11 th SGA Biennial Meeting

Let’s Talk Ore Deposits

26-29th September 2011 Antofagasta, Chile

Supergene copper isotope systematics at the Bayugo

Cu-Au porphyry deposit, Philippines: fluid pathways
and exploration implications
David P. Braxton
Anglo American Chile, Piso 4, Pedro de Valdivia 291, Providencia, Santiago, Chile

Ryan Mathur
Department of Geology, Juniata College, Huntingdon, Pa, 16652, USA

Abstract. Measurement of copper isotope compositions the heavier copper isotope (65Cu). Based on evidence for
for secondary phases from the supergene profile of the a fractionation effect between dissolved and precipitated
Bayugo porphyry copper-gold deposit (Philippines) copper, the potential exists for isotopic differences to
shows significant isotopic fractionation relative to develop between precipitated solids and weathering-
hypogene sulfide phases. The results vary
systematically, with isotopic enrichment in the leached
derived fluids moving down-gradient through an exotic
cap iron oxides and supergene copper sulfides. copper deposit.
Measurements for 39 iron oxide, copper oxide, and
65
copper sulfide minerals yielded � Cu values between 120° E PHILIPPINES
-3.4 and +6.9‰. Hypogene sulfides have a narrow range
of isotopic values near zero per mil (-0.6‰ to +1.0‰). In 20° N
contrast, supergene sulfides (chalcocite and djurleite)
samples collected from the exotic and enriched copper
65
zones define a trend of decreasing � Cu from the Philippine
enriched source area and proximal exotic zone (>3‰) Sea
down-gradient to the distal portions (<1‰) of the exotic
Luzon
zone. The higher isotopic values in the source area and
proximal zones can be interpreted with a series of Manila Boyongan
Rayleigh fractionation models depicting multiple cycles of and Bayugo
oxidation, leaching, and enrichment of copper. Enriched South Deposits
(+1.8 to +2.7‰) copper isotope ratios measured for China
leached cap iron oxides provide evidence for a pre- Sea
existing sulfide enrichment zone that was removed in 10° N
subsequent cycles of oxidation, leaching, and N
enrichment. These findings highlight the potential Sulu
Sea
applications of copper isotopes within supergene exotic
and leached cap environments.
Celebes Mindanao
Malaysia
Keywords. supergene enrichment, porphyry copper-gold Sea
deposit, copper isotope systematics
Figure 1. Location of Boyongan and Bayugo Porphyry Cu-Au
deposits in NE Mindanao, Philippines.
1 Introduction
This study investigates copper isotope systematics
within the well-understood hypogene, leached, enriched
Recent developmental work (Mathur et al. 2005; Mathur
and exotic copper zones in the Boyongan/Bayugo
et al. 2009) on the copper isotope systematics of
porphyry copper-gold district, Philippines to test the
supergene copper minerals has highlighted the
potential for applying copper isotopes in the exploration
development of distinct copper isotope reservoirs during
for weathered porphyry systems.
weathering of porphyry copper deposits. These studies
have shown that the copper isotope ratios in the
chalcocite and the leached cap iron oxides relate to the 2 Location and geological framework
degree of leaching, and have implications in the
exploration for well-developed enrichment blankets. The Bayugo and Boyongan porphyry Cu-Au deposits are
Weathering of pyrite-rich portions of porphyry located in the Surigao Gold District of NE Mindanao
deposits produces a copper-depleted leached cap, with (Fig. 1), known previously for its epithermal and
consequent production of oxidized copper-bearing acidic sediment-hosted gold mineralization (Waters 2004). The
groundwater (Sillitoe 2005 and references therein). This deposits, currently undeveloped, are covered by
fluid migrates in response to the local hydrogeologic Quaternary material. Diamond drilling by Anglo
regime, and ultimately begins to deposit copper as the American geologists resulted in the discovery of
controls (e.g., electrochemical/pH) of solubility change. Boyongan (2000) and Bayugo (2003).
Recent studies of experimental and natural fractionations At Bayugo and adjacent Boyongan, hypogene copper
(e.g., Mathur et al. 2005) have demonstrated that and gold, as chalcopyrite, bornite, and electrum, are
oxidative dissolution of copper enriches the solution in associated with K-silicate-stage copper-sulfide ± quartz

