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
for secondary phases from the supergene profile of the
Bayugo porphyry copper-gold deposit (Philippines)
shows significant isotopic fractionation relative to
hypogene sulfide phases. The results vary
systematically, with isotopic enrichment in the leached
cap iron oxides and supergene copper sulfides.
Measurements for 39 iron oxide, copper oxide, and
65
copper sulfide minerals yielded � Cu values between
-3.4 and +6.9‰. Hypogene sulfides have a narrow range
of isotopic values near zero per mil (-0.6‰ to +1.0‰). In
contrast, supergene sulfides (chalcocite and djurleite)
samples collected from the exotic and enriched copper
65
zones define a trend of decreasing � Cu from the
enriched source area and proximal exotic zone (>3‰)
down-gradient to the distal portions (<1‰) of the exotic
zone. The higher isotopic values in the source area and
proximal zones can be interpreted with a series of
Rayleigh fractionation models depicting multiple cycles of
oxidation, leaching, and enrichment of copper. Enriched
(+1.8 to +2.7‰) copper isotope ratios measured for
leached cap iron oxides provide evidence for a pre-
existing sulfide enrichment zone that was removed in
subsequent cycles of oxidation, leaching, and
enrichment. These findings highlight the potential
applications of copper isotopes within supergene exotic
and leached cap environments.
Keywords. supergene enrichment, porphyry copper-gold
deposit, copper isotope systematics
1 Introduction
Recent developmental work (Mathur et al. 2005; Mathur
et al. 2009) on the copper isotope systematics of
supergene copper minerals has highlighted the
development of distinct copper isotope reservoirs during
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
degree of leaching, and have implications in the
exploration for well-developed enrichment blankets.
Weathering of pyrite-rich portions of porphyry
deposits produces a copper-depleted leached cap, with
consequent production of oxidized copper-bearing acidic
groundwater (Sillitoe 2005 and references therein). This
fluid migrates in response to the local hydrogeologic
regime, and ultimately begins to deposit copper as the
controls (e.g., electrochemical/pH) of solubility change.
Recent studies of experimental and natural fractionations
(e.g., Mathur et al. 2005) have demonstrated that
oxidative dissolution of copper enriches the solution in
the heavier copper isotope (65Cu). Based on evidence for
a fractionation effect between dissolved and precipitated
copper, the potential exists for isotopic differences to
develop between precipitated solids and weathering-
derived fluids moving down-gradient through an exotic
copper deposit.
120° E PHILIPPINES
20° N
Philippine
Sea
Luzon
Manila Boyongan
and Bayugo
South Deposits
China
Sea
10° N
N
Sulu
Sea
Celebes Mindanao
Malaysia
Sea
Figure 1. Location of Boyongan and Bayugo Porphyry Cu-Au
deposits in NE Mindanao, Philippines.
This study investigates copper isotope systematics
within the well-understood hypogene, leached, enriched
and exotic copper zones in the Boyongan/Bayugo
porphyry copper-gold district, Philippines to test the
potential for applying copper isotopes in the exploration
for weathered porphyry systems.
2 Location and geological framework
The Bayugo and Boyongan porphyry Cu-Au deposits are
located in the Surigao Gold District of NE Mindanao
(Fig. 1), known previously for its epithermal and
sediment-hosted gold mineralization (Waters 2004). The
deposits, currently undeveloped, are covered by
Quaternary material. Diamond drilling by Anglo
American geologists resulted in the discovery of
Boyongan (2000) and Bayugo (2003).
At Bayugo and adjacent Boyongan, hypogene copper
and gold, as chalcopyrite, bornite, and electrum, are
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
diorite porphyry stocks (Braxton et al. 2009). At
Boyongan, these progenitor stocks were emplaced into a
silt-sand-matrix diatreme breccia complex, while those
at Bayugo (Fig. 2) intruded an earlier Pliocene diorite
complex, and Oligo-Miocene-aged volcano-sedimentary
rocks.
3 Supergene profile
At Bayugo, supergene processes have created a goethite-
dominated leached cap (10-50 m) overlying a
discontinuous zone of oxide copper (10-50 m). A thicker
(50-140 m) zone of enriched copper sulfides, (chalcocite,
and minor digenite, djurleite, and covellite) lies below
the oxide zone and above the hypogene sulfide zone.
Copper ‘enrichment’ is here defined as domains
containing supergene copper phases occurring in spatial
association with quartz stockworks and/or related K-
silicate alteration assemblages, that generally overlie,
and grade vertically downward into, quartz stockwork
zones with lower copper grade and an exclusively
hypogene copper sulfide (chalcopyrite ± bornite)
assemblage.
A tabular zone of exotic supergene copper sulfides
(principally chalcocite) and minor copper oxides extends
southeast from the early-mineralization stock at East
Bayugo, steepening as it enters the diatreme breccia
complex (Fig. 2). The term ‘exotic’ is used here to
describe a zone of supergene copper phases in a domain
lacking evidence of pre-existing hypogene copper and
gold mineralization. In the supergene copper zone,
exotic supergene copper sulfides have largely replaced
hypogene pyrite in the pyritic halo peripheral to Bayugo,
a zone characterized by an absence of K-silicate-stage
quartz vein stockworks, and by generally low (<<0.01
g/t) gold grades. Braxton et al (2009) and Braxton and
Mathur (in press) provide a detailed description of the
supergene characteristics of the Bayugo and Boyongan
deposits.
