208 sxe of Eames, ne Be ey Hem any tne Center for Mineral Resources, Department of Geosciences, Unicersty of Arsona, 1040 East Fourth Street, Tueson, Arison $5 Porphyry Deposits: Characteristics and Origin of Hypogene Features Enic SeepOR®,! : Joun H. Diutes, Department of Geosciences, Wilkinson Hall 104, Oregon State University, Corvallis Oregon 97331-5506 JOHN M, Paorrern, Ja, Profjett Exploration, Inc, PO, Box 772066, Engle Bier, Alaska 99577 Maaco. Ervavpt, wlronmental Sciences, Stanford University, Stanford, California 94305-2115 Department of Ceologival and & LUKAS ZURCHER, WILLIAM J. A. STAVAST, DAVID A. JOHNSON, AND MARK D. BAnTON: Center for Mineral Resources, Department of Geosciences, University of Arizona, 1040 East Fourth Street, Tucson, Arizona Abstract Porphyry deposits anguably represent the most economically important cass of nonferrous metalic mineral resources. These magmatic hydrothermal deposits are charaeteri2ed by sulfide and oxide ore minerals in vein- lets and dissemination in large volumes of hydrothermally altered rock (up to 4 km). Porphyry deposits ocenr within maginatc belts worldwide and are spatially, temporally, and genetically related to hypabyssal diontc 10 tic intrusons that are porphyritic and that commonly have an aplitic groundmass, The preponderance are Bhaneroroic and most typical Conoote in age, whic reflects the domtnance of magmas rated to sb- duction tectonics and preservation in young rocks Porphyry depoats ae here grouped into five clases based on the economically Jominant metal nthe da- posits: Au, Cu, Mo, W. and Sn. For each porphyry class, the major metal concentration is enriched by a factor 100 to 1,000 relative to unmiaeralied rocks oa simular composton, The inss of porphyry depots ranges cover four orders of magnitude, with the mean size of a deposit ordered Cu > Mo ~ Au > Sn > W. Hydrother- ral alteration is a guide to ore because it produces a series of mineral assemblages both within the ore zones and extending into a larger volume (>10 kn) of adjacent rock. The typically observed temporal evolution in Porphyry ore is from eany, high-temperature biotite » K-foldspar assemblages (potassi alteration) to mus- couite = chlorite assemblages (sericitic alteration) to low-temperature, clay-bearing assemblages (advanced argillic and intermediate argilic alteration), which is consistent with progressively greater acidity and higher fluid-to-ock ratios of fluids, prior to their eventual neutralization. Although advanced argilc alteration is rel- atively late inthe deposits where itis superimposed on ore and potassi alteration, inthe deposits where ad- vanced argillic alteration (especially as quartz + alunite) is preserved spatially above ore and commonly ex- tending to the paleosurface, it ean form tary, broadly contemporaneous with potassic alteration. In contrat assemblages of Na plagioclase-ctinolte(sodie-caleie alteration) and albite-epidote-chloite-earbonate (propy- ltt altoration) form from a fuid with low acidity and commonly lick ore minerals. Geolege, fluid inclusion, and isotopic tracer evidence indicate magmatic fluids dominate acidic alteration associated with ore anc non ‘magmatic uid dominate sodic-calec and propylitic alteration, Veins contain a large percentage of ore miner- alsin porphyry deposits and include high-temperature sugary-textured quartz veinlets associated with ore min- Cras and botte-fldspar alteration nd moderate temperature pyc vein ith sete envelopes, “Tho compositions of igneous rocks related to porphyry deposts cover tually the entire range observed for present-day volcanic rocks. Mineralizing porphyries are intermediate to silicic (=56 we % SiOx) and their aplte-textured groundmass represents crystallization as a result of abrupt depressutiation of water-rich ‘magma; however, small volumes of ultramafic to intermediate rocks inckuding lamprophyres, exhibit 2 close spatial and temporal relationship to porphyry ore formation in some deposit “The understanding of porphyry systems depends critically on determination of the relative ages of events and correlition of ages of vents in florentlnctons, hich i part depend on expose. ystems withthe prea est degree and continuity of exposure generally have been tilted and dismembered by postmineraliztion de- formation, Most porphyry intrusions associated with ore are small-volume (<0.5 km?) dikes and plugs that were emplaced at depths of 1 to 6 km, though some were omplaced deeper. Deposits commonly occur in clusters above one or more cupolas on the roof of an underlying intermediate to silicic intrusion. Altered rocks extend "upward toward the paleosurface, downward into the granitoid intrusion from which the porphyry magana ane aqueous fluids were generated, and laterally for soveral kilometers on either side of a deposit. The underlying, * Corresponding author: e-mail, seedorff@geoarizonaedu 251 85721-0077252 SEEDOMEF ET AL. magma chambers operated as open systems via mafic magma recharge, wall-rock assimilation, ersstilization, and intevsion, but mineralizing intrusions dd not erupt Present-day distributions of hydrothermally altered cock and sulfide-oxide ore minerals are time-integrated products of fracture-guided fluid flow. We distinguish three spatial configurations characteristic of all five classes of porphyry deposits, the first of hil has two variant: (1a} serictc alteration largely les above and beside potase alteration in a bell or hood-shaped volume that narrows upward, as at Chorolque, Henderson, snd San Manuel-Kalamazoo; (Ib) sericitie alteration is presont with advanced argilic alteration, and the latter in some cases forms a broader zone at higher levels in the system, as at Batu Hijau, Cerro Rico, and Fl Sal- vador; (2) intense sercitie and local advanced argilic alteration cus through enclosing potasic alteration near ore but also extends above polassc alteration in an upwardly expanding zone with an overall geometry ofa fun- nel, as at Butte, Chugoicantata, and Resolution; 3) sodic-alc, in addition to potasss alteration fs widespread the center of the system and has an inverted cup-shaped velume under potassc alteration, with fingerike rojections of sodie alteration extending up through the overlying orebody. as