18.93 19.08 CaO 0.02 0.00 0.00 0.00 3.51 0.00 0.00 0.00 0.05 0.04

TiO2 0.01 0.00 0.00 0.00 0.00 0.02 0.01 0.04 0.02 0.02 FeO 0.06 0.19 0.06 0.21 0.12 0.11 0.26 0.10 0.10 0.16 MnO 0.00 0.04 0.00 0.01 0.00 0.00 0.01 0.01 0.04 0.00 BaO 0.27 0.24 0.56 0.33 0.16 0.03 0.22 0.35 0.24 0.07 Total 98.97 98.28 99.16 99.05 98.04 100.01 96.62 99.69 99.83 99.23

Or 0.94 0.97 0.96 0.95 0.65 0.94 0.96 0.95 0.94 0.91 An 0.00 0.00 0.00 0.00 0.25 0.00 0.00 0.00 0.00 0.00 Ab 0.06 0.03 0.04 0.05 0.09 0.06 0.04 0.05 0.06 0.09

S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-7 S-8 Sample # 1537 1537 1537 1537 1537 1537 1537 1537 1537 1686.8 mineral K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld.

Na2O 0.52 0.61 0.55 1.02 1.30 0.74 1.21 0.62 0.95 0.82

K2O 15.52 15.62 15.94 15.29 14.94 15.78 14.90 16.02 15.57 15.46

SiO2 64.55 63.66 63.95 64.18 64.06 63.50 64.07 63.99 64.39 64.04

Al2O3 18.73 18.78 18.68 18.97 18.90 18.66 18.89 18.86 18.99 18.68 CaO 0.02 0.00 0.00 0.03 0.03 0.08 0.04 0.00 0.00 0.00

TiO2 0.00 0.01 0.00 0.02 0.00 0.00 0.04 0.02 0.04 0.03 FeO 0.05 0.11 0.00 0.08 0.03 0.26 0.15 0.23 0.28 0.07 MnO 0.00 0.00 0.00 0.03 0.01 0.00 0.02 0.05 0.03 BaO 0.08 0.16 0.16 0.32 0.27 0.33 0.13 0.15 0.14 0.16 Total 99.47 98.96 99.29 99.93 99.53 99.35 99.45 99.93 100.39 99.26

Or 0.97 0.97 0.97 0.94 0.93 0.96 0.93 0.97 0.95 0.95 An 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 92 Ab 0.03 0.03 0.03 0.06 0.07 0.04 0.07 0.03 0.05 0.05

Table C1 (continued)

S-15 S-15 S-15 S-15 S-15 S-15 S-15 Sample # 2041 2041 2056 2056 2056 2056 2056 mineral K-feld. K-feld. K-feld. K-feld. K-feld. K-feld. K-feld.

Na2O 0.65 0.80 0.24 0.48 0.69 0.02 0.50

K2O 15.86 15.55 15.48 14.84 14.77 11.17 14.81

SiO2 65.11 64.25 62.71 63.62 49.81 35.72 49.79

Al2O3 19.05 18.98 18.93 18.60 15.29 11.06 15.37 CaO 0.04 0.00 0.08 0.09 0.00 19.15 0.00

TiO2 0.03 0.02 0.01 0.00 0.00 0.01 0.02 FeO 0.15 0.11 0.06 0.06 0.13 0.00 0.25 MnO 0.00 0.01 0.00 0.00 0.00 BaO 0.07 0.16 1.44 0.17 0.52 0.21 0.54 Total 100.95 99.86 98.94 97.88 81.20 77.36 81.28

Or 0.96 0.96 0.98 0.97 0.96 0.40 0.97 An 0.00 0.00 0.00 0.01 0.00 0.60 0.00 Ab 0.04 0.04 0.01 0.03 0.04 0.00 0.03 93 94 Table C2: analyses

RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1610 1610 1610 1610 1610 1610 2140.7 2140.7 2303 2303

mineral magn. magn. magn. magn. magn. magn. magn. magn. magn. magn.

SiO2 0.08 0.00 0.04 0.00 0.10 0.00 0.80 0.55 0.01 0.04

MgO 0.00 0.02 0.00 0.00 0.00 0.02 0.03 0.01 0.00 0.01

Al2O3 0.05 0.05 0.05 0.04 0.05 0.04 0.27 0.16 0.11 0.02

FeO 93.58 93.82 93.41 93.48 92.40 86.78 93.74 93.52 92.95 92.91

MnO 0.06 0.01 0.02 0.02 0.06 0.01 0.01 0.07 0.05 0.05

TiO2 0.04 0.08 0.02 0.04 0.02 0.13 0.12 0.12 0.26 0.02

Cr2O3 0.04 0.03 0.02 0.02 0.04 0.04 0.02 0.04 0.05 0.00

V2O3 0.14 0.18 0.23 0.17 0.14 0.16 0.14 0.18 0.43 0.15

Total 94.00 94.20 93.79 93.78 92.81 87.19 95.12 94.64 93.85 93.18

RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 S-5 S-5 S-5 Sample # 1985 1985 1985 1985 1985 1985 1985 2003 2003 2003

mineral magn. magn. magn. magn. magn. magn. magn. magn. magn. magn.

SiO2 0.05 0.02 0.22 0.03 0.02 0.09 0.02 0.10 0.08 4.20

MgO 0.00 0.00 0.02 0.00 0.00 0.00 0.01 0.01 0.01 0.16

Al2O3 0.07 0.11 0.10 0.14 0.08 0.05 0.08 0.04 0.06 1.22

FeO 92.29 93.41 92.50 93.31 93.74 91.75 93.28 93.57 94.06 79.79

MnO 0.10 0.06 0.04 0.03 0.03 0.02 0.19 0.05 0.02 0.03

TiO2 0.19 0.38 0.32 0.10 0.05 0.00 0.06 0.99 0.04 0.07

Cr2O3 0.02 0.05 0.17 0.05 0.02 0.04 0.02 0.03 0.03 0.39

V2O3 0.27 0.29 0.26 0.23 0.25 0.21 0.20 0.40 0.40 0.46

Total 93.00 94.33 93.63 93.88 94.20 92.16 93.87 95.20 94.70 86.32

S-7 S-7 S-7 S-7 S-10 S-10 S-10 S-10 S-14 S-14 Sample # 1537 1537 1537 1537 2041 2041 2121.5 2121.5 1942.5 1942.5

mineral magn. magn. magn. magn. magn. magn. magn. magn. magn. magn. 95

SiO2 0.06 0.36 3.73 0.03 0.00 0.02 0.01 0.03 0.04 0.07

MgO 0.03 0.13 0.04 0.01 0.00 0.01 0.00 0.02 0.00 0.00

Al2O3 0.08 0.10 0.82 0.04 0.13 0.08 0.08 0.07 0.09 0.05

FeO 92.83 92.20 84.90 93.76 95.03 94.42 91.39 91.85 92.37 92.36

MnO 0.07 0.04 0.00 0.00 0.05 0.01 0.02 0.00 0.07 0.07

TiO2 0.05 0.03 0.37 0.05 0.10 0.07 0.05 0.04 0.07 0.52

Cr2O3 0.03 0.01 0.00 0.01 0.00 0.07 0.03 0.03 0.01 0.10

V2O3 0.14 0.08 0.00 0.16 0.12 0.25 0.58 0.29 0.16 0.27

Total 93.29 92.94 89.86 94.07 95.44 94.92 92.16 92.32 92.82 93.42 Table C2 (continued)

S-16 S-16 RL-10 RL-10 S-10 S-14 RL-4 RL-4 RL-4 RL-4 Sample # 2056 2056 2140.7 2303 2041 1942.5 2117.5 2117.5 2117.5 2117.5

mineral magn. magn. ilmen. ilmen. ilmen. ilmen. rutile rutile rutile rutile

SiO2 0.01 0.16 0.01 0.00 0.08 0.25 0.31 0.00 0.00 0.00

MgO 0.00 0.20 0.05 0.07 0.02 0.04 0.01 0.06 0.01 0.00

Al2O3 0.04 0.14 0.00 0.01 0.00 0.18 0.04 0.13 0.02 0.02

FeO 92.05 92.71 44.16 48.29 47.31 47.20 1.69 1.21 3.86 1.17

MnO 0.01 0.02 2.23 2.88 2.67 3.08 0.00 0.05 0.00 0.01

TiO2 0.13 0.68 47.18 38.67 44.21 45.25 92.39 93.60 86.57 94.78

Cr2O3 0.46 0.50 0.02 0.01 0.18 0.00 0.25 0.06 0.14 0.05

V2O3 0.27 0.13 0.27 0.37 0.36 0.27 0.94 0.76 1.34 0.65

Total 92.97 94.53 93.92 90.31 94.82 96.27 95.65 95.87 91.95 96.67

S-2 S-2 S-2 S-2 S-5 S-5 S-7 Sample # 1182.5 1182.5 1182.5 1182.5 2003 2003 1537

mineral rutile rutile rutile rutile rutile rutile rutile

SiO2 0.03 0.27 0.12 0.06 2.87 0.15 1.17

MgO 0.00 0.02 0.01 0.02 0.00 0.01 0.00

Al2O3 0.02 0.06 0.04 0.08 0.01 0.03 0.53

FeO 0.51 0.99 0.90 1.01 1.34 0.55 1.10 96

MnO 0.03 0.02 0.00 0.00 0.00 0.00 0.00

TiO2 97.08 96.09 96.08 93.66 94.41 95.89 94.66

Cr2O3 0.01 0.04 0.09 0.36 0.02 0.10 0.00

V2O3 0.44 0.60 0.67 0.64 0.60 0.69 0.50

Total 98.13 98.09 97.90 95.84 99.25 97.42 97.96

Table C3: Other analyses

RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1610 1610 1610 1610 1610 1610 1610 1610 1610 1610 mineral amph. amph. amph. amph. amph. amph. amph. amph. amph. amph.

