Poot SSNS ie NEWSLETTER APRIL 2000 SOCIETY OF ECONOMIC GEOLOGISTS NUMBER 41 Supergene Oxidation of Copper Deposits: Zoning and Distribution of Copper Oxide Minerals ME WILLIAM X. CHAVEZ, JR. (SEG 1990) MINERALS & EWVIRORENTAL ENGINEERING DEPARTMENT # NEW MEXICO SCHOOL OF MINES + SOCORRO, NEW HEXICO, USA 87601 TEL #1805055 8917 FAK 41505 5 ABSTRACT Copper oxides represent an attractive exploration target because even low-grade prospects have the potential to produce low-cost copper in an environmentally friendly lashion, Derived from hypogene and/or supergene sulfides, copper oxides comprise a series of distinct assemblages that characterize # variable pH, oxidizing geochemical environment known as “the oxide zone." Development of oxide copper minerals is 4 function of source-rock and hhost-rock mineralogy, pyrite and other (copper) sulfide abundance and distribution, fracture density and distribution, phreatic and/or vadose zone occurrence and stability, and maturity of the weathering profil, ‘The paragenesis of copper oxide mineral formation reflecis local, dynamic changes in supergene solution composition attributable 10 reaction between host-rock ‘mineral components and dissolved species. Especially important are the concentrations of Ret (vs, Fe"), SO, HF, and Cu" (vs, Cu‘), Because mineral assemblages, even those that are metastable, represent the geochemical ‘environment in which they formed, identification and mapping of copper oxides is useful in interpreting the geochemical history of an oxide zone. Furthermore, practical application of oxide zone geochemistry is significant in the reéognition and solution of problems associated with weathering-engendered metals oxidation and transport from mine wastes, SPECIAL NOTE: Readers wil ind more information about the copper axide minerals mention in this arti by refering tothe SFG web site (htp://mmw-segweb.org). Photographs showing ‘mineral relationships and paragenetic aeeocations alow readers to further understand the nature of copper oxide assemblages and thor goochemical and physical settings. 2 EMBL: WXCHAVEZQNIMT ES RESUMEN Oxidos de cobre comprenden una fuente importante del metal rojo, especialmente en yacimientos aptos para tratamiento del tipo “ixivincion— recuperacién por solventes—electrowinning” Este articlo describe la zonacién ocurtencia de los Oxidos de cabre derivados por procesos supérgenos afectando 2 un protalito con sulfuros de cobre y fiero, hospedado por varias asociciones mineralogicas de altracin, os yacimientos considerados son Prineipalmente pérfidas de cobre y molibdeno, y sistemas tipo skarn, Geoquimicamente, el mineral més importante que influye la dstibucién de Jos productos ce meteorizacn de un yavimiento metaifero del ipo psf de cobre es la pirta, ste mineral genera, en canidades importantes, &ido sulfsco (SO, y H" y flerto Ge" y Fe"). Estos componentes de soluciones metesrices (supérgenas) funcionan com lixviantes, produciend mobilizacin de cobre y oiros metales bésicos desde el votumen de fa coca lixiviada y resultando en la formacién de la "apa lixviada” Cached capping; véase Figura 1. Estos componentes zcumulan, infuido por la geoquiica dela roca huésped Yd las soluciones que tansportan estos componentes, en foxma de 6xidos y/o sulfuros,formando un volumen de roca ensiquecida en metals yazuc En la zona de dios, minerales que contienen cobe oxidado (Gu, con menor Cut y cobre nativo) comprenden la fuente principal de cobre. La paragénesis ce los Oxios refeja los cambios geoquimicas en fs soluciones que proveen el cobse con respeto al tiempo. As, la precipitacin de los Oxides ‘sigue, por lo general a secueneia derallada en las figuras 3y 4. Desarrollo de la secencia vetical y/ lateral de Gxidas de cobre es una fucién de (1) e tempo to» goethit jrosto Sink | Chaleanthito, bonatit, ‘Atacamite,brochentite, anti, brochantte, native copper, posniakte; local native chalcosiderte, cupite, copper ‘tenor, paramelaconite, Cholcccite, covelite, pyrite, malachite, phosphates; chaleopyrte local alunite; esidusl, ‘Also; alunite, AsFe oxides, | chalcopyit, bonite, arsenates pyrite Protolith | Pyrite, chalcopyrite; traces of | Borie, hypagene chalcocito, bornit, pirate chalcopyrite, pyrite Well-developed copper oxide zones appear wo form through two distinct mechanisms: (1) via substantial copper addition toa volume being oxidized, including the formation of exotic copper deposits, and (2) through in situ oxidation of a copper-bearing sulfide resource. Importanily, the fist type of copper oxide system requires ‘copper transpotation from a source region, but the protore does not need to have high copper content if leaching and precipitation are ficient. Conversely, the second type requites substantiat protlth copper content if the copper oxide zone developed is to be of potential ore grade, and requires also that removal of copper be ‘minim. Distinction between these protore environments is signifcan exploration for copper oxide and supergene sulfide enrichment targets because prospects dominated by reactive rock units ace likely to display only incipient copper entichment unless an adjacent or eroded non teactive source-rock volume was avalable to provide transported copper. For example, an eroding phyllic or a alteration zone of a porphyry system may provide copper to a sink comprising a reactive (K sicate or propyii) rock mass, whether in situ or exotic. This is why in situ copper occurs at El Abra (see below), Lomas Bayas, Mantos Blancos, and Radomiro omic, and ‘exotic copper occurs at Mina Sur (Fx6tca), Huinguintipa, HI Tesoro, Jehuno, and La Cascada, Chile (Minchmeyer, 1997). To generate the fist ype of copper oxide occurrence, a source region must be available to supply copper via oxidation and leaching. Pyrite isthe most significant source of oxidized § and, indirectly, hydrogen ions, in a sulfide-bearing rock volume undergoing weathering. It is also a substantial if not dominant, source of oxidized iron. As these components are intimately involved with copper mobilization from the source region, oxidation ‘of pyrite is important to generate a well-developed copper oxide ore deposit va copper ation, SEG NEWSLETTER W Oxidation of pyrite involves a series of stepwise processes resulting in the generation of “protominerals" such as schwertmannite and ferihycite, the solubility of whieh is a function of the production of Fe and Fe", pH, and SO," activity (Murad et al, 1994), The combination of sulfate as a complexing anion, hydrogen ions (.e., acid conditions), and atmospheric oxygen to enhance and maintain an oxidizing environment results in destruction of sulfides, oxides, and silicate minerals Titey, 1982; Tilley and Marozas, 1995). Importantly, the relative susceptibility to oxidation of sulfide minerals determines the sequence of sulfide ‘mineral destruction, the consequent availability of metals for supergene transport, and the nature and zoning of resulting minerals (Bladh, 1982). Figure 2 shows the general succession of sulfide ‘mineral destruction by chalcocite replacement, as observed from paragenetic relationships shown by oxide sulfide zone assemblages. Boyle (1994) shows a similar sequence for sulfide replacement within sulfdic tailings undergoing oxidation. Hierarchy of sulfide mineral destruction via ‘supergene chaleocite replacement Fi I S1ov Sphalerite, Borite Galena, Sulfosalts, Enargite Arsenopyrite, Chalconyrite, Pyrhotit, Pentlandite Marcasite, Pyrite Poragenetio diagram