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SEG
NEWSLETTER NEWSLETTER
APRIL 2000 HSOCIETY OF ECONOMIC GEOLOGISTSH NUMBER 41

Supergene Oxidation of Copper Deposits:

Zoning and Distribution of
Copper Oxide Minerals
WILLIAM X. CHÁVEZ, JR. (SEG 1990)
MINERALS & ENVIRONMENTAL ENGINEERING DEPARTMENT • NEW MEXICO SCHOOL OF MINES • SOCORRO, NEW MEXICO, USA
87801 TEL. +1.505.835.5317 / FAX: +1.505.835.5252 • E-MAIL: [email protected]

ABSTRACT SUMMARY
Copper oxides represent an attractive exploration Copper oxides comprise an important source of the red metal, especially
target because even low-grade prospects have the in deposits suitable for “leaching—solvent recovery—electrowinning” type
potential to produce low-cost copper in an environmentally treatment. This article describes the zonation and occurrence of copper
friendly fashion. Derived from hypogene and/or oxides derived by supergene processes affecting a protolith with copper
supergene sulfides, copper oxides comprise a series of and iron sulfides, hosted by several mineralogical associations of alteration.
distinct assemblages that characterize a variable pH, The deposits considered are mainly copper and molybdenum porphyries,
oxidizing geochemical environment known as “the oxide and skarn-type systems.
zone.” Development of oxide copper minerals is a Geochemically, the most important mineral that influences the
function of source-rock and host-rock mineralogy, pyrite distribution of weathering products in a metalliferous deposit of the
and other (copper) sulfide abundance and distribution, porphyry copper type is pyrite. This mineral generates, in significant
fracture density and distribution, phreatic and/or vadose quantities, sulfuric acid (SO4 = and H+) and iron (Fe+++ and Fe++). These
zone occurrence and stability, and maturity of the weatheringcomponents profile . of meteoric (supergene) solutions function as leachants,
The paragenesis of copper oxide mineral formation producing mobilization of copper and other base metals from the volume
reflects local, dynamic changes in supergene solution of the leached rock and resulting in the formation of the “leached
composition attributable to reaction between host-rock capping” (see Figure 1). These components accumulate, influenced by
mineral components and dissolved species. Especially the geochemistry of the host rock and the solutions that transport these
important are the concentrations of Fe+++ (vs. Fe++), components, in the form of oxides and/or sulfides, forming a volume of rock enriche
SO4 =, H+, and Cu++ (vs. Cu+). Because mineral In the oxide zone, minerals containing oxidized copper (Cu++, with
assemblages, even those that are metastable, represent lower Cu+ and native copper) comprise the main source of copper. The
the geochemical environment in which they formed, paragenesis of oxides reflects geochemical changes in the solutions that
identification and mapping of copper oxides is useful in provide copper over time. Thus, the precipitation of the oxides generally
interpreting the geochemical history of an oxide zone. follows the sequence detailed in Figures 3 and 4. Development of the
Furthermore, practical application of oxide zone vertical and/or lateral sequence of copper oxides is a function of (1) the
geochemistry is significant in the recognition and solution time available for weathering and accumulation (maturity of supply and
of problems associated with weathering-engendered
storage) of metals derived from sulfides (maturity of weathering profile),
metals oxidation and transport from mine wastes.
(2) composition and reactivity of source rock(s) and host rock(s) (3) pH of
transport solutions metals, (4) distribution and density of structures
SPECIAL NOTE: Readers will find more information about the copper (fractures, fracturing zones), and (5) tectonic stability and vertical
oxide minerals mentioned in this article by referring to the SEG web site
fluctuation of the water table. Applications of oxide zone geochemistry is
[http://www.segweb.org]. Photographs showing mineral relationships
and paragenetic associations allow readers to further understand the
important in solving environmental problems associated with mine waste,
nature of copper oxide assemblages and their geochemical and physical especially oxidation and leaching from tailings, waste
settings. rocks, and abandoned leach pads. to page 10 ...
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10 SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF COPPER deposits are characterized by minerals containing base metals and
... from 1 SULFIDE DEPOSITS, CONT. reduced Fe and S. Figure 1 shows a schematic model of the
components of an oxidizing rock volume containing sulfides and
INTRODUCTION AND BACKGROUND the location of the “oxide zone.” In examples considered in this
Despite low metal prices, mining and exploration for copper article, the pre-oxidation sulfide assemblage (protore) consists of
continue at a significant pace. Recovery of copper by leaching pyrite and chalcopyrite, and contains sufficient pyrite to overcome
methods is economically more attractive than by conventional ore at least some neutralizing capacity of host-rock minerals. The
milling, so many companies are concentrating their mining and “oxide zone” consists of the rock volume in which copper oxide
exploration efforts on copper oxide minerals. This article describes minerals are stable and are the dominant copper minerals.
the nature and distribution of copper minerals occurring in oxide THE WEATHERING ENVIRONMENT
accumulations associated with weathering of copper sulfide
The weathering environment may be considered to have three
deposits, with emphasis on minerals that occur in the supergene
main geochemical domains. Although the contacts between these
oxide zones of porphyry copper and skarn ore deposits. “Copper
domains are gradational, each is characterized by distinct
oxides” are defined as those copper minerals containing oxidized
conditions of oxidation state and pH. These three domains are (1)
anions, especially copper oxides, sensu strictu, sulfates,
a source region, comprising the volume of rock undergoing
phosphates, carbonates, and arsenates.
oxidation and mass loss; (2) a sink region(s), where mass from the
The oxidation of sulfide minerals, especially pyrite, is critical in
source region accumulates and which includes residual (unreacted)
determining the geochemical environment that characterizes a hypogene minerals — the oxide zone discussed in this paper
weathering sulfide-bearing rock volume. Sulfide destruction creates comprises part of this geochemical sink; and (3) protolith, the
solutions containing hydrogen ions, metal ions, and sulfate; these essentially unreacted material comprising pre-oxidation mineral
solutions must be at least partially neutralized if the metals of assemblages. In some cases, if warranted by the metal
economic significance are to be redeposited. One of the most concentrations, the protolith is termed protore or quasiprotore
important factors influencing the generation of the acid sulfate- (Alpers and Brimhall, 1989). The mineralogy of the source, sink,
bearing solutions is the ratio of reduced sulfur to metal in sulfide and protolith rock volumes varies according to whether mass
minerals before oxidation. transport from the source region to the sink region is geochemically
Weathering results in significant geochemical changes in the significant or minor. These geochemical domains are summarized
oxidation state of a sulfide-bearing mineral deposit because most ore in Table 1.

Figure 1: Schematic diagram showing the weathering environment of a sulfide-bearing mineral occurrence. Three component zones comprising the simplified
weathering profile are shown, with mineral assemblages characteristic of the oxide zone displayed to the right of the diagram. See Table 2 for ranges of copper
values in the zone of leaching.
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APRIL 2000 • No. 41 SEG NEWSLETTER eleven