Na2O 0.27 0.24 0.26 0.21 0.60 0.32 0.36 0.71 0.29 0.25 F 0.00 0.00 0.00 0.00 0.00 0.11 0.04 0.05 0.03 0.00

K2O 0.11 0.05 0.12 0.15 0.52 0.22 0.36 0.54 0.09 0.13 MgO 16.74 17.60 17.01 17.62 12.84 14.93 15.89 15.66 16.22 15.91

Al2O3 3.84 2.48 3.70 2.62 7.02 4.45 5.31 6.24 4.11 4.35

P2O5 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.01 0.01

SiO2 52.06 53.59 51.49 52.97 46.60 50.08 50.24 47.77 51.67 51.51 97 CaO 12.43 12.55 12.43 12.39 12.26 12.45 12.42 11.66 12.09 11.41 Cl 0.09 0.00 0.03 0.06 0.14 0.05 0.10 0.14 0.06 0.04

TiO2 0.23 0.12 0.26 0.23 0.32 0.36 0.34 1.46 0.24 0.22

SO2 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.02 FeO 10.33 9.65 10.00 9.23 15.49 12.70 11.33 11.61 10.02 9.76 MnO 0.26 0.23 0.20 0.21 0.30 0.28 0.19 0.26 0.24 0.13 BaO 0.00 0.04 0.02 0.00 0.02 0.00 0.03 0.01 0.03 0.00 Total 96.37 96.60 95.52 95.70 96.09 95.95 96.65 96.12 95.13 93.74

RL-10 RL-10 RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 Sample # 1610 1610 1610 1610 1985 1985 1985 1985 1985 1985 mineral amph. amph. amph. amph. amph. amph. amph. amph. amph. amph.

Na2O 0.24 0.36 0.54 0.52 0.56 0.91 0.73 0.34 0.81 0.90 F 0.16 0.00 0.00 0.00 0.14 0.05 0.09 0.05 0.18 0.14

K2O 0.10 0.09 0.25 0.29 0.46 0.64 0.51 0.10 0.80 1.26 MgO 17.06 17.02 15.43 17.32 14.95 15.39 13.68 16.03 12.76 10.42

Al2O3 2.83 3.60 5.33 3.96 6.99 8.42 7.04 4.77 10.44 11.89

P2O5 0.00 0.01 0.03 0.03 0.03 0.03 0.02 0.00 0.00 0.00

SiO2 52.42 51.55 49.44 51.00 48.41 46.90 48.67 51.01 44.27 41.46 CaO 12.44 12.24 12.40 11.78 12.70 12.66 12.54 12.45 12.29 12.05 Cl 0.02 0.05 0.04 0.13 0.05 0.09 0.10 0.04 0.17 0.31

TiO2 0.21 0.28 0.36 0.68 0.48 0.98 0.36 0.47 0.74 1.10

SO2 0.03 0.01 0.00 0.00 0.00 0.02 0.00 0.02 0.00 0.00 FeO 10.09 10.18 12.15 9.85 12.63 10.96 14.06 11.38 14.53 17.35 MnO 0.30 0.20 0.26 0.31 0.29 0.21 0.22 0.35 0.20 0.21 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 Total 95.89 95.58 96.23 95.89 97.70 97.26 98.02 97.06 97.19 97.10

Table C3 (continued) 98

RL-14 RL-14 RL-14 RL-14 RL-14 S-10 S-14 S-14 S-14 S-14 Sample # 1985 1985 1985 1985 1985 2041 1942.5 1942.5 1942.5 1942.5 mineral amph. amph. amph. amph. amph. amph. amph. amph. amph. amph.

Na2O 0.28 0.23 0.61 0.58 0.51 0.37 0.25 3.64 1.02 0.27 F 0.12 0.12 0.00 0.00 0.00 0.00 0.14 0.00 0.05 0.07

K2O 0.13 0.06 0.48 0.38 0.23 0.17 0.13 5.74 0.47 0.15 MgO 17.10 16.84 12.77 14.46 15.82 15.02 17.51 4.06 14.50 17.01

Al2O3 3.20 3.48 8.62 7.38 5.84 3.44 3.32 23.21 8.19 3.66

P2O5 0.00 0.01 0.03 0.03 0.03 0.00 0.02 0.00 0.03 0.01

SiO2 53.23 52.66 46.38 48.21 50.36 49.48 53.33 53.85 52.40 52.38 CaO 12.70 12.61 12.14 12.61 12.45 12.51 12.60 3.56 11.29 12.28 Cl 0.02 0.04 0.10 0.07 0.05 0.08 0.03 0.02 0.04 0.03

TiO2 0.19 0.21 0.40 0.40 0.52 0.00 0.43 0.50 0.30 0.33

SO2 0.01 0.00 0.04 0.02 0.00 0.00 0.01 0.01 0.01 0.01 FeO 10.33 10.87 14.92 13.33 11.56 12.37 9.74 5.31 11.59 10.32 MnO 0.28 0.28 0.23 0.24 0.37 0.43 0.23 0.04 0.24 0.28 BaO 0.08 0.00 0.00 0.00 0.14 0.00 0.00 0.00 0.00 0.00 Total 97.67 97.42 96.73 97.70 97.89 93.87 97.76 99.96 100.14 96.79

S-14 S-14 S-14 S-14 RL-4 RL-4 RL-4 RL-4 S-14 S-14 Sample # 1942.5 1942.5 1942.5 1942.5 2117.5 2117.5 2117.5 2117.5 1942.5 1942.5 mineral amph. amph. amph. amph. anhyd. anhyd. anhyd. anhyd. anhyd. anhyd.

Na2O 1.99 0.30 0.20 0.25 0.04 0.05 0.04 0.00 0.01 0.04 F 0.12 0.07 0.00 0.07 0.13 0.00 0.06 0.06 0.00 0.00

K2O 0.18 0.09 0.12 0.07 0.04 0.02 0.02 0.00 0.00 0.00 MgO 8.41 15.97 16.72 17.18 0.00 0.00 0.00 0.00 0.00 0.00

Al2O3 14.78 4.47 2.96 3.25 0.04 0.01 0.00 0.02 0.02 0.01

P2O5 0.07 0.00 0.00 0.00 0.07 0.06 0.06 0.08 0.06 0.05

SiO2 53.72 50.63 51.83 53.33 0.20 0.12 0.06 0.06 0.08 0.04 CaO 11.12 12.20 12.13 12.54 43.16 43.71 43.63 43.60 43.52 40.75 99 Cl 0.03 0.05 0.02 0.03 0.00 0.00 0.01 0.00 0.00 0.00

TiO2 0.25 0.45 0.36 0.44 0.00 0.00 0.00 0.00 0.00 0.00

SO2 0.00 0.01 0.00 0.00 32.41 39.30 36.84 36.17 37.47 40.75 FeO 5.80 10.78 9.29 10.22 0.27 0.01 0.08 0.01 0.09 0.34 MnO 0.15 0.32 0.32 0.34 0.00 0.02 0.02 0.04 0.00 0.00 BaO 0.07 0.00 0.06 0.00 0.00 0.04 0.07 0.00 0.00 0.00 Total 96.71 95.35 94.02 97.72 76.36 83.35 80.91 80.04 81.25 81.99

Table C3 (continued)

RL-10 RL-10 RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 Sample # 1610 1610 1610 1836.5 1985 1985 1985 1985 1985 1985 mineral apat. apat. apat. apat. apat. apat. apat. apat. apat. apat.