showing the gonoral succession of sulide destruction by chalcocite replacement, as observed fi aageretic relationships shown by oxide suifide zone assemblage Boyle (1994) shows a similar sequance for sulfide replacement within sulci tangs undergoing oxidation. Figure “The oxidation of sulfides other than those of iron produces only modest quantities of acid sulfate-beating solutions (Anderson, 1982; ‘Williams, 1990), a factor which i significant in determining the types and distribution of oxide minerals developed within a zone of ‘weathering (see below), Therefore, pyrite oxidation is generally the ‘most important source ofthe acidic solutions responsible for mineral destruction during the weathering of a rock vohume. This means that pyrite quantity i critical in determining oxide zone mineralogy. Pyrite sa relatively refractory mineral in the replacement sequence; smarcaste oxidizes more quickly than pyrite (Mason and Berry, 1968), and pyrthotite oxidation is as much as two orders of magnitude Faster than oxidation of pyrite (Nicholson and Scharer, 1994). Laboratory observations of Fe sulfide oxidation are corroborated by the par sgeneses of oxide and sulfide minerals reported from oxide zones it is observed that pyrite shows incipient or no significant corrasion- replacement even when other sulfides in the same oxide volume display substantial oxidation, asin leached caps or gossans, or variable replacement by oxides or sulfides—as seen at Chuquicamata Flores, 1985; G- Ossand6n eta, unpub data!) and Mantos Blancos (Chavez, 1963), Chile; and Lakeshore, Arizona (Cook, 1988; Huyck, 1994), Therefore, for pyrite to provide a significant source of acid sulfate-bearing solutions, weathering conditions mast be strongly oxidizing, TOsandén, C, Féavt R, Ros J, and Gitafson Ui, ln revew, Geology of (Chuguicunaia Revised: Eeonemic Geology.12 EERE 25 SENE QHATION OF cori PER SULFIDE DEPOSITS, CONT. Other sources of acidic solutions, albeit generally minor compared to sulfides, include magnetite and Fe-beating silicates, Silicate minerals that Contain Pe" are susceptible to oxidation, ancl minerals such as biotite, Fe amphiboles, Fe pyroxenes, and Fe- bearing garnets (eg, the La Democrata skarn system in the Cananea dist, México) may contribute to the generation of acid solutions uring weathering, This is because ferric iron, produced during ‘mafic mineral exidstion, generates goethite plus hydrogen ions via reactions such as: Fe" + 31,0 ~ Fe(OH)s(s) + 3H" (aq) o ‘The same type of reaction explains why magnetite, « common ‘component of are deposits, is capable of producing acid solutions ‘even from mineralized rocks having scant or no sulfide minerals, LEACHED CAPPINGS: SOURCES OF METALS ‘The metals that ultimately accumulate in the oxide of sulfide centichment zone are derived from the volume of rock that has undergone oxidation and metal removal, referred to as the leached capping (developed from disseminated and fracture-controlled SEG NEWSLETTER NP 41» APRIL 2000 sulfides; Locke, 1926) or gossan (developed from massive sulfide bodies, including skamn-hosted sulfides). ‘The extent ta which the leached capping, oxide volume, and sulfide enrichment volurne are developed depends on the amount of acid-prodicing sulfides in the rock volume, the neutralizing capacity of the minerals in the host rocks, the density and extent of host-rock fracturing, and the nature and duration of local and regional ‘weathering conditions (Lapez and Tiley, 1995). Although removal ‘of metals from the leached capping may be very efficent, residual copper and iron are always present in detectable quantities and comprise the geochemical anomalies~both positive and nega important to minerals exploration and to environmental considerations of waste-ock disposal “Table 2 provides examples ofthe residual copper values reported from leached rock volumes aver porphyry copper deposits. Copper contibuted from rock masses undergoing oxidation and removal of metals and sulfate is transported by acid solutions, dorninantly as caipric copper. Figure 3 shows the general parageneses for coppet phases related to different protolth sulfide assemblages for relatively reactive protliths Copper is mobile at low pH, so copper occurrence in some environments may be represented by cupric ion as well as by | minerals. Although copper oxide minerals display @ wide range of Nominal total pyrite [CuSx: FeSx >> 5:1] PARAGENESIS OF COPPER OXIDES S uprte= Brochanite,texorte endo i valves ramelsonte scant covellite, shel " cut a) y & Red hematite +“ almagrado” (= red hm + variable CuO, sly as cprite native copper, tative copper, curt ert, paramelaconte, adsorbed Cu", Cu", neotocite, wad, “pitch copper” (lack cxyrocolla", ber bt oxide") OXIDATION PATH tonort, adsorbed Cu Scoroite, chenevixite ‘Chenevixite, ceruleite, lavendulan Figure & Oddation path dagram showing paragenos ‘Of copper oxides Geived from low to moderate total pyle proto. Note that the ending paragenesie, developed in geachemicaly matute copper oxde zones, comprises & series of Cu + Fe 4 Mn exides, dominated by hematite (rather than goethite of josie)APRIL 2000 * N° 47 le 2. Coppet Content of Leached Cap Volumes, bistaicT LEACHED CAP COPPER CONTENT 0 to fow X00 ppm Cu derived fam pyro Cananea, México brotith wth aostc goetite dominant capping Upto 2,000 ppm, as contamination from reli hypogene sulides and residul supergene cheloacke + Cu oxides Cerro Colorado, Chile 700 to 1,500 ppmn in a hematite leached cap, ‘brobably derived fom the incomplet oxidation offormer chaloctte Less than ~100 pam in “superlvacked” cap, enhanced through chorde activity end essentially inert hast racks No leached cap in well-developed K silcate ‘stable protalth with cp + bn + cc protore (~0.65% Cu) andin situ chrysocofa + brochentite + psoudomalacite + nec ‘Cu-oxide zone (avg ~0.55% Cu) ‘Quebrada Blanca, Chile Lascondide, Chilo El Abra, Chie X0 to 800 ppm Cu; protore Cu concentration approximately 1,200 1,500 ppm 200 to 400 ppm in ersitic to goetitc leached 2p dveloped from pyrite protolith containing 700—1,200 pam copper ‘Morenci, Azone ‘Tyrone, New Mexico ‘0 to low X00 ppm Cu in hematite to goetitic leached cap developed over phytic argc iteration of monzontic hosts; local native copper Santa Rta, New Mexico Up to 1,000 ppm in poorly developed leached volumes derived from K sifcate protolth Lenched and oxidized rack volumes contain X00 _Ppm copper with residual Cu values to > 1,000, mm as sulfates, chorides Radomizo Tomic, Chile Lomas Bayes. Chile No significant leeched cap in hud, high-ainfa {24,000 mnvyear,steop tern; protolth copper concentrations 4,000-3,000 ppm Cerro Colorado, Penarné stability, speciic suites of copper oxides are useful in tinting the inierpretations concemning weathering envizonments and the genesis of copper oxide minerals (Locke, 1926; Schwartz, 1984). This indicates that copper oxide minerals represent broad conkltions of oxidation and pH; nonetheless, the mineralogy of « given oxide assemblage is very useful in assessing the BipH conditions of copper oxide formation, including those conditions responsible for copper transportation and deposition. The following section describes the formation of copper oxides and associated minerals in the oxide zonc of a weathering mineral deposit containing disseminated and fracture-contolled slides. SEG NEWSLETTER 13 | COPPER OXIDE ZONE DEVELOPMENT ‘The oxide zone is defined as the rock volume representing a ‘redox environment transitional between the very oxidized conditions Present in the leached capping and the reduced conditions characterizing the supergene sulfide zone. Oxide zone mineralogy reflects variably oxidized and reduced conditions, with mineral zoning exhibited on both large and small scale. Table 3 lists ‘minerals commonly found in the oxide zone and leached capping of porphyry copper deposits, Table 3. Minerals Commonly Found in he Oxite Zone of Copper Deposits RAL{SO.