Use of Cu isotopes to distinguish primary

and secondary Cu mineralization in the

Cañariaco Norte porphyry copper deposit,
Northern Peru

Ryan Mathur, Joaquin Ruiz, Michael

J. Casselman, Peter Megaw & Robert van
Egmond

Mineralium Deposita
International Journal for Geology,
Mineralogy and Geochemistry of
Mineral Deposits

ISSN 0026-4598

Miner Deposita
DOI 10.1007/s00126-012-0439-y

1 23
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 Author's personal copy
Miner Deposita
DOI 10.1007/s00126-012-0439-y

LETTER

Use of Cu isotopes to distinguish primary and secondary Cu

mineralization in the Cañariaco Norte porphyry copper
deposit, Northern Peru
Ryan Mathur & Joaquin Ruiz & Michael J. Casselman &
Peter Megaw & Robert van Egmond

Received: 11 December 2011 / Accepted: 15 August 2012

# Springer-Verlag 2012

Abstract A significant proportion of the copper in the Keywords Cu isotope . Supergene . Hypogene . Porphyry
Cañariaco Norte porphyry copper deposit in northern Peru copper . Cañariaco . Peru
occurs in chalcocite and covellite-rich veins and dissemina-
tions that exist from the surface to depths greater than 1 km.
The overall range of Cu isotopic ratios of 42 mineral sepa-
rates from Cañariaco varies from −8.42 to 0.61‰, with Introduction
near-surface chalcocite and Fe oxides having isotopically
depleted values compared to chalcocite, covellite, and chal- The application of Cu isotopes to understanding both high-
copyrite from deeper levels. The majority (34 of 36) of and low-temperature aqueous processes is gaining momentum
measured Cu sulfides have a typical hypogene copper iso- (Kimball et al. 2009; Mathur et al. 2005, 2009, 2010; Mathur
tope composition of δ65Cu00.18±0.38‰, with no enriched and Schlitt 2010; Asael et al. 2007, 2009; Haest et al. 2009;
isotopic signature existing in the Cañariaco Norte sulfide Larson et al. 2003; Maher and Larson 2007; Rouxel et al.
data. Thus, the copper isotope data indicate that most of the 2004; Li et al. 2010; Palacios et al. 2011). Low-temperature
chalcocite and covellite formed from high-temperature hypo- aqueous reactions clearly lead to high fractionation of Cu
gene mineralization processes and that only a minor portion of isotopes in residual minerals, aqueous solutions, and the min-
the deposit is enriched by supergene processes. The nonexis- erals precipitated from them. Thus, the deposition of Cu from
tence of an enriched δ65Cu reservoir suggest the presence of low-temperature aqueous solutions can be identified by highly
an undiscovered lateral/exotic Cu occurrence that enriched fractionated Cu isotope ratios in minerals or solutions as
65
Cu that remained in solution during weathering. Regardless demonstrated by several studies of actively weathering and
of the cause, the comparative analysis of the Cu isotope data- preserved weathered rocks (Mathur et al. 2005, 2009, 2010;
set reveals that little exploration potential for an extensive 2012; Haest et al. 2009; Mirnejad et al. 2010; Palacios et al.
supergene enrichment blanket exists because the weathering 2011). All of these studies have demonstrated that the redox
history at Cañariaco Norte was not conducive to preservation reactions occurring during weathering lead to patterns in the
of enriched Cu at depth beneath the leach cap. copper isotope signatures of minerals found in vertical profiles
in supergene ore bodies. In contrast, copper minerals precip-
itated from higher-temperature fluids show much lower frac-
Editorial handling: F. Barra tionation (Seo et al. 2007; Maher and Larson 2007; Graham et
R. Mathur (*) al. 2004; Ikehata et al. 2011).
Juniata College, The Cañariaco system possesses abundant chalcocite-
Huntingdon, PA 16652, USA dominant veins that occur from near surface to great depths.
e-mail: [email protected]
However, despite having mineralogy throughout that
J. Ruiz appeared favorable for copper recovery by solvent extrac-
University of Arizona, tion, it was found that only the most near-surface chalcocite
Tucson, AZ 85721, USA ores responded well to this treatment. This suggested not
M. J. Casselman : P. Megaw : R. van Egmond
only that both hypogene and supergene chalcocite were
Candente Copper Corp, present, but also that chalcocite genesis also affects metal-
Vancouver, Canada lurgical behavior. In order to resolve this question and
 Author's personal copy
Miner Deposita