Na2O 0.00 0.03 0.17 0.31 0.02 0.02 0.03 0.01 0.02 0.03 F 0.48 1.28 0.70 0.58 2.35 1.10 1.88 1.74 2.03 0.17

K2O 0.01 0.00 0.01 0.05 0.00 0.00 0.00 0.22 0.15 0.02 MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Al2O3 0.01 0.02 0.01 1.78 0.01 0.00 0.01 0.09 0.05 0.01

P2O5 41.66 41.83 40.66 38.75 40.39 39.33 41.83 38.32 41.75 0.03

SiO2 0.12 0.37 0.16 0.89 0.11 0.09 0.13 1.16 0.17 0.06 CaO 56.05 55.21 53.95 51.92 54.42 53.90 55.47 53.85 56.03 50.18 Cl 0.15 0.18 1.05 0.97 0.86 1.77 1.13 0.97 0.61 0.01

TiO2 0.00 0.03 0.00 0.04 0.01 0.02 0.00 1.32 0.00 0.00

SO2 0.00 0.00 0.02 0.60 0.04 0.02 0.06 0.04 0.01 0.28 FeO 0.28 0.04 0.17 0.36 0.33 0.74 0.32 0.21 0.24 0.02 MnO 0.05 0.02 0.09 0.09 0.13 0.04 0.07 0.03 0.03 0.01 BaO 0.00 0.01 0.03 0.04 0.00 0.02 0.00 0.00 0.15 0.00 Total 98.82 99.03 97.02 96.37 98.68 97.05 100.94 98.00 101.24 50.83 100 S-14 S-14 S-14 S-16 S-2 S-5 S-5 S-7 S-7 S-7 Sample # 1942.5 1942.5 1942.5 2056 2085.4 2003 2003 1537 1537 1537 mineral apat. apat. apat. apat. apat. apat. apat. apat. apat. apat.

Na2O 0.03 0.08 0.00 0.01 0.05 0.10 0.14 0.25 0.00 0.35 F 2.21 2.40 1.79 0.36 0.90 1.79 1.36 1.23 1.67 1.21

K2O 0.21 0.02 0.31 0.00 0.01 0.12 0.14 0.01 0.00 0.04 MgO 0.36 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Al2O3 0.51 0.09 3.13 0.00 0.00 0.09 0.03 0.02 0.01 0.00

P2O5 39.55 41.49 36.91 35.08 40.66 38.64 41.27 41.10 41.74 39.81

SiO2 1.46 0.34 0.74 0.30 0.08 0.31 0.25 0.25 0.26 0.38 CaO 53.79 55.94 52.76 53.45 55.02 51.37 54.26 54.94 55.29 53.75 Cl 0.53 0.52 0.62 0.58 0.10 0.83 0.59 0.56 0.10 0.69

TiO2 0.38 0.15 0.01 0.00 0.00 0.01 0.02 0.00 0.00 0.02

SO2 0.08 0.00 0.03 0.00 0.02 0.11 0.12 0.06 0.01 0.38 FeO 0.65 0.24 3.16 0.10 0.00 0.28 0.33 0.23 0.00 0.30 MnO 0.07 0.12 0.17 0.07 0.00 0.17 0.16 0.22 0.08 0.28 BaO 0.00 0.04 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.05 Total 99.84 101.43 99.71 89.94 96.84 93.83 98.68 98.88 99.15 97.27

Table C3 (continued)

S-7 S-7 S-8 S-8 S-8 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1537 1537 1833 1833 1833 1610 1610 1836.5 1836.5 2140.7 mineral apat. apat. apat. apat. apat. biot. biot. biot. biot. biot.

Na2O 1.16 0.13 0.24 0.31 0.10 0.09 0.05 0.06 0.11 0.06 F 0.95 1.97 2.43 3.72 1.63 0.04 0.10 0.10 0.10 0.24

K2O 0.03 0.03 0.17 0.26 0.00 6.39 8.89 7.53 6.39 8.17 MgO 0.00 0.00 0.05 0.13 0.10 8.74 11.75 9.05 8.82 11.89

Al2O3 5.90 0.00 0.03 0.09 0.06 18.46 12.27 18.22 26.70 16.65

P2O5 30.20 41.86 40.04 39.36 41.49 0.00 0.00 0.01 0.00 0.90

SiO2 11.77 0.04 0.18 0.35 0.20 48.54 28.16 37.59 39.06 35.69 CaO 44.56 55.01 52.95 52.81 55.58 0.11 0.05 0.46 0.84 0.85 101 Cl 0.58 0.19 0.64 0.59 0.22 0.01 0.16 0.15 0.11 0.09

TiO2 0.00 0.03 0.05 0.04 0.05 0.02 2.38 1.89 1.66 2.46

SO2 0.11 0.07 0.24 0.08 0.04 0.02 0.02 0.01 0.03 0.04 FeO 0.35 0.17 0.84 0.82 0.24 11.39 14.91 16.12 12.37 18.34 MnO 0.18 0.24 0.28 0.30 0.26 0.10 0.13 0.09 0.16 0.14 BaO 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Total 95.80 99.73 98.14 98.89 99.96 93.92 78.87 91.29 96.36 95.52

RL-10 RL-10 RL-2 RL-4 RL-4 RL-4 RL-4 RL-4 S-10 S-10 Sample # 2140.7 2303 1982 2117.5 2117.5 2117.5 2117.5 2117.5 2121.5 2121.5 mineral biot. biot. biot. biot. biot. biot. biot. biot. biot. biot.

Na2O 0.06 0.08 0.12 0.11 0.10 0.12 0.00 0.03 0.18 0.07 F 0.02 0.13 0.15 0.24 0.18 0.11 0.00 0.22 0.22 0.20

K2O 9.05 7.77 8.82 9.26 9.27 9.62 7.65 8.72 8.48 9.15 MgO 11.19 13.39 12.31 12.92 13.13 12.50 13.57 12.50 12.95 11.62

Al2O3 16.79 16.22 16.14 16.18 15.96 15.80 16.44 14.91 16.85 15.82

P2O5 0.00 0.02 0.00 0.05 0.03 0.01 0.02 0.00 0.00 0.01

SiO2 36.43 36.12 37.13 37.10 37.54 37.61 35.95 39.97 38.73 33.53 CaO 0.22 0.56 0.07 0.33 0.36 0.16 0.07 0.06 0.16 0.12 Cl 0.14 0.14 0.21 0.15 0.15 0.15 0.12 0.09 0.16 0.17

TiO2 2.34 2.39 2.46 2.46 2.49 2.42 2.17 2.28 2.95 2.86

SO2 0.01 0.03 0.02 0.03 0.02 0.05 0.02 0.03 0.03 0.03 FeO 18.27 17.66 16.60 15.83 16.85 16.35 17.08 16.99 16.31 16.12 MnO 0.10 0.15 0.15 0.22 0.16 0.14 0.20 0.16 0.14 0.19 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 94.61 94.67 94.19 94.88 96.24 95.05 93.28 95.96 97.17 89.88

Table C3 (continued) 102 S-10 S-14 S-14 S-16 S-16 S-16 S-16 S-5 S-5 S-5 Sample # 2121.5 1942.5 1942.5 2056 2056 2056 2056 2003 2003 2003 mineral biot. biot. biot. biot. biot. biot. biot. biot. biot. biot.

Na2O 0.03 0.09 0.07 0.15 0.15 0.14 0.18 1.18 0.10 0.11 F 0.00 0.00 0.26 0.30 0.25 0.35 0.39 0.06 0.08 0.09

K2O 6.16 9.05 7.34 7.48 8.50 9.09 9.09 7.25 9.03 8.55 MgO 13.24 13.30 12.47 14.42 10.72 14.19 12.22 12.00 13.59 14.06

Al2O3 17.30 15.26 16.41 15.58 12.49 14.28 15.72 14.13 14.82 15.19

P2O5 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.00 0.03 0.00

SiO2 34.44 37.23 26.77 37.19 28.15 36.20 35.30 28.57 31.87 37.15 CaO 0.55 0.30 0.68 0.08 0.04 0.01 0.03 0.25 0.24 0.08 Cl 0.17 0.15 0.16 0.09 0.15 0.15 0.14 0.09 0.15 0.16

TiO2 3.02 2.71 1.78 3.43 3.59 4.01 3.34 1.88 2.47 3.04

SO2 0.02 0.00 0.05 0.02 0.00 0.01 0.00 0.00 0.01 0.03 FeO 16.78 17.41 14.93 15.93 16.65 15.93 16.73 11.75 13.59 15.26 MnO 0.12 0.15 0.08 0.13 0.15 0.13 0.14 0.16 0.15 0.07 BaO 0.00 0.00 0.00 0.00 0.11 0.16 0.00 0.00 0.00 0.00 Total 91.84 95.65 81.01 94.82 80.97 94.64 93.31 77.32 86.12 93.80

S-5 S-5 S-5 S-5 S-5 S-5 S-7 S-7 S-7 S-7 Sample # 2003 2003 2003 2003 2003 2003 1537 1537 1537 1537 mineral biot. biot. biot. biot. biot. biot. biot. biot. biot. biot.

