©2013 Society of Economic Geologists, Inc.

Economic Geology, v. 108, pp. 495–527

Summary of Exploration Geochemical and Mineralogical Studies at the Giant Pebble

Porphyry Cu-Au-Mo Deposit, Alaska: Implications for Exploration Under Cover
ROBERT G. EPPINGER,1,† DAVID L. FEY,1 STUART A. GILES,1 ERIC C. GRUNSKY,2 KAREN D. KELLEY,1 BURKE J. MINSLEY,1
LEEANN MUNK,3 AND STEVEN M. SMITH1
1 U.S. Geological Survey, P.O. Box 25046, Mail Stop 973, Denver, Colorado 80225
2 Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario, Canada K1A 0E8
3 Department of Geological Sciences, University of Alaska, 3211 Providence Drive, Anchorage, Alaska 99508

Abstract
Exploration geochemical and mineralogical studies by the U.S. Geological Survey at the Pebble porphyry
Cu-Au-Mo deposit were designed to (1) determine whether the concealed deposit can be detected with surface
samples, (2) better understand the processes of metal migration from the deposit to the surface, and (3) test
existing methods for assessing concealed mineral resources and/or develop new ones. Surface water (ponds,
streams, and springs), pond and stream sediment, soils subjected to various leaching techniques, and glacial till
samples were collected. The tilted nature of the undisturbed orebody, varying depth of cover, and later glacial
processes, strongly influence the geochemical responses and processes active on the various sample media. The
multimedia approach aids in identifying possible processes that caused the significant geochemical variations
within and among the various media. These processes include the following:

1. In the Pebble West zone, thin cover and local exposure of the orebody have facilitated the oxidation of
pyrite and other sulfides, and associated ferrous-ferric iron reactions, resulting in the local natural acidification
of ponds observed in the West zone, and in associated metal anomalies in waters, sediments, and soils.
2. In contrast, the East zone is concealed by both glacial deposits and underlying thick cover rocks, which
precludes the oxidation of sulfides in the underlying orebody. Low-level geochemical anomalies in circumneu-
tral spring and pond waters from the East zone are discernible only by using high resolution-inductively
coupled plasma-mass spectrometry with lower limits of determination two and perhaps three orders of magni-
tude lower than traditional methods. A variety of partial leaches of soils over the East zone reveal geochemical
anomalies in a similar suite of elements that may be related to upwelling waters from depth along graben-
bounding faults.
3. The indicator minerals gold, jarosite, and andradite in till reveal a displaced mineralogical anomaly to the
west and south of the Pebble orebody, as ore-related minerals were scraped from the orebody and deposited
in till downice of the deposit. Geochemical anomalies in pond water and sediment over the displaced till are
attributed to the ore-related minerals in till. This orientation study demonstrates the strong control of local
geologic and geochemical settings on the effectiveness of different traditional and newer reconnaissance geo-
chemical exploration techniques and thus has important implications for exploration.

Introduction A variety of sample media were collected in the deposit and

EXPLORATION for economically important mineral deposits is
becoming more challenging as it extends increasingly into
areas having shallow to deep cover. It is critical, therefore, to
evaluate existing and develop new innovative exploration
methods that will assist in the search for concealed deposits.
Exploration geochemical and mineralogical studies by the
U.S. Geological Survey (USGS) were undertaken between
2007 and 2010 at the giant Pebble deposit, Alaska, one of the
largest porphyry Cu-Au-Mo deposits in the world with a 2010
measured and indicated resource of 5,940 million metric tons
(Mt) at 0.42% copper, 0.35 g/t gold, and 0.025% molybdenum
(0.30% Cu equiv cutoff), and significant concentrations of Ag,
Pd, and Re (Pebble Limited Partnership, 2012). The goals of
this study were to develop geochemical methods, utilizing
surface samples, which are useful in exploration for concealed
deposits in terranes such as southwest Alaska, and better un-
derstand the processes of metal migration from the deposit to
the surface.
† Corresponding author: e-mail, eppinger@usgs.gov
district area, and from background sites, in order to charac-
terize the surface expression of Pebble and other smaller oc-
currences in the district (Fig. 1). These include a total of 70
glacial tills for indicator mineral studies and, for geochem-
istry, 168 waters (ponds, streams, and springs), 99 pond and
stream sediments, and 142 soils that were subjected to vari-
ous leaching techniques (Fig. 1). Pond sediment core samples
were also collected at eight ponds. The sampling was under-
taken prior to any surface disturbance of the deposit; explo-
ration activity to date has been limited to helicopter-sup-
ported drilling to minimize surficial disturbances.
The techniques described here were not utilized in the dis-
covery of the Pebble orebody. Based initially on a pilot’s ob-
servation from the air of a color anomaly in rubble crop, the
deposit was discovered by conventional rock and soil sampling
and subsequent drilling (Bouley et al., 1995). However, the
Pebble deposit is an ideal location for orientation geochemi-
cal and mineralogical studies because the surface setting is
undisturbed and the subsurface geology, structure, and litho-
geochemistry are well characterized, allowing discernment of