Oxidation of pyrite involves a series of stepwise processes

Table 1. Mineral Assemblages in Geochemical Domains in High and resulting in the generation of “protominerals” such as schwertmannite
Low Mass Flux Conditions and ferrihydrite, the solubility of which is a function of the production
of Fe+++ and Fe++, pH, and SO4 = activity (Murad et al., 1994).
Dominantly Transported Dominantly In Situ The combination of sulfate as a complexing anion, hydrogen ions
Fe and Cu oxidation (ie, acid conditions), and atmospheric oxygen to enhance and
maintain an oxidizing environment results in destruction of sulfides,
Source Reactivate sulfides Low total sulfide volumes or oxides, and silicate minerals (Titley, 1982; Titley and Marozas,
with jarosite, low S/metal sulfides 1995) . Importantly, the relative susceptibility to oxidation of sulfide
goethite » hematite; Quasi-in situ oxidation and minerals determines the sequence of sulfide mineral destruction,
Residual pyrite, chalcopyrite; precipitation of hematite; the consequent availability of metals for supergene transport, and
alunite, Al-Fe sulfates hematite> to » goethite, the nature and zoning of resulting minerals (Bladh, 1982). Figure 2
jarosite shows the general succession of sulfide mineral destruction by
chalcocite replacement, as observed from paragenetic relationships
sink Chalcanthite, bonattite, Atacamite, brochantite, shown by oxide-sulfide zone assemblages.
antlerite, brochantite, native copper, Boyle (1994) shows a similar sequence for sulfide replacement
posnjakite; local native chalcosiderite, cuprite, within sulfidic tailings undergoing oxidation.
copper tenorite, paramelaconite,
Chalcocite, covellite, pyrite, malachite, phosphates; Hierarchy of sulfide mineral destruction via
chalcopyrite local alunite; residual supergene chalcocite replacement
Also: alunite, As-Fe oxides, chalcopyrite, bornite,
arsenates pyrite
Rapid Slow
Protolith Pyrite, chalcopyrite; traces of Bornite, hypogene chalcocite, Sphalerite, Bornite
bornite, pyrrhotite chalcopyrite, ±pyrite
Galena, Sulfosalts, Enargite
Arsenopyrite, Chalcopyrite, Pyrrhotite, Pentlandite
Well-developed copper oxide zones appear to form through two Marcasite, Pyrite
distinct mechanisms: (1) via substantial copper addition to a volume Figure 2: Paragenetic diagram showing the general succession of sulfide
being oxidized, including the formation of exotic copper deposits, mineral destruction by chalcocite replacement, as observed from paragenetic
and (2) through in situ oxidation of a copper-bearing sulfide relationships shown by oxide-sulfide zone assemblages.
resource . Importantly, the first type of copper oxide system requires Boyle (1994) shows a similar sequence for sulfide replacement within sulfidic
copper transportation from a source region, but the protore does not tailings undergoing oxidation.

need to have high copper content if leaching and precipitation are

efficient. Conversely, the second type requires substantial protolith The oxidation of sulfides other than those of iron produces only
copper content if the copper oxide zone developed is to be of modest quantities of acid sulfate-bearing solutions (Anderson, 1982;
potential ore grade, and also requires that removal of copper be Williams, 1990), a factor which is significant in determining the types
minimal. and distribution of oxide minerals developed within a zone of
Distinction between these protore environments is significant in weathering ( see below). Therefore, pyrite oxidation is generally the
exploration for copper oxide and supergene sulfide enrichment most important source of the acidic solutions responsible for mineral
targets because prospects dominated by reactive rock units are destruction during the weathering of a rock volume. This means that
likely to display only incipient copper enrichment unless an adjacent pyrite quantity is critical in determining oxide zone mineralogy.
or eroded non-reactive source-rock volume was available to provide Pyrite is a relatively refractory mineral in the replacement
transported copper . For example, an eroding phyllic or argillic sequence; Marcasite oxidizes more quickly than pyrite (Mason and
alteration zone of a porphyry system may provide copper to a sink Berry, 1968), and pyrrhotite oxidation is as much as two orders of
comprising a reactive (K silicate or propylitic) rock mass, whether in magnitude faster than oxidation of pyrite (Nicholson and Scharer,
situ or exotic. This is why in situ copper occurs at El Abra (see 1994). Laboratory observations of Fe sulfide oxidation are
below), Lomas Bayas, Mantos Blancos, and Radomiro Tomic, and corroborated by the para-geneses of oxide and sulfide minerals
exotic copper occurs at Mina Sur (Exótica), Huinquintipa, El Tesoro, reported from oxide zones: it is observed that pyrite shows incipient
Ichuno, and La Cascada, Chile (Münchmeyer , 1997). or no significant corrosion- replacement even when other sulfides in
To generate the first type of copper oxide occurrence, a source the same oxide volume display substantial oxidation, as in leached
caps or gossans, or variable replacement by oxides or sulfides —
region must be available to supply copper via oxidation and leaching.
as seen at Chuquicamata (Flores, 1985; G. Ossandón et al., unpub
Pyrite is the most significant source of oxidized S and, indirectly,
data1) and Mantos Blancos (Chávez, 1983), Chile; and Lakeshore,
hydrogen ions, in a sulfide-bearing rock volume undergoing
Arizona (Cook, 1988; Huyck, 1990). Therefore, for pyrite to provide
weathering. It is also a substantial, if not dominant, source of
a significant source of acid sulfate-bearing
oxidized iron. As these components are intimately involved with to page 12 ...
solutions, weathering conditions must be strongly oxidizing.
copper mobilization from the source region, oxidation of pyrite is
important to generate a well-developed copper oxide ore deposit via 1 Ossandón, G., Fréraut, R., Rojas, J., and Gustafson, LB, in review, Geology of
copper addition. Chuquicamata Revisited: Economic Geology.
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12 SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF COPPER sulfides; Locke, 1926) or gossan (developed from massive sulfide bodies,
... from 11 SULFIDE DEPOSITS, CONT. including skarn-hosted sulfides).
The extent to which the leached capping, oxide volume, and sulfide
Other sources of acidic solutions, although generally minor compared
enrichment volume are developed depends on the amount of acid-
to sulfides, include magnetite and Fe-bearing silicates.
producing sulfides in the rock volume, the neutralizing capacity of the
Silicate minerals that contain Fe++ are susceptible to oxidation, and
minerals in the host rocks, the density and extent of host-rock fracturing,
minerals such as biotite, Fe amphiboles, Fe pyroxenes, and Fe-bearing
garnets (eg, the La Democrata skarn system in the Cananea district, and the nature and duration of local and regional weathering conditions
México) may contribute to the generation of acid solutions during (López and Titley, 1995). Although removal of metals from the leached
weathering. This is because ferric iron, produced during mafic mineral capping may be very efficient, residual copper and iron are always
oxidation, generates goethite plus hydrogen ions via reactions such as: present in detectable quantities and comprise the geochemical anomalies
—both positive and negative—important to minerals exploration and to
environmental considerations of waste-rock disposal.
Fe+++ + 3H2O = Fe(OH)3(s) + 3H+ (aq) (1)

The same type of reaction explains why magnetite, a common Table 2 provides examples of the residual copper values reported
component of ore deposits, is capable of producing acid solutions even from leaked rock volumes over porphyry copper deposits. Copper
from mineralized rocks having scant or no sulfide minerals. contributed from rock masses undergoing oxidation and removal of
metals and sulfate is transported by acid solutions, dominantly as cupric
LEACHED CAPPINGS: copper. Figure 3 shows the general parageneses for copper phases
SOURCES OF METALS related to different protolith sulfide assemblages for relatively reactive
The metals that ultimately accumulate in the oxide or sulfide protoliths.
enrichment zone are derived from the volume of rock that has undergone Copper is mobile at low pH, so copper occurrence in some
oxidation and metal removal, referred to as the leached capping environments may be represented by cupric ion as well as by minerals.
(developed from disseminated and fracture-controlled Although copper oxide minerals display a wide range of

Figure 3: Oxidation path diagram showing paragenesis of copper oxides derived from low to moderate total pyrite protoliths. Note that the ending paragenesis,
developed in geochemically mature copper oxide zones, comprises a series of Cu + Fe ± Mn oxides, dominated by hematite (rather than goethite or jarosite).
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APRIL 2000 • No. 41 SEG NEWSLETTER 13