Na2O 0.25 0.11 0.10 0.09 4.46 0.16 0.11 0.03 0.06 0.10 F 0.06 0.09 0.07 0.19 0.16 0.20 0.22 0.11 0.08 0.06

K2O 7.93 6.02 8.48 6.74 5.19 8.09 9.35 9.23 9.69 9.65 MgO 15.59 15.83 13.27 14.87 11.94 13.90 13.08 12.14 12.44 12.22

Al2O3 15.73 17.43 14.89 17.83 17.90 15.28 15.59 15.49 15.62 15.48

P2O5 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00

SiO2 36.82 33.76 37.20 35.31 39.38 36.70 37.66 37.75 37.82 36.62 CaO 0.26 0.13 0.31 0.11 0.44 0.17 0.05 0.03 0.02 0.01 Cl 0.14 0.13 0.16 0.10 0.09 0.07 0.17 0.14 0.00 0.17 103

TiO2 2.23 2.87 3.38 2.11 2.12 3.69 3.27 3.07 3.40 3.62

SO2 0.02 0.00 0.00 0.01 0.01 0.03 0.01 0.03 0.03 0.02 FeO 14.32 16.06 14.66 15.97 14.87 15.42 16.31 16.38 16.58 16.86 MnO 0.19 0.11 0.18 0.15 0.14 0.11 0.18 0.16 0.21 0.16 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 93.56 92.56 92.71 93.49 96.70 93.83 96.02 94.57 95.96 94.97

Table C3 (continued)

S-7 S-7 S-7 S-7 S-7 S-7 S-8 S-8 S-8 S-8 Sample # 1537 1537 1537 1537 1537 1537 1833 1833 1833 1833 mineral biot. biot. biot. biot. biot. biot. biot. biot. biot. biot.

Na2O 0.11 0.13 0.14 0.10 0.12 0.08 0.22 0.21 0.08 0.07 F 0.22 0.16 0.31 0.12 0.29 0.23 0.02 0.05 0.16 0.07

K2O 9.27 8.96 7.49 9.28 7.67 9.58 8.86 8.92 9.65 6.35 MgO 12.41 11.17 14.41 12.59 9.27 12.95 13.56 14.66 14.20 15.56

Al2O3 15.31 18.91 16.93 15.13 10.09 16.24 15.06 15.24 18.78 20.11

P2O5 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.02

SiO2 37.14 38.58 36.74 36.66 24.49 38.45 37.30 37.71 36.09 34.46 CaO 0.06 0.08 0.17 0.03 0.04 0.02 0.00 0.02 0.00 0.17 Cl 0.17 0.15 0.10 0.15 0.16 0.19 0.16 0.18 0.13 0.14

TiO2 3.49 2.21 2.13 4.10 2.88 3.16 3.98 4.23 2.59 2.46

SO2 0.03 0.02 0.04 0.03 0.03 0.01 0.02 0.05 0.03 0.00 FeO 16.54 12.97 15.69 15.86 13.85 16.05 16.14 14.37 12.78 13.55 MnO 0.13 0.16 0.17 0.11 0.11 0.18 0.07 0.14 0.27 0.17 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.06 0.00 0.00 Total 94.87 93.50 94.32 94.16 69.00 97.14 95.43 95.84 94.77 93.12

S-8 S-8 S-8 RL-14 S-16 S-2 S-5 S-7 S-7 S-7 Sample # 1833 1833 1833 1985 2056 1182.5 2003 1537 1537 1537 104 mineral biot. biot. biot. calc. calc. calc. calc. calc. calc. calc.

Na2O 0.15 0.13 0.14 0.02 0.06 0.03 0.06 0.00 0.03 0.05 F 0.00 0.04 0.11 0.00 0.00 0.07 0.00 0.00 0.00 0.18

K2O 9.60 9.87 9.47 2.00 0.05 0.00 0.02 0.03 0.00 0.02 MgO 13.09 13.53 14.20 0.09 0.41 0.01 0.00 0.08 0.00 0.12

Al2O3 18.61 18.60 18.41 1.71 0.11 0.04 0.02 0.02 0.03 0.00

P2O5 0.00 0.00 0.00 0.08 0.08 0.13 0.08 0.09 0.08 0.12

SiO2 35.61 35.54 36.78 2.84 0.46 0.07 0.09 0.14 0.24 0.39 CaO 0.03 0.02 0.02 55.52 60.71 61.25 62.82 60.29 61.18 60.66 Cl 0.15 0.16 0.16 0.00 0.00 0.00 0.01 0.00 0.00 0.02

TiO2 2.36 2.51 2.84 0.10 0.00 0.00 0.00 0.00 0.02 0.00

SO2 0.06 0.02 0.02 0.27 0.31 0.03 0.00 0.01 0.09 0.36 FeO 15.25 15.28 14.15 0.93 0.16 0.01 0.00 0.09 0.08 0.24 MnO 0.09 0.14 0.13 0.31 0.08 0.66 0.00 0.94 0.22 0.09 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 Total 95.00 95.85 96.44 63.88 62.42 62.29 63.10 61.72 61.97 62.24

Table C3 (continued)

RL-2 RL-4 RL-4 RL-4 RL-4 RL-4 RL-4 RL-4 RL-4 RL-4 Sample # 1982 2117.5 2117.5 2117.5 2117.5 2117.5 2117.5 2117.5 2117.5 2117.5 mineral chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor.

Na2O 0.02 0.03 0.03 0.00 0.00 0.02 0.00 0.03 0.01 0.00 F 0.00 0.00 0.10 0.06 0.00 0.12 0.00 0.12 0.00 0.00

K2O 0.01 0.01 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.01 MgO 15.67 21.24 21.20 21.25 20.57 20.41 19.85 20.59 21.26 20.84

Al2O3 18.57 20.98 20.93 21.74 20.86 20.80 21.18 21.20 21.27 20.81

P2O5 0.00 0.00 0.01 0.00 0.00 0.02 0.00 0.00 0.00 0.00

SiO2 26.58 27.57 27.64 27.49 27.28 27.28 26.68 27.19 27.55 27.76 CaO 0.04 0.03 0.02 0.01 0.03 0.02 0.04 0.04 0.01 0.01 Cl 0.01 0.01 0.01 0.01 0.01 0.02 0.00 0.02 0.00 0.00

TiO2 0.01 0.06 0.07 0.13 0.07 0.08 0.08 0.07 0.13 0.06 105

SO2 0.01 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 FeO 24.81 18.19 18.16 17.93 18.30 18.55 18.80 19.13 18.29 18.46 MnO 0.30 0.23 0.22 0.27 0.17 0.15 0.28 0.23 0.25 0.20 BaO 0.00 0.05 0.00 0.07 0.02 0.10 0.00 0.02 0.00 0.00 Total 86.03 88.42 88.41 88.95 87.33 87.57 86.92 88.65 88.78 88.15

S-10 S-10 S-10 S-10 S-14 S-14 S-16 S-16 S-16 S-16 Sample # 2041 2041 2121.5 2121.5 1942.5 1942.5 2056 2056 2056 2056 mineral chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor.