understand the potential extent of supergene effects in the Copper mineralization was introduced during series of
Cañariaco deposit, the copper isotopic composition was events closely following the emplacement of each of the
measured on 42 mineral separates from drill core intercepts three major intrusive units and the polymictic breccia unit.
ranging from the near surface leached, through the inter- In general, the highest copper grades (>0.5 % Cu) occur in
preted supergene enrichment zone to deep hypogene zones. the biotite–feldspar porphyry and polymictic breccia units.
Intermediate copper grades (0.35 to 0.5 % Cu) are most
common in the hydrothermal breccia and the coarse quartz
porphyry, and the lowest grades (0.2 to 0.35 % Cu) domi-
Geology nate in the crowded quartz feldspar porphyry, tourmaline
breccia, and volcanic host rocks.
The Cañariaco project contains a major porphyry–copper– Alteration forms distinct concentric zones with central
gold deposit, Cañariaco Norte, and two porphyry–copper– potassic alteration; central to intermediate, overlapping, and
gold-mineralized centers that are at a prospect stage of partly overprinting phyllic, argillic, and advanced argillic alter-
evaluation, Cañariaco Sur and Quebrada Verde. ation; and fringing propylitic and minor silicic alteration. Alter-
The Cañariaco property is located at latitude 06°05′ South ation development is directly related to the density of fracturing
and longitude 79°17′ West, in the Western Cordillera of the in the hosting lithologies and brecciation in the polymictic
Peruvian Andes, in the Cañaris District of the Province of breccia unit. Locally, alteration distribution and intensity are
Ferreñafe, Department of Lambayeque of northwestern Peru. controlled by northeast- and northwest-trending faults.
The property is situated approximately 700 km northwest of Mineralization occurs primarily as disseminations and in
Lima, the capital of Peru, and approximately 110 km to the fractures, sulfide and quartz veins, faults, and breccias.
northeast of the city of Chiclayo. The property is located at Fracture density is the single most important factor influ-
elevations between 2,700 and 3,600 m above sea level and encing copper grades, although breccias and faults can lo-
encompasses both tropical forest in the Cañariaco River Val- cally be important.
ley and open grassland on ridges and plains at higher eleva- Three main zones have been recognized in the deposit: a
tions. The deposit is located on the west side of the Cañariaco variable-thickness leached cap, minor supergene copper min-
River valley. The topography of the deposit area is very eralization under the leached cap, and hypogene copper miner-
rugged and is made up of a series of steep valleys and narrow alization; the main component of the deposit. Hypogene copper
ridges. There is significant rainfall during the November to mineralization consists mainly of chalcopyrite, chalcocite, and
March rainy season. The water table is at or near surface. covellite, with lesser enargite and minor bornite, tennantite, and
Copper was first discovered at Cañariaco Norte in the digenite. Supergene copper consists of chalcocite and covellite.
early 1970s during a regional exploration program carried
out by the Peruvian Servicio National de Geología y Min-
ería (“INGEMMET”), in cooperation with a British Geolog- Sampling and methods
ical Survey Team. Exploration was sporadic with phases of
exploration and drilling in the 1970s and 1990s. Candente Figure 1 shows the location of the sampled drill holes and
Resource Corp acquired the Cañariaco property in 2002 and shows that samples were taken from Cu-rich ores vertically
did extensive exploration and drilling from 2004 to 2010. from the leach cap through the supergene and hypogene zones
The Cañariaco Norte deposit has a resource of 750 Mtonne within the major igneous intrusion phases. Mineralization
at 0.46 % Cu, 0.07 g/tonne Au, and 1.80 g/tonne Ag. commonly occurred as veins and fine-grained mineral dissem-
Cañariaco Norte is an example of a primary porphyry– inations. Minerals from veins were handpicked, whereas rocks
copper–gold system. The Cañariaco Norte Early to Late containing disseminated sulfide mineralization were either
Tertiary polyphase intrusive-breccia complex is approxi- powdered and handpicked, or the whole rock powder (<250-
mately 1.7 km in strike extent, 1.1 km wide, and has μm fraction) was used. X-ray diffraction (XRD) of the pure
been drilled to a depth of about 770 m. The complex has mineral powders was done to verify the minerals present
intruded Early Tertiary volcanic units of the Llama and where approximately 0.2 g of powder was used for analysis
Porculla Formations of the Calipuy Group. Three major on a Scintag Pad V X-ray powder diffractometer. XRD scans
intrusive generations have been identified, a crowded were completed in slow, step scan mode. Table 1 reports the
quartz–feldspar porphyry, a biotite–feldspar porphyry, major sulfide or Fe oxide minerals present.
and a coarse quartz porphyry. These intrusive units are Potentially, different copper minerals could possess dif-
cross-cut by feldspar porphyry dykes. Three breccia bod- ferent Cu isotopic compositions caused by either high- or
ies that post-date the intrusive rocks are also recognized: low-temperature aqueous processes. Due to the disseminat-
hydrothermal breccias, tourmaline breccias, and polymic- ed nature of the ores, multiple copper-bearing phases exist
tic breccias. in the samples as shown in Table 1. To test for isotopic
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Fig. 1 Geologic map and drill