Table 2. Copper Content of Leached Cap Volumes

COPPER OXIDE ZONE DEVELOPMENT
The oxide zone is defined as the rock volume representing a
DISTRICT LEACHED CAP COPPER CONTENT redox environment transitional between the very oxidized
conditions present in the leaked capping and the reduced
X0 to low X00 ppm Cu derived from pyritic
conditions characterizing the supergene sulfide zone. Oxide
Cananea, Mexico protolith with jarositic-goethite dominant
zone mineralogy reflects variably oxidized and reduced
capping
conditions, with mineral zoning exhibited on both large and small
Up to 2,000 ppm, as contamination from relic
scale. Table 3 lists minerals commonly found in the oxide zone
Cerro Colorado, Chile hypogene sulfides and residual supergene
and leaked capping of porphyry copper deposits.
chalcocite ± Cu oxides
Table 3. Minerals Commonly Found in the Oxide Zone of Copper
700 to 1,500 ppm in a hematitic leached cap, Deposits
Quebrada Blanca, Chile probably derived from the incomplete oxidation
of former chalcocite
Alunite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . KAl3(SO4)2(OH)6
Antlerite . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cu3SO4(OH)4
Less than ~100 ppm in “superleached” cap,
Atacamite (paratacamite, botallackite). . . . . Cu2Cl(OH)3
La Escondida, Chile enhanced through chloride activity and
Bonattite . . . . . . . . . . . . . . . . . . . . . . . . . . . . CuSO4·3H2O
essentially inert host rocks
Brochantite . . . . . . . . . . . . . . . . . . . . . . . . . . Cu4SO4(OH)6
No leached cap in well-developed K silicate Ceruleite . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cu2Al7(AsO4)4(OH)13·12H2O
stable protolith with cp + bn + cc protore Chalcanthite (compare to kröhnkite) . . . . . . . CuSO4·5H2O
El Abra, Chile (~0.65% Cu) and in situ chrysocolla + Chalcosiderite (compare to turquoise) . . . . . CuFe6(PO4)4(OH)8·4H2O
brochantite + pseudomalachite + neotocite Cu- Chenevixite . . . . . . . . . . . . . . . . . . . . . . . . . . Cu2 Fe+++2(AsO4)2(OH)4·H2O
oxide zone (avg ~0.55% Cu) Chrysocolla (mineraloid) . . . . . . . . . . . . . . . . Cu(Fe,Mn)Ox-SiO2- H2O, with
copper content varying from
X0 to 800 ppm Cu; protore Cu concentration ~20-40 wt-% Cu
Morenci, Arizona
approximately 1,200–1,500 ppm Copiapite. . . . . . . . . . . . . . . . . . . . . . . . . . . . Fe5(SO4)6(OH)2·20H2O
Coquimbite . . . . . . . . . . . . . . . . . . . . . . . . . . Fe2(SO4)3·9H2O
200 to 400 ppm in jarositic to goethitic leached
Goethite . . . . . . . . . . . . . . . . . . . . . . . . . . . . ÿ-FeOOH
Tyrone, New Mexico cap developed from pyritic protolith containing
Jarosite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . KFe3(SO4)2(OH)6
700–1,200 ppm copper
Kröhnkite. . . . . . . . . . . . . . . . . . . . . . . . . . . . Na2Cu(SO4)2·2H2O
X0 to low X00 ppm Cu in hematitic to goethitic Lavendulan . . . . . . . . . . . . . . . . . . . . . . . . . . NaCaCu++5(AsO4)4Cl·5H2O
leached cap developed over phyllic-argillic Libethenite . . . . . . . . . . . . . . . . . . . . . . . . . . Cu2PO4(OH)
Santa Rita, New Mexico
alteration of monzonitic hosts; local native Paramelaconite. . . . . . . . . . . . . . . . . . . . . . . Cu4O3 (see tenorite (CuO) and
copper cuprite (Cu2O))
Poitevinite. . . . . . . . . . . . . . . . . . . . . . . . . . . (Cu,Fe,Zn)SO4·H2O
Up to 1,000 ppm in poorly developed leached Posnjakite . . . . . . . . . . . . . . . . . . . . . . . . . . . Cu4SO4(OH)6·H2O
Radomiro Tomic, Chile
volumes derived from K silicate protolith Pseudomalachite (see libethenite) . . . . . . . . Cu5(PO4)2(OH)4
Scorodite (see chenevixite) . . . . . . . . . . . . . Fe+++AsO4·2H2O
Leached and oxidized rock volumes contain X00
Turquoise . . . . . . . . . . . . . . . . . . . . . . . . . . . CuAl6(PO4)4(OH)8·4H2O
Lomas Bayas, Chile ppm copper with residual Cu values to >1,000
Voltaite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . K2Fe8Al(SO4)12·18H2O
ppm as sulfates, chlorides
Wroewolfeite (Langite) . . . . . . . . . . . . . . . . . Cu4SO4(OH)6·2H2O
No significant leaked cap in humid, high-rainfall
Cerro Colorado, Panama (>4,000 mm/year), steep terrain; protolith
Copper oxide minerals form (1) though direct precipitation as
copper concentrations 4,000–9,000 ppm
supergene solutions reach saturation with a specific mineral
component(s), or (2) via replacement of sulfides, oxides, or
silicate minerals. In most environments, oxidation of hypogene
stability, specific suites of copper oxides are useful in limiting the sulfides with high S/metal (S/Me) mole ratios, such as
interpretations concerning weathering environments and the pyrite,marcasite, and pyrrhotite, results in at least incipient
genesis of copper oxide minerals (Locke, 1926; Schwartz, 1934). destruction of the original sulfide and the resulting dissolution of
This indicates that copper oxide minerals represent broad iron as Fe+++ and sulfur as SO4 =. However, oxidation of sulfide-
conditions of oxidation and pH; Nevertheless, the mineralogy of bearing rocks with low total pyrite content and of minerals with S/
a given oxide assemblage is very useful in assessing the Eh-pH Me ratios of approximately unity, such as chalcopyrite, idaite
conditions of copper oxide formation, including those conditions (Cu3FeS4), pentlandite, enargite, and arsenopyrite, usually
responsible for copper transportation and deposition. The results in the formation of combined Fe and metal oxides having
following section describes the formation of copper oxides and geochemically limited mobilities because there is insufficient
associated minerals in the oxide zone of a weathering mineral acidity generated during weathering to ensure
deposit containing disseminated and fracture-controlled sulfides. to page 14 ...
complete removal of the original mineral components. For this reason, cha
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14 SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF COPPER mineralogically distinct because the geochemical conditions that
... from 13 SULFIDE DEPOSITS, CONT. form the various assemblages are dictated by specific combinations
of sulfide and host-rock mineralogy, structural setting of the
Oxidation generally leads to the development of local hematite ±
weathering rock mass, and lithological variations.
goethite halos adjacent to the replaced mineral grain, accompanied
These geochemical conditions produce the mappable mineral
by copper oxides that are stable in the near-neutral to moderately
low pH range. assemblages characteristic of the oxide zone. Interpretation of the
Figure 4 shows reaction paths for copper oxide minerals formed environment of formation of the mineral assemblages is an
within (1) reactive host rock and (2) relatively non-reactive host important part of the economic evaluation of copper oxide (and
rock, starting with a protolith containing pyrite, chalcopyrite, and sulfide) prospects. For example, chalcocite oxidation and leaching
minor bornite. The geochemical reactivity of host rocks is significant produces an assemblage of Fe oxides referred to as “live
(Marozas, 1982; Pinson, 1992) because the quantity of silicate limonites”; This term really refers to “red hematite-dominant” Fe
minerals available for acid neutralization directly influences the oxide assemblages, generated as a result of copper removal by
local leaching and oxide zone geochemical environment. Although supergene solutions derived from residual acid production. Thus,
the abundance of reactive minerals is important in determining the generation of red hematite during oxidation of supergene
how a rock mass will react to acidic solutions, reaction kinetics sulfides having very minor iron may be explained by the oxidation
may inhibit the ability of a reactive protolith to neutralize acid, of chalcocite in low-pyrite or high-pyrite environments, as in the
sulfate-bearing solutions. The relatively slow reaction of most following reactions.
silicates with acidic solutions
generated via pyritic sulfide
oxidation is especially notable in
mine environmental remediation
studies in which reactive silicates
comprise part of the acid-buffering
component of a mine waste
(Walder and Chávez, 1995).
The mineralogy of the host rock
plays a very significant
geochemical role in the
development of the gangue and
ore mineral assemblages occurring
in the copper oxide zone. This is
because host-rock silicates and
oxides, compris-ing the
volumetrically dominant minerals
in the weathering environment,
offer exchangeable cations and
thus 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
of a wall rock to neutralize acid,
sulfate-bearing solutions. This
buffering capacity is limited in rock
that has already been subjected
to phyllic, argillic, and advanced
argillic alteration, because
phyllosilicates and clays
characteristic of these assemblages have only limited capacity to exchange cations for H+.
In Figure 4, arrows show the
sequential development of copper
oxide and associated sulfides, Figure 4: Paragenesis of copper oxides starting with a pyrite-dominant protolith. Copper oxide assemblages are a
function of successive oxidation-mobilization-accumulation cycles, with paths shown for geochemically reactive and
with paths determined by protolith
nonreactive host rocks. Lower tier shows mineral assemblages resulting from various oxidation scenarios, beginning
sulfide ratios and the completeness with a supergene sulfide assemblage. The oxidation of sulfidic mine wastes mimics that shown here for natural
of weathering reactions. The paths systems, with corresponding applications for environmental remediation of abandoned minesites.
lead to oxide assemblages that are
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APRIL 2000 • No. 41 SEG NEWSLETTER fifteen