Na2O 0.00 0.10 0.00 0.05 0.02 0.03 0.20 0.01 0.06 0.04 F 0.00 0.02 0.00 0.04 0.00 0.06 0.02 0.07 0.09 0.00

K2O 0.05 0.03 0.05 0.04 0.02 0.02 0.00 0.02 0.02 0.01 MgO 13.77 18.04 17.97 17.65 19.43 18.05 16.90 18.86 19.08 16.09

Al2O3 17.21 20.90 15.45 18.80 18.31 19.01 17.62 19.83 18.29 15.54

P2O5 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.01 0.01 0.00

SiO2 22.22 25.98 17.83 28.19 21.94 23.82 25.84 27.59 27.51 21.97 CaO 0.15 0.01 0.07 0.61 0.12 0.10 0.25 0.11 0.07 0.07 Cl 0.02 0.02 0.00 0.11 0.02 0.01 0.00 0.01 0.00 0.01

TiO2 0.00 0.01 0.17 2.60 0.06 0.08 0.03 0.07 0.04 0.06

SO2 0.00 0.01 0.00 0.02 0.05 0.00 0.02 0.03 0.00 0.00 FeO 25.90 22.95 15.21 18.86 17.26 18.40 23.83 20.82 20.40 21.42 MnO 0.56 0.27 0.16 0.11 0.22 0.20 0.20 0.31 0.25 0.25 BaO 0.11 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.00 0.04 Total 79.99 88.35 66.91 87.09 77.45 79.79 84.91 87.75 85.82 75.51

Table C3 (continued)

S-16 S-2 S-2 S-2 S-2 S-2 S-2 S-5 S-5 S-7 Sample # 2056 1182.5 1182.5 1182.5 1182.5 2085.4 2085.4 2003 2003 1537 mineral chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. 106

Na2O 0.07 0.00 0.00 0.02 0.00 0.04 0.06 0.01 0.02 0.00 F 0.00 0.04 0.00 0.00 0.00 0.13 0.14 0.04 0.00 0.10

K2O 1.69 0.01 0.02 0.00 0.01 0.62 0.03 0.00 0.02 0.17 MgO 15.07 19.57 19.27 19.85 18.33 16.87 17.46 21.10 20.95 18.51

Al2O3 16.83 22.78 21.88 23.02 21.54 19.66 19.49 20.40 20.52 17.55

P2O5 0.01 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

SiO2 31.50 25.87 26.48 26.29 26.61 26.18 27.27 27.39 27.48 29.71 CaO 0.50 0.04 0.05 0.04 0.01 0.09 0.11 0.18 0.09 0.11 Cl 0.08 0.01 0.03 0.01 0.00 0.01 0.00 0.01 0.01 0.00

TiO2 1.94 0.08 0.10 0.07 0.10 0.09 0.25 0.02 0.03 0.15

SO2 0.01 0.00 0.00 0.01 0.00 0.02 0.00 0.01 0.01 0.00 FeO 18.77 18.99 19.55 19.50 20.77 22.98 22.80 16.29 16.79 20.59 MnO 0.15 0.15 0.16 0.16 0.21 0.24 0.19 0.26 0.21 0.25 BaO 0.00 0.02 0.00 0.04 0.00 0.00 0.00 0.00 0.00 0.00 Total 86.61 87.60 87.53 89.00 87.59 86.93 87.79 85.72 86.13 87.14

S-7 S-7 S-7 S-7 S-8 S-8 S-8 S-8 RL-10 RL-10 Sample # 1537 1537 1537 1537 1833 1833 1833 1833 1836.5 2303 mineral chlor. chlor. chlor. chlor. chlor. chlor. chlor. chlor. epid. epid.

Na2O 0.01 0.03 0.04 0.01 0.04 0.00 0.00 0.04 0.00 0.01 F 0.07 0.00 0.09 0.03 0.00 0.00 0.00 0.10 0.04 0.00

K2O 0.00 0.91 0.00 0.02 0.02 0.01 0.11 0.04 0.01 0.01 MgO 20.11 18.05 13.13 14.58 23.54 20.96 22.95 24.03 0.01 0.00

Al2O3 20.81 16.39 13.32 13.76 20.82 18.53 19.30 20.89 23.41 24.23

P2O5 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.03 0.04

SiO2 27.42 29.93 17.48 18.79 28.19 28.79 29.12 28.54 37.26 37.58 CaO 0.03 0.19 0.02 0.03 0.08 0.06 0.03 0.00 23.04 23.07 Cl 0.00 0.03 0.00 0.01 0.01 0.00 0.00 0.00 0.00 0.00

TiO2 0.07 0.83 0.03 0.04 0.03 0.10 0.08 0.07 0.35 0.04

SO2 0.01 0.00 0.03 0.00 0.00 0.01 0.02 0.00 0.01 0.00 107 FeO 18.57 20.58 18.21 17.32 13.04 19.63 14.91 13.56 12.01 11.61 MnO 0.29 0.17 0.25 0.24 0.33 0.14 0.23 0.26 0.11 0.26 BaO 0.12 0.00 0.06 0.00 0.13 0.00 0.07 0.00 0.00 0.00 Total 87.50 87.12 62.68 64.85 86.22 88.26 86.83 87.55 96.30 96.86

Table C3 (continued)

RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 RL-14 RL-4 S-10 Sample # 1985 1985 1985 1985 1985 1985 1985 1985 2117.5 2041 mineral epid. epid. epid. epid. epid. epid. epid. epid. epid. epid.

Na2O 0.00 0.02 0.03 0.00 0.02 0.00 0.00 0.14 0.01 0.00 F 0.00 0.07 0.00 0.05 0.00 0.08 0.12 0.16 0.00 0.02

K2O 0.00 0.01 0.00 0.00 0.06 0.11 0.05 0.50 0.00 0.01 MgO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00

Al2O3 22.71 22.96 24.82 29.49 25.95 23.75 23.69 31.27 24.96 21.69

P2O5 0.02 0.02 0.04 0.06 0.04 0.01 0.03 0.03 0.22 0.03

SiO2 33.64 37.50 37.82 38.48 38.20 37.49 37.49 39.08 36.59 34.82 CaO 23.40 23.51 23.77 23.90 23.57 23.76 23.38 24.10 22.39 22.98 Cl 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.03 0.05 0.00

TiO2 0.03 0.00 0.05 0.04 0.00 0.00 0.02 0.03 0.03 0.01

SO2 0.00 0.01 0.02 0.01 0.00 0.03 0.02 0.01 0.07 0.00 FeO 13.53 12.78 10.64 5.86 10.22 11.73 12.07 3.60 10.08 12.72 MnO 0.00 0.09 0.00 0.11 0.00 0.04 0.02 0.14 0.44 0.09 BaO 0.00 0.02 0.03 0.00 0.03 0.15 0.13 0.00 0.00 0.00 Total 93.33 96.99 97.22 98.01 98.10 97.15 97.03 99.10 94.86 92.38

S-10 S-10 S-16 S-16 S-16 S-2 S-2 S-7 S-7 S-7 Sample # 2041 2041 2056 2056 2056 1182.5 2085.4 1537 1537 1537 mineral epid. epid. epid. epid. epid. epid. epid. epid. epid. epid.

Na2O 0.01 0.01 0.10 0.08 0.19 0.04 0.10 0.05 0.00 0.03 108 F 0.03 0.18 0.00 0.07 0.00 0.05 0.05 0.00 0.03 0.03

K2O 0.01 0.00 0.00 0.02 0.06 0.00 0.02 0.11 0.05 0.05 MgO 0.00 0.00 0.14 0.01 0.00 0.00 0.00 0.24 0.06 0.01

Al2O3 29.87 25.42 20.63 19.70 26.39 22.24 23.45 17.34 24.04 23.05

P2O5 0.03 0.09 0.05 0.00 0.02 0.05 0.01 0.02 0.07 0.01

SiO2 38.64 35.62 36.77 35.95 37.60 37.58 36.80 36.54 36.69 36.87 CaO 24.17 23.25 22.30 22.27 23.16 23.07 23.06 21.78 23.00 22.23 Cl 0.03 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01

TiO2 0.01 0.09 0.25 0.21 0.03 0.10 0.12 0.18 0.34 1.20

SO2 0.01 0.00 0.01 0.01 0.02 0.02 0.00 0.01 0.02 0.01 FeO 5.30 9.64 14.78 15.86 9.44 14.09 12.15 18.33 11.62 11.81 MnO 0.08 0.08 0.11 0.15 0.10 0.04 0.13 0.04 0.24 0.53 BaO 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 98.33 94.40 95.16 94.34 97.01 97.30 95.89 94.66 96.17 95.82

Table C3 (continued)

S-8 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1833 1610 1610 1610 1610 1610 1610 1836.5 2303 2303 mineral epid. qtz. qtz. qtz. qtz. qtz. qtz. qtz. qtz. qtz.

Na2O 0.04 0.19 0.12 0.03 0.03 0.33 0.20 0.02 0.04 0.03 F 0.00 0.00 0.00 0.05 0.03 0.04 0.00 0.00 0.00 0.08

K2O 0.05 0.00 0.00 0.01 0.04 0.00 0.01 1.11 0.10 1.99 MgO 0.00 0.00 0.00 0.01 0.00 0.01 0.01 2.11 0.05 3.53

Al2O3 24.43 0.43 0.39 0.29 0.02 0.03 0.19 5.21 0.07 3.33

P2O5 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00

SiO2 38.03 96.20 97.92 98.08 98.67 98.00 98.17 84.42 98.32 83.18 CaO 23.36 0.07 0.08 0.12 0.03 0.11 0.05 0.22 0.01 0.15 Cl 0.00 0.03 0.01 0.00 0.00 0.00 0.00 0.02 0.01 0.05

TiO2 0.00 0.02 0.07 0.07 0.00 0.08 0.00 0.40 0.01 0.41

SO2 0.02 0.03 0.00 0.00 0.00 0.00 0.00 0.21 0.01 0.00 109 FeO 10.91 0.09 0.02 0.03 0.12 0.11 0.04 3.86 0.11 3.79 MnO 0.03 0.00 0.00 0.00 0.02 0.02 0.00 0.01 0.00 0.02 BaO 0.01 0.01 0.00 0.07 0.01 0.05 0.00 0.00 0.01 0.13 Total 96.88 97.07 98.61 98.74 98.96 98.83 98.68 97.59 98.75 96.68

RL-10 RL-14 RL-14 RL-4 RL-4 RL-4 S-14 S-16 S-2 S-5 Sample # 2303 1985 1985 2117.5 2117.5 2117.5 1942.5 2056 2085.4 2003 mineral qtz. qtz. qtz. qtz. qtz. qtz. qtz. qtz. qtz. qtz.