0361-0128/13/4104/495-33 495
 155°40'W 155°30'W 155°20'W 155°10'W 496
Sample sites in the Pebble deposit area (A) and region (B)
B

Groun
Sample Media

dhog
Soil sample site, n = 142

Cree

60°0'N
k
Till sample site, n = 70

Cone V V
V V Surface water sample site, n = 129
Mountain V
V
V Black Groundhog Ground water sample site, n = 39
V

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Lake Mountain
Big VV Stream sediment sample site, n = 21
Wiggly
Lake Pond sediment sample site, n = 78
VV Pond sediment core sample site, n = 8
V
Inset
V V

59°55'N
V VVV Geology
V
VV V
V
V V Pebble Limited Partnership claim boundary
V V
V
VV V
V
V VVV VVV V
V
V
V
VV
VVV
VV V
VV V
V
V VV
V VV V V +
V VVV V V VV V
VV V
Mineral occurrences or zones (labeled)
V VV
V V VVV V V
VV V
V VV V VV V
V
V VV V Pebble 0.3 % Cu eq. ore zone outline

v er
Kaskanak Koktuli

Ri
V
V V
li Mountain Mtn.
ok t u Arbitrary line indicating the West
North Fork K V Frying
V
25 Pan Sill and East Zones of the Pebble
V
V + +
V
Lake V ore body, described in text
V V

59°50'N
V

496
V V
V
V
155°20'W 155°18'W 155°16'W 155°14'W
rk Koktuli Riv
South Fo er VV
EPPINGER ET AL.

52 38 Inset
+V
VV
65 V V
V V + A
VV
V V
VVV
V + V
VV V V V
ek
59°55'N

+ V Sharp V
VV 37 V V
st Cre
VV V Mountain Fir
V+ V U.

ek
V 308 V V
V V

Cre
V Ta .
Chiquita lar Ck
ik
Lake V
V V
V V V V
VVV

59°45'N
e r Talarik
V V V V
V V
V V VVV
VV
59°54'N

VV V VV V

Up p
V V VV
V VV V V
V VV VV V
V
V VV
V V V
V
Lincoln V
Lakes V V
V VV VV
V VV
V V V
0 1 2 3 4 5 6 7 8 MILES V V V V V
Base from U.S. Geological Survey National V V
Elevation dataset; Hydrology derived from V V
0 1 2 3 4 5 6 7 8 KILOMETERS V V V
59°53'N

USGS and unpublished aerial photography; V

Ore zone boundary and exploration zones ALASKA
from Pebble Limited Partnership. V
VV V
Map V
area
Universal Transverse Mercator Zone 5N
Central Meridian 153°W 0 1 2 MILES Koktuli
World Geodetic System of 1984 Frying V Pan Mountain
0 1 2 KILOMETERS Lake
59°52'N