A low total residual pyrite environment results in the formation of substantial Discusses copper mineral paragenesis and spatial zoning in the context of
ferrous sulfate, which participates in oxidation reactions as follows: mineralogical associations, protolith compositions, and host-rock alteration
assemblages.
Copper deposits in which pyrite is a volumetrically significant component
Cu2S(s) + 2Fe++SO4(aq) + H2O + 3O2 = are characterized by copper oxide assemblages reflecting low pH environments.
chalcocite + ferrous sulfate
Pyrite rarely shows direct replacement by copper oxides because the
+ H2SO4 microenvironment developed by pyrite oxidation is usually so acidic that only
Fe2O3(s) + 2CuSO4(aq) red
hematite + cupric sulfate (2) copper sulfates and an attending series of iron sulfates, such as jarosite,
coquimbite, copypite, melanterite, and voltaite, are stable. For example, if
If residual pyrite content of an oxidizing protore is relatively high, this results pyrite contents are such that the neutralizing capacity of host rock is exceeded
in generation of ferric sulfate, which participates in oxidation reactions as and pH of <2 solutions are generated, the copper sulfate minerals bonattite,
follows: chalcanthite, kröhnkite and wroewulfite are stable (Table 3). These minerals
form in the uppermost parts of the oxidation system, topographically above
Cu2S(s) + Fe+++2(SO4)3(aq) + 2H2O + 2.5O2 = near-neutral pH-stable sulfates such as brochantite, posnajkite, and antlerite.
chalcocite + ferric sulfate
Evidence of such low pH conditions and the mineralogy produced in the oxide
zone is present at Chuquicamata (Jarrell, 1944), Fortuna de Cobre (R.
Fe2O3(s) + 2CuSO4(aq) + 2H2SO4 red
hematite + cupric sulfate (3)

In each environment, copper is released and hematite takes the place of Nordin and R. Chavarría, pers. comm., 1999), Lomas Bayas, and Cerro
the now oxidized and dissolved copper sulfide. At least traces of copper remain Alcaparosa, Chile. A similar environment is generated during the post-mining
associated with the newly generated red hematite. This copper may occur as oxidation of pyritic sulfide ore deposits and mine
“geochemical copper” adsorbed onto the surface of iron oxides or as minute wastes.
grains of distinct copper minerals admixed with the red hematite. The If sufficient copper is available in an oxidized solution, and if reduced sulfur
association of abundant hematitic Fe oxides with trace copper is common in is present, the minerals chalcocite, djurleite, and digenite replace pyrite.
leaked environments, which otherwise show no obvious copper oxide Covellite, idaite, and covellite-like sulfides replace chalcopyrite and bornite,
occurrence. These oxides are termed “almagre” or “sangre de toro” in Central and rarely, pyrite. Chalcocite and digenite are the most common replacement
and South America, and may contain economically important quantities of products in the upper portions of a sulfide enrichment zone, with covellite at
copper. In some cases, the copper may occur as cuprite or native metal, greater depths (Flores, 1985); djurleite is the most abundant supergene copper
rendering copper recovery difficult (eg, portions of the Ray, Arizona, oxide sulfide in some ore deposits, eg, Michilla (Soto and Dreyer, 1985) and San
zone). In cases where pyrite was present in stoichiometric excess (usually Bartolo (Flint, 1986), Chile. However, successive replacement of chalcocite
greater than 5–7 vol % pyrite), its oxidation may produce enough acid to and digenite is common when the composition of an oxidized supergene
remove essentially all iron and copper, such that supergene iron oxide solution changes as pyrite is consumed in the source region(s). Hence,
abundance and copper content may each be minor. moderate pH stable oxide minerals are favored, resulting in copper sulfide
replacement by geochemically appropriate copper oxides.