}(0M, Atacanite (paratacanite,botlacklt).... CuyS04(OH, Bonatie u,CK0H), Brochantte 6uS03H0 Contato sc. CusO,0H Ghalarthite (compare to kaki)... CuyAh{ASOq)OMhs12H,0 Chaleosideite (compare to trqusse).... CuSO 3H,0 Chev : CuFefPO,) (0H 840 Chryscol (ine) + Gu, Fo 4904 (0H)e 1,0 CafFeMn}0x-Si0, #40, with oppor content varying om ~20-40 we Cu Conicnit Fea{SO,) {0H} 204,0 Coquimbite FeSO, 2440 Goottite -F200H aos KFoS0,}(0, Koinkte. a,Cu{S04) 2440 Laverdden NaCaCu*(As0,)CH5H,0 Libethenito Cu,POy(oH} Paramelaonte + CuO (50 tent (0v0) ond cupite (C01) Poitevne + (CuFeZnISO;#,0 Postigite..e.scec ss CusosoH 4,0 Pecudomalachi (see Rotheita).......CuPOy{OHy ‘Scorvat (see chenevsite) Fo" **As042H40 Turquoise CuAlePO,)(OH)-4H,0 -KaFopAISO3} 218H,O Cu,S0{ Ole 2840 — Copper oxide minerals form (1) though direct precipitation as supergene solutions reach saturation with a specific mineral ccomponent(s), oF (2) via replacement of sulfides, oxides, or silicate minerals. In most environments, oxidation of hypogene sulfides with high S/metal ($/Me) mole ratios, such as pyrite, marcasite, and pyrthotite, results in at least incipient destruction of the original sulfide and the resultant dissolution of iron as Fe" and sulfur as 804", However, oxidation of sulfide-bearing rocks with low total Pyrite content and of minerals with S/Me ratios of approximately unity, such as chalcopyrite, idaite (CujFeS), pentlandite, enargite, and arsenopyrite, usually results in the formation of combined Fe and metal oxides having geochemically limited mobilities because there is insufficient acidity generated cluring weathering to ensure complete removal of the original mineral = components. For this reason, chalcopyrite14 SUPERGENE OXIDATION OF COPPER SULFIDE DEPOSITS, CONT. oxidation generally leads tothe development of local hematite £ fgoethite Talos adjcent tothe replaced mineral grain, accompanied by copper oxides that sre stable in the near-neural to moderately Low pH range igure 4 shows reaction paths for copper oxide minerals formed. within (1 reactive host rock and (2) relatively non-reactive host rock, stating with « protolth containing pyrite, chalcopyrite, and tninor bomite, The geochemical reactivity of host rocks is significant (tarozas, 1982; Pinson, 1992) because the quantity of silicate minerals available for acid neutralization directly influences the local leaching and oxide zone geochemical environment. Although the abundance of reactive minerals i important in detenmiing hose a rock mass will act to acidic solutions, reaction kinetics may inhibit the ability of a reactive protolith to neutralize acid, sulfate-bearing solutions. The relatively slow reaction of most silicates with acidic solutions generated via pyrtitic SEG NEWSLETTER N241 © APRIL 2000 _ rinerslogically distinct because the geochemical conditions thst form the various assemblages are dictated by specific combinations of sulfide and host-rock mineralogy, structural setting of the ‘weathering rock mass, nd lthologic variations. "These geochemical conditions produce the mappable mineral assemblages characteristic of the oxide zone, Interpretation ofthe environment of formation of the mineral assemblages is important part of the economic evaluation of copper oxide (and sulfide) prospects. For example, chalcocite oxidation and leaching produces an ascembage of Fe oxides referred to as "lve limonites; this term really refers to *red hematite-dominant” Fe oxide | enblgs enened aa ent of oper removal by supergene solutions derived from residual acid production. Thus, the | gzation fed eae dig onan of uperen sulfides having very minor iron may be explained by the oxidation of ctnieocte in low pyrite oF high-ppete environments, a ithe | allowing reactions. sulfide oxidation is especially notable in mine environmental remediation studies in which reactive silicates comprise part of the acid-baffering component of mine waste (Walder and Chavez, 1995). ‘The mineralogy of the host rock plays a very significant geochem- ical role in the development of the gangue and ore mineral assem- blages occurring in the copper oxide zone, This is because host- rock silicates and oxides, compris- ing the volumetrically dominant ‘minerals in the weathering environ- ‘ment, offer exchangeable cations and ths are capable of consuming. hydrogen ions via hydrolysis. The greater the quantity of reactive sili cates and oxides such as feldspars, mafic minerals, and carbonates, the greater the ability ofa wall rock to | tfyetbdevcloped _——_Wefinued ow. p incsiy oxidative Sfony partial Co™ neutralize acid, sulfate-bearing Co" removal (mmulti- ‘oxidation and ‘replacement: ‘removal (Weak leaching, solutions. This buffering capacity is ee fea ‘or pyro coasuangtion: limited in rock that has already been subjected to phylic, agile, and advanced argillic alteration, because phyllosliates and clays Cale, tonatte, rohan anleile, _Covelitafier chant; laracteristic of these assemblages luahnite Feed Pe sates acme cysocalle red bemalt + goethite, have only limited capacity to {eg Como Acapars, Ferns, singers, Custos Te'Live Limosite™ (Residual Blanket] ‘exchange cations for H In Figure 4, arrows show the sequential development of copper DS sevncscre neste ‘rom Assemblage: epaite jrosite> red hematite anattreptay gece gptierepledyroste Upper partof enrichment volume: ‘Chaleocite Agente, djuete) sequently replace bcp, and ny “Chile uper pats ofreoxiized ‘ystems, mi Teach piles and wines) Red hematite>, >> gostite “jai f= MnO. ‘Atacamite, malachite, [REACTIVE HOSTROCK eerctecanconpyliie,_ ochantite, anti, cuprite, ‘otermediate agi, ‘kam cali wad, native Cu, erysocoit sstenblages local Savatable, then ‘sequence: caleoete> coppes > Plo, angle, danced org intermediate ails wsemblages 4g ~~ Lower part of enrichment volume, Ccovelite > chaloocte; Cv replaces tty Kate + Crlke mineral [Residaal Blanket) ‘west damp, oxide and associated sulfides, with paths determined by protolith sulfide ratios and the completeness cf weathering reactions. The paths lead to oxide assemblages that are are @ function of rminesites. reactive and nonreactive host rocks. Lowe ter shows beerarios, beginning with @ supergene sulfide assemblege Saiepete fa nateral system, wth corsponding applications for envfonmental remedltion of abandoned Figure 4 Paragoncals of Copper ondos storing with a pyrte-dominantprotolth, Copper oxide essomblages ‘Scceessive oxdation mobilization accumulation cycles. with paths shown for geochemical rrineral assembiages resulting ftom verious oxidation "Tho enldation of suite mine wastes mimes thatAPRIL 2000 * N° 41 A lov total residual pyrite environment results in the formation of substantial ferrous sulfate, which paticipates in oxidation reactions as follows CuS(s) + 2Fe*SO(aq) +10 +30, _ chalcocite + ferrous sulfate 7 FeO) + 2CuSO{aq) + 4,80, ted hematite + cupric sulfate @ If residual pyrite content of an oxidizing protore is relatively high, this results in generation of ferric sulfate, which participates in