FIG. 1. Location and sample site map for Pebble deposit area (A) and surrounding region (B).
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT
subtle linkages between the surficial geochemistry and min-
eralogy to the underlying orebody.
Summarized in this paper are some of the critical findings
from our geochemical and mineralogical studies. Many tech-
niques applied in the study area have not been routinely used
in exploration of porphyry deposits, have not been applied in
southwest Alaska, and/or have been used but without associ-
ated publication of results. These include the porphyry cop-
per indicator minerals (PCIM®) method, hydrogeochemistry
using high resolution-inductively coupled plasma-mass spec-
trometry (HR-ICP-MS), pond sediment geochemistry, and
soil geochemistry utilizing several partial leach methods. In-
dicator minerals in till and other sampling media have been
used for decades for diamond exploration but have only re-
cently been developed for a wide variety of base metal de-
posits including porphyry deposits (Averill, 2001, 2007, 2011;
McClenaghan, 2005). Hydrogeochemistry has also been used
for decades in exploration (Eppinger et al., 2012, and refer-
ences therein), but this is one of the first studies to describe
results from a relatively new, highly sensitive analytical tech-
nique (HR-ICP-MS) that has lower determination limits in
the nanograms per liter (ng/l) range, two and perhaps three
orders of magnitude lower than traditional ICP-MS. Lake
and pond sediment geochemistry is an exploration method
used extensively in glacially covered areas in Canada (e.g.,
Cook and McConnell, 2001) but few studies have been de-
scribed in Alaska. Soils have been used effectively in explo-
ration programs for many years, but traditional total or near-
total digestion methods of soil analyses are commonly unable
to detect subtle surface anomalies associated with concealed
deposits. Partial leach methods may enhance these subtle el-
emental signals in the soils by attacking noncrystalline Fe and
Mn coatings or other weakly held exchangeable ions in the
soil matrix (Cameron et al., 2004; Cook and Dunn, 2007; Lett
and Sandwith, 2008; Heberlein and Samson, 2010; and
Heberlein, 2010).
FIG. 2. A View across Pebble West zone looking east. Iron-stained rubble crop in foreground with naturally acidic ponds
behind. Shaded hill in center distance is till ridge overlying the Pebble East zone. B. Looking northwest across glacial fea-
tures over the deeply concealed Pebble East zone. Slope of lateral moraine in foreground. Ponds in (B) have circumneutral
pH. Photos by R.G. Eppinger.
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497
The utility of geochemistry in exploring for deeply buried
mineral deposits is often hampered by a lack of understand-
ing of the processes by which ore-associated species migrate
through overburden. Without this understanding, geochemi-
cal anomalies are difficult to interpret in areas that lack sub-
surface control. Based on the results from this study, some of
the possible processes of metal migration from the concealed
deposit to the surface are discussed.
Physiographic and climatic setting
The Pebble deposit is situated in a broad glacially sculpted
topographic low at the head of three drainages: Upper Talarik
Creek, the North Fork of the Koktuli River, and the South
Fork of the Koktuli River (Fig. 1). Elevations range from
around 300 m at the deposit itself to 686 and 841 m at the ad-
jacent Koktuli and Kaskanak Mountains, respectively. The
area falls within the polar domain/subarctic regime ecoregion
(section M131C) as defined by Bailey (U.S. Forest Service,
2007). The study area is in a zone of discontinuous permafrost.
Frozen ground was encountered locally in lowland peat-rich
and boggy areas at depths of 20 to 40 cm. The entire area is
masked by lichen-rich tundra vegetation, with willow varieties
and alder trees that commonly flank drainages (Fig. 2A, B).
Long-term climatic data are not available for the Pebble
deposit area. Detailed climate data for 2007 indicated a max-
imum summertime high temperature of +22.8°C and winter-
time low of −33.8°C, total precipitation of 879 mm, and high-
est rainfall in early September (Hoefler Consulting Group,
2008). Temperature extremes are greater than at nearby Il-
iamna, where climate is moderated by the 2,600 km2 Lake Il-
iamna. Average temperatures at Iliamna ranged from winter-
time lows of −8.8° to −7.2°C to summer-time highs of 10.5°
to 13.3°C, with overall average yearly precipitation of 635
mm, during the 30-year period from 1971 to 2000 (ACRC,
2009). Similar to Pebble, the highest precipitation period was
August to September.
497
498 EPPINGER ET AL.
Previous reconnaissance geochemical surveys in the region
Existing publically available regional geochemical data cov-
ering the Pebble area are sparse. The 1° × 3° quadrangle-
based USGS Alaska Mineral Resource Assessment stream-
sediment sampling program from the 1970s through early
1990s did not include the Iliamna quadrangle in which Peb-
ble is located. The U.S. Department of Energy’s National
Uranium Resource Evaluation program of the late 1970s to
early 1980s included the collection of pond sediment samples
in the Iliamna quadrangle, but no samples were collected
within a 6-km radius of the Pebble deposit and the closest
downgradient pond sediment location was about 11 km dis-
tant (Smith, 1997; Anderson et al., 2009; U.S. Geological Sur-
vey, 2011a). Review of the USGS National Water Information
System database indicates two surface water sites located
about 20 km downstream of the deposit area (U.S. Geological
Survey, 2011b). Therefore, there were no existing publicly