With the descent of metal-bearing, acid sulfate-rich fluids, hypogene

sulfides may be replaced initially by chalcocite, djurleite (Cu1.96S) or digenite Copper oxide mineral associations generally are consistent because
(Cu1.8S), with subsequent replacement of these sulfides by copper oxides as oxidizing sulfide systems experience a consistent series of chemical reactions
availability of reduced Sulfides diminish as sulfides are consumed. Covellite that allow only the development of characteristic mineral paragenetic
develops in environments that lack abundant dissolved Cu++, usually by in relationships. Brochantite replaces chalcocite in weathering systems in which
situ oxidation and replacement of chalcopyrite or bornite, rarely pyrite. Hence, moderately low to near-neutral pH values are maintained, such as in portions
the paragenesis of sulfide replacement may involve several copper sulfides of the orebodies at Quebrada “M”, Cerro Colorado, and Quebrada Blanca,
prior to ultimate copper oxide development. Replacement of sulfide Chile, and Morenci, Arizona. If chloride activity is high in a near-neutral pH
assemblages having low S/Me ratios or high copper contents (covellite, weathering environment (Rose, 1976), the copper hydroxychloride Atacamite
chalcocite, digenite, bornite) may result in the direct precipitation of copper [Cu2Cl(OH)3] replaces chalcocite (Mantos Blancos, Michilla, Santo Domingo,
oxides—eg, at Radomiro Tomic (Arcuri and Brimhall, 1998); Quebrada “M” in and Buena Esperanza, Chile; Florence Junction, Arizona). Antlerite replaces
the El Salvador district, Chile, and Morenci, Arizona — because the local chalcocite in environments having lower pH than characterizes brochantite
geochemical environment is moderately low to near-neutral pH, which is (Anderson, 1982); eg, La Escondida and Chuquicamata, Chile. Ore petrography
favorable for copper oxides that are stable in the range of pH 4 to 9 (Fig . 3; studies (Chávez, 1983; Arcuri and Brimhall, 1998) suggest that most of the
see also Anderson, 1982). brochantite-antlerite-atacamite formed through chalcocite replacement
represents in situ oxidative replacement of chalcocite rather than copper
addition as a sulfate or chloride. Indeed, these green copper oxides contain
less copper than chalcocite, so destruction of chalcocite via simple replacement
COPPER OXIDE PARAGENESIS usually represents copper loss (leaching) rather than enhancement. In some
AND ZONING systems, these copper sulfates replace cuprite (for example, at Collahuasi and
The paragenetic sequence of copper oxide minerals observed from many El Abra, Chile),
oxidized copper-bearing orebodies reveals that a specific series of progressive
mineralogical changes takes place during supergene oxidation, transport, and
to page 16 ...
precipitation. This section
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16 SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF distance from the former erosional surface. The observed
... from 15 COPPER SULFIDE DEPOSITS, CONT. paragenesis, in which black copper oxides replace the assemblage
cuprite +native copper ± brochantite, supports the argument that
representing an in situ replacement assemblage with little or no the occurrence of tenorite ± paramelaconite ± neotocite indicates
significant copper addition or transport. the most oxidized zones of a weathering, low total sulfide protolith.
In systems characterized by near-neutral or slightly alkaline pH The paragenetic paths shown in Figures 3 and 4 summarize
environments, cuprite replaces chalcocite (eg, Cerro Colorado, the observations above. Oxidation products for arsenic-bearing
Copucha (Sierra Gorda), and El Abra, Chile; locally at Ray, ores, common components of hydrothermal ore deposits, are
Arizona, and Santa Rita, New Mexico). Cuprite represents an summarized in Figure 3. Arsenopyrite, when oxidized in an
intermediate replacement product in many oxide zones, and is environment containing pyrite, yields the iron arsenate scorodite
almost always replaced by other copper oxide minerals. Native characteristic of the upper portions of an oxide zone. Similarly,
copper usually occurs with cuprite—El Abra, Chile; Santa Rita, enargite oxidation in the presence of pyrite produces scorodite
New Mexico; Ray, Arizona; Piedras Verdes, Mexico (Dreier and (Summitville, Colorado; La Candelaria breccia at Morenci, Arizona;
Braun, 1995); San Jorge, Argentina (Williams et al., 1999)—but La Grande, Collahuasi district, Chile). In a low pyrite environment,
rarely directly replaces chalcocite. Native copper generally occurs enargite is replaced by a series of apple green to pastel blue
at greater depth than cuprite (Anderson, 1982). copper arsenates such as chenevixite, ceruleite, and lavendulan
Malachite and azurite are common constituents of copper oxide (eg, in the weathered epithermal Cu-Au-As systems at El Guanaco
zones in which carbonate is available from sedimentary sources and La Grande, Chile, and in the oxide zone at Chuquicamata, Chile).
(notably in oxidized skarn systems, eg, Christmas, Koski and
Cook, 1982; Morenci, Arizona, and Cananea, Mexico, Velasco, EXAMPLES OF COPPER OXIDE
1966), atmospheric sources, and/or indigenous bacterial cells DEPOSITS
(Enders, 2000). Carbonates, along with the mineraloid chrysocolla, The following examples of settings in which copper oxides of
generally comprise paragenetically late minerals, replacing earlier economic importance have developed demonstrate that both the
oxides and sulfides and occurring as transported constituents mineralogy and amount of copper oxides vary significantly.
occupying otherwise “clean” fractures, including fractures showing
Systems Displaying Limited Copper Mobility
no evidence of prior mineralization (eg, southern Peru coastal batholith).
The Abra. The El Abra porphyry copper deposit of northern
In geochemically mature copper oxide systems developed
Chile is an example of supergene oxidation generated within a
under near-neutral to alkaline pH conditions, malachite and
reactive host-rock environment (Fig. 5). This world-class ore
chrysocolla are typically the most important copper minerals, with
deposit comprises a well-developed, fracture-controlled copper
tenorite, paramelaconite, and neotocite are volumetrically minor.
oxide orebody derived from essentially in situ oxidation of a low-
This is probably because carbonates and silicates are most stable
pyrite, chalcopyrite + bornite + chalcocite protolith assemblage
in a well-developed oxidation environment in which sources of low
hosted by dioritic intrusions. Host-rock alteration consists of
pH solutions have been consumed, and because indigenous and ubiquitous biotite with subordinate K feldspar replacement and
atmospheric sources of silica and carbonate, respectively, are veining. Incipient white phyllosilicate overprint of the K silicate
readily available. Incipient and generally subeconomic fracture- assemblage occurs locally and distal to the K silicate assemblages.
controlled copper carbonates and chrysocolla occur paragenetically Copper oxides at El Abra comprise assemblages characteristic
late in oxidized copper deposits at Cerro Colorado and Cerro of moderate-pH weathering environments because insufficient
Chorcha, Panama; along the southern Peru coastal batholith and pyrite was available for production of low-pH supergene solutions.
in adjacent northern Chile, and in late-stage oxidation assemblages The oxide orebody outcrops, with surface and near-surface oxides
in the southwest United States. Exotic copper deposits (Newberg, comprising chrysocolla, paramelaconite (Cu4O3, similar in
1967; Angúita, 1997; Mote and Brimhall, 1997; Münchmeyer, occurrence to tenorite, CuO), and neotocite, shown by X-ray
1997) are almost exclusively chrysocolla dominant, with minor diffraction studies to be a physical mixture of Fe and Cu oxides,
Atacamite, copper wad, tenorite, and/or Fe-Mn-Cu oxides (including neotocite)
notably .tenorite. This assemblage gives way at depth to brochantite
Tenorite and paramelaconite, the black copper oxides, occur in and copper phosphates, such as pseudomalachite. Suprajacent
the upper zones of copper systems in which high host-rock to and within the weakly developed chalcocite enrichment volume
reactivity and low pyrite content produce alkaline to neutral pH and in the upper portions of the hypogene sulfide zone, cuprite,
environments. If carbonate is available to buffer low pH solutions native copper, brochantite, and chrysocolla are developed. This
produced through sulfide oxidation, tenorite and paramelaconite latter assemblage displays a typical paragenetic sequence in
may occur in local environments characterizing oxidized pyritic which chalcocite is replaced by the sequence:
sulfide systems, especially skarns (eg, Morenci, Arizona). At El
Abra, Chile, tenorite and paramelaconite comprise the constituent Chalcocite ÿ cuprite±native copper ÿ brochantite ÿ chrysocolla
minerals in neotocite; Along with chrysocolla, neotocite occurs in Because copper grades in the oxide zone are essentially the
surface outcrops and at shallow depths of the El Abra oxide same as those in the hypogene protolith, it is interpreted that the
orebody within reactive host rock comprising biotite-stable diorite porphyry.
El Abra copper oxide-copper sulfide orebody represents in situ
The tenorite and paramelaconite association grades with increasing oxidation of the hypogene sulfide assemblage, with copper
depth to the assemblage cuprite ± native copper (A. Moraga, pers. transport limited to perhaps several tens of meters. The
comm., 1999); this assemblage is replaced by and grades with development of copper oxides from oxidation of a low-pyrite,
depth to brochantite. This change with depth is consistent with a reactive protolith containing low S/Me ratio minerals at El Abra is
gradual change in copper oxidation state, decreasing with increasing similar to that observed at Radomiro Tomìc (Acuri and Brimhall, 1998, 1999)
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APRIL 2000 • No. 41 SEG NEWSLETTER 17

Figure 5: Generalized vertical cross section through the El Abra porphyry system, Region II, northern Chile. In situ development of copper oxides
from a low pyrite, K silicate stable, (bn + cp + cc)-bearing protolith engendered near-neutral pH stable minerals and no significant copper grade
enhancement in the oxide zone. The copper oxide zone consists of up to approximately 200 m of mineralized host rock, beginning at the present
topographic surface. Upper and lower portions of the El Abra oxide zone may be defined on the basis of dominant copper mineralogy, as shown;
the lower oxide zone displays a gradational contact with underlying and erratically-developed chalcocite enrichment. Simplified from Hawley, Moraga,
and Molina (pers. comm., 1999)

northern Chile ore deposits hosted by

intermediate volcanic rocks, such as the
Atacamite-chrysocolla assemblages at Mantos
Blancos (Chávez, 1983) and Michilla (Soto
and Dreyer, 1985). An exotic copper oxide
resource (Ichuno) exists adjacent to the main
copper oxide orebody at El Abra.
This occurrence may be explained by an
eroded copper source rock, possibly a phyllic
alteration assemblage, formerly located
suprajacent to the present potassic core of the
El Abra porphyry system (A. Moraga and A.
Molina, pers. comm., 1999).
Green Stones. Dreier and Braun (1995)
describe the occurrence of incipient copper
oxide development from the Piedras Verdes
porphyry copper deposit, Sonora, Mexico (Fig.
6). This occurrence comprises a low-grade,
low total sulfide protolith hosted by an alteration
assemblage of biotite + K feldspar + quartz +
tourmaline, with adjacent pyritic protolith
hosted by a phyllic alteration assemblage.
Protolith copper concentrations are on the
order of 1,500 ppm, as chalcopyrite.