oxidation rezetions as follows: GuSis) + Fe™{SOPy(aq) + 2H,0 + 2.50, chalcocte + feaie sutate FeOfs) + 2CusO\(aq) red hematite + cupric sulfate +2880, o Jn each environment, copper is liberated and hematite takes the place of the now oxidized and dissolved copper sulfide. At least traces of copper remain associated with the newly generated red haematite. This copper may occur as “geochemical copper" adsorbed ‘onto the surface of ron oxides or as minute grain of distinct copper tminerals admixed with the red hematite. The association of abundant hemattic Fe oxides with trace copper is common in leached environments, which otherwise show no obvious copper oxide occurrence, These oxides are termed “aimagre” or “sangre de toro" in Cental and South America, and may contain economically important quantities of copper. In some eases, the copper may ‘occur as cuprite or native metal, rendering copper recovery dificult, Ga, portions of the Ray, Arizona, oxide zone). in cases where pyste was present in stichiomeuic excess (usualy greater than 5-7 vol % pyrite), it oxidation may produce enough acid to remove essentially a iron and copper, such that supergene iron oxide abundance and copper content may each be minor. With the descent of meta-beating, acid sullate-rich fluids, hhypogene sulfides may be replaced intially by chaleocte, julete (ig) oF digente (C9), with subsequent replacement ofthese sulfides by copper axides as avaiabily of reduced sulfur dninishes 4s sulfides are consumed. Covelite develops in environments that lack abundant dissolved Cu'*, usually by in situ oxidation and replacement of chalcopyrite ot bomite, ately pyrite. Hence, the paragencsis of sulfide replacement may involve several copper sulfides prior to ultimate copper oxide development, Replacement ‘of sulfide assemblages having low S/ife ratios or high copper contents (covellite, chalcocite, digenite, bomite) may zesult in the direct precipitation of copper oxides—e.g., at Radomiro Tomie (Arcuri and Brimhall, 1998); Quebrada *M" in the El Salvador distict, Chile, and Morenci, Arizona—because the local geochemical environment is moderately low to near-neutral pit, which is favorable fr copper oxides that ae stable inthe range of pl 4to 9 (Fig. 3; see also Anderson, 1982. COPPER OXIDE PARAGENESIS AND ZONING ‘The paragenetic sequence of copper oxide minerals observed from many oxidized copper-bearing orebodies reveals that a specific series of progresive mineralogic changes takes place during supergene oxidation, transport, and precipitation. This section | SEG NEWSLETTER | 15 discusses copper mineral paragenesis and spatial zoning in the context of mineralogic associations, protolith compositions, and hhost-rock alteration assemblages. Copper deposits in which pyrite is 2 volumetically significant ‘component are characterized by copper oxide assemblages reflecting low pH environments. Pyrite rarely shows dizect replacement by copper oxides because the microenvironment developed by pyrite oxidation is usually s0 acidic that only copper sulfates and an attendant seties of iron sulfates, such as jarosite, coquimbite, copiapite, melanterte, and votate, are stable. For example, if pyre contents are such that the neutralizing capacity of host rock is exceeded and pHi of <2 solutions are generated, the copper sulfate minerals bonatite, chaleanthite, krShnkite and wrocwallite are stable (Table 3), These minerals form in the uppesmost pars ofthe ‘oxidation system, topographically above near-nevtral pH-stable sulfates such as brochamtte, posnajkite, and antlerte, Evidence of such low pH condifons and the mineralogy produced in the oxide zone is present at Chuquicamata Jarrell, 1944), Fortuna de Cobre (R Nordin and R. Chavartia, pers. comm., 1999), Lomas Rayas, and os, Chile, A similar envionment is genccated during ‘oxidation of pyriic sulfide ore deposits and mine If sullicient copper is available in an oxidized solution, and if reduced sulfur is present, the minerals chalcocite, djuleite, and digente replace pyrite, Covell, idaite, and covellte-like sulfides replace chalcopyrite and bomite, and rately, pyrite. Chaleocite and dligenite are the most common replacement products in the upper portions of a sulfide enrichment zone, with covellite at greater depths (Flores, 1985); djurleite is the most abundant supergene copper sulfide in some ore deposits, ¢., Micilla Soto and Dreyer, 1985) and San Bartolo (Flint, 1986), Chile. However, successive replacement of chalcocite and digenite is common when the ‘composition of an oxidized supergene solution changes as pyrite is ‘consumed inthe source region(s). Hence, moderate pi stable oxide minerals are favored, resulting in copper sulfide replacement by eochemically appropriate copper oxides, Copper oxide mineral associations generally are consistent, because oxidizing sulide systems experience a consistent series of ‘chemical reactions that permit only the development of characteristic ‘mineral paragenetic relationships. Brochantite replaces chaleocite in ‘weathering systems in which moderately low to near-neuttal pH values are maintained, such as in portions of the orebodies at ‘Quebrada °M", Cerro Colorado, and Quebrada Blanca, Chile, and Morenci, Atizona. If chlovie activity is high in a near-nevtral pF ‘weathering environment (Rose, 1976), the copper hydroxychloride atacamite (Cu MOH), replaces chaleocte (Mantos Blancos, Michill, Santo Domingo, and Buena Esperanza, Chile; Florence Junction, Arizona). Anvlerte replaces chalcoite in environments having lower pH than characterizes brochantite (Anderson, 1982); e.g., La Escondida and Chuquicamata, Chile. Ore petrography sivdies (Chavez, 1963; Arcuri and Brimhall, 1998) suggest that most of the brochantite-antlerite-atacamite formed through chalcocite replacement represents in sita oxidative replacement of chaleocite zathet than copper addition as a sulfate or chloride. Indeed, these green copper oxides contain less copper than chalcocite, 50 destruction of chalocte via simple replacement usually represents copper loss leaching) rather than enhancement. In some systems, | these copper sulfates replace cuprite (for ‘example, at Cotlahuasi and El Abra, Chile),16 SEG NEWSLETTER SUPERGENE OXIDATION OF COPPER SULFIDE DEPOSITS, CONT representing an in situ replacement assemblage with litle or no significant copper acktion or transport In systems characterized by near-neutral or slighty alkaline pH. environments, cuprite replaces chalcocite (e.g., Cerro Colorado, Copucha (Sierra Gorda), and El Abra, Chile; locally at Ray, Arizona, and Santa Rita, New Mexico). Cuprte represents an intermediate replacement product in many oxide zones, anc! is almost always replaced by other copper oxide minerals. Native copper usually occurs with cuprite—EI Abra, Chile; Santa Rita, New Mexico; Re Arizona; Piedras Verdes, Mexico (Dreier and Braun, 1995); San Jorge, Argentina (Wiliams etal, 1999)—but rarely directly replaces chaleocite. Native copper occurs generally at greater depth than cprite (Anderson, 1982) Malachite and azurite are common constituents of coppet oxide zones in which carbonate is available from sedimentary sources (notably in oxidized skarn systems, e.g, Christmas, Koski and Cook, 1982; Morenci, Arizona, and Cenanea, Mexico, Velasco, 1966), atmospheric sources, and/or indigenous bacteria cells (Enders, 2000). Carbonates, along with the mineraloid cheysocola, generally Comprise paragenctcally late mineral, replacing earlier Oxides