hole location for samples

heterogeneity in the samples, different mineral separates residue because the handpicking did not completely eliminate
were analyzed from two samples (samples with an asterisk all silicate and other trace minerals. The XRD did not detect
in Table 1). Regardless of the aliquot, the copper isotopic the silicate minerals because they were <3 % of the powder.
composition remained consistent, and copper isotope values The presence of silicates or other phases that could provide
of the minerals overlap within reported error. For instance, ions into solution could impact measurements (Pribil et al.
the mineral powder for sample 07–137-depth 620 m has the 2009; Marechal and Albarede 2002) on the multicollector
same δ65Cu0−0.07±0.14‰ as the pure sulfide separate inductively coupled mass spectrometer (MC-ICP-MS); there-
obtained through handpicking δ65Cu00.15±0.14‰. fore, ion exchange chromatography, with the use of the MP-1
The minerals were dissolved in heated aqua regia (approx- BioRad 200–400 mesh size resin, was used to separate Cu
imately 100 °C) in Teflon beakers for approximately 18 h. All from the samples following the procedure described by
samples possessed a small amount of nondissolved silicate Mathur et al. (2005), Marechal et al. (1999), and Chapman
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Table 1 Sample location, mineralogy (hem hematite, goe goethite, cpy and Na were measured on an inductively coupled plasma
chalcopyrite, py pyrite, cc chalcocite, dj djurleite, cv covellite) and Cu
atomic emission spectrometer at the Pennsylvania State Uni-
isotope measurements
versity Materials Characterization Lab to determine the
Drill core Elevation (m) Mineralogy δ65Cu (per mil) amount of ions needed for ion exchange chromatography.
The volume of ion exchange resin used here (1.6–1.8 ml)
07–135 2,933 hem/goe −3.74
can accommodate approximately 2,000 meq. Fe and Cu were
07–135 2,906 hem/goe −2.29
the dominant ions in solution by at least one order of magni-
07–146 2,865 hem/goe −4.31
tude in comparison to the other ions. In order to ensure
07–183 2,856 hem/goe −5.81
chromatographic separation of Cu, no more than 900 meq of
07–183 2,842 hem/goe −4.69 all measured ions was loaded onto the ion exchange resins.
07–200 2,952 hem/goe −8.42 The samples were measured on the MC-ICP-MS at
07–200a 2,952 hem/goe −8.21 Washington State University. All samples were diluted to
004–008 2,702 cc+cpy 0.10 approximately 100 ppb and produced a 1- to 1.8-V 65Cu
004–008 2,657 cc+cpy 0.12 signal on the instrument. Background peaks were measured
004–008 2,833 cc+cpy 0.06 on peak and subtracted out of each analysis. The combined