Piedras Verdes represents an excellent

example of the control of copper oxide
development by alteration mineralogy. Where Figure 6: Vertical south-north cross section through a portion of the Piedras Verdes porphyry copper
reactive K silicate assemblages exist, deposit, Sonora, Mexico, simplified from figure 4 of Dreier and Braun (1995). Upper diagram shows
weathering has resulted in the in situ general alteration mineral assemblage distribution, with host rock consisting of quartz-biotite schist and
development of a hematitic-goethitic oxide minor granodiorite porphyry. Dashed line shows basis of significant supergene-derived host-rock
assemblage of nearer-surface chrysocolla, alteration, thickening in the portion of the deposit characterized by phyllic alteration and developed only
to a limited extent in K silicate stable assemblages. Lower diagram depicts copper oxide and sulfide
neotocite, and tenorite, changing with depth to
zones. Piedras Verdes copper oxides are well developed within the K silicate stable alteration
cuprite + native copper. Copper-oxide-zone assemblages but show only incipient occurrence in the phyllic zone. Copper sulfides, dominated by
copper grades at chalcocite, are found subjacent to phyllic assemblages but are weakly developed in the K silicate stable
Piedras Verdes are to page 18 ...
assemblages. Protore sulfides consist of pyrite ÿ chalcopyrite ± molybdenite.
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18 SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF
... from 17 COPPER SULFIDE DEPOSITS, CONT.

essentially equal to those of the hypogene sulfides from

which 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 protolith. 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 chalcocite enrichment blanket yielded an in
situ assemblage of chrysocolla, neotocite, tenorite, and
malachite. Figure 7: Schematic east-west cross section through the Mantos Blancos Cu-Ag system,
White Mantles. The Mantos Blancos district of Antofagasta II Region, northern Chile. Host andesites and rhyolites have been albitized and variably
chloritized, so rocks have substantial capacity for acid-neutralizing hydrolysis reactions.
province, northern Chile (Chávez, 1983, 1984), hosts a
Such reactions buffer low pH solutions generated via weathering-related destruction of
generally low-pyrite, andesite- to rhyolite-hosted series of protolith sulfides and determine the resulting Atacamite + Chrysocolla oxide mineral
bornite + digenite + chalcopyrite ± covellite ± specularite assemblage. Copper transport distances were very restricted in this environment,
orebodies. Figure 7 shows a portion of the Nora orebody, probably limited to several tens of meters and generally along through-going fractures.
and the general occurrence of copper oxides comprising Scant but widespread native copper and silver occur within the copper oxide zone and
paratacamite (mapped locally as Atacamite) and chrysocolla. generally below Atacamite-chrysocolla.
Host-rock 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 specularite relics within some oxide

volumes indicates that acidic solutions capable of
transporting cupric ion did not react on a wholesale basis
with Mantos Blancos host rocks because specularite would
have been destroyed during such interaction. The near-
surface occurrence of chrysocolla and subjacent Atacamite
at Mantos Blancos suggests high chloride activity relative
to that of available sulfate; this is similar to the mineral Figure 8: Generalized vertical cross section through the Quetena skarn-breccia system
zoning and paragenesis described by Arcuri and Brimhall southwest of Chuquicamata, Chile. Holocene gravels derived from carbonates and
(1998, 1999) for the Radomiro Tomic deposit immediately calcareous clastic sedimentary rocks conducted acid copper-bearing solutions near or
north of Chuquicamata. at gravel-bedrock contact, forming incipiently developed malachite + Atacamite +
anhydrite as clast coatings. Although supergene solution pH was likely very low during
Quetena. Figure 8 shows the Quetena skarn-breccia
initial oxidation of pyrite-bearing protolith, transport distances for copper were restricted
system, northern Chile, in which exotic malachite and by the highly reactive paleochannel gravels; maximum transport distances at Quetena
Atacamite are developed in carbonate clast conglomerates are on the order of 200 m.
derived from erosion of silty limestones. The protolith
mineral assemblage at Quetena consists of pyrite-dominant
sulfides in marble skarn and hornfels derived from intercalated precipitation alternated, despite the obvious carbonate source within
limestones and mudstones, with locally developed white phyllosilicate the local wall rock and gravels. This is probably because source-
replacement of siliciclastic components within the limestones. rock carbonates, although serving as pH buffers, had elevated local
Malachite and Atacamite occur as millimeter-scale coatings on sulfide contents of 4 to 5 vol percent pyrite. Under such conditions,
carbonate clasts; these minerals form interlayered rinds, indicating acidic solutions were generated during weathering and were
that conditions favoring carbonate and chloride capable of liberating and transporting copper from protolith chalcopyrite into
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APRIL 2000 • No. 41 SEG NEWSLETTER 19

the alluvial gravels developed on hill slopes adjacent to the eroding Within the K silicate assemblage, weathering has produced only
skarn-breccia system. Paragenetically latest anhydrite occurs as limited oxidation, with an assemblage of hematite > goethite,
millimeter-scale patinas covering copper oxides, probably the result Atacamite, and local turquoise-chalcosiderite typical of near-neutral
of gypsum dehydration. The maximum copper transport distance at pH conditions. However, the depth of enrichment is greatly
Quetena is on the order of 200 m. enhanced in the phyllic alteration assemblage, with oxidation on
the order of nearly 1 km deep, resulting in a well-developed low
Systems with Evidence for Enhanced Copper Mobility One of
pH, stable assemblage of natrojarosite, goethite, chalcanthite,
the best-developed leached capping–copper oxide zone–copper
kröhnkite, and antlerite. Below this deeply oxidized rock column is
sulfide enrichment zone sequences is shown by the giant
a well-developed supergene chalcocite ± covellite enrichment zone
Chuquicamata porphyry system, northern Chile (Little, 1926; G.
that displays an apparently gradual and poorly defined contact with
Ossandón et al., unpub. data). Jarrell (1944) described the
hypogene pyrite + enargite + covellite ± tennantite.
occurrence of copper oxides in the near-surface environment,
Because the host-rock phyllic alteration assemblage has only
suggesting that in-place oxidation of supergene sulfides produced
minor capacity to neutralize acidity, solutions generated from the
the thick and well-developed copper oxide zones in the original
oxidation of protolith with very high pyrite content produced a very
Chuquicamata orebody. Because the Chuquicamata orebody
low pH, stable copper and iron oxide assemblage, dominated by
comprises two mineralogically distinct ore types, supergene
oxidation and consequent development of copper oxide mineral sulfates. These solutions were also able to transport copper away
assemblages are also spatially and mineralogically distinct. Figure from the near-surface environment until they reacted with reduced
9 is a schematic west-east vertical cross section through the sulfur, producing the exceptionally well developed chalcocite ±
Chuquicamata mine area, showing the general distribution of oxide covellite enrichment volume at Chuquicamata. Lateral transport of
minerals in the upper parts of the orebody. copper at the southern margin of the Chuquicamata orebody
Detailed mapping (J. Rojas de la Rivera, pers. comm., 1999) produced the economically important Mina Sur (Exótica) exotic
shows that two general alteration zones can be defined, comprising copper deposit (Angúita, 1997; Münchmeyer, 1997), which is a
K silicates (with chalcopyrite + bornite + digenite) and phyllic with paleodrainage system containing copper transported at least 6 km
incipient advanced argillic alteration (with pyrite + enargite + away from the Chuquicamata mine area. This scale of copper
covellite). These alteration assemblages appear to have developed transport is similar to that noted in the mineralized gravels of the
within a single intrusive rock unit. The Domeyko fault zone (“West Huinquintipa Este sector of the Collahuasi district north of
Fissure” in Figure 9), has faulted the Chuquicamata orebody along Chuquicamata and the Damiana copper resource within the El
its western margin, forming an abrupt contact against the phyllic Salvador district, Chile (Mote and Brimhall,
alteration assemblage. 1997). to page 20 ...