and sulfides and occurring 2s transported constituents occupying ‘otherwise ‘clean fractures, including fractures showing no evidence of prior mineralization (eg, southern Peri coastal batho. In geochemical mature copper oxide systems developed under rnear-neutral to alkaline pH! conditions, malachite and cbrysocolla are typically che most important copper minerals, with tenorite, paramelaconite, and neotocite are volumetrically minor. This is probably because carbonates and silicates are most stable in a well developed oxidation environment in which sources of low pH solutions have been consumed, and because indigenous and atmospheric sources of silica and carbonate, respectively, are readily available. Incipient and generally subeconomic fracture-controlled copper carbonates and chrysocolla occur paragenetically late in ‘oxidized copper deposits at Cerro Colorado and Cerro Chorch, Panama; along the southern Peni coastal batholith and in adjacent northern Chile, and in late-stage oxidation assemblages in the southwest United States. Exotic copper deposits (Newberg, 1967; Angtita, 1997; Mote and Brimall, 1997; Manchmeyer, 1997) are almost exclusively chrysocolla dominant, with minor atacamite, copper wad, renorite, and/or Fe-Mn-Cu oxides (including ncotocie) Tenotite and paramelaconite, the black copper oxides, occur in, the upper zones of copper systems in which high host-rock reactivity and low pysite content produce alkaline to neutral pH environments. If carbonate i available to bulfer low pH solutions produced through sulfide oxidation, tenorite and paramelaconite ‘may occur in local environments characterizing oxidized pysitic sulfide systems, especially skarns (eg, Morenci, Arizona). AC El Abra, Chile, tenorte and paramelaconite comprise the constituent rmineralsin'neotocite; along with chrysocolla, neotocite occu in surface outcrops and at shallow depths of the El Abra oxide orebody within reactive host rock comprising biotite-stable diorte porphyry. ‘The tenorie and paramelaconite association graces with increasing depth to the assemblage cuprite + native copper (A. Moraga, pers ccomm., 1999); this assemblage is replaced by and grades with depth to brodkantitc, This change with depth is consistent with a gradual change in copper oxidation state, decreasing with increasing N241 © APRIL 2000 distance from the former erosional surface, The observed paragenesis, in which black copper oxides replace the assemblage Cuprie-+ative copper + brochantt, suppor the argument that the ‘ovcurtence of tenorite £ paramelaconite # neotocite indicates the ‘most oxidized zones of a weathering, low otal sulfide proclith, ‘The paragenetic paths shown in Figures 3 and 4 summarize the observations above. Oxidation produets for arsenic-bearing ores, common components of hydrothermal ore deposits, are summaized in Figure 3. Arsenopyrite, when oxidized in an environment contziing pyrite, yields the ion arsenate scorodite characteristic of the upper portions ofan oxide zone. Simily,enargte oxidation in the presence of pyrite produces scordite (Summitville, Colorado; La Candelaria breecia at Morenci, Arizona; La Grande, Collabuasi distr, Chile). In alow pyrite environment, enagite is replaced by 4 series of apple green to pastel blue copper arsenates such as chenevixite, ceruleite, and lavendulan (e.g, in the weathered epithermal Cu-Au-As systems at El Guanaco and La Grande, Chile, and inte oxide zone at Chuquicamata Chil). EXAMPLES OF COPPER OXIDE DEPOSITS ‘The following examples of setings in which copper oxides of economic importance have developed demonstrate that both the mineralogy ancl amount of copper oxides vary significantly Systems Displaying Limited Copper Mobility 1 Abra. The Fl Abra porphyey copper deposit of northern Chile is an example of supergene oxidation generated within @ reactive hostrock environment (Fig. 5). This world-class ore deposit comprises a well-developed, fracture-controlled copper oxide ‘orebody derived from essentially in sity oxidation of a low-pyite, chaleopyite + bomite + chaleocite protoith assemblage hosted by ore intusions. Host-rock alteration consists of ubiquitous biotite with subordinate K feldspar replacement and veining. Incipient white phyllosilicate overprint of the K silicate assemblage occurs locally and distal tothe K silicate assemblages Copper oxides at El Abra comprise assemblages characteristic of smoderate-pH weathering environments because insuicient pyrite ‘was avaiable for production of low-pH supergene solutions, The oxide orebody outcrops, with surface and near-surface oxides comprising chrysocolla, paramelaconite (Cv,Os, similar in occurrence to tenorite, CuO), and neotocite, shown by X-ray aiffaction studies to be physical misture of Fe and Gu oxides, notably tenon, This assemblage gives way at depth to brochantite and copper phosphates, such as pseudomalachite. Suprajacent to and within the weally developed chaleocite enrichment volume and inthe upper portions ofthe hypogeae sulfide zone, cuprte, native copper, brochantite, and chrysocolla are developed. This latter assemblage displays 2 typical paragenetic sequence in which chaleocit is replaced by the sequence: CChalcocite + cuprite native copper — brochan ite > cheysocolla Because copper graces in the oxide zone are essentially the same as those in the hypogene protlit, i is interpreted that the E} Abra copper oxide-copper sulfide orebody represents in sit oxidation of the hypogene sulfide assemblage, with copper transport limited to perhaps several tens of meters. The development of copper oxides from oxidation of a low-pytite, reactive protolith containing low S/Me ratio minerals at El Abra is similae to that observed at Radomiro Tomic (Acurl and Brimhall, 1998, 1999), and otherAPRIL 2000 * N° 41 SEG NEWSLETTER 7 w E Copper oxides outcrp, with chrysocalla, neotocite (= peramelaconite+tenorite+ FeOx + MnOx), and cuprian clays in upper pars of ‘weathered rock volumes Neotocite+ chrysocolla+ paramelaconite grade downvrard to assemblage of brochantie + Cu-phosphates ‘tecuprian clays; i lower part of oxide zone, supergene ‘haleocit is replaced by cuprite, native copper, local hrysocola, Oxide zone copper grades = 0.55% Cu Protoith comprises borite + 31600 — chalcopyrite + chalcacite ‘with only scant pyrite, protore grades = 0.60% Cu Figure &: Generalized vertical crass section thicugh the El Abra porphyry system, Region, norhem Chile. In sku development of commer ‘onides tem a low pyrite, K i {bn + op + cc) bearing protolkh engendered nearneural pH stable minerals end no signiféent copper grade eniencement in the oxide zone. The copper oxide zone consists of up to approximately 200 m of mineraized host rock, beginning atthe prosent topographic surface. Upper and lower portions ofthe El Abra oxide zone may be defined on tho basis of dominant ‘oppor mineralogy. a8 shown; the lower axide zone alapiays a gradational contact with undetying and erratically developed chaleocke enrichment, Simpitied from Hawley, Moraga, and Molina (pers. cornm., 1999), northern Chile ore deposits hosted by imtermediate volcanic rocks, such as the atacamite-chrysocolla assemblages at Mantos Blancos (Chavez, 1985) and Michilla Soto and Dreyer, 1985). An exotic copper oxide resource (Ichuno) exists adjacent to the principal copper oxide orebody at Et Abra This occurrence may be explained by an Sees exaded copper source rock, possibly a philic Spee alteration assemblage, formerly located Sees ae