at Yerington. Metal grades are Eire related to where ore minerals orginally prciptate and the degree of subsequent remobilzation. Pe~ cio of meta isa fonction of mulpie vanes, fypallyinsding tomnporatre acy nd ion and a fide availabilty. Hence, the shape of an orebody depends on the number and postions of mineralizing versus barten intrusions the proportions, shapes, and orientations of veins, lodes, or breccias; and pressure-tempera ture changes and wall woe reaction that govern or nineral stab. ‘Geockronology and thermal models suggest that durations of hydrothermal activity of 50,000 to 500,000 yr are common, but several large porphyry Cu deposits include multiple events spanning several milion years Crosscutting relationships, including offset veins, provide definitive evidence for the relative ages of hy. 10 km and time scales of up to 5-my. duration, which we refer to as space-time evolution. Silitoe and Perellé (2005) review the tectonic and magmatic evolution of porphyry de~ posits in the South American Cordillera over greater dis- tances and longer time scales. During the past 25 yr new an- alytical chemical methodology and physical modeling techniques have expanded the scientific approaches to un- derstanding chemical and physical processes that produce porphyry ore deposits. We take a more traditional approach, and due to space limitations only briefly summarize the key Conclusions from studies of stable isotopes, Muid inclusions, etsy Meg ors aaa vow ee eee 3 Bitee, ee 1m Phanerozoic gneous Provinces g + Porphyry Deposit ° oe 233 radiometric ages, and the trace elemen anc radiogente tope studies ‘see review by Hedenquist anc! Richards, 1995), The overall purpose of this review is to sumamarize the cvs rent data and the understanding of processes that form por- plvty ore deposits, with an emphasis on dliversity and com= plexity of these systems, : Geologic Framework and Context In the early 1900s, the only known porphyry deposits were Cu rich, and these were ‘mostly desori edas ‘dosemin ated Cu deposits. According to Titley (1997), the first formal use of the term porphyry Ca deposit may have been by Eanmnons (1918), A few Mo-rich members became recognized about the same time. Porphyry deposits ere intimately associated with magnnatic ares Pormed slong, consuming plate margins (Silver 192 1976), although the association with ares breaks down for ver- tain deposits (Sillitoe, 1980, 2000; Westra and Keith, 1981 Because of their broad distribution in space and time, por- phyries can be used to monitor Earth evolution (Meyer, 1981), Classification scheme ‘The porphyry deposit type is divided into five classes based on the bridcipal contained metals: porphyry Au, porphyry Cu, hhyry Mo, porphyry W, and porphyry Sn. The classes are Rorhor divided into subclasses that are based on compositions of intrusive rocks, major and by-product metals, and other distinctive features (Table 1), as flly discussed in a later sec- Global-scale distribution in space and time ‘The global spatial distribution of porphyry de ally outlines Phanerozoic orogenic belts (Fig. 1). Since the ap- pearance of the Economic Geology Seventy-Fifth Anniver- sary Volume, many new deposits have been discovered; these include discoveries in the Andes (eg, Escondida Nort, 2,500 5.000 Kilometers Fic. 1. Global distibution of porphyry deposits, showing distribution of Phanerozoic igneous provinces, selected por phys ditriete, and porphyry belvous ld = Td 20840 = NO PEON = AN SOIR Y9OOS MON = ANSN FOOEOGY MON = NN OUASUNIE MON Smug = Vo Sap = Ip SIRUM|OD I = 9y weve © Zy SEY © ay seRIMAaNEEY isan endea = ON pn = eqn. sons usau9 (3) ‘dopo ‘AN SEEDOREF EY AL. an y@0:9 fenson sesdeiour, 2A, mp ong, oa same KN ONY PUNE OR 4 709, 209, ‘waoen no He ‘oo ners aoe Tyion Wen RAVES yap Jayhod —biod aya “eiod “elie Gaydon sued utuacs omracaxory neo “oniewog, canaapaae on cas Wining aa ‘hog taking 254 SUL weed Lying 0) SUS TORT TALSEEDORF ET AL, gl z +2 3° 3 45 Be 6 || 6* al 83 a3, i ile Hs roman =| z. ieee Boeken z re pat ne é 4 Haas ropa yoo § 2 Smee 6 2 et ae bs 3 O Sinan 2 Hct onenm-camcne-ce Creare PRN een cs) , =) Se ectnete Lego t > Sameera fe Porgy Gold roan? Fic. 8. Gradetonnage dagrams tion, verve, resources, and Togtog sales Sbclases outlines include all date Compostons of selected igneous rocks sealed by 1,000 6 for copper. Exploitation of porphyry deposits benefited from key tec nological developments (Fig, 4), including the suocess of Dane! Jecklings bulk tonnage aper-pit mining method 'n 1908, coupled with advances in miling Cu ores and in smelt ing and refining (Navin, 1978). The economic and wing ire ir also strongly influence scientific studies of porphyry deposits asihastated inthe teling (Fig. 4 by speci sues cere nomic Geology, a few key books, and collections of pax pers on porphyry deposits. Hydrothermal Alteration and Mineralization ‘been dealt with in detail; but the jacent rocks of known composi- fon briefly dismissed, or even i= Ores and structure have important changes which a tion have suffered are too o correctly indicated. —-W. Lindgren, 1002 ‘The host rocks of porphyry deposits are hydrothermally al- tered to form characteristic types of gangue ‘mineral wall-rock \sferation, and they are mineralized by sulfide and oxide siner- 2 Together these consttate specific processes and elects chat Characterize and unite deposits of the porphyry type and thatwe refer to as alteration ant ‘mineralization, Wall-rock alteration we Mencralization studies are relevant because they provide ne i cpr for copper inl opens inchug ae prospect) lst on revues Sm ae those ae cased bythe scheme show "gen pnb peti to 1 Ads m agin fis of dost Tiger and Wedepot (1961) and tungsten. Datapoints are mitures of produc- ceept fora few outlier da points. Average Jimits on the pressure-temperature conditions and composition er fuids and understanding of the controls on ore deposi, tion, Furthermore, they represent the most easily recognized and broadly spatially distributed guides used in the exploration for new ore deposits. About the time of the golden anniversary ‘of Economic Geology in 1955, economic geologists benefited from deeper open-pit exposures, where effects of hypogen? processes could be