004–008 2,754 cc+cpy 0.08 background of the 2 % nitric acid the solutions were run
005–033 2,624 cc+cpy 0.18 with and procedural blanks (running acid through the col-
07–103 2,861 cc −0.43 umn without samples and measuring the Cu) never reached
07–135 2,903 cc 0.33 a value greater than 0.001 V for 65Cu. Thirty ratios were
07–135 2,852 cpy+cc −3.31 collected for each block and two blocks were measured for
07–146 2,841 cc 0.50 each sample. Mass bias was corrected using the standard–
07–183 2,822 cc 0.58 sample–standard bracketing technique. The NIST 976 stan-
004–001 2,897 dj −2.98 dard was used and isotope ratios are reported as:
004–001 2,876 dj 0.92 "
 #
65Cu
sample
004–001 2,867 dj 0.32 d Cu ¼
65Cu 
65 63Cu
 1  1; 000
005–033 2,573 cc+cv 0.14 63Cu standard
006–74 2,769 cpy+py 0.31
006–74 2,724 cpy 0.37 Isobaric interferences from Mg and Na were checked
006–74 2,619 cpy+py 0.16 because elevated concentrations of these and other elements
07–135 2,788 cpy 0.06 can cause matrix effects and result in spurious data
07–135 2,737 cpy 0.29 (Marechal and Albarede 2002; Marechal et al. 1999; Pribil
07–135 2,633 cpy −0.03 et al. 2009; Mathur et al. 2005; Zhu et al. 2000). None of the
07–135 2,617 cpy −1.20 samples contained significant concentrations of the possible
07–135 2,398 cpy 0.10 isobars. Measurement errors for these values are in the sixth
07–135 2,684 cpy 0.45 decimal place for all reported values. This does not represent
07–135 2,627 cpy+cv 0.30 the true instrument error. In order to assess the error, we
07–135 2,589 cpy+cv 0.61 analyzed the variation of the standard over 300 times where
07–135 2,536 cpy 0.55 the 2 σ error is 0.14‰.
07–137 2,596 cpy+py 0.07
07–137 2,310 cpy 0.15
07–137a 2,310 cpy −0.07 Results
07–183 2,802 cpy 0.41
07–183 2,668 cpy 0.28 Mineralogy and isotope data are presented in Table 1. The
07–183 2,659 cpy+cv 0.20
mineralogy of the samples is typical of those found in
07–183 2,573 cpy+cv 0.37
leached caps, hypogene and supergene zones in porphyry
07–183 2,468 cpy+cv 0.32
copper deposits (Sillitoe 2010; Titley 1981; Titley and
Beane 1981; Seedorff et al. 2008). Reported mineral
07–183 2,366 cpy 0.42
phases were identified from XRD peaks which have ap-
07–183 2182 cpy 0.32
proximately 5 % resolution. Therefore, the reported min-
a
indicates samples of rock powder replicates eral phases represent the dominant Cu sulfide species in
the diffraction pattern. At the micron scale, all of the Cu
et al. (2006). All reported results have yields of Cu from the species most likely exist throughout the deposit (and in all
columns at greater than 90 %. Concentrations of Fe, Cu, Mg, of the samples analyzed).
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Values of δ65Cu ranged from −8.42 to 0.92‰ for all