4 Copper isotope results
Figure 2 presents the copper isotopic results and
geological context at Bayugo. Braxton and Mathur (in
press) provide a detailed discussion of the sampling and
analytical methodology employed in this study. Results
for hypogene minerals yielded a narrow range of �65Cu
values near zero (-0.6‰ to +1.0 ‰). Supergene minerals
have a broader range between -3.4 and +6.9 per mil.
Copper �65Cu values for supergene sulfides in the copper
enrichment zone generally exceed hypogene values
(+1.1 to + 6.3‰, n = 3). A broad range of �65Cu values
(-2.0 to + 6.9‰) is evident for supergene copper sulfides
in the exotic copper zone in the pyrite halo around
Bayugo, with mostly higher values (>+4‰) in the
proximal portion, and lower values (<+1‰) in the distal
portion (Fig. 2). In the leached cap iron oxides (goethite
and minor hematite) there appear to be two groups (-0.3
to +0.1‰; and +1.8 to +2.7‰; Fig. 2).
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5 Discussion
Because oxidation and leaching of copper from the
vadose zone is essentially a process of copper depletion
from a finite reservoir, Rayleigh equations provide an
appropriate means to describe the isotopic evolution of
the leach fluid [�65Cuaq= (�65Cuºcpy + 103)�fmin � -1 - 103]
and residual solid phase [�65Culeached = (�65Cuºcpy +
103)fmin � -1 - 103]. Here the variables are: �65Cuºcpy =
starting isotopic composition of leached mineral
(chalcopyrite); �65Cu leached = evolving isotopic
composition of leached cap (chalcopyrite � iron
oxides); �65Cuaq = evolving isotopic composition of
fluids responsible for oxidative leaching; fmin = mass
fraction of copper remaining in solid phase relative to
starting conditions; and 103ln� = fluid-solid fractionation
factor ��Cu2+-chalcopyrite: +1.5‰ (Mathur et al. 2005).
Braxton and Mathur (in press) describe in detail the
Rayleigh model describing isotopic fraction applied in
the current context, and explore potential alternative
mechanisms that may have contributed to the observed
isotopic fractionation.
The copper isotope patterns are here interpreted in a
model whereby (1) Copper in the leached cap follows a
Rayleigh fractionation process of isotopic depletion, in
which successive batches of fluid become progressively
depleted in 65Cu; (2) Periods of static sulfide oxidation
are punctuated by leaching events when heavy seasonal
rainfall flushes accumulated soluble copper into
underlying/peripheral zones of copper
enrichment/dispersion, and replacement of hypogene
sulfides by chalcocite occurs progressively further down-
gradient (deeper or more distal, depending on the
component of horizontal flow of supergene solutions),
contributing to systematically depleted isotopic values
for copper in supergene sulfides down-gradient; and (3)
As earlier supergene copper sulfide enriched and exotic
zones are exposed to leaching and oxidation by a falling
water table (e.g., following exhumation), ‘reworking’ of
pre-existing isotopically enriched chalcocite contributes
to progressive increase in �65Cu values for newly-formed
supergene copper sulfides in the enrichment and/or
exotic copper zones. Isotopically enriched �65Cu values
of iron oxide residue in leached cap minerals are
interpreted to reflect oxidation of an earlier-formed
supergene sulfide zone rather than a leached cap formed
by oxidative dissolution of hypogene copper sulfides.
These findings suggest that within ‘headless’ exotic
copper zones, copper isotopic values of supergene
sulfides can provide an indication both of proximity and
direction to the source area. Independently, copper
isotope ratios of iron oxides in surface samples or fossil
leached caps might be used to focus drilling in areas with
the greatest potential for mature enrichment profiles, by
mapping the distribution of isotopically enriched leached
cap iron oxides. This technique would enhance the iron
oxide mapping techniques traditionally applied in
leached cap interpretation and exploration.
 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

The authors wish to thank Anglo American for the
generous financial support of this project, and in
particular acknowledge that company’s Philippine
exploration staff for the logistical support provided.
References
Braxton DP, Cooke DR, Ignacio AM, Rye RO, Waters PJ (2009)
Ultra-deep oxidation and exotic copper formation at the late
Pliocene Boyongan and Bayugo porphyry copper-gold
deposits, Surigao, Philippines; geology, mineralogy,
paleoaltimetry, and their implications for geologic,
physiographic, and tectonic controls. Econ Geol 104:333-349
Braxton DP, Mathur R (in press) Exploration applications of
copper isotopes in the supergene environment: a case study of
Philippines. Econ Geol
Mathur R, Ruiz J, Titley S, Liermann L, Buss H, Brantley SL
(2005) Cu isotopic fractionation in the supergene environment
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Mathur R, Titley S, Barra F, Brantley S, Wilson M, Phillips A,
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