more easily understood: During te period, Pro entfon was paid to alteration and mineralization and the Fist syntheses onthe topic were written (Schwartz, 1947; Bur ham, 1962; Creasey, 1966; ‘Nakovnik, 1968). The physical- ‘hemical foundation of economic geology was strengthen uperimental al theoretical studies in ydrtereal fds 0 erating in soveral seminal review papers (Barton and Skinner 1967, Meyer and Hemley, 1967; Barton, 1970) that subse- only were updated and supplemented (eg, Barton and Renner, 1979; Baxton etal, 1981a; Einaudi et a, 2000) ‘Terminology Veins and their alteration envelopes seeettato but informally adopt names based on the vein-fil ing utdths of 91 m for lodes, Lm to Lem for veins, and 7 ov #28 vtnlets, Typed veins in porphyry deposits have widths of less han few centimeters nd most are only a few milime- ~ ters wide. We use the term veinPORPHYRY DEPOSITS: CHARACTERISTICS AND ORIGIN OF HYPOGENE FEATURES Ujina, Gaby, Spence, and Toki, Chile; Antapaccay, Peru), Southwest Pacific (e.g., Grasberg and Batu Hijau, Indonesia; Boyongan, and Tampakan, Philippines), Australia (Cadia, New South Wales), and North America (eg., Resolution or Magma Porphyry, Arizona; Mount Milligan, British Colum- bia; Pebble Copper, Alaska). Especially since the mid-1990s, central Asia has become the latest new frontier of porphyry exploration with the discovery of Oyu Tolgei, Mongolia “the distribution of ages of Phanerozoic deposits (Fig. 2) is consistent with earlier recognition of the dominance of Ceno- zoe and Mesozoic deposits (Meyer, 1981; Titley and Beane, 1981; Hunt, 1991). More deposits of Paleozoic age, however, are beng covered and developed, fr exemple the Atd belt of Eurasia (Watanabe and Stein, 2000; Perell6 et al. 2001; Yakubchuk et al, 2001, 2005), and the Tasman belt of ‘Australia (Perkins et al, 1995) ‘Archean and Proterozoic examples of porphyry deposits ‘ocaur in Fennoscandia and Canada (Gaél and Isohanni, 1879; Fraser, 1990, Wanainen et al, 2008), although most have small to moderate quantities of contained metal. In addition, there are probable porphyry Cu occurrences in the Pan-African oro- gen in Egypt, Jordan, and Saudi Arabia (eg., Burgath et al. 1984; Jaques et a, 1999; Bekbit et al., 2001). Possible Precam- brian porphyry Mo deposits include those in Ontario and Fin- land (Gaal and Isohanni, 1979; Nunes and Ayres, 1982) “The global distribution of pomphyry deposits is a complex function of numerous factors, including the uneven distribution of magmatism through tne tha is related to changes in plate configurations (eg, Burke and Kidd, 1980), The Phanerozoic distribution, however, is in large part explained in terms of preservation and exposure of deposits. Porphyry deposits form Felatively near the surface, typically from 1- to 6-km depth and some deeper than 6 km, and are subject to subsequent tecton- ism, erosion, and burial (eg, Staude and Barton, 2001). Mass-balance perspectives Estimates of ore reserves and mineral resources, though critically dependent on the availability of data, mining method, 255 and economic and social inputs, are useful for first-order com- parison of deposits (Fig, 3). For any one class of deposits, the sizes vary by two to three orders of fnagnitude, The average grade of the major metal inal five class-s of porphyry deposits isenriched by 100- to 1,000-fold compared to the average con- centration in unmineralized rocks of a similar composition. ‘The sizes of porphyry deposits of all classes range over about four orders of magnitude, and both the size of the largest deposits and the mean size of a deposit in a elas type cally vary in the order Cu > Mo ~ Au > Sn > W (Fig. 3). The largest porphyry Cu deposits have two orders of magnitude more Cu than deposits of other classes. In contrast, the lgest pop Mo depots have contain es fo than sev- eral porphyry Cu deposits, and the largest porphyry Au de- posits contain less Au than many porphyry Er deposits (Fig 3). ‘Many dozens of other major and trace elements are con- centrated, redistributed, or depleted within the much larger Volume of rock (~10-100 times) affected by hydrothermnal aids. The total mass transfer in porphyry systems is, there- fore, enormous. Alter magmatism and sedimentation, por- phyry hydrothermal systems play a key role in redistributing Elements in continental crust within the Phanerozoic Economic and historical perspectives Porphyry deposits currently annually contribute in excess of US8d0 billion globally. principally af Cu, Mo, Au. and Ag (U.S. Geological Survey, 2005); the economic impact of por- phyry deposits is similar im magnitude to aluminum end is Enly exceeded by iron and stel. Porphyries are the most im- portant source of Cu and are the source of nearly all Mo. Cer- tain porphyry Cu deposits are important producers of Au or ‘Ag but not Sn or W. Porphyry Cu and Mo deposits played leading roles in economic growth of the American Westin the first half of the twentieth century (Hyde, 1998). More re- cently, they have been important in establishing industrial feconoinies in Chile and Peru and could have a similar impact in countries such as Mongolia No. of Deposits 12 Porphyry Tin 1 Porphyry Tungsten ‘5 Porphyry Molybdenum Porphyry Copper Age (Ma) ¢.2. Histogram of ages by cases of porpiyr, keyed to porphyry belts.PORPHYRY DEPOSITS. CHARACTERISTICS AND ORIGIN OF HYPOGENE FEATURES we i 2 S| Fl pst rs act] tecoe Bu & coe t : 1 ws sed spice SS Ste vagenagay [Fre 204 RE) in Technology a tncnzescon ct 2 ences ee o> Sivenentin emcees Trin ie” ee * eT, sonewnte aman wn = Pe natin perry relapse Selected Deposits ‘Known dopoctsabveoped (Noah Arcica} cosmo mrevan Mai dacoveros ‘an Sn te err Pree tae) ‘sem oa Tin lana ns neat Te ‘at Sine Se See on son) om ns pase toe (Canifal and South America Cucistinee wo wicenNs ‘Como Cokorado Mariage tet (Spence) en ormanye ory 8 percomnsy “Cnt Industry ssn scepeg ents “Sones mame ae ovules TESTERS ona CMRI. ony MESTEM: Cobban IES, [Companies] gi SS ox Reams Neeima cay : Science [Coneapis and approaches} sre qe sun eee yet ene tin eR TT nmi an Sie rept oa [RBIS BESS and COTE of ae oa Locke IGE 7 Baum ‘(i978) ‘Whew & Seteter i bigest nce a aa as mate 10 ‘m0 eo yey ‘0 xo Fc. & Crphiel summary ofthe histo