available geochemical data that could provide clues to the
presence of the Pebble deposit prior to its discovery.
Geology and Mineralization
A summary of the geology and mineralization is provided
here. Detailed descriptions of the geology, alteration, and
mineralization are provided elsewhere in this issue by Gold-
farb et al. (2013), Gregory et al. (2013), and Lang et al.
(2013).
Geology
The Pebble deposit is hosted within the southern part of
the Kahiltna terrane, a variably metamorphosed suite of rocks
that consists predominantly of Late Triassic basalt, andesite,
and sedimentary rocks overlain by Jurassic to Cretaceous vol-
caniclastic turbidites (Fig. 3; Bouley et al., 1995; Lang et al.,
2008, 2013). A diverse suite of Cretaceous to Tertiary plutons
intrudes the older rocks and is related to the still-active sub-
duction zone located about 500 km to the southeast. The plu-
tons occupy a NE-trending structural corridor that is likely
related to the crustal-scale Lake Clark translational fault
(Lang et al., 2008, 2013).
At Pebble, Jurassic to Cretaceous argillite, siltstone, and
graywacke of the Kahiltna flysch sequence were first intruded
by subparallel ~96 Ma granodiorite and diorite sills (Fig. 3).
In the west, these sills were cut by a ~96 Ma alkalic intrusive
complex. Hornblende granodiorite stocks (Kaskanak batholith
and related satellites) intruded all other rock types at 91 to 89
Ma (Lang et al., 2008, 2013; Rebagliati and Lang, 2008) and
are spatially and genetically related to Cu-Au-Mo mineraliza-
tion. Rhenium-osmium ages in molybdenite suggest the age
of mineralization is 89.5 Ma (Schrader et al., 2001; Gregory
and Lang, 2009). Well-bedded sedimentary, volcaniclastic,
and volcanic rocks that range in age from late Cretaceous to
Eocene unconformably overlie the older rocks. Informally
called the Cover sequence, these rocks are up to 799 m thick
over the Pebble deposit (Lang et al., 2012).
The surficial geology of southwest Alaska is dominated by
materials deposited during a series of late Pleistocene glacia-
tions (Hamilton and Klieforth, 2010). The most important
glaciation in the Pebble area corresponds to the Late Wis-
consin Brooks Lake glaciation event (Detterman and Reed,
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1973), dated at about 25,000 to 10,000 years BP by 14C (Stil-
well and Kaufman, 1996). The Kvichak stade was the initial
and most extensive advance of the Brooks Lake glaciation in
the region (Hamilton and Klieforth, 2010). Ice filled the Lake
Clark structural trough, flowed southwestward, and then split
into separate ice tongues that flowed south and southwest
into the Pebble region. A second major ice body overflowed
westward from Cook Inlet and filled the broad basin of Il-
iamna Lake. At various times, these glaciers blocked each of
the three major drainages in the Pebble area—Upper Talarik
Creek and the North and South Forks of the Koktuli River
(Fig. 1). The resulting ice-dammed lakes filled lowlands in
headward parts of each drainage resulting in large areas of
glaciolacustrine deposits (Hamilton and Klieforth, 2010).
Glaciers from subsequent stades of the Brooks Lake glacia-
tion did not extend into the Pebble area (Hamilton and
Klieforth, 2010). The distinctive sets of arcuate moraines,
meltwater channels, outwash deposits, numerous kettle de-
pressions now occupied by ponds, and ice-dam glaciolacus-
trine deposits throughout most of the lowlands in the Pebble
region are primarily the result of the Kvichak stade. Uncon-
solidated glacial deposits at Pebble vary in thickness from 0 m
locally in the West zone to 50 m thick elsewhere (Hamilton
and Klieforth, 2010).
Mineralization
The eastward tilted Pebble deposit comprises the contigu-
ous West (under shallow cover) and East (under deeper
cover) zones, which may represent two hydrothermal centers
within a single, large magmatic-hydrothermal system (Lang et
al., 2008, 2013). The West zone extends from the surface to
about 500-m depth, whereas the East zone extends to at least
1,650-m depth (Fig. 4). The deposit is open at depth. Miner-
alized rock in the West zone is centered around several small
granodiorite cupolas intruding sedimentary rocks, diorite
sills, and breccias, whereas the East zone is generally cen-
tered on a large granodiorite pluton (Lang et al., 2013). The
East zone is unconformably overlain by an eastward-thicken-
ing, 300- to 600-m thick wedge of Late Cretaceous to
Eocene, postmineralization, volcanic and sedimentary rocks
(Fig. 4; Lang et al., 2008, 2013). On the eastern side of the
East zone, high-grade mineralization has been truncated and
dropped 600 to 900 m by graben-bounding normal faults
(Lang et al., 2013).
The most highly mineralized rock is associated with strong
potassic or sodic-potassic alteration characterized by dominant
K-feldspar, variable biotite, and almost no magnetite, and is
cut by multigenerational stockwork veins containing quartz,
carbonate, and sulfides (Lang et al., 2013). Most molybdenite
is in quartz veins that accompanied potassic or sodic-potassic
alteration. Laterally extensive sericite-altered rocks are pe-
ripheral to and overprint the margins of the deposit and yield
outward to propylitically altered rock. The highest grade min-
eralization is in the East zone and resulted from advanced
argillic alteration processes that overprinted previously altered
rocks along a synhydrothermal brittle-ductile fault zone (Gre-
gory et al., 2013). Quartz-sericite-pyrite alteration zones on
the distal margins of the deposit do not contain significant Cu
or Mo but consistently exhibit high concentrations of Au (Gre-
gory et al., 2013). Dominant ore minerals are chalcopyrite,
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 499