Figure 9: Simplified east-west vertical profile of the Chuquicamata, Chile ore deposit, modified slightly from José Rojas (pers. comm., 1999). As with the Piedras
Verdes system, alteration mineral assemblages control copper and iron oxide distribution and zoning. Protolith at Chuquicamata appears to have been a single,
large-scale intrusive unit of intermediate composition (Ossandón et al., unpub. data), so copper and iron oxide distributions are a function of fracture density and
alteration mineralogy, including sulfide types and abundance , rather than protolith composition. Although the contact between supergene and hypogene mineral
assemblages is difficult to define, the vertical column of preserved leaching-oxidation-enrichment at Chuquicamata approaches 1 km.
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twenty SEG NEWSLETTER No. 41 • APRIL 2000

SUPERGENE OXIDATION OF The lateral mineral zoning at the margins of a weathered sulfide
... from 19 COPPER SULFIDE DEPOSITS, CONT. ore deposit, including exotic mineral occurrences, can be used to
assess the geochemical maturity of the oxidation environment and
EXPLORATION IMPLICATIONS the direction(s) from which supergene solutions deposited copper
Copper oxide zones are the product of sulfide destruction minerals. Integration of geochronologic results with studies of
produced by weathering under oxidizing conditions. Supergene landform development, geomorphology, and the distribution of copper
sulfides produced by the same process are not preserved unless oxides and sulfides (eg, Clark, 1967; Sillitoe and McKee, 1996)
development of an oxide profile is limited by water table ascent or provides complementary information useful in assessing the
the onset of an arid climate (Alpers and Brimhall, 1989), lack of acid- geological history of an exploration target, and the consequent
generating sulfides in a source region, and/ or presence of reactive economic potential of copper oxide ore deposit occurrence.
silicates and oxides. Current exploration for copper ore deposits Metallurgical studies will dictate which portions of a copper oxide
favors oxide targets because the leaching technologies developed assemblage, if any, are economically extractable if host-rock reactivity
for metal recovery permit mining of relatively low grade materials. is recognized to be high. At the termination of mining, understanding
Consequently, knowledge of the mineral zoning and mineralogical copper oxide mineral genesis is useful in directing efforts at mine
composition of copper oxide deposits is important in exploration and remediation and ultimate recovery of copper from mine wastes.
economic evaluation of these systems.
Copper oxide occurrences display consistent vertical and lateral ACKNOWLEDGMENTS
zoning patterns that mimic the hand specimen-scale paragenesis
It is a pleasure to acknowledge thoughtful and constructive
shown by individual copper oxide minerals. Weathering-derived
reviews of the initial draft of this manuscript by Jeff W. Hedenquist,
copper mineral distribution is characterized by a supergene
Pepe Perelló, and David Hopper. Continued study of supergene
geochemical stratigraphy comprising copper oxides, iron ±
copper ore deposits by the author has benefited by the contributions
manganese oxides, and copper sulfides. This stratigraphy begins at
of New Mexico School of Mines graduate students JA Amarante, D.
the surface with a leached rock volume typified by the occurrence of
Djikine, W. Jonas, A. Mioduchowski, P. Pinson, W. Seibert III, and C.
iron oxides and residual copper and manganese minerals.
Spencer. Discussions with DS Andrews, W. Gálvez, A. Moraga, A.
Depending on the distribution of fractures in the host-rock mass,
Molina, W. Orquera, J. Pizarro C., J. Rojas de la Rivera, F. Ramírez
leaked zones may occur within and below both copper oxide and
and J. Vega E. were instrumental in developing ideas concerning
copper sulfide horizons. Indigenous copper oxide zones, generated
the paragenesis of weathering copper deposits. Roger Nordin and
via in situ oxidation of a sulfide-bearing rock, are usually developed
Rafael Chavarría of Compañía Minera Boliden and Fernando León
so that the most reduced copper oxides (native copper and cuprite)
P. of Minera Lomas Bayas provided useful commentary on copper
are formed in the lower portions of the oxide column, suprajacent to mineralogy and the depths of oxidation in some areas of northern
and replacing supergene copper sulfides. Chile. Field observations by R. Ayala F., S. Enders, JW Hawley, RM
As oxidation continues, hydroxy-sulfates are developed at the North, R. Stegen, and SR Titley were especially useful in interpreting
expense of native copper and cupite, so brochantite, antlerite, and southwest North America oxidized orebodies.
related sulfates comprise minerals in the topographic middle of an Erich U. Petersen suggested the idea of using the SEG web page
oxide column. As oxidation matures and acid-generating minerals to include additional information and photographic documentation of
are consumed, supergene solution pH becomes more moderate, copper oxide mineralogy; his savvy and skill are very grateful.
and the upper parts of the geochemical stratigraphy develop The patience and support of Noel C. White during the development
chlorides, silicates, and phosphates. Contacts between mineral sub- and review of this article are appreciated and gratefully acknowledged.
zones within the copper oxide zone are gradational, and may be
erratic if tectonic and/or structural settings allow the phreatic zone
and capillary fringe to vary vertically and/or laterally. Very soluble ····················· REFERENCES ······················
iron and copper sulfates develop throughout the oxide zone column Alpers, CN, and Brimhall, GH, 1989, Paleohydrologic evolution and
geochemical dynamics of cumulative supergene metal enrichment at La
if oxidizing pyritic sulfides continue to supply acidic solutions.
Escondida, Atacama Desert, Chile: Economic Geology, v. 84, p. 229–255.
This bottom-to-top copper oxide zoning is mappable vertically,
and in exotic systems, laterally (Angúita, 1997; Münchmeyer, 1997). Anderson, J., 1982, Characteristics of leaked capping and techniques of
Interpretation of the distribution and mineralogy of copper oxides appraisal; in Titley, Spencer R., ed., Advances in the geology of the
porphyry copper deposits; Tucson, University of Arizona Press, p. 275–296.
encountered in surface outcrops and in drill hole intervals allows
development of a model for the geochemical environment(s) Angúita VP, 1997, Geochemical Characterization of the Mina Sur Deposit:
responsible for metals oxidation, transport, and precipitation within a Internal Report to CODELCO–Chile, Superintendence of Geology,
Chuquicamata, Chile, January 1997.
sampled oxidation profile. Copper oxide prospects may then be
Arcuri, T., and Brimhall, GH, 1998, Formation of Atacamite through direct
evaluated for their potential for the occurrence of a target ore mineral oxidation of chalcocite in the Radomiro Tomic deposit, Chile [abs.]:
assemblage. For example, in exploration for large-tonnage, low- Geological Society of America Annual Meeting, Abstracts with Program,
Abs no. 13964.
grade deposits, green copper oxides are a more metallurgically
——1999, Using relic sulfides to determine exotic vs. in situ copper
favorable target than a cuprite-native copper mineral assemblage. mineralization in the Radomiro Tomic deposit, Chile [abs.]: Geological
Exploration for brochantite-antlerite-chrysocolla would target the Society of America Annual Meeting, Cordilleran Section, Abstracts with
middle of a well-developed copper oxide zone or the upper portions Program, v. 31, no. 6, p. A-34.
Bladh, K.W., 1982, The formation of goethite, jarosite, and alunite during the
of a weathering profile showing only incipient development. weathering of sulfide-bearing felsic rocks: Economic Geology, v. 77, p. 176–
184.
Machine Translated by Google
APRIL 2000 • No. 41
SEG NEWSLETTER twenty-one