cntst of porplyry depos in the 2 cent. Myo cteges ae word gala nd ches conn ape aml lodeni al poe pedo, mig nd protang tsi Bon cnanory and development cops, tenis n industry. sot approaches, and nab books and calecions of Sipes, Principal soutces ae Mastard 1976, US. Hureas Of Mines (070, Sagat and Lawl 1070, Samonor and Peary 8, Navin 178), Lacy UBDD, Silos 158 aor 1905), Tiley (1007, and pd (1208) Near thet tom of dram, 106 13)" rler to the lntertonl Colgel Congres that wa eld a Wesingtn, D.C. 108, the proce thar ere pubs ter contained papers sucha Emmons (1038), “Ore Depot W States 15) the258 Veins may have distinet, mesoscopically visible wall-rock ul- teration envelopes (also known as Selvages or halos) that are generally developed symmetrically on either side of a vein as {result of diffusion of reactive components from vein into wall rock in pore fluids. Vein envelopes in porphyry systeins can have a single mineral assemblage or can develop zoned convelopes (Meyer and Hemley, 1967). Zoned envelopes are ‘well described from the Main Stage lodes (Sales and Meyer, 1948) and porphyry Cu-(Mo) pre-Main Stage veins (Meyer, 1965; Brimhall, 1977) at Butte, Montana, from sericitic, sodic-calcic, and endoskarn assemblages at _Yerington Nevada (Dilles and Einaudi, 1982), and in a range of settings at Henderson, Colorado (Carten et al, 1988b; Seedorff and Einaudi, 2004). “Textures: Hydrothermal alteration produces textures that are distinct from replacement textures developed in the magmatic environment, For example, secondary (hydro- thermal) biotite after magmatic hornblende commionly con- sisteof randomly oriented aggregates of fine-grained biotite (shreddy biotite) intermixed with rutile, magnetite, and an- hydrite (Carson and Jambor, 1974; Brimhall et al., 1985). Destruction of hornblende can range from partial to com- plete, but the outline of the former amphibole site may be Qrell preserved, In contrast, magmatic reaction textures produced by a shift from stability of hornblende to biotite in the presence of melt produces a single, optically contin~ uuous crystal of bictite that overgrows and variably replaces horablende. “The degree of textural preservation depends on the envi- ronment of formation and the intensity of alteration. For ex- ample, if hydrothermal biotite forms readily in both igneous feldspar and mafic mineral sites, or if hydrothermal feldspar forms readily in both igneous mafic and feldspar sites, then the igneous texture wil be obscured or destroyed. In some cases, textural destruction may be characteristic of envelopes fon certain types of veins: in other cases, it may develop in {reas where alteration is so intense that adjacent alteration ‘envelopes overlap about closely spaced veins or due to low of fluids along fractures that are not resolved mesoscopically (Gustafson and Hunt, 1975; Titley, 1982b). Distinction between mineral assemblages and mineral asso- ciations: A hydrothermal mineral assemblage is group of ‘minerals that appears to be stable together at the mesoscopic scale and to have formed contemporaneously, Assemblages are geochemical significant because they can be used to e3- timate restricted physico-chemical conditions of formation assuming loeal equilbrium theemodynamies, The concept of lassemblages is equally applicable to vein fillings and alter- ation envelopes. The complete mineral assemblage includes Ml sninera’s ies, safe, oxide, and other gangue phases such as anhydrite or titanite. ‘A hydrothermal mineral association is a group of minerals that occurs together, regardless of whether the minerals formed at the same time oF in local equilibrium. Mineral as- sociations are commonly reported in the geologic literature (and sometimes are mistakenly used as assemblages). For ex ample, alteration zones (e., potassic zones) and sulfide ‘ones (eg, pyrite zone) are based on individual minerals or fon mineral associations. Although these associations have Value in exploration and science, by themselves they have SEEDORPP ET Mt lite utility for understanding of dynamics because they are the result of time-integration of a mumber of events Principal variables ‘Temperature: Thermal decline drives hydrothermal Aids toward supersaturation with respect o many ore and alter- ation minerals (Hemley et al,, 1992; Redmond et al., 2004), Hydrothermal systems operate from ebove magmatic solidus temperatures (~750°-600°C, depending on magmatic compo- Aitee) tol temperatures (200°C), The exposed portions of rnany porphyry systems formed over at least 2 400°C range of temperatures (e.g,, ~600"-200°C; eg, Wilson et a., 1980: Uleeh et al., 2001). One of the persistent controversies in po phyry deposits is the temperature of hypogene ore deposition, Which may take place at the higher end of the temperature range in some deposits (e.g, Gustafson and Hlunt, 1975; Bas- {oe, 1978; Carten et al, 1988b; Dilles et al, 2000a) or be co fined to the lower end in others (e.g., Ttley and Beane, 1981; Hedenquist et al., 1998; Redmond et al. 2004), Pressure: Fluid pressure is a key variable because at <1.5 bars low-salinity aqueous fluids undergo brine-vapor phase separation (Henley and MeNabb, 1978) due to fluid immis bility below a solvas, which in turn ean have a pronounced fect on metal partitioning and solubility (Hemley and Hunt, 1992; Hemley et al, 1998, Heinrich et al., 1999). Pressure is a function not only of depth but also of the hydrologic regime. Overpressured and lithostatic conditions occur near magma, but hydrostatic conditions dominate and characterize all tem- peratures ~<375°C (eg., Fournier, 1999). Silica solubility fo is a strong function of pressure at >375°C (Fournier and. Potter, 1982), as well as salinity (Xie and Walther, 1993), Quartz exhibits retrograde solubility at pressures of <800 bars, and the change from lithostatic to hydrostatic pressure is allkely cause for formation of abundant quartz veins (Rusk and Reed, 2002; Redmond et al., 2004). Pressure, however, Is commonly poorly known, Geologic reconstructions, both Stratigraphic and structural, are generally used to determine depth, and these lead to pressure estimates when coupled “with interpretation of rock fabrics and vein characteristics, Geochemical methods for