Na2O 0.00 0.04 0.04 0.01 0.00 0.01 0.01 0.04 4.23 0.02 F 0.18 0.00 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00

K2O 0.04 0.08 0.02 0.00 0.00 0.01 0.00 0.00 0.09 0.01 MgO 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00

Al2O3 0.10 0.74 0.18 0.06 0.00 0.02 0.03 0.02 7.80 0.04

P2O5 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.04 0.00

SiO2 96.25 97.30 98.60 98.43 98.36 99.37 96.49 98.14 84.05 94.69 CaO 0.06 0.15 0.10 0.03 0.00 0.06 0.02 0.01 1.59 0.00 Cl 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.01 0.00

TiO2 0.01 0.01 0.01 0.02 0.00 0.00 0.02 0.04 0.10 0.01

SO2 0.03 0.00 0.02 0.00 0.02 0.08 0.00 0.03 0.01 0.00 FeO 0.11 0.21 0.15 0.17 0.21 0.00 0.06 0.26 0.03 0.00 MnO 0.01 0.00 0.02 0.00 0.01 0.00 0.00 0.02 0.00 0.00 BaO 0.04 0.00 0.00 0.00 0.01 0.01 0.00 0.01 0.03 0.00 Total 96.84 98.53 99.22 98.75 98.63 99.56 96.65 98.58 97.97 94.79

Table C3 (continued)

S-7 S-7 S-7 S-7 S-7 RL-26 S-8 RL-10 RL-10 RL-10 Sample # 1537 1537 1537 1537 1537 2001 1686.8 1610 1610 1610 mineral qtz. qtz. qtz. qtz. qtz. seric. seric. sph. sph. sph. 110

Na2O 0.04 0.00 0.04 0.00 0.04 0.31 0.14 0.02 0.06 0.06 F 0.00 0.00 0.00 0.00 0.03 0.07 0.00 0.00 0.03 0.37

K2O 0.02 0.02 0.00 0.01 0.00 8.98 9.16 0.01 0.02 0.04 MgO 0.01 0.00 0.00 0.01 0.00 1.78 1.21 0.00 0.00 0.00

Al2O3 0.01 0.02 0.09 0.04 0.04 27.80 35.71 0.89 1.17 0.92

P2O5 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.09 0.07

SiO2 99.71 89.73 98.61 98.02 98.71 36.02 49.46 29.60 29.59 29.42 CaO 0.01 0.00 0.00 0.00 0.01 0.03 0.01 27.91 27.38 27.35 Cl 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02

TiO2 0.04 0.00 0.02 0.02 0.02 0.52 1.36 37.06 37.38 38.09

SO2 0.00 0.01 0.02 0.02 0.02 0.01 0.02 0.01 0.00 0.00 FeO 0.17 0.05 0.00 0.00 0.02 1.39 1.09 1.70 1.22 1.86 MnO 0.00 0.01 0.04 0.02 0.00 0.02 0.04 0.03 0.12 0.02 BaO 0.00 0.01 0.00 0.03 0.08 0.09 0.08 0.00 0.00 0.00 Total 100.04 89.86 98.82 98.16 98.95 77.04 98.28 97.26 97.07 98.21

RL-10 RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 RL-2 RL-4 RL-4 Sample # 1836.5 1836.5 2303 1985 1985 1985 1985 1982 2117.5 2117.5 mineral sph. sph. sph. sph. sph. sph. sph. sph. sph. sph.

Na2O 0.07 0.03 0.00 0.05 0.04 0.01 0.01 0.00 0.04 0.01 F 0.17 0.12 0.13 0.10 0.00 0.23 0.00 0.00 0.10 0.07

K2O 0.02 0.09 0.45 0.02 0.08 0.06 0.00 0.00 0.01 0.00 MgO 0.00 0.00 0.11 0.00 0.00 1.27 0.00 0.00 0.00 0.00

Al2O3 2.85 3.35 1.15 1.62 0.72 1.19 1.13 2.19 3.53 2.12

P2O5 0.06 0.03 0.03 0.09 0.06 0.06 0.08 0.10 0.25 0.06

SiO2 30.34 30.10 30.62 30.37 30.42 32.25 30.52 25.49 30.50 30.39 CaO 28.65 28.25 28.01 28.33 28.65 27.18 28.40 26.52 28.69 28.75 Cl 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00

TiO2 35.54 34.29 37.81 36.00 38.29 35.07 37.52 33.62 32.56 36.03

SO2 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.00 111 FeO 0.68 0.70 1.03 2.19 1.13 1.50 1.08 1.11 1.48 0.92 MnO 0.02 0.00 0.03 0.01 0.00 0.03 0.00 0.04 0.02 0.06 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 98.42 96.97 99.38 98.79 99.40 98.87 98.77 89.07 97.18 98.41

Table C3 (continued)

RL-4 S-10 S-14 S-14 S-14 S-16 S-16 S-2 S-5 S-7 Sample # 2117.5 2041 1942.5 1942.5 1942.5 2056 2056 1182.5 2003 1537 mineral sph. sph. sph. sph. sph. sph. sph. sph. sph. sph.

Na2O 0.00 0.01 0.00 0.00 0.09 0.05 0.03 0.87 0.01 0.05 F 0.00 0.00 0.16 0.00 0.07 0.40 0.35 0.19 0.20 0.17

K2O 0.04 0.00 0.03 0.05 0.04 0.03 0.02 0.04 0.03 0.09 MgO 0.00 0.00 0.05 0.04 0.33 0.00 0.01 0.00 0.46 0.00

Al2O3 4.50 1.06 2.58 2.22 1.49 4.83 4.15 4.30 0.14 2.62

P2O5 0.47 0.04 0.11 0.05 0.04 0.03 0.00 0.07 0.04 0.04

SiO2 30.69 30.32 30.65 26.82 31.03 30.58 23.50 33.67 30.30 30.20 CaO 28.87 28.39 28.51 26.68 27.99 28.60 26.45 26.08 27.64 28.27 Cl 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00

TiO2 33.68 37.82 35.19 32.87 36.61 32.69 28.43 32.98 39.12 35.57

SO2 0.00 0.01 0.01 0.02 0.00 0.00 0.00 0.03 0.01 0.00 FeO 0.29 0.95 1.01 1.48 1.09 0.83 2.31 0.72 0.34 0.93 MnO 0.00 0.07 0.03 0.01 0.06 0.00 0.00 0.02 0.03 0.03 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Total 98.55 98.66 98.34 90.24 98.84 98.03 85.25 98.97 98.33 97.98

S-7 S-7 S-8 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 Sample # 1537 1537 1833 1610 1836.5 1836.5 1836.5 2140.7 2140.7 2303 mineral sph. sph. sph. zeo/clyy zeo/clyy zeo/clyy zeo/cly zeo/cly zeo/cly zeo/cly

Na2O 0.01 0.01 0.12 0.34 0.17 0.10 0.13 1.42 6.20 9.79 112 F 0.23 0.10 0.31 0.00 0.00 0.24 0.19 0.00 0.15 0.05

K2O 0.20 0.06 1.79 0.18 0.92 0.33 0.20 0.02 0.04 0.00 MgO 0.04 0.00 0.15 4.00 2.46 0.93 0.63 0.00 0.00 0.00

Al2O3 3.23 1.85 8.48 21.13 28.42 25.72 31.19 18.64 14.12 28.74

P2O5 0.22 0.02 0.04 0.01 0.02 0.01 0.00 0.00 0.02 0.00

SiO2 30.56 30.48 33.36 54.74 55.45 52.22 51.45 62.98 53.21 51.06 CaO 28.20 27.89 22.63 2.80 3.06 2.04 1.85 8.30 7.66 4.87 Cl 0.01 0.00 0.00 0.06 0.03 0.01 0.01 0.00 0.01 0.00