KUSKOKWIM E

E
N k

RAN
GROUP A lar
RR ke
C
155o18’ W 155o16’ W TE La

TER
Gs PEBBLE
N Gs

AR
59 55’ N

G A
TN

UL
K IL Iliamna Lake

NS
H
o

G KA Cook

NI
K

PE
CENOZOIC COVER Inlet
0 50 Km 0 50 Mi
Ga
Gs

G
D
D
K G

Gs
D D G K G
D
D
59o54’ N

G
Gs
Gs
G K G Gs
G
K
Gs D
K Gs

D Gs
G
D Gs
G

A G
K
K
Gs

G
59 53’ N

0 1MI G
o

0 1KM Gs
K
G

Cretaceous Rocks Jura-Cretaceous Rocks

A Alkalic intrusions & breccias (~96 Ma) K Kahiltna flysch
G Granodiorite sills (~96 Ma)
Ga Gabbro
D Diorite sills (~96 Ma)
Fault
Gs Granodiorite stocks (~90 Ma)
Pebble deposit resource outline
FIG. 3. Geologic map of the Pebble deposit showing pre-Tertiary units projected to the surface, based on drill core data,
and inset map showing lithotectonic terranes. Geology modified from Lang et al. (2013); inset regional geology from Wal-
lace et al. (1989).

molybdenite, and native gold. Gold occurs mostly as free gold
inclusions in pyrite and chalcopyrite (Gregory et al., 2013).
High-grade gold-bearing bornite-covellite-digenite ± enar-
gite mineralization was discovered at Pebble East in 2006
(Gregory and Lang, 2009; Lang et al., 2013). Supergene chal-
cocite and covellite occur in the upper parts of the West zone,
but supergene minerals are not present in the East zone.
Other mineral occurrences in proximity to Pebble and
under active exploration by the Pebble Limited Partnership
include the 38, 37, 25, 52, 65, 308, and Sill zones (Fig. 1).
Published information on these occurrences is sparse (Lang
et al., 2013). Hawley (2004) speculated that the 38 (porphyry)
and 37 (skarn) zones, and an adjacent unnamed porphyry oc-
currence (= IL003, Hawley, 2004) probably have ages similar
to Pebble. The unnamed occurrence is located about 1 to 2
km immediately north of the 52 zone (Fig. 1). Also present in
the vicinity of Pebble are at least two Tertiary (?) epithermal
precious metal occurrences: the Sill zone (Schrader, 2001;
Lang et al., 2013) and unnamed precious metal veinlets on
Sharp Mountain (Lang et al., 2013). There are scant reports
of minor historic placer gold occurrences downstream of Peb-
ble along the Koktuli River (Hawley, 2004).