estimating pressure include fluid inclusion petrology (e.g.. Roedder and Bodnar, 1980; Heden- Gquist et a, 1998) and mineral barometry (eg, Anderson and Sinith, 1985). Horizons of immiscible phase separation (“boil ing’) have been documented in porphyry deposits as well, but they do not have a direet temporal and spatial link to ore de- position (eg., John, 19594, Gustafson and Quiroga, 1995; Redmond el 2001) Chemical composition: The bulk chemical composition per- tinght tow roekalteraion is dictated by the magmati fuid composition (see below), wall-rock composition, and the pro- pportions of these two which is also known as the luid-to-rock fatio. Hence, wall-rock composition partly dictates alteration and ore mineral assemblages, particularly at low fluid-to-rock ratios typical of weak alteration. Wall-rock composition can buffer pi through reactions with carbonate or feldspar or ox- ‘dation state through reaction with iron-bearing minerals, or- ganie matter, or reduced pore fluids. Because neutralization and reduction of sulfate to sulfide directly promotes sulfide inineral deposition (Barton, 1970), wall-rock reaction may be ‘coupled with ore deposition. Wall rocks also can supply keyPORPHYRY DEFOSITS. CHARACTERISTICS heinical constituents necessary to form hydrothermal miner- als, such as matic or oxide minerals supplying iron for Cu-Fe sullides or feldspars supplying ahumninum For epidote or gar= net (cg, Carten et al. 1088b; Seedorff, 1984; Zweng and Clark, 1905; Maher, 1996) Wail-rock effects commonly are visible at the seale of dis- seminated grains to veins but also atthe scale of ore zones ancl entire deposits, such as transitions between silicie and potassic alteration (Carten et al., 1988) and contacts between silicic ‘and mafic rocks (¢.g., Metz and Rose, 1966; Manske and Paul £2002). Considering the differing behavior of metals ke Cu and Mo, contrasting wall-rock compositions affeet metal depos tion, zoning, and ratios in otherwise similar deposits. There~ fore, wall-rock effects have practical consequences for explo ration targeting, ore reserve calculation, and grade control Composition of external fluids: The types of external fluids that participate in porphyry hydrothermal systems include saline formation waters related to coeval or older evaporite basins (eg., Dilles et al., 1992, 1995; Battles and Baston, 1995), dilute meteoric waters (e.g,, Sheppard et al, 1971; Selby et al., 2000), and seawater (e-g., Osatenko and Jones, 1976, Chivas et al, 1984). The paleohydrologic environment may be deduced by integrating evidence from regional geo- logic relationships, system-scale alteration map patterns, and the mineralogy and orientations of fracture patterns, mineral compositions, fluid inclusion compositions, stable isotope analyses, and studies of chemical gains and losses (e.g, Bow- ‘man et al, 1987; Dilles et al, 2000). Structural style: The three most common end members of structural styles of porphyry deposits are (1) the disseminated style, in which mineralization occurs predominantly in thin veinlets (Tiley, 1982b); (2) the lode style (Einaudi, 1977; AND ORIGIN OF HYPOGENE FEATURES 259 1982a}; and (3) the breccia style (Sillitoe, 1955; Skewes and Stern, 1996). The structural styles in part control the egree, of involvement and timing of ingress of external ‘luis We use lode style loosely to refer to any of the major char= acteristics of zoned base metal veins such as the Main Stage at Butte (Meyer et al., 1968). Lodes are characterized by the presence of major throughgoing Cu-rich veins, minerals that are characteristic of high- and very high sulfidation states, and intense seriitic alteration with silicfieation anor advanced angilic alteration (regardless of geometry). Other types of late veins and lodes, e.g. those with weak serieitic or intermediate argilic envelopes, are specifically excluded from the lode des ignation herein Wall-rock alteration-mineralization assemblages Alteration types are groups of mineral assemblages that formed in geochemically similar environments (Meyer and Hemley, 1967). Alteration types can be divided into those hosted by aluminosilicate rocks (most igneous, meta-igneous, metavoleanie, and clastic sedimentary rocks) and. those formed in carbonate and ultramafic rocks (Barton et al., 19912). Here we eoncentrate on the aluminosilicate rocks but address the consequences of encountering mafic host rocks. Four broad processes or types of chemical reactions are re- sponsible fr the principal stertion types in porphyry env ronments: (1) volatile addition (propylitic alteration) (2) hy- deolysis (sericitic, advanced argilic, and intermediate argilic alteration); (3) alkali exchange (e-., potassic and sodic-calcic alteration); and (4) addition of silica (silicic alteration). Wo outline a geologic and geochemical framework for al- teratonsmineaation assemblages and aeration pes that ‘ean be used descriptively by geologists (Tables 2, 3), without “To 2 List of Mineral Abbnevitins a alte elite lg plaiose fe tiie dias daspore pe prntotte Sts Raminun phosphatase minerals ck Dy pne Get wth) oe date Preph rope shin lone topade ee une mph Snphibte door damortente Nea deehronte ik ase cn enargte nile nde) date sp pide Sh shelte ih nko fonte {rz sorte FeAl(POUAOH: mk kee FranieitePSnSbSu fer” erate ine grained) i apa fenaite ST phaente th onto gplena Smec_tmectite AP ate arsenic eve Man Stanie CoFeSnSs Sp mae Fens Kereblende ff temhedite br ante lar heratite ft tani pene) Bate bismuth ‘Be tour tourmaline bio Hee stdin lo) cn te tennant mba donor te topen brie brooke vem vermilee Hint muti Bass vif Yolfamite create or carbonate of ooo undiferentited Stietermined eompostion Inulte ALK PO.)MOWs ar acon cos Sterne SO, Ielingte Fee a ate ce Gaeonte marcato mn nye cl ont ineybdenite inate tmonsate fo conndum ‘mentoronte ford sonore imagretite cp chaleopye smuscot (coe grine®)ier argo) (vod) 1a de yor Fe PD, nay POH mq 'sav' sur 0g. and ylury ‘ag pur 2N Jo wontppe aurMOsRO TY os ong ‘saaunwe ain o7 OL Stuy ue # JO WORIPF MELONI da 0 op om 40) "SX ssn ayes sed 1052 0, so yp (da os vo) el po dy se Y 1s poe serous ge a sana. saa 00 dN a (Bey de oy yo suanovas isfy payeseuad i J0 UORIPPR AICS ‘ganas spuaut 910 “PAE OFH ‘gun ppt poznaoseion AAPM, xpi Bd. ame Poe fy aaou pur yor aye surmurss ds, 056 HE eh ay uessinp HAL 54 89 FG OH ‘.096~ pur ogc~ woarod 1 slap pes syeseed19° pes sppoo1p5 ons ouiyidong se aespeato;yy (mop amie pooumey eyempooos say my wy un ng 90 ip 9 or uns ee se fuspien woues (L299) are pHSUAPY & = exmpnios sa we ko poouENPY 8 Puyennn! 