TiO2 34.79 36.63 29.18 0.02 0.01 0.01 0.09 0.00 0.00 0.00

SO2 0.02 0.01 0.02 0.01 0.01 0.05 0.02 0.00 0.00 0.00 FeO 1.10 1.01 0.87 1.54 0.72 2.16 1.74 0.05 0.03 0.01 MnO 0.05 0.00 0.03 0.03 0.07 0.00 0.01 0.00 0.00 0.01 BaO 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.01 Total 98.67 98.07 96.98 84.85 91.33 83.81 87.53 91.43 81.46 94.54

Table C3 (continued)

RL-10 RL-10 RL-10 RL-10 RL-10 RL-10 RL-14 RL-14 RL-14 RL-14 Sample # 2303 2303 2303 2303 2303 2303 1985 1985 1985 1985 mineral zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly

Na2O 0.12 0.18 7.62 3.08 0.54 0.04 0.17 0.06 2.78 0.09 F 0.03 0.05 0.00 0.00 0.13 0.00 0.27 0.00 0.08 0.00

K2O 0.06 0.37 0.00 0.02 0.43 0.21 1.41 0.56 0.53 0.88 MgO 0.00 0.01 0.00 0.00 0.00 0.01 0.72 0.88 0.19 1.00

Al2O3 18.74 16.94 31.03 16.25 16.91 17.05 31.03 21.43 22.10 19.88

P2O5 0.02 0.00 0.00 0.00 0.02 0.00 0.00 0.02 0.00 0.00

SiO2 64.68 65.71 50.96 59.38 59.22 58.33 43.20 37.20 35.60 37.93 CaO 8.52 6.48 4.00 7.93 6.30 6.17 2.16 1.93 11.09 2.18 Cl 0.01 0.00 0.00 0.00 0.00 0.00 0.02 0.01 0.01 0.08

TiO2 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.03 0.00

SO2 0.00 0.00 0.00 0.00 0.00 0.02 0.02 0.00 0.00 0.00 113 FeO 0.32 0.01 0.04 0.00 0.01 0.00 1.21 0.31 0.30 0.34 MnO 0.00 0.00 0.00 0.04 0.00 0.00 0.00 0.02 0.00 0.02 BaO 0.08 0.00 0.10 0.05 0.12 0.16 0.03 0.03 0.02 0.00 Total 92.57 89.77 93.76 86.76 83.69 81.98 80.27 62.45 72.72 62.41

S-10 S-10 S-10 S-16 S-16 S-16 S-16 S-16 S-16 S-16 Sample # 2041 2041 2121.5 2056 2056 2056 2056 2056 2056 2056 mineral zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly

Na2O 1.60 1.76 0.15 0.33 0.04 0.10 0.48 0.27 0.27 0.22 F 0.00 0.00 0.08 0.19 0.00 0.00 0.02 0.14 0.00 0.00

K2O 0.90 0.01 0.86 0.04 0.04 0.11 0.01 0.08 0.15 0.13 MgO 0.00 0.00 1.48 0.01 0.02 2.71 0.00 3.08 2.58 2.39

Al2O3 21.96 27.24 26.65 14.86 15.87 16.96 15.37 21.14 17.38 20.82

P2O5 0.00 0.00 0.15 0.00 0.01 0.01 0.01 0.01 0.00 0.01

SiO2 53.87 47.31 47.17 52.24 60.93 41.49 52.16 50.36 43.10 44.98 CaO 9.43 9.70 2.94 8.33 8.75 2.49 8.26 3.62 3.16 2.76 Cl 0.00 0.00 0.13 0.00 0.00 0.18 0.01 0.03 0.25 0.12

TiO2 0.01 0.00 0.02 0.01 0.01 0.01 0.00 0.01 0.01 0.01

SO2 0.01 0.00 0.07 0.01 0.04 0.00 0.01 0.03 0.02 0.02 FeO 0.01 0.13 0.33 0.04 0.04 0.69 0.02 0.45 0.58 0.85 MnO 0.04 0.01 0.01 0.00 0.02 0.00 0.00 0.01 0.02 0.05 BaO 0.00 0.11 0.01 0.00 0.00 0.00 0.00 0.01 0.00 0.03 Total 87.84 86.28 80.05 76.06 85.77 64.75 76.36 79.24 67.52 72.39

Table C3 (continued)

S-16 S-16 S-16 S-2 S-2 S-2 S-2 S-2 S-2 S-5 Sample # 2056 2056 2056 1182.5 1182.5 1182.5 1182.5 1182.5 1182.5 2003 mineral zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly

Na2O 0.23 0.27 0.07 0.15 0.21 0.16 0.10 0.13 0.08 0.15 114 F 0.00 0.00 0.00 0.10 0.03 0.12 0.00 0.00 0.00 0.00

K2O 0.05 0.00 0.07 0.69 0.29 0.84 0.89 0.83 0.81 0.46 MgO 0.00 0.00 1.67 3.06 0.48 3.20 2.20 1.82 2.77 0.07

Al2O3 10.88 16.29 18.33 23.57 17.07 25.57 30.42 27.88 32.71 17.97

P2O5 0.00 0.03 0.00 0.00 0.00 0.02 0.01 0.01 0.03 0.01

SiO2 42.09 58.29 39.54 54.10 55.67 56.38 50.59 44.79 49.03 31.06 CaO 7.32 7.80 2.37 2.56 5.33 2.37 2.38 2.89 2.59 2.71 Cl 0.00 0.00 0.14 0.01 0.02 0.03 0.02 0.02 0.03 0.04

TiO2 0.00 0.00 0.02 0.01 0.00 0.01 0.01 0.03 0.02 0.02

SO2 0.02 0.00 0.01 0.02 0.01 0.03 0.02 0.02 0.05 0.01 FeO 0.00 0.03 1.12 1.52 0.01 1.83 0.68 0.67 0.69 0.64 MnO 0.00 0.02 0.00 0.02 0.01 0.02 0.01 0.00 0.00 0.00 BaO 0.00 0.16 0.08 0.11 0.11 0.00 0.00 0.00 0.07 0.00 Total 60.59 82.88 63.43 85.94 79.22 90.59 87.34 79.09 88.88 53.14

S-5 S-5 S-5 S-5 S-7 S-7 S-7 S-7 S-7 S-8 Sample # 2003 2003 2003 2003 1537 1537 1537 1537 1537 1833 mineral zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly zeo/cly

Na2O 0.23 0.42 0.14 0.23 0.32 0.02 0.25 0.09 0.10 2.04 F 0.00 0.00 0.00 0.09 0.00 0.07 0.07 0.16 0.20 0.05

K2O 0.34 2.07 0.34 0.66 0.30 0.16 0.41 0.09 0.16 5.90 MgO 1.43 1.39 3.29 2.97 3.50 5.29 3.09 3.34 3.15 1.87

Al2O3 16.19 32.49 18.51 14.09 23.46 25.59 28.81 23.34 22.48 19.16

P2O5 0.02 0.00 0.01 0.01 0.00 0.02 0.00 0.01 0.02 0.01

SiO2 37.13 48.39 51.76 31.26 50.97 52.40 50.93 53.74 54.17 49.73 CaO 2.94 2.20 2.46 1.88 2.75 2.52 2.49 3.19 2.69 2.03 Cl 0.02 0.02 0.04 0.10 0.08 0.04 0.07 0.04 0.05 0.03

TiO2 0.03 0.00 0.00 0.00 0.02 0.02 0.02 0.02 0.01 0.00

SO2 0.01 0.00 0.02 0.00 0.04 0.02 0.03 0.08 0.03 0.03 FeO 0.53 0.35 0.49 0.47 0.96 1.21 1.07 2.01 1.26 0.33 115 MnO 0.02 0.00 0.00 0.02 0.00 0.00 0.00 0.04 0.00 0.00 BaO 0.10 0.00 0.00 0.00 0.01 0.02 0.09 0.00 0.00 0.03 Total 58.99 87.35 77.08 51.77 82.43 87.37 87.33 86.15 84.35 81.22

Table C3 (continued)

S-8 S-8 Sample # 1833 1833 mineral zeo/cly zeo/cly

Na2O 0.12 0.48 F 0.00 0.13

K2O 0.23 0.20 MgO 3.09 2.64

Al2O3 23.54 24.73

P2O5 0.03 0.00

SiO2 53.38 53.55 CaO 3.14 3.49 Cl 0.04 0.02

TiO2 0.05 0.02

SO2 0.02 0.03 FeO 0.80 0.52 MnO 0.02 0.01 BaO 0.03 0.00 Total 84.49 85.81 116

Table C4: Sulfide, telluride, and native metal analyses

RL-7 S-11 S-2 S-2 S-2 S-2 S-7 S-7 S-7 S-8 Sample # 1989.5 2017 1718 2038 2038 2066 1518 1537 1537 1678

mineral born. born. born. born. born. born. born. born. born. born.