suprajacent (o the present potassic core of the SEES Lowe limit of SESE OS spe thealon El Abra porphyry system (A. Moraga and A. eae Boling, pers com 199), Pats Vordes, ‘Dreier and Braun (1995) describe the occurence of incipient copper oxide development from the Plt Verdes porphyry copper depen, Sonera, Mesias ——- (Fig, 6). This occurrence comprises a low- si low toa sulle pli hed by an smo se Cees alteration assemblage of biotite + K feldspar + ‘eration assemblage Ahostock) gue *tonmaline, with adjacent ppc provolith Hosted by a phic stration | ———) yee ramen a SSonblge retin copper conenatons “mg ike entero are on the order of 1,500 ppm, as chaleopysite Piedras Verdes represents an excellent ‘example of the conttol of copper oxide cevctopmrent by alteration mineralogy, Whee Figure 6; Varia south noth ooo voaton Wvough a porn f tho Feros Verdes pay epper reactive K silicate assemblages exist, depos, Sonora, México, simplified fom fgue of Dreier and Broun (1995), Upper elagrmn shows weathering has resulted in the in sity gonrl ateretion mineral assemblage dtr, wih host rock corsating of ratio shel evelopment of a hematte-goethitic oxide and minor waredirta porphyry. Dashed tne shows baco of signitcant supergene-desieshostrock assemblage of nearersurface chrysocolla, ateaton thickening int potion of te Gepost charectoried by pie akeretion and developed neotocte, and tenorte, changing with depth 172 a initee extent in K'sloato ateble assomteges. Lower dlagiom depicts copper oxide and Sete create anangiog wih depth Sinise zone. Pedra Verde copper xis ne Wal Joveloped wit the Rete tle cone nepmer putts copper. Copperoxide- eration assembiagos bu show ony Maplent occurence the pic tone. Copper sulides, Pele eee SS EEERERREED vrtesy econ, ar tas jeer to ot essonblges but ae way Svcloped Piedras Verdes are the K siete stala assemblages. Protoresuldes consist of pte = chalopyite & molodente. Overlapping Kia an yl atertion eselages18 SEG NEWSLETTER N° 41 © APRIL 2000 Fra, SUPERGENE OXIDATION OF COPPER SULFIDE DEPOSITS, CONT. essentially equal to those of the hypogene sulfides from th they were derived, indicating that no significant copper transport has taken place (Dreier and Braun, 1995). ‘This spatial distribution of copper oxides and similarity in hypogene-supergene copper oxide grades mimics that ‘observed in portions of the copper oxide zone at San Jorge, Argentina (Williams et al., 1999), and at El Abra, and is interpreted to indicate restricted copper mobility within a ‘weakly mineralized, reactive provolith. The copper oxide minerals observed also indicate a near-neutral pH environment of formation (Anderson, 1982). Notably, where there is phyllic alteration with high pyrite content, weathering-generated oxidation is deeper and better developed, resulting in the formation of a moderately developed chalcocite resource. Dreier and Braun (1995) report that oxidation of the chaleocite enrichment blanket yielded an in situ assemblage of chrysocolla, neotacite, tenorite, and malachite, ‘Mantos Blancos. The Mantos Blancos district of Antofagasta province, northern Chile (Chavez, 1983, 1984), hosts # generally low-pyrite, andesite- to rhyolite-hosted series of bornite + digenite + chalcopyrite # covellite * specularite orebodies. Figure 7 shows a portion of the Nora ‘orebody, and the general occurrence of copper oxides comprising paratacamite (inapped locally as atacamite) and chrysocolla. Hostxock alteration comprises well-developed albitization with subordinate but geochemically important chloritization, specular hematite development, and local replacement by carbonates, Because albitic feldspar and chlorite were available for hydrolysis, and because only limited amounts of pyrite were available for acid generation, the oxide assemblage at Mantos Blancos is characteristic of a near-neutral pH environment, and the copper oxides are thought to represent only local (tens of meters) metal mobility ‘The occurrence of specularte relics within some oxide volumes indicates that acidic solutions capable of transporting cupric ion did not ceact on a wholesale basis with Mantos Blancos host rocks because specularite would have been destroyed during such interaction. The neat- surface occurrence of chrysocolla and subjacent atacamite at Manos Blancos suggests high chloride activity relative to that of available sulfate; this is similar to the mineral zooing and paragenesis described by Arcusi and Brimball (1998, 1999) for the Radomiro Tomic deposit immediately north of Chuquicamata ‘Quetena, Figure 8 shows the Quetona skara-breccia system, northern Chile, in which exotic malachite and alacamite are developed in carbonate clast conglomerates derived from erosion of silty limestones. The protolith mineral assemblage at Quetena consists of pyrite-dominant Monosks are spectre eaieg dees sed styltes wih Joa! som ‘requ deep, ep conta it overing no uct ‘Guenidn Pore dg ee oa epand ty Figure 7: Schemalio eastwost crass section through the Mantos Blancos CuAg system, II Regfon, northern Chile. Host andesitos and tyoltes have been albitzed ‘and vatlaby chloritized, so rocks have substantial capecty for acidneutralizing hydrolysis reactions, Suen reactions Dutter low pH solutions generated vie Westhoringrelated cestruction of protolth sulfides and cetermine the resulting ‘tecamite + chrysocolla oxida minaral assemblage. Copper trensport distances \were very rostrcted inthis environment, probably limited to several tens of meters fend generally along thvaughrgoing fractures, Scant but widespread native copper ‘and silver occur within the copper oxide zone and generally below atacemite: chrysocola Quetena skarn-breccla = system, northern Chile Malachite-tearing gravels miniseanyanie Sedimentary sequence with Limestone, ‘alearoous shale, and pyiie mud stones. Local hydrothermal breccias with py>> op. Graves derived mostly ‘fom carbonate and ranodiorite procliths. Figure 8: Generalized vorlleal orose section through the Quotena ekam-breccla system southwest of Chuquicamata, Chile. Holocene gravels derived from ‘carbonates and calcareous clastic sedimentary rocks conducted acid copper ‘bearing sokations near or at gravetbedrack contact, forming Incpienty developed malachite + atacamte + anhydite as clast coatings. Although supergene solution i was likely very low during Initial oxidation of pyritobearing proto, transport ‘istances for copper were restricted by the highty reactive paleachannel graves; ‘maximum transport distances at Quetena are on the ore af 200 m. sulfides in marble skam and hornfels derived from intercalated | precipitation alternated, despite the obvious carbonate source within stones and mudstones, with locally developed white | the local wall rock and gravels, This is probably because source. phyllosilicate replacement of silciclastic components within the | rock carbor es, although serving as pH bulfers, had elevated local limestones. Malachite and atacamite occur as millimeter-scale | sulfide contents of & to 5 vol percent pyrite. Under such conditions, coatings on carbonate clasts; these minerals form intrlayered rinds, | acidic solutions were generated during weathering and were capable indicating that conditions favoring carbonate and chloride | of liberating and transporting copper from protlth chaloopytite intoAPRIL 2000 « NP 41 the alluvial gravels developed on hill slopes adjacent to the eroding skarn-breccia system, Paragenetically latest anhydrite occurs as millimeterscale