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500
A Pebble West
Quaternary surface deposits
152 m
500 ft
305 m
1000 ft
N CuEQ (wt.%)
PW PE
A 0.25 - 0.50
B
FIG. 4. West-east cross section through Pebble deposit showing equivalent Cu, postmineralization cover rocks, and over-
lying glacial deposits. Glacial deposits vary from 0 to 50 m in thickness in the area. Cross section is modified from that of
Gregory et al. (2013).
Methods
Sample media collected in and around the Pebble deposit
and from nearby mineral occurrences in the district include
stream, pond, and spring waters; bedload stream and basal
pond sediment; pond sediment core; soils; tills, and limited
rocks. Thorough descriptions of collection, analysis, qual-
ity-control procedures, quality-control charts, an assess-
ment of data quality, and databases containing analytical re-
sults for all sample media are in Anderson et al. (2011),
which contains all USGS geochemical and geophysical data
collected by the USGS at Pebble. In addition, specific pa-
pers describe the methods for indicator mineral studies
(Kelley et al., 2011a) and hydrogeochemistry (Eppinger et
al., 2012).
Indicator minerals in till
Seventy till samples (6−15 kg) were collected up- and
downice from the deposit over a total distance of about 42
km (Fig. 1). Till samples were collected primarily from
moraine ridges deposited during the Kvichak stade (Hamil-
ton and Klieforth, 2010) and consist of poorly sorted to un-
sorted material ranging from muddy gravel to sandy coarse
gravel. The till samples were dried, disaggregated, and
sieved in the laboratory to obtain the <2-mm fraction that
was subsequently fed across a shaking table. Visible gold
grains recovered from the table concentrate by panning were
counted and described morphologically, then returned to the
table concentrate after examination. After heavy liquid sepa-
rations at specific gravities of 2.8 and 3.2 and ferromagnetic
separation, the nonferromagnetic heavy mineral concentrate
fraction was sieved at 0.25 mm to obtain the 0.25- to 2-mm
fraction, which was subsequently sieved to 0.25- to 0.50-,
0.5- to 1.0-, and 1.0- to 2.0-mm fractions. All fractions from
till were examined under a binocular microscope at Over-
burden Drilling Management Ltd. to determine the abun-
dance of PCIM and other minerals.
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EPPINGER ET AL.
Pebble East B
Late Cretaceous to Eocene
post-mineralization
sedimentary and
volcanic rocks
< 0.001
0.001 - 0.25
0.50 - 0.75
0.75 - 1.0
1.0 - 1.5
> 1.5
Waters
A total of 168 water samples were collected from ponds (n
= 98), emerging springs/seeps (n = 39), and streams (n = 31),
from numerous sites in a 22-km2 area around Pebble, and
from a greater 760-km2 surrounding region (Fig. 1). Waters
were collected in midsummer, generally during precipitation-
free periods. On-site measurements included pH, specific
conductance, alkalinity, acidity, dissolved oxygen, turbidity,
water temperature, and a qualitative discharge estimate. The
samples were filtered on-site using disposable filters (0.45
μm) and subsamples for cation analysis were acidified imme-
diately with ultrapure HNO3. Filtered, unacidified subsam-
ples for anion analysis were refrigerated until analyzed. Fil-
tered and acidified samples were analyzed for 63 cations by
HR-ICP-MS (also known as double-focusing magnetic-sector
ICP-MS). Anions were determined on unfiltered and unacid-
ified samples by ion chromatography. Acidified (HCl), fil-
tered samples were analyzed for Fe2+ and dissolved organic
carbon (DOC) by spectrophotometry, and for Hg by cold
vapor-atomic fluorescence (CVAF) spectrometry.
Bedload stream and basal pond sediments
Bottom sediments from ponds (n = 78) and bedload stream
sediments (n = 21) were collected most densely near the Peb-
ble deposit area but were also collected at intervals down-
stream of the deposit along Upper Talarik Creek and the
South Fork of the Koktuli River and at regional background
sites (Fig. 1). Sites sampled include open-system lakes and
ponds with inlets and outlets, closed-system seepage lakes
and ponds supplied by groundwater, and small first-order
streams. Most sediment sites were situated in glacial drift
(kettles), but some were in glacial beach, deltaic, or lacustrine
deposits. The size of the ponds was typically between 0.005
and 0.05 km2. At each site, about 20 subsamples were com-
posited using a long-handled PVC scoop. Sample material in-
cluded detrital gravel, sand, and silt, and commonly contained
500
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 501