As 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00

Cu 64.01 66.53 62.78 64.32 62.48 57.17 58.09 67.33 71.06 66.09

Fe 6.10 5.93 8.07 6.99 9.81 11.20 11.60 5.71 4.86 8.13

S 28.78 24.52 26.31 24.94 26.01 27.48 27.21 24.45 22.80 25.07

Te 0.00 0.00 0.00 0.02 0.02 0.02 0.01 0.00 0.03 0.00

Ag 0.02 0.02 0.09 0.03 0.06 0.66 0.05 0.01 0.08 0.09

Pb 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Au 0.15 0.34 0.00 0.39 0.18 0.00

Ni 0.02 0.00 0.02 0.00 0.04 0.03 0.01 0.00 0.04 0.00

Co 0.02 0.01 0.00 0.00 0.00 0.01 0.02 0.01 0.00 0.00

Se 0.00 0.07 0.29 0.00 0.00 0.37 0.43 0.13 0.26 0.26

Total 98.94 97.07 97.72 96.65 98.42 97.34 97.59 97.64 99.11 99.63 117

S-8 S-8 S-8 S-8 S-8 U-2 U-4 U-4 RL-7 RL-7 Sample # 1678 2592 2592 2592 2592 445.7 451 451 1989.5 1989.5

mineral born. born. born. born. born. born. born. born. chc. chc.

As 0.00 0.00 0.00 0.00 0.00 0.00 0.57 0.00 0.01 0.00

Cu 67.42 63.85 65.71 61.52 68.59 60.59 68.60 66.29 74.76 73.03

Fe 7.07 9.00 6.99 9.16 5.72 9.37 4.93 4.63 0.05 0.11

S 24.99 25.66 24.77 24.90 24.14 26.62 24.11 23.34 21.02 21.90

Te 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.03

Ag 0.07 0.08 0.04 0.42 0.05 0.04 0.07 0.10 0.00 0.00

Pb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Au 0.00 0.31 0.06 1.95 0.00 0.07 0.18

Ni 0.00 0.00 0.01 0.01 0.00 0.00 0.01 0.03 0.00 0.00

Co 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Se 0.71 0.00 0.45 0.00 0.22 0.00 0.00 0.14 0.31 0.00

Total 100.29 98.90 98.02 97.96 98.71 96.68 98.28 94.52 96.17 95.26

Table C4 (continued)

S-11 S-7 RL-10 RL-10 RL-10 RL-10 RL-9 S-18 S-18 S-18 Sample # 2017 1537 2140.7 2140.7 2172.5 2452 2023 1995 1995 1995

mineral chc. chc. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr.

As 0.00 0.00 0.01 0.01 0.04 0.02 0.00 0.01 0.00 0.02

Cu 75.95 76.35 33.36 42.56 33.08 33.19 33.59 34.03 31.64 33.81 118

Fe 0.49 0.74 30.19 24.66 29.32 28.83 29.21 29.77 25.14 30.06

S 20.46 21.85 34.35 31.67 34.33 34.34 34.27 34.10 34.07 34.73

Te 0.02 0.00 0.01 0.00 0.02 0.00 0.03 0.01 0.01 0.00

Ag 0.01 0.02 0.02 0.01 0.00 0.01 0.00 0.00 0.01 0.00

Pb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Au 0.15 0.16 0.31 0.00 0.00 0.00 0.00 0.06

Ni 0.00 0.00 0.00 0.02 0.00 0.01 0.00 0.01 0.00 0.01

Co 0.00 0.02 0.00 0.00 0.00 0.00 0.00 0.02 0.02 0.00

Se 0.00 0.31 0.07 0.00 0.00 0.35 0.00 0.00 0.00 0.13

Total 96.92 99.29 98.15 99.09 97.10 96.74 97.10 97.96 90.90 98.82

S-18 S-2 S-2 S-2 S-2 S-2 S-2 S-7 S-7 S-8 Sample # 1995 1601 1601 1601 1718 2038 2066 1518 1518 1678 mineral cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. cpyr.

As 0.02 0.00 0.00 0.03 0.00 0.00 0.01 0.00 0.00 0.02

Cu 33.73 33.86 34.28 33.60 33.36 33.43 32.80 33.79 33.66 34.05

Fe 29.66 29.41 30.00 29.27 28.95 29.17 29.21 30.13 28.44 29.67

S 34.58 33.91 34.40 34.08 33.43 34.20 33.98 34.31 33.75 34.28

Te 0.01 0.05 0.02 0.00 0.00 0.01 0.00 0.03 0.00 0.00

Ag 0.00 0.07 0.01 0.02 0.01 0.03 0.00 0.01 0.00 0.00

Pb 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Au 0.00 0.02 0.00 0.00 0.00 0.33 0.17 0.24 0.18 0.41

Ni 0.02 0.00 0.00 0.02 0.00 0.02 0.01 0.00 0.01 0.00

Co 0.00 0.00 0.02 0.01 0.00 0.00 0.00 0.01 0.00 0.01

Se 0.35 0.19 0.04 0.39 0.42 0.00 0.12 0.76 0.00 0.36

Total 98.36 97.51 98.75 97.42 96.16 97.18 96.31 99.27 96.05 98.80 119

Table C4 (continued)

S-8 S-8 S-8 S-8 S-8 U-4 RL-7 S-18 S-2 RL-7 Sample # 1678 1678 2592 2592 2592 482.3 2017.5 1995 2038 2017.5

mineral cpyr. cpyr. cpyr. cpyr. cpyr. cpyr. elec. elec. elec. gal.

As 0.00 0.00 0.00 0.00 0.01 0.05 0.00 0.00 0.00 0.00

Cu 33.18 33.72 33.44 34.07 33.35 33.11 0.13 1.91 1.06 0.70

Fe 29.15 29.20 29.48 29.20 29.72 28.18 0.09 0.07 0.24 0.60

S 34.42 34.16 34.27 34.18 34.31 33.96 0.05 0.62 0.18 10.29

Te 0.01 0.00 0.01 0.03 0.00 0.00 0.03 0.02 0.00 0.05

Ag 0.02 0.00 0.04 0.05 0.01 0.02 13.61 19.37 13.33 0.02

Pb 0.00 0.00 0.00 0.00 0.00 0.08 0.00 0.06 82.38

Au 0.25 0.00 0.22 0.09 0.00 84.67 67.90 86.27 0.30

Ni 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00

Co 0.01 0.00 0.00 0.00 0.00 0.02 0.00 0.00 0.01 0.02

Se 0.22 0.09 0.07 0.28 0.20 0.37 0.00 0.00 0.00 6.29

Total 97.28 97.17 97.51 97.89 97.62 95.70 98.66 89.88 101.15 100.64

S-8 U-2 S-7 S-7 RL-10 RL-10 RL-10 RL-10 RL-10 S-2 Sample # 2592 445.7 1518 1518 2140.7 2140.7 2172.5 2172.5 2452 1601

mineral gal gal hess. hess. pyr. pyr. pyr. pyr. pyr. pyr.

As 0.01 0.00 0.01 0.00 0.00 0.01 0.01 0.00 0.00 0.02

Cu 39.96 4.51 0.37 0.27 0.04 0.00 0.03 0.00 0.08 0.00

Fe 4.57 1.12 0.00 0.01 45.86 46.58 46.34 45.99 46.17 45.86

S 19.87 11.65 0.21 0.28 53.40 53.52 52.99 52.86 53.47 53.29

Te 0.01 0.09 35.51 35.74 0.01 0.03 0.00 0.00 0.03 0.03 120

Ag 0.03 0.08 58.73 59.17 0.00 0.00 0.02 0.00 0.01 0.00

Pb 35.99 81.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

Au 0.07 0.05 0.48 0.00 0.00 0.00 0.00 0.16 0.03 0.00

Ni 0.00 0.03 0.02 0.01 0.00 0.05 0.01 0.03 0.00 0.00

Co 0.00 0.00 0.01 0.00 0.04 0.10 0.05 0.02 0.04 0.00

Se 0.11 4.39 0.82 0.22 0.00 0.41 0.36 0.27 0.31 0.29

Total 100.62 103.05 96.15 95.70 99.35 100.70 99.81 99.33 100.15 99.49

Table C4 (continued)

S-2 S-8 Sample # 1601 2592

mineral pyr. sylvan.

As 0.00 0.00

Cu 0.04 4.39

Fe 43.29 0.84

S 52.73 0.51

Te 0.00 28.91

Ag 0.00 40.98

Pb 0.00 0.00

Au 0.06 20.71

Ni 0.00 0.00

Co 0.00 0.00

Se 0.27 0.00

Total 96.40 96.33 121