patinas covering copper oxides, probably the result of gypsum dehyctraion. The maximum copper teanspor distance at (Quetena ison the order of 200 m, Systems with Evidence for Enhanced Copper Mobility (One of the best-developed leached eapping-copper oxide zone copper sulfide entichment zone sequences is shown by the giant Chuquicamata porphyry system, northern Chile (Little, 1926, 6. Ossandén et al., unpub. data). Jarrell (1944) described the ‘occurrence of copper oxides in the near-surface environment, stuggesting that in-place oxidation of supergene sulfides produced the thick and well-developed copper oxide zones in the original Chuquicamata orebody. Because the Chuquicamata orebody comprises two mineralogically distinct ore types, supergene Oxidation and consequent development of copper oxide mineral assemblages are also spatially and mineralogically distinct. Figure 9 is a schematic west-east vertical cross section through the ‘Chuquicamata mine area, showing the general distribution of oxide ‘minerals in the upper parts of the oreboly Detailed mapping (). Rojas de la Rivera, pers. comm., 1999) shows that two general alteration zones can be defined, comprising K silicates (oith chalcopyrite + bornite + digenite) and phyilic with incipient advanced argillic alteration (with pytite + enargite + goethite, atacamite, and local turquoise-chalcosiderite typical of near-ncutral PH conditions. However, the depth of enrichment is greatly «enhanced in the phylic alteration assemblage, with oxidation on the order of nearly 1 km deep, resulting in a well-developed low pH, sable assembiage of natrojarosite, goethite, chalcanthite, krohinkite, ‘nd antlerite, Below this deeply oxidized rock column is a well. developed supergene chalcocite + covellite enrichment zone that displays an apparently gradual and poorly defined contact with hhypogene pyrite + enargite + covellte + tennantie Because the host-rock phyllic alteration assemblage has only | minor capacity to neutralize acidity, solutions generated from the oxidation of protolith with very high pyrite content produced a very low pHi, stable copper and iron oxide assemblage, dominated by sulfates. These solutions were also able to transport copper away from the near-surface environment until they reacted with reduced sulfur, producing the exceptionally well developed chalcocite + covellte enrichment yolume at Chuquicamata, Lateral transport of copper at the southern margin of the Chuquicamata orebody produced the economically important Mina Sur (Exética) exotic copper deposit (Anguita, 1997; Munchmeyer, 1997), which is paleodrainage system containing copper transported at least 6 km away ftom the Chuquicamata mine area, This scale of copper transport fs similar to that noted in the mineralized gravels of the Huinquintipa Este sector of the Collahuasi district north of Chuquicamata and the Damiana copper resource withi the BI Salvador district, Chile (Mote and = | Brimnall, 197), w Very well developed leached capping and subjacent copper oxide and sulfide enrichment zones: Na-jarosite, alunite, seorodite, chenevixite; goethite >> hm. Cu oxides: krohnkite, marshi ‘chalcanthite, sampleite; anterite > brochantite; Cu sulfides: chalcacite overlies covellite “West Fissure” segment of Domeyko Fault Zone; this structure truncates ‘Chuquicamata hypogene and supergene assemblages Thin leached cap and copper oxide zones comprising red hematite with subordinate goathite; stacamite, brochantte, and turquoise ¢ \— assemblages. Tis also ropresents change from \ en + py + dg + cv hypogene assemblage to bn + y ep + dg assomblage. As a consequence, this | Bradational boundary also delineates change I fom low-pH to near-ncatral-pH oxide ' assemblages. ‘Approximate ce ~ ev contact, ‘Approximate and gradational contact between ‘mapped phyllic and K-silicate alteration ~2000m, Approximate base of supergene enrichment; ‘contact difficult to define due to presence of hypogene covellite, digenite, chaloocite(?) Fieuro 9: Simolfed oastwest vertical profile of the Chuaulcameta, Chile ore deposi, modified silghly from José Rees (pers, comm, 1598), ha wih he Piras Verdes oystem, alteration mineral assemblages control copper and ion oxide dstbuton and zoning. Protolth at Chugulcareta apoees to ave bean a single, large-scale intrusive unt of intermediate composition (Ossandn et a, unpub. datal, $0 copper and itn oxide Sstibutions ave o taneticn of frecture density and alteration mineralogy, including eulbde types ‘supergone and typogene mineral assemblages is difeult to define, appreacnes 4 km. ‘and abundance, rather tan protolth composition, although the contact between vertical column of preserved leaching oxidation enrichment at Chuguloamata20 SEG NEWSLETTER NP 41 © APRIL 2000 ENE OXIDATION OF ‘SULFIDE DEPOSITS, CONT EXPLORATION IMPLICATIONS Copper oxide zones are the product of sulfide destruction produced by weathering under oxidizing conditions, Supesgene sulfides procuced by the same process are not preserved unless development of an oxide profile is limited by water table ascent or the onset of an arid climate (Alpers and Brimhall, 1989), lack of acid-generating sulfides ia a source region, and/or presence of reactive silicates and oxides. Current exploration for copper ore Geposits favors oxide targets because the leaching technologies ‘developed for metal recovery permit mining of relatively low grade imaterials. Consequently, knowledge of the mineral zoning ancl ‘mineralogic composition of copper oxide deposits is important in ‘exploration and economic evaluation of these systems, Copper oxide occurrences display consistent vertical and lateral zoning pateins that mimic the hand specimen-scale paragenesis shown by individual copper oxide minerals. Weathering-derived copper mineral distribution is characterized by a supergene ‘geochemical stratigraphy comprising copper oxides, iron manganese oxides, and copper sulfides, This stratigraphy begins at the surface with a leacied sock volume typified by the occurrence of iron oxides and residual copper and manganese minesals Depending on the distribution of fractures in the host-rock mass, leached zones may occur within and below both copper oxide and copper sulfide horizons, Indigenous copper oxide zones, generated via in situ oxidation ofa sulfide-beasing rock, are usually developed 0 that the most reduced copper oxides (native copper and cuprite) 2re formed in the lower portions of the oxide columa, suprajacent to and replacing supergene copper sulfides. ’As oxidation continues, hydroxy-sulfates ate developed at the expense of native copper and cupite, so brochantit, antlesite, and related sulfates comprise minerals in the topographic middle of an cexide column. AS oxidation matures and acid-generating minerals ‘are consumed, supergene solution pH becomes more moderate, and the upper parts of the geochemical stratigraphy develop chlorides, silicates, and phosphates. Contacts between mineral sub-zones ‘within the copper oxide zone are gradational, and may be erratic if tectonic and/or structural settings allow the phreatic zone and capillary fiinge to vary vertically and/or laterally, Very soluble iron and copper sulfates develop throughout the oxide zone column if oxidizing pyritic sulfides continue to supply acide solutions ‘This bottom-to-op copper oxide zoning is mappable vertically, ‘and in exotic system, laterally (AngKita, 1997; Minchmeyer, 1997). Interpretation of the distibution and mineralogy