high amounts of organic debris. The material was washed and
screened on site through a 2 mm (10 mesh) stainless steel
screen. Subsequently, samples were air-dried, sieved to <0.18
mm (80 mesh), and the −80-mesh fraction was ground to
−100 mesh (<0.149 mm) for analysis. Samples were split and
subsamples were digested using a near-total, four-acid (hy-
drochloric, nitric, perchloric, and hydrofluoric acids) diges-
tion and a total sodium peroxide sinter, and analyzed for 66 el-
ements by ICP-AES and MS methods. Gold was determined
by atomic absorption spectrophotometry following a fire assay
preconcentration.
Pond sediment cores
Pond sediment core samples were taken from four ponds
within the deposit area (based on the presence of anom-
alous metal contents in the pond waters), three that are dis-
tal from known mineral deposits, and from Frying Pan
Lake, just downstream of the deposit area (Fig. 1). The
cores were collected by pounding either a simple 10-cm-
diam (4 in) PVC pipe with cap or a 10-cm polycarbonate
core barrel with an aluminum head and antisuction valve
into the sediment with a sledge hammer until refusal. The
cores were extracted by hand, capped, and kept upright
during transport to the Iliamna field facility. In all cases, the
sediment core lengths were 0.5 m or less. The cores were
frozen and transported either to USGS laboratories in Den-
ver, or to the University of Alaska, Anchorage (Frying Pan
Lake core). In the laboratory, the cores were sectioned into
increments between 0.5 and 2.5 cm, described, air-dried,
sieved to −80 mesh (<0.18 mm) and ground to −100 mesh
(<0.149 mm) before analysis. Samples were digested and
analyzed by the four-acid and sinter methods previously
described.
Soils
Soil samples were collected along three traverses over the
Pebble deposit (Fig. 1). Soil sampling intervals were about 60
m over the deposit, about 150 m on deposit margins, and
about 300 m on ends of traverse lines (Fig. 1A). At each site,
a pit about 0.5 m wide and 0.7 m deep was dug through the
tundra, exposing the soil profile. Four different soil subsam-
ples were collected based on either soil horizons or at prede-
termined depths, following procedures as specified for vari-
ous leach techniques. These samples were analyzed by up to
11 partial leach, near-total, and total digestion analytical
methods (Table 1). Soil pH was measured on unsieved soil
samples collected between 10 and 25 cm below the root zone,
using a 1:2 ratio of dry soil to deionized water. All the leach
techniques were used during the first field season, but in sub-
sequent seasons a much smaller arsenal of analytical methods
was used (Smith et al., 2009).
Quality control
For waters, sediments, and soils, quality assurance/quality
control concerns were addressed through the use of site dupli-
cates (i.e., replicating the entire collection procedure), analyti-
cal duplicates, standards, and (for waters only) deionized
water field blanks, which altogether comprised about 15% of
the samples analyzed. Instrumental precision was constrained
by analysis of laboratory duplicate solutions and is typically less
than 5%. Quality-control standard reference materials (SRM)
appropriate to each sample medium were analyzed with sample
batches to assess instrumental accuracy. All aspects of the qual-
ity-control assessment yielded impressive results (Anderson et
al., 2011). There was no contamination by sample processing.
In deionized water blanks, very low concentrations of <5 μg/l

TABLE 1. Partial Leach and Total Digestion Analytical Methods Used on Soil Samples
(listed in approximate order of increasing digestion and/or extraction strength)