805
 11 th SGA Biennial Meeting
Let’s Talk Ore Deposits
26-29th September 2011 Antofagasta, Chile

vein stockworks that developed in spatial and temporal

association with Pliocene-aged early-mineralization 5 Discussion
diorite porphyry stocks (Braxton et al. 2009). At
Boyongan, these progenitor stocks were emplaced into a Because oxidation and leaching of copper from the
silt-sand-matrix diatreme breccia complex, while those vadose zone is essentially a process of copper depletion
at Bayugo (Fig. 2) intruded an earlier Pliocene diorite from a finite reservoir, Rayleigh equations provide an
complex, and Oligo-Miocene-aged volcano-sedimentary appropriate means to describe the isotopic evolution of
rocks. the leach fluid [�65Cuaq= (�65Cuºcpy + 103)�fmin � -1 - 103]
and residual solid phase [�65Culeached = (�65Cuºcpy +
3 Supergene profile 103)fmin � -1 - 103]. Here the variables are: �65Cuºcpy =
starting isotopic composition of leached mineral
At Bayugo, supergene processes have created a goethite- (chalcopyrite); �65Cu leached = evolving isotopic
dominated leached cap (10-50 m) overlying a composition of leached cap (chalcopyrite � iron
discontinuous zone of oxide copper (10-50 m). A thicker oxides); �65Cuaq = evolving isotopic composition of
(50-140 m) zone of enriched copper sulfides, (chalcocite, fluids responsible for oxidative leaching; fmin = mass
and minor digenite, djurleite, and covellite) lies below fraction of copper remaining in solid phase relative to
the oxide zone and above the hypogene sulfide zone. starting conditions; and 103ln� = fluid-solid fractionation
Copper ‘enrichment’ is here defined as domains factor ��Cu2+-chalcopyrite: +1.5‰ (Mathur et al. 2005).
containing supergene copper phases occurring in spatial Braxton and Mathur (in press) describe in detail the
association with quartz stockworks and/or related K- Rayleigh model describing isotopic fraction applied in
silicate alteration assemblages, that generally overlie, the current context, and explore potential alternative
and grade vertically downward into, quartz stockwork mechanisms that may have contributed to the observed
zones with lower copper grade and an exclusively isotopic fractionation.
hypogene copper sulfide (chalcopyrite ± bornite) The copper isotope patterns are here interpreted in a
assemblage. model whereby (1) Copper in the leached cap follows a
A tabular zone of exotic supergene copper sulfides Rayleigh fractionation process of isotopic depletion, in
(principally chalcocite) and minor copper oxides extends which successive batches of fluid become progressively
southeast from the early-mineralization stock at East depleted in 65Cu; (2) Periods of static sulfide oxidation
Bayugo, steepening as it enters the diatreme breccia are punctuated by leaching events when heavy seasonal
complex (Fig. 2). The term ‘exotic’ is used here to rainfall flushes accumulated soluble copper into
describe a zone of supergene copper phases in a domain underlying/peripheral zones of copper
lacking evidence of pre-existing hypogene copper and enrichment/dispersion, and replacement of hypogene
gold mineralization. In the supergene copper zone, sulfides by chalcocite occurs progressively further down-
exotic supergene copper sulfides have largely replaced gradient (deeper or more distal, depending on the
hypogene pyrite in the pyritic halo peripheral to Bayugo, component of horizontal flow of supergene solutions),
a zone characterized by an absence of K-silicate-stage contributing to systematically depleted isotopic values
quartz vein stockworks, and by generally low (<<0.01 for copper in supergene sulfides down-gradient; and (3)
g/t) gold grades. Braxton et al (2009) and Braxton and As earlier supergene copper sulfide enriched and exotic
Mathur (in press) provide a detailed description of the zones are exposed to leaching and oxidation by a falling
supergene characteristics of the Bayugo and Boyongan water table (e.g., following exhumation), ‘reworking’ of
deposits. pre-existing isotopically enriched chalcocite contributes
to progressive increase in �65Cu values for newly-formed
4 Copper isotope results supergene copper sulfides in the enrichment and/or
exotic copper zones. Isotopically enriched �65Cu values
Figure 2 presents the copper isotopic results and of iron oxide residue in leached cap minerals are
geological context at Bayugo. Braxton and Mathur (in interpreted to reflect oxidation of an earlier-formed
press) provide a detailed discussion of the sampling and supergene sulfide zone rather than a leached cap formed
analytical methodology employed in this study. Results by oxidative dissolution of hypogene copper sulfides.
for hypogene minerals yielded a narrow range of �65Cu These findings suggest that within ‘headless’ exotic
values near zero (-0.6‰ to +1.0 ‰). Supergene minerals copper zones, copper isotopic values of supergene
have a broader range between -3.4 and +6.9 per mil. sulfides can provide an indication both of proximity and
Copper �65Cu values for supergene sulfides in the copper direction to the source area. Independently, copper
enrichment zone generally exceed hypogene values isotope ratios of iron oxides in surface samples or fossil
(+1.1 to + 6.3‰, n = 3). A broad range of �65Cu values leached caps might be used to focus drilling in areas with
(-2.0 to + 6.9‰) is evident for supergene copper sulfides the greatest potential for mature enrichment profiles, by
in the exotic copper zone in the pyrite halo around mapping the distribution of isotopically enriched leached
Bayugo, with mostly higher values (>+4‰) in the cap iron oxides. This technique would enhance the iron
proximal portion, and lower values (<+1‰) in the distal oxide mapping techniques traditionally applied in
portion (Fig. 2). In the leached cap iron oxides (goethite leached cap interpretation and exploration.
and minor hematite) there appear to be two groups (-0.3
to +0.1‰; and +1.8 to +2.7‰; Fig. 2).