8 se westep Ht 1.508 anys psounpe 5 eens sav wo 4d “do 89 + “pu (amu voamng Sepang SuoTy vane OSL, doe ou ung jo. w uinp HK 3.90599 nice pour ogeues amo) tis fo doa #9 +o doa dana ou S04, Seered pao, ase yen wee HI 5. 1 pautape ww ‘ou'do Rept doy sen Sauna -osseed one, prog sno gy tne 6 ase feo) satu ody om AB) exp doy yoo ag) 205 Tueiup Ha U9 BY 5] oH. i sop epg (ups 'yon ssa) ‘ou (201 0) Bap HX 4, v0 rpunoy Geyory ry Abe Aga Tea sag yp ase 2 96) 28% oe Serer saus pomusyooo —— spnuas-asmod eu, cy gun spose Uy uous a po rg gue a0 75 qu dy Seo pu cog ippang) pooeS-oy jo sna Fy de yor U0 py 01 ed george eon aap Hk SL UO PP AL (emo asm0a tore Suara par noe Rea pa Pans poe wom ‘Faraon) spongy sun Mouye pur saegurcase a aS ad woney “Foc aps g Tang hog na co TAL61 PORPHYRY DEPOSITS. CHARACTERISTICS AND ORIGIN OF HYPOGENE FEATURES auqunyy ean) OB Toons por aay ‘ano auruen-uou 20 ayeuier aarq fe spray uo 9 os 0 pared tas Sexpn “sprig Seo “ap on posoye Boyd yun“ oda Kat {domnpSay in er ial rsp 94 Buuren 1 aup w8n0 yd Fe 5 uy stoquas Boueg-zh spay Jo Bion 850809 o cota pu ue sulted sodap no fied a ood sain JIE Sion Ups JO 09 ag crops przgesdsduro peop ‘.08e oF Buase fq pou pp a ‘ya! moan fo sassy ye ut jdm a sd say ad uasse ood vo 2d tg) ue gun sna wo 295 so1 sou w ane souquinag $07 0 0H So 9p sdanay ews, dquo unouy sasedap us pre no hed woursos mye ako ous yoq on axe yd jo Sess Rw UII spn id ered oun sovsen a ft ee a ‘asso po ssoua370500 oo PRON c yea orgs tout 20 (598) 98 FPNRUTE 295 ¢ crys “tet 9 Asuna ‘oper “ye Kepuayy “e) Systoewoys paw amnssud 9 ypns Sioa Ho apusdap “km Suoweanane ‘Gxg omppaiie par opoayde ‘suvauiiou AG porwayio0p sue, sounydar ossew se Kprouraro> sodojaaue aqeo-pes (ve supa da pus Dy sdojanno anyldaod poeyop- ‘gen suron jp pe uy > squauioeydar fnsseo pr 808 PIS dK wos arrose ducuswey rus aimsaduray 305 2 19 95 aay p95, asseod-9I°9) xpos oqr-spp0s ons onuptona ove epomsoey (Sn peoey (u2rapo) ou peseany “nus youonisuey, nee pooweape ones used juan, -stsspod yeuontsoea, {avonte-x) soa ahaa, 2G uonaayy262 SEEDORFF ET AL requiring chemical analyses of minerals or rocks. ‘The choice 700) of terms and related semantic issues are addressed in Appen- div 1. The summary in Table 3 defines eaclt alteration type, 600) identifies key mineral replacement reactions and estimated s00| formation temperatures partly based on phase petrology, and lists essential and accessory minerals, associated vein types, 400 and examples with references, Although veins are an integral & part of alteration and mineralization processes, certain vein 900 types span multiple alteration types; hence, veins are dis- 200) cussed separately below. The system K,0-AlzO;-SiOs-HsO-KCI-HCL The phase dia- 109 gram of this system is a usefal starting point for organizing al- teration types (Fig. 5), as the bulk composition of the system 270 7234567 is ideal for quartz-bearing aluminosilicate rocks. Figure 5A log (mciek+/MHcirs+) displays the relative stabilities of K-feldspar, muscovite (proxy for “sercite,” the traditional textural term for fine-grained K- mica), and the aluminosilicate minerals kaolinite, pyrophyl- lite, and andalusite. The principal phase boundaries inthis di- gran define the Relis for potssie (potassium slate), sericitic (phyllic, quartz-sericite-pyrite), and advanced argillic alteration, listed in order of lower KCVHCI and pH of the fluid, An assemblage that plots in a phase boundary can be defined as transitional between the various types adjacent to the boundary (e.g, K-feldspar and sericte 1s a transitional ppotassic-sericitic assemblage ‘An important restriction on the definition of soricitic altor- ation, which is implicit in the phase diagram of Figure 5A. is that K-feldspar (not just plagioctase), if present, be altered to sericite + quartz. Advanced argilic alteration involves forma- 6 tion of kaolinite, pyrophyllite, or andalusite. Serictic and ad- pee: a vanced agile alteration chemically represent progressively 5+ chi eaten e more intense hydrogen metasomatism and base-cation leach- sore POO T yD, ing, which in the extreme results in vuggy silica, though only Potassic i Tale. 5 See at hn gray € ae | Cate) -067 Fic, 5: A. Phase dagram for the system KiO-AlOySiOr H:0-KCLHCt 3 Andel @ Ksp at P(HO) = 1 kbar, plotting temperature versus log (mec. xlmics Muse Phase equi are efed fom Hemley and jones (004), Montoya and Hesnly (1975), and Herley et al U980) Phase bandanescorespond to nits of aeration pes, B Phase dram forthe ystem KiO-ANGrsiOr Bg glee ps2 Phas dn ort ten 30 pci rem torea apernee aE ie i er ee po 2 a ge eee ca ie te pg te et ee wach ete lp et wed i ie teeta sedan fue opucen te amen fg ° cae geen eae ders ome be emt Seren cg ne ees Gln a comes ‘Stacked series of phase diagrams that plot log (aye. /ab.) versus fog (ax-faw’) Seek ee cle ens a eg them eo) peer renee yokes thie Pe 100s of log (ayi/ah.) as temperature declines. Mineral abbreviations aro in ° map aS Bi Table 2. Shaded circles are keyed to alteration types (se text) in eppropriate Cord oat) = DAT = w,)-0 7 pales inthe phase dagram. Labels for tranetionlateraton Spe = - Tanda (mdora Pensa eres oc nsec)’ or sy Dats magnate sp from SUPCRT ar reported by Bowors etal. (1884), wth adions from a SUPCRT92 database Johnson etl, 192). Phase boundaries shown at 60” 2 0 2 4 6 6 and TOO'C ae approximate with respect to angly. Clinochlore felon, loglaxr/an*) from Walshe, 1980, cordert (Kg = 06), an bitte (ug » 06) actives ataxr la avo gon by an ied, siple salon move forthe Ng end member. Pos Key: @intermeciate Agile: @ Propyitc tons af eden hormbionde ar estimated fom natural phase asemblages @revanced Aric @ erste @ Potassc snd Ne/K buffered by feldsparPORPHYRY DEPOSITS. CHARACTERISTICS AND ORIGIY OF HYPOGENE FEATURES in shallow environments characteristic of high-sulfidation ep- ithermal systems (¢.g,, Stoffregen, 1987). We use the term sgroisen only as a textural modifier