samples analyzed (Table 1). No relationships with the Cu
isotope composition and type of host rock exist. Two signif-
icant trends exist in the data. First, both Fe oxides and Cu-
bearing minerals in the leach cap possess more depleted
copper isotope signatures than the hypogene minerals
(Table 2) (Mathur and Schlitt 2010). A plot of copper isotope
composition versus the elevation (Fig. 2) shows that all sam-
ples (Fe oxide or Cu-bearing) within 90 m of the surface have
depleted copper isotopic compositions in comparison to Cu
sulfide samples from below 90 m depth. The second important
trend is illustrated in a histogram of copper-bearing minerals
and Fe oxide leach cap minerals (Fig. 3) where all of the Cu
isotope ratios of the sample plot within the leach cap and
hypogene ranges. Porphyry copper deposits that have signif-
icant supergene enrichment generally display three distinct
copper isotope reservoirs (Mathur et al. 2005, 2009). The
basic pattern observed is that the δ65Cu values of leach cap Fig. 2 Plots from specific cores of δ65Cu versus elevation
minerals<hypogene minerals<enrichment minerals. Figure 3
has data from several sources (Kimball et al. 2009; Mathur et shallower portions of the leach cap to greater degrees of
al. 2005; Maher and Larson 2007; Larson et al. 2003; Zhu et oxidative weathering while the deeper portions of the system
al. 2000; Borrok et al. 2008; Graham et al. 2004). Importantly, did not experience as much oxidative weathering. For in-
no ores from Cañariaco Norte have enriched copper iso- stance, dissolution of Cu-rich minerals leaves isotopically
tope ratios in comparison to hypogene mineralization. The depleted residues; thus, as Cu-rich minerals weather for longer
copper isotopic compositions from the leach cap are sim- time intervals in the shallower part of the system, the Cu
ilar to the range of copper isotope ratios measured from isotope composition of the residue will become progressively
mineral powders tested in batch leach experiments of depleted. The reprecipitated copper in the supergene enrich-
Mathur and Schlitt (2010). ment zone beneath the leach cap should possess the enriched
copper leached from above.
The data presented here clearly display a similar Cu
Discussion isotopic composition of minerals in the leach cap. Both Fe
oxides and Cu sulfide minerals in the leach cap have mea-
The weathering of Cu-rich rocks results in an unequal isotopic sured Cu isotope ratios significantly depleted in comparison
redistribution of Cu from hypogene into oxidized species to typical hypogene mineralization value of approximately 0
during supergene enrichment. Low-temperature aqueous reac- ‰. The results indicate that oxidative weathering has re-
tions involving oxidation of Cu cause significant fractionation moved heavy 65Cu during leaching. Interestingly, the
of Cu isotopes and result in the development of distinct leached cap minerals at the highest elevations possess rela-
isotopic reservoirs. Mathur et al. (2009, 2010) measured sev- tively more depleted copper isotope signatures than minerals
eral samples from all three isotopic reservoirs in the Silver at lower elevations. More specifically, examination of each
Bell, Morenci, and Ray porphyry Cu deposits in southern drill core (07–135 and 07–183) reveals that the most deplet-
Arizona and showed a Cu isotopic pattern in the leach cap ed δ65Cu values exist at the highest elevation and the iso-
where the lighter isotopic Fe oxide and Cu oxides occur in the tope composition becomes progressively enriched with
shallowest portions of the deposit whereas deeper portions of lower elevations. This general observation could be inter-
the leach cap possess isotopically heavier Fe oxides and Cu preted that the higher elevations experienced greater degrees
oxides. The pattern most likely reflects the continual weath- of oxidative weathering and removal of Cu in contrast to
ering history caused by regional uplift, which exposed the areas at lower elevations.