Boyle, D.R., 1994, Oxidation of massive sulfide deposits in the Bathurst Mining Pinson, Pamela, 1992, Quantitative supergene mineralogical study of a
Camp, New Brunswick: Natural analogues for acid drainage in temperate porphyry copper system in the southwestern United States: Unpublished
climates, in Alpers, CN, and Blowes, DW, eds., Environmental geochemistry MS thesis, Socorro, New Mexico: New Mexico School of Mines, 140 p.
of sulfide oxidation: American Chemical Society Symposium Series 550, p. Rose, A.W., 1976, The effect of cuprous chloride complexes on the origin of
535–550. red-bed copper and related deposits: Economic Geology, v. 71, p. 1036 –
Chávez, WX, Jr., 1983, The geological setting of disseminated copper sulfide 1048. (See especially Figures 2 and 4).
mineralization of the Mantos Blancos copper-silver district, Antofagasta Schwartz, GM, 1934, Paragenesis of the oxidized ores of copper: Economic
Geology, v. 29, p. 55–75.
province, northern Chile: SME Preprint no. 83-193, 20 p.
Sillitoe, RH, and McKee, E., 1996, Age of supergene oxidation and enrichment
——1984, Alteration mineralogy and chemistry of rhyolitic and andesitic volcanic
in the Chilean porphyry copper province: Economic Geology, v. 91, p. 164–
rocks of the Mantos Blancos copper-silver district, Chile: Society of Mining, 179.
Metallurgy, and Exploration, Preprint no. 84-153, 6 p. Soto P., H., Dreyer P., H., 1985, Geology of “Mina Susana,” A novel site in
Clark, A.H., 1967, Relationships between supergene mineral alteration and Carolina de Michilla: Fourth Chilean Geological Congress, v. 2 P. 3-354–
geomorphology, southern Atacama Desert: Chilean interim report, 3-382. (in Spanish with English abstract)
Transactions of the Institution of Mining and Metallurgy, Section B (Applied Titley, SR, 1982, The style and progress of mineralization and alteration in
Earth Sciences), v. 76, p. B89–96. porphyry copper systems, American Southwest, in Titley, SR, ed., Advances
Cook, S.S., 1988, Supergene copper mineralization at the Lakeshore mine, in geology of the porphyry copper deposits, Southwestern North America:
Pinal county, Arizona: Economic Geology, v. 83, p. 297–309. Tucson, Arizona, University of Arizona Press, p. 93–166.
Dreier, JE, and Braun, ER, 1995, Piedras Verdes, Sonora, Mexico: A Titley, SR, and Marozas, DC, 1995, Processes and products of supergene
structurally controlled porphyry copper deposit, in Pierce, W., and Bolm, copper enrichment, in Pierce, W., and Bolm, JG, eds., Porphyry copper
John G., eds., Porphyry copper deposits of the American Cordillera: Arizona deposits of the American Cordillera: Arizona Geological Society Digest 20,
Geological Society, Digest 20, p. 535–543. p. 156–168.
Enders, M.S., 2000, The evolution of supergene enrichment in the Morenci Velasco, JR, 1966, Geology of the Cananea district, in Titley, SR, and Hicks,
CL, eds., Geology of the porphyry copper deposits southwestern North
porphyry copper deposit, Greenlee County, Arizona: Unpublished Ph.D.
America: Tucson, Arizona, The University of Arizona Press, p. 245–251.
dissertation, Tucson, Arizona, University of Arizona, 234 p.
Flint, S., 1986, Sedimentary and diagenetic controls on red-bed ore genesis: Walder, IF, and Chávez, WX, Jr., 1995, Mineralogical and geochemical
The Middle Tertiary San Bartolo copper deposit, Antofagasta province, behavior of mill tailing material produced from lead-zinc skarn mineralization,
Chile: Economic Geology, v. 81, p. 761–778. Hanover, Grant County, New Mexico: Environmental Geology, v. 26, p. 1–
Flores, R., 1985, Control of supergene enrichment in the Chuquicamata 18.
deposit, Chile: Fourth Chilean Geological Congress, v. 2 P. 3-228 to 3-249. Williams, PA, 1990, Oxide zone geochemistry: Chichester, England, Ellis
Horwood Limited, 286 p.
Huyck, HLO, 1990, The Lakeshore porphyry copper deposit, Pinal county, Williams, WC, Meissl, E., Madrid, J., and de Machuca, BC, 1999, The San
Arizona: Geologic setting and physical controls of mineralization: CIM Jorge porphyry copper deposit, Mendoza, Argentina: A combination of
Bulletin, v. 83, no. 973, p. 77–88. orthomagmatic and hydrothermal mineralization: Ore Geology Reviews, v.
Jarrell, O.W., 1944, Oxidation at Chuquicamata, Chile: Economic Geology, 14, p. 185–201. 1
v. 39, p. 251–286.
Koski, RA, and Cook, DS, 1982, Geology of the Christmas porphyry copper
deposit, in Titley, SR, ed., Advances in the geology of the porphyry copper
deposits: Tucson, University of Arizona Press, p.353– 374.

Little, J.M., 1926, The geology and ore deposits of Chile: New York,
Bramwell Company, 198 p.
Locke, A., 1926, Leached outcrops as guides to copper ore: The Williams
and Wilkins Company, 175 p.
López, JA, and Titley, SR, 1995, Outcrop and capping characteristics of the
supergene sulfide enrichment at North Silver Bell, Pima County, Arizona, in
Pierce, W., and Bolm, JG, eds., Porphyry copper deposits of the American
Range: Arizona Geological Society Digest 20, p. 424–435.

Marozas, DC, 1982, The role of silicate mineral alteration in the supergene
enrichment process: Unpublished MS thesis, Tucson, Arizona, University of
Arizona, 57 p.
Mason, B., and Berry, LG, 1968, Elements of mineralogy: WH Freeman and
Company, 550 p.
Mote, T., and Brimhall, GH, 1997, Linking secondary mineralization at El
Salvador, Chile to middle Miocene climate transitions by geochronology and
mass balance [abs.]: Geological Society of America, Abstracts with
Programs, p. A-17.
Münchmeyer, C., 1997, Exotic deposits—products of lateral migration of
supergene solutions from porphyry copper deposits, in Camus, F., Sillitoe,
RH, and Petersen, R., eds., Andean copper deposits: New discoveries,
mineralization, styles, and metallogeny: Society of Economic Geologists
Special Publication 5, p. 43–58.
Murad, E., Schwertmann, U., Bigham, JM, and Carlson, L., 1994,
Mineralogical characteristics of poorly crystallized precipitates formed by
oxidation of Fe2+ in acid sulfate waters, in Alpers, CN and Blowes, DW,
eds., Environmental geochemistry of sulfide oxidation: American Chemical
Society Symposium Series 550, chapter 14, p. 190–200.
Newberg, D.W., 1967, Geochemical implications of chrysocolla-bearing gravels:
Economic Geology, v. 62, p. 932–956.
Nicholson, RV, and Scharer, JM, 1994, Laboratory studies of pyrrhotite
oxidation kinetics, in Alpers, CN and Blowes, DW, eds., Environmental
geochemistry of sulfide oxidation: American Chemical Society Symposium
Series 550, chapter 2, p. 14–30.
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