of copper oxides encountered in surface outerops and in dil hole intervals permits development of a model for the geochemical environments) responsible for metals oxidation, transpor, and precipitation within ‘2 simpled oxidation profile. Copper oxide prospects may then be evaluated for their potential for the occurrence of a target ore ‘mineral assemblage. For example, in exploration for large-tonnage, low-grade deposits, geen copper oxides are a more metllugically favorable taget than a cupste-native copper mineral assemblage. Exploration for brochantte-anterite-chrysocolla would target the middle of a well-developed copper oxide zone or the upper portions of a weathering profile showing only incipient development ‘The lateral mineral zoning a the margins of a weathered sulfide ore deposi including exotic mineral occurrences, can be used 10 fssess the geochemical maturity of the oxidation environment and the dlsection() fiom which supergene solutions deposited copper minerals, Integration of geochronologic results with studies of, landform development, geomorphology, and the distribution of copper oxides and sulfides (eg, Clark, 1967; Silltoe and McKee, 1996) provides complementary information useful in assessing the geologic history of an exploration target, and the consequent economic potential of copper oxide ore deposit occurrence Metallurgical studies will dicate which porns of a copper oxide assemblage, if any, are economically extractable if host-rock reactivky i recognized to be high. At the termination of mining, Understanding copper oxide mineral genesis is useful in diecting efforts at mine remediation and ultimate recovery of copper from mine wastes. ACKNOWLEDGMENTS It is a pleasure t0 acknowledge thoughtful and constructive reviews ofthe intial draft ofthis manuscript by Jeff W. Hedenquist, Pepe Perellé, and David Hopper. Continued study of supergene copper ore deposits by the author has benefited by the contsibutions ‘of New Mexico School of Mines graduate students J.A. Amarante, D. Diikine, W. Jonas, A. Miockichowski, P, Pinson, W. Seibert I, and C. Spencet. Discussions with D. 8. Andrews, W. Galvez, A. Moraga, A. ‘Molina, W. Orquera, J. Pizarto C, J. Rojas de la Rivera, F. Ramizez and J. Vega E. were instrumental in developing ideas concerning the paragenesis of weathering copper deposits. Roger Nordin and Rafae! wavartia of Compania Minera Boliden and Femando Le6n P. of Minera Lomas Bayas provided useful commentary on copper mineralogy and the depths of oxidation in some areas of noxthern Chile. Field observations by . Ayala F., S. Enders, j.W. Hawley, RAM. North, R Stegen, and S.R. Titley were especially useful in interpreting southwest North America oxidized orebodies. rich U. Petersen suggested the idea of using the SEG web page to include additional information and photographic documentation of copper oxide mineralogy, his savvy and skill are muy agradecido, ‘The patience and support of Noel C. 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(See especially Figures 2 and} Schwartz, G.M., 1834, Paragenasis of he oxidized oree of copper Economic Geaiogy. v.29, p. §5=75, Sitltoe, P.M, and HicKee, E., 1090, Age of supergene oxidation and ‘enrichment in ie Chilean parpyy Copper prownce: Econersie Geology, V9, p. 164-179, ‘Soto PH, Dreyer P., Hy, 1985, Geobgla de ‘Mina Susana,” Un yacerianto ‘ovedoso en Carita de Michi: Cuarto Congresa Geokscn Chen, ¥-2,p. 3543-382, (ri Spanssh mth Engish aberact) Titey, S.A, 1882, The sie and progress Of mineralzaton and altoraton in orpiy'y copper systems, Ametican Southwast, in Tiley, St 0. Advances. in goology of the porphvy copper deposits, Scuthwester Nort America Tucson, Aizen, University of Atizona Prass, 0. 23-166. Tite, S.A. end Marazas, D.C, 1995, Processes and precuts 0! super pene ‘copper ervichment, inPerce, W., and Gam, J.G,, eds, Porphyry copper deposits of ine American Cerdilera: Azone Geological Socity Dies! 20, p. 186-168. Velasco, J.A, 1966, Geology of the Cananea clstict, in Tiley. SR, and Hicks, C.L, ed, Geology of tho porphyry copper donesits southwestern Nonh'Amerca: Tusson, Arizona, The Unwocsyof Azona Press, p. 248 234 Walder, LF, and Chévez, W.X, Jt, 1995, Winetaiogical and gaochemical behavior of mill tailing material produced trom lead zinc skarn mineralization, Hanover, Grant County, Now Mexioo: Environmental Geciogy, v.28, p. 1-18 Williams, P.A., 1990, Oxide zone geochemistry: Chichester, England, Ells Howwond Lime, 285 p. ‘atlas, W.C., Melssl, E, Madrid, J, and de Machuca, B.C., 1999, The ‘San Jorge porpyry copper deposi, Mendoza, argentina: A combination Of ofthamagmatie ane hygromermal mineralization; Ore Goology Fovows, v.14, 185-201. @D ncyme Leach the discriminating selective extraction ‘Osodium Pyrophosphate - the selective extraction for organics ‘Geght adltionatsalectve extractions for speciic purposes ‘Explore for bind deposits with Acinbseelectve ‘gxtractions fr gold base metal, REE, ‘lamonds, petroleum... succesfully used ina varaty of climates, types ‘tcover,terrsine and terrane. ‘Activation Laboratories Ltd 1336 Sanahit Drive SOURED “Ancaster, Ontario ecu ven oman avs briesce “Hibosicen gen Sethe Fo $1.905648.9013 — pendetiaceey E-mait ancestarGactiabr.com a Acti Styling Actinbs Pacinc Pty Ltd 11775 West SshuaroDrive 25 Bungana Avenue, “Tueson, arizona Redelife, Wester Australis 6305 astral ‘el: ¥61.8.977:708.95, Fae $61.8927.770.08 ‘Email: perth@aclabs.com tp oeactadscom Uutogeochemisry —Sogeochemisry Mpérogecchenisy Enzyne LacJULY 2000 © N° 42 SEG NEWSLETTER 3 We’ve Moved! Our new Headquarters address is: Society of Economic Geologists. Inc. Society of Economic Gi Economic Geology 7811 Shatfor Parke Ne > Tel. *720.981 768 xo Esmall: seg@segweb.org, — suff Phond cot ¢ John A. Thoms .» development@segweb ore Thomas A Lowey 207 nn oatuerOstgveb os membership@segveb.org| ~sitktng@segveh ort Jounal Sutserptione Hoan Thome enn 208 suman SUDSCriptionsesegwe.org Publications Production Lis Lalla: 208 snnrn publications @segwen.org Pubcon Bing ‘Alice Bouley..... editing@segwod org Corrections and Amplifications Several of the mineral formulae in Table 3 (p.13) of the article by William X. Chavez, Jr, in the April 2000 issue (No. 41) of the SEG Newsletter were misaligned with respedt to siineral names. The conect {able is reprinted below, You may also download an updated version of Page 13 ints entirety, Featuring the corected table, from the SEG website: worn. segwch.org/seghome/Segframes/newslerer/p pal. Table 3. Minerals Commonly Found in the Oxide Zone of Copper Deposits + CugChOH), = CuSO, 3H40 uSO,(0H) + CugA (AsO (OH) 12,0 uso, CChalcantite (compare to hr)... CuSO, 8H,0 Shlomo toi)... Cage Cheneviste.... Cup Fe? ¥71As0,) {OH HLO Chysocolefineraoid) + CulFe.Mtn)Ox-Sid,- HO, with ‘copper content varying fom ~20-40 1% Cu opiapite ss... 7 -Fo{SO,le OH); 20H,0 Coquinbite. sesscsse Fe{SO,ly9H20 Goetite. . + -F0O0H darosite +s KFoy{SOh(OMls Krthaite + NagCufS04)y 24,0 Lavandlan, 2.0000 NabaCu®*(AsOly0 54,0 Uiethente, 2 Cu,P0,(08) Parameleconito : 2405 (600 tonoite (CuO) and cuprite (40) Potente {Cu.FeZn}SO¢H,0 Postakite CuSO4OH HO Pseudomalecite see Wbetherte)..........Cux(PO,h(OHly ‘Scorodite {see choneviit) + Fort *AS0,-2H,0 Turquoise Vols... Wrowwolete Langit uA PO (OH}4H,0 + ef Al{S0,)10H,0 u,S,(0H 24,0 EXPLORATION TRAINING ON CD-ROM BS Ea ere eS ET delivered in the workplace s in the EXPLORE! scries include: ed ea NNT ott BE Cake Sen Rca ce aa rt} Mer ae spirit.com.au