Table 2 Average Cu isotope

values for the leach cap and Cu Average depth from top of drill core Mineral δ65Cu (per mil) 1σ Number
mineralized zone
0–90 m Fe oxide −4.88 1.85 7
0–90 m Cu sulfides −0.44 1.58 8
90–687 m Cu sulfides 0.18 0.32 28
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Miner Deposita

cross cutting and overgrowth mineral textures that indicate

that multiple overprinting high-temperature mineralization
events occurred, so samples must be considered composites
of several hypogene events. Cu isotopes can be used to
understand high-temperature mineralization (Maher and
Larson 2007); however, this requires individual grain analysis
which could not be achieved with the mineral separation
technique employed here.
The Cu isotope data indicate that supergene enrichment
did not generate the chalcocite or covellite present at depth
in the deposit, but does not provide insight for why little to
no supergene enrichment occurred. Mass balance must exist
in the copper isotope reservoirs measured. Why does en-
richment occur only in weathered remnants within the leach
cap and not as a typical enrichment blanket as found in other
PCDs? The leach cap is depleted in terms of copper, and the
Fig. 3 Histogram plot of copper isotope composition of minerals from whereabouts of “lost” 65Cu copper remains unknown. The
porphyry copper deposits; data taken from Mathur et al. (2005, 2010) migration and sequestration of Cu can be controlled by
and Zhu et al. (2000) many factors such as climate, pyrite/chalcopyrite ratio (abil-
ity to generate sulfuric acid), fracture abundance (secondary
The Cañariaco dataset significantly differs from other permeability), metallic surfaces for copper to precipitate on,
PCDs with regard to supergene enrichment minerals that uplift, erosion, preservation, solubility/precipitation of min-
possess enriched Cu isotopic signatures. The Cañariaco erals, and preservation of enrichment blankets (Reich et al.
dataset lacks any isotopic reservoir that possesses the 2008; Blanchard 1968; Chavez 2000; Sillitoe and McKee
enriched isotopic signature typical of supergene chalcocites 1996; Hartley and Rice 2005; Anderson 1982). Some or all
found in the other PCD analyzed to date (Fig. 3). Mass of these factors probably explain the lack of supergene
balance must exist in the system, and theoretically, there enrichment; however, the current humid climate and lack
are two possible places the heavier could reside: the copper of units to “preserve” the enrichment blankets most likely
moved laterally to form an “exotic” deposit or the copper inhibited supergene enrichment. For instance, the isotopi-
remained in solution. Only 2 of 36 total Cu sulfide-rich cally depleted Cu enrichment minerals found in the leach
samples had measured Cu isotope ratios different from cap indicate current weathering actively dissolves
typical hypogene copper isotopic signatures (0±1‰). The enriched layers in the subsurface without preserving en-
two samples clearly exist in the leach cap (because Fe richment. Further copper isotopic measurements of
oxides coexist in the sample drill core sample). Therefore, ground- and surface waters from the area should show
the data indicate that no significant supergene enrichment an enriched isotopic signature and confirm that copper is
exists beneath the leached cap. “lost” from the system.
The data do not rule out the possibility that a super- Alternatively, the 65Cu copper isotopic reservoir could
gene enrichment blanket existed at some point in the exist as lateral “exotic” copper deposits. Instead of envision-
geologic past. Notice that the two chalcocite samples in ing only vertical flow commonplace in traditional supergene
the leached cap possess isotopically depleted signatures. models, lateral flow regimes could be conduits for the
A possible interpretation of these depleted copper isoto- copper in solution. So, the enriched copper isotopic reser-
pic compositions could be that supergene chalcocite voir could exist on the periphery of the deposit but it has not
formed below the water table and was subsequently been discovered.
uplifted above the water table. The chalcocite then
experienced oxidative weathering which consequently
stripped 65Cu copper leaving the isotopically depleted Conclusions and future directions
residual copper mineralization.
The bulk of the copper isotope data possesses a hypogene Copper isotope analyses can be used to distinguish between
copper isotope composition (0.18±0.32‰, Table 2) suggest- high- and low-temperature mineralization processes. In this
ing that the bulk of the mineralization is of high-temperature instance, the copper isotope data from Cañariaco Norte
hypogene origin. In other words, hypogene mineralization indicate that high-temperature mineralization events provid-
conditions were such that primary covellite, chalcocite, and ed the majority of copper mineralization and supergene
chalcopyrite were deposited. Petrographic analysis shows enrichment is negligible.
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Miner Deposita