for coarse-grained aggre- gates, generally of muscovite, quartz, and other minerals, fol Towing the usage of Shaver (1991), Reed (1997), and Seedorf and Einaudi (20042). . Adding F and other anions: In the presence of fluorine-rich fluids with high activity of HF, K-feldspar gives way to topaz, muscovite gives way to topaz, and the aluminum silicate phases andalusite, pyrophylite, and kaolinite aso give way to topaz (Fig, 5B; Seedorff and Einaudi, 200da), In other words, depending on the geologic environment, topaz ean be a mem- ber of potassic, sericitic, or advanced argillic alteration types, ‘The same approach can be used to deal with sulfate, boron, and other anions (Table 3). Addition of sulfate provides for stability of alunite. Quartz + alunite is an important mineral assomblage in advanced argilic alteration, which may form by Iypegene vapor condensation in the pet levels of some porphyry systems (e.g., Silitoe, 2000). Tn boron-rich solu- tions, K-feldspar and muscovite give way to tourmaline, and aluminum silicate phases give way to dumortierite. Hence, potassic alteration has an analogue in the assemblage quart ‘and tourmaline. Indeed, the spatial position and salinity char- acteristics of the quartz and tourmaline assemblage in por- phyry Sn deposits are similar to those of potassic assemblages in many other porphyry deposits (Grant ot al., 1980), ‘Adding Mg and other cations: The component MgO can be added to model mafic wall rocks or minerals (Fig. 5C). In the advanced argillic environment, corresponding’ to the left hand side of the diagram at low values of ax./ay., andalusite, yrophiyllite, or kaolinite are joined by cordierite, chlorite, ot Plotite at high values of ayyulah. Condirte i favored at high tomperatures and chlorite at low temperatures, but the tale field may not be accessible to natural solutions at such low values of ax./ay.. Cordierite occurs as a hydrothermal ‘mineral in the porphyry systems of Green Tale, Nevada (Fud- son, 1983), El Salvador, Chile (Custafson and Quiroga, 1995), and Batu Hijau (PA. Mitchell, pers. commun., 1998). At the intermediate values of ax./ax. that characterize the sericitic environment (Table 3), the prineipal sericitie mineral mus- covite can be joined by other minerals such as chlorite and rarely biotite (Fig. 5). The environment of potassic alteration on the right-hand side of Figure 5 at high values of ax./ay.. and relatively low values of dvg2./at,, can contain K-feldspar, K-feldspar and bi- ‘tite, or biotite only. At higher values of avg2./aii., however, cordicrite could form at high temperatures and chlorite could form at lower temperatures as part of the potassic alteration assemblages (¢.g., Tiley and Beane, 1981; Preece and Beane, 1982), For some alteration types, reference to the ax./av. scale cannot be the sole eriterion for classification, An example is, ppropylitic alteration, where we follow Meyer and Hemley (1967) in zeserving the term for weakly metasomatized rocks, in which the main change in chemical composition is addition of volatiles such as COs, HO, +5. Where this criterion of propylitic alteration is met in porphyry deposits (Table 3), propyliticaltoration is characterized by (1) presence of relict K feldspar, if present in the original rock, with albite, calcite, epidote, and a dusting of sericite or illite as alteration 263 products of plagioclase; (2) absence or scarcity of ore mniner- Als; (3) paucity of iron sulfide and oxide minerals, typically in cluding minor pyrite, Tocal homatite, and relict magnetite; and (4) chlorite and/or actinolite with local relict biotite. In Figure 5, propvlitie alteration plots along the chlorite feldspar phase ‘boundary; projected back onto the Tog ax./an. diagram, propylitic alleration plots inside the K- feldspar field at moderate to low temperatures (Fig. 5). Care, must be exercised in applying the term propylitic where K- feldspar ino present in the wal sock 5 an aid in monitor- ing the chemical environment. For example, altered rocks with abundant chlorite « sericite im mafic protolths represent a similar log ax/au, environment to that of quartz + sericite alteration in felsic protoliths, not propyltic alteration (Fig. 5; og., Seedorff et al, 1991). ‘intermediate argilic alteration (Meyer and Hemley, 1967), is a weaker and lower temperature form of hydrolytic alter ation as compared to sericitic alteration, and it forms as sericitic alteration wanes (cf. Sillitoe, 1993, 2000; Arancibia ‘and Clark, 1996). A key characteristic is the presence of relict alkali feldspar in K-rieh rocks. Clay minerals such as Kaolinite, ilite-smectite, and smectite are present with illite (sericite) and chlorite (Table 3), but these minerals tend to replace bi- otite or plagioclase rather than K-feldspar or Na-tich plagio- clase, Stability of these elay minerals, with the rarity of dick- ite and absence of muscovite and pyrophyllite. restricts intermediate argillic alteration to temperatures below to ~200°C (Fig. 5). Silcic alteration, as used here, is a high-temperature, prox- imal alteration type that occurs in the core of certain por- phyry Mo deposits, in which quartz veinlets exhibit inner sil- tic and outer potassie envelopes (eg., Carten et al, 1988b), In the inner envelopes, there is metasomatie addition of sil- ica, with feldspars replaced by quartz and minor fluorite. Co alescence of the inner silicified envelopes in the vicinity of closely spaced quartz veinlets produces the deposit-scale high-silica alteration zones. High-temperature quartz-tour- maline alteration in porphyry Sn deposits might be regarded as an analog of silicic or transitional silicie-potassic alteration, with tourmaline proxying for K-feldspar at high boron con- centrations in the Hd Gee below), Silk alteration f wn. common in porphyry Cu deposits but is found locally. At Robinson, Nevaeh, for example. wall rock Is ro laced over tens of meters mostly by granular quartz, with a few percent each of hydrothermal biotite and chalcopyrite and may have ‘once had anhydrite (Seedorff, 1993; ef. Westra, 1982). Al- though the rock contains remarkably few obvious veins, its overall textural appearance is like a glant A vein in the sense of Gustafson and Hunt (1975; see below), and it