806
 11 th SGA Biennial Meeting
Let’s Talk Ore Deposits
26-29th September 2011 Antofagasta, Chile

Figure 2. A: Geological map of the paleosurface at East Bayugo, depicting copper isotope compositions of supergene copper
sulfides (chalcocite and djurleite) from the enrichment and exotic copper zones. Values for �65Cu are highest in the source area and
proximal exotic zone, and decrease systematically down-gradient toward the distal portions of the exotic zone. B: Geological section
through East Bayugo, depicting copper isotope compositions of hypogene sulfides (pyrite and chalcopyrite) and supergene copper
sulfides (chalcocite and djurleite) from the enrichment and exotic copper zones, and iron oxides (goethite ± hematite) from the
leached cap. Values for �65Cu decrease toward the distal portions of the exotic zone, as well as toward the base of the enrichment
zone. Figure modified from Braxton and Mathur (in press).

Acknowledgements the Bayugo porphyry copper-gold deposit, southern

Philippines. Econ Geol
Mathur R, Ruiz J, Titley S, Liermann L, Buss H, Brantley SL
The authors wish to thank Anglo American for the (2005) Cu isotopic fractionation in the supergene environment
generous financial support of this project, and in with and without bacteria. Geochim Cosmochim Acta
particular acknowledge that company’s Philippine 69:5233-5246
exploration staff for the logistical support provided. Mathur R, Titley S, Barra F, Brantley S, Wilson M, Phillips A,
Munizaga F, Maksaev V, Vervoort J, Hart G (2009)
Exploration potential of Cu isotope fractionation in porphyry
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