The implications possess a twofold significance for ex- Hartley AJ, Rice CM (2005) Controls on supergene enrichment of
ploration geology and hydrometallurgy: (1) From an explo- porphyry copper deposits in the Central Andes: a review and
discussion. Miner Deposita 40(5):515–525
ration geologic standpoint, the lack of a supergene blanket Ikehata K, Notsu K, Hirata T, Navarrete JU, Borrok DM, Viveros M,
throughout the deposit eliminates the need to explore for Ellzey JT (2011) Copper isotope characteristics of copper-rich
horizontal copper mineralization. However, the data could minerals from Besshi-type volcanogenic massive sulfide deposits,
be congruent with the existence of lateral flow of copper and Japan, determined using a femtosecond LA-MC-ICM-MS. Econ
Geol 106(2):307–316. doi:10.2113/econgeo.106.2.307
the existence of “exotic” copper deposits trapped down- Kimball BE, Mathur R, Dohnalkova AC, Wall AJ, Runkel RL, Brantley
stream by a suitable reductant. (2) From a hydrometallugical SL (2009) Copper isotope fractionation in acid mine drainage. Geo-
standpoint, process of the ores should focus on treating chim Cosmochim Acta 73(5):1247–1263
hypogene mineral assemblages. Larson PB, Maher K, Ramos FC, Chang Z, Gaspar M, Meinert LD
(2003) Copper isotope ratios in magmatic and hydrothermal ore-
In order to further augment the dataset collected here, forming environments. Chem Geol 201(3–4):337–350
copper isotope measurements of fluids actively weathering Li W, Jackson SE, Pearson NJ, Graham S (2010) Copper isotopic
the deposit would be ideal. The solutions should possess a zonation in the Northparkes porphyry Cu-Au deposit, SE Aus-
relatively enriched copper isotopic signature. Equally im- tralia. Geochimica et Cosmochimica Acta 74(14):4078–4096
Maher KC, Larson PB (2007) Variation in copper isotope ratios and
portant in understanding the overall mass balance of copper controls on fractionation in hypogene skarn mineralization at
in the system would be copper isotopic measurements from Coroccohuayco and Tintaya, Peru. Econ Geol 102(2):225–237.
soils derived from the weathering of the igneous rocks at doi:10.2113/gsecongeo.102.2.225
Cañariaco Norte. Marechal C, Albarede F (2002) Ion-exchange fractionation of copper
and zinc isotopes. Geochim Cosmochim Acta 66(9):1499–1509
Marechal CN, Telouk P, Albarede F (1999) Precise analysis of copper
and zinc isotopic compositions by plasma-source mass spectrom-
Acknowledgments We would like to thank Candente Resources for etry. Chem Geol 156(1–4):251–273
their financial support and willingness to supply relevant samples with Mathur R, Schlitt WJ (2010) Identification of the dominant Cu ore minerals
excellent geologic context. We also thank the editor, M. Reich, and two providing soluble copper at Cañariaco, Peru through Cu isotope anal-
other reviewers for helpful comments and constructive criticism during yses of batch leach experiments. Hydrometallurgy 101(1–2):15–19
the editing of this document. Mathur R, Ruiz J, Titley S, Liermann L, Buss H, Brantley SL (2005)
Cu isotopic fractionation in the supergene environment with and
without bacteria. Geochim Cosmochim Acta 69(22):5233–5246
Mathur R, Titley S, Barra F, Brantley S, Wilson M, Phillips A,
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