hosts the highest copper and gold grades in the entire deposit. ‘few porphyry Cu deposits, including Ok Ted, Papua New Guinea, exhibit “quartz cores,” which are areas of high densities of quartz veins, also located in the core of orebodies (Watmuff, 1978; Silitoe and Gappe, 1984; Rush and Seegers, 1990; Zvezdov et al., 1993; Einaudi, 1994). In some deposit these quartz veins lack associated silicic alteration envelopes (ie., are B veins in the sonse of Gustafson and Hunt, 1975; see below) and thus are distinct from the silicic alteration en- vironment described above, but from the descriptions of other deposits we cannot tell if they have silicic alteration.264 Other types of silicification occur in porphyry systems. In- tense serititic alteration can include a component of sill cation, as at Butte and Resolution (Meyer et al, 1966 Manske and Pau, 2002), where an inner zone of silcification is enclosed in sercitic alteration and locally encloses an in- nermost zone of advanced argillic alteratio’. In many other porphyry Cu deposits, inner silicified sericitic envelopes are Enclosed in outer envelopes of serictic alteration (Dilles et al, 2000b). A pyrite-poor form of quartz + sericite alteration of breccia fragments involves siieifcation in many breccia pipes (eg.. Zweng and Clark, 1995; Skewes et al, 2003). In these sets, magmatic ampeons ids dominate. Tn the shallow parts of many porphyry copper systems and in certain related high-sulidation apithermal deposits, other forms of slcie alteration are common, if not ubiquitous (e.., Hedenquist et al, 2000, table 4), One important form is suggy silica zones enclosed in quartz-alunite-pyrite » pyro- Phslitediekite assemblages of adhanced aril alteration that characterize shallow, high-sulfidation epithermal de- posits (e.g, Stofiregen, 1987; Hedenquist et al., 1994) and Felatively shallowly emplaced porphyry copper systems where the nearsurface environment is preserved, including Far Southeast, Yerington, and El Salvador (Hedenquist et al. 1008; Lpske ‘nt Dilles, 2000; Watanabe and edenquist, 2001), These zones may be restricted to steep structures but commonly are blanketlike (eg., lithocap of sillitoe, 2000) ‘with roots extending to depth; the zones may be flanked by propylitic alteration and overlie sercitic alteration. The vu Silica zones are produced where a low-density magmatic-hy- drothermal gas containing SOx rises and condenses into shal low ground water to produce extremely low pH, § rich alter- ation (eg, Hedenquist and Lowenstern, 1994). The adiltional condition required to define sodie-caleic and sodic alteration (albitization of Meyer and Hemley, 1967) is that thore be mineralogic evidence of metasomatic intro- duction of sodium + calcium. Sodie-calce alteration can be tered the vere of poss alteration (Caren, 10 Dilles etal, 1995), whereby K-feldspar is replaced by oligo- clase, mafic minerals are replaced by aetinolite and ttanite, or they are destroyed, In contrast sodic alteration is character- ized by lower temperature assemblages invelving albite, chlo- tte, and epidote: in ths ease, the distinction wth propyitic alteration telies on recognition of metasomatic introduction ‘of sodium based on replacement of K-feldspar by abite. Significant metasomatisin of additional components, other than those involving the cations K*, Na‘, Ca¥, and SiO, o¢- ‘curs in certain porphyry deposits. Coupled sodium and iron metasomatism occurred in certain deposits where the asse blage amphibole = plagioclase + magnetite formed (Clark, 1999). Coupled caleium and potassium metasomatism is re- ported atallale porphyry Cu Geposits (Lang et a, 1995, Wil son et al, . ‘Sulfide and oxide minerals: Porphyry deposits contain many sulfide and oxide minerals, Sulfide and oxide phases com- ‘monly reequilibrate with decline in temperature (eg., Barton eral 1963), bot the original sulfide-oxide assemblages com- monly can be inferred. Sulfation state (Barton, 1970), which isa function of both fe and temperature, provides a coave- nient and consistent framework for systematizing sulfide- Gnide mineral assemblages and studying the evolution of SEEDOBBP ETAL, hat are less directly must be considered ols hydrothermal systems. Other variable constrained, such as total sulfur, alse when evaluating hydrothermal processes. In aqueous tions, sulfur may occur in the oxidized state as SO} (n = +6) or in ee as HS (n = ae choose to use a phase diagram that plots the fugacity of sulfur gas (fs.) versus temporatize for ongmizng Sulfle-ccde mineral assemblages from porphyry deposits, although other representations, such. as Rs (Rs = log (frgfis)) versus temperature, are equivalent (Binaudi etal, 2008), A characteristic of such diagrams isthat the fs, covaries directly with fo, for low temperature ore sol- tions that are dominated by aqueous H2S, as related by the reaction Sr + 2H:0 = 2HDS + Op a In aqueous fluids at high temperature where SOP may be the dloininant sulfur species, fy is inversely proportional to the cube root of fo, at constant pH as follows: 250% + AH” = S2 + 302 + 2H20. @ Because sulfide ore minerals are directly precipitated from reduced sulfur, whereas sulfates suchas anhydrite and barte precipitate from oxidized sulfur, total sulfur, sulfidation state, oxidation state, salinity, and acidity are key variables that con- trol ore mineral deposition (e.g, Barton, 1970). Five categories of sulfidation state can be delimited as bands across the phase diagram, each Lounded by a slid: tion reaction of the form A’+ Sz = B where A and B are sul- fur-poor and sulfur-rich minerals, respectively (Fig. 6), as de- fined by Einaudi et al. (2003). These reactions have a positive slope on the plot of log fs, versus 1,000/T (temperature in K), so both sulfur fugacity {f,) and temperature vary for any given sulfidation state. A few key reactions dofine the limits of the various sulfidation environments, ranging from low- to Soest Flo, 6. Log fr LODUT diagram from Einaul otal (209) defining the rave sullen dates of hydrothermal Migs besod on slide reac tors iooving two or ore copper and ron-bearng mineral phases. The Maine fe forming ernment is hom Baton 1970) an the gone. ‘Ee eam pat acm pry per aed oye Sein depois sted in Einaudi t 200)