Analytical method Targeted phase Collection method1 References

Deionized Water Leach2
BioLeach2
Enzyme Leach
TerraSol Leach
Mobile Metal Ions (MMI®) Leach2
Ionic Leach
Cold Hydroxylamine HCl Leach
Sodium Pyrophosphate Leach2
Aqua Regia Digestion
Four-Acid Digestion
Sodium Peroxide Sinter Digestion
Water soluble salts
Bacterial remnants
Amorphous manganese oxide
coatings
Amorphous iron and
manganese oxides
Weakly bound mobile metals
Weakly bound mobile metals
Amorphous manganese oxides
Organic, humic materials in soil
Sulfides and amorphous oxides
Near-total digestion but incompletely
dissolves some refractory minerals
Total digestion
Composited along profile 10-25 cm
below base of organic layer
Composited from upper part of
B horizon
Composited along profile 10-15 cm
below the surface
Composited along profile 10-15 cm
below the surface
Composited along profile 10-25 cm
below base of organic layer
Composited along profile 10-25 cm
below base of organic layer
Composited along profile 10-25 cm
below base of organic layer
Composited from lower part of
organic-rich Ao horizon
Composited along profile 10-25 cm
below base of organic layer
Composited along profile 10-25 cm
below base of organic layer
Composited along profile 10-25 cm
below base of organic layer
Lamothe et al. (2002)
Activation Laboratories (2008)
Skyline Assayers and
Laboratories (2011)
Skyline Assayers and
Laboratories (2011)
SGS Mineral Services (2011a)
ALS Minerals (2008, 2010)
Chao (1984), ALS Minerals (2010)
Chao (1984), ALS Minerals (2010)
Chao (1984), Acme Analytical
Laboratories (2010)
SGS Mineral Services (2011b)
SGS Mineral Services (2011b)

1 Analytical data and collection/preparation details available in Anderson et al. (2011)

2 Method was not used for samples collected in 2008

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502 EPPINGER ET AL.
for some major elements were detected and most trace ele-
ments were not detected at low ng/l levels. Comparison of site
duplicate pairs showed agreement within 20% for most and
within 10% for some elements. Comparison of the SRMs with
accepted values showed that almost all elements were ana-
lyzed with an accuracy of 10 to 15%. Adequate agreement ex-
ists for site and analytical duplicate pairs, but the ultralow
HR-ICP-MS determination limits for many trace elements in
waters are beyond the range for most currently available
SRMs. Thus, the ng/l and sub-ng/l trace element data for wa-
ters are fairly well constrained in terms of precision but not in
accuracy. There is a need for development of new SRMs for
low-level trace elements analyzed by HR-ICP-MS.
Results
Drill core results are presented first to define geochemical
characteristics of major lithologies, an aid for interpreting re-
sults from other sample media; secondly results are presented
for indicator minerals and waters—media that show promise
for regional targeting; and thirdly, results for sediments and
soils, the latter probably being most useful at the deposit-area
scale. Results for indicator mineral and water studies are
summarized here from recent indepth publications on these
media by Kelley et al. (2011a) and Eppinger et al. (2012), re-
spectively. Results from sediment and soil studies are more
extensively covered because they have not been described
previously in detail.
Geochemical characteristics of major rock units
Fifty-nine rock samples from drill core in the deposit area
were submitted for geochemical analysis to geochemically
characterize the major lithologic units at Pebble (Table 2).
Lithologies include those that predate the Cretaceous
Kaskanak batholith (Jurassic to Cretaceous mudstone, silt-
stone, and andesitic wacke), those that postdate the Kaskanak
Batholith (Late Cretaceous to Eocene wacke, mudstone,
basalt, and andesite), and various Cretaceous intrusive phases
that are either genetically related to mineralizing hydrother-
mal fluids or preore rocks that were mineralized by the mag-
matic-hydrothermal fluids (monzodiorite, granodiorite sills,
granodiorite plutons, and diorite). In spite of the low number
of samples for several of the lithologies, a few characteristics
are evident. Based on median concentrations, Cretaceous in-
trusive rocks are highest in Ag, Cu, F, Mo, Re, S, Tl, V, and W.
Postmineralization basalts and andesites are highest in Fe,
Mn, Na, Ni, Zn, and the rare earth elements (REE). All post-
mineralization rocks are highest in Pb, Th, and U. Finally,
mudstones, regardless of age, are highest in As, Bi, and Hg.
These geochemical characteristics provide a framework for
evaluating geochemical results for the various sample media
collected in this study.
Indicator minerals in till
Knowledge of glacial history and till transport directions are
critical in discerning patterns obtained from PCIM analysis;
the recent Quaternary mapping in the Pebble region (Hamil-
ton and Klieforth, 2010) was of paramount importance in this
study. The most effective indicator minerals in till samples for
targeting porphyry and/or related skarn deposits in the Peb-
ble area are andradite garnet, Mn epidote, gold, and jarosite.
0361-0128/98/000/000-00 $6.00 502
Other indicator minerals, such as apatite, are present in one
or more till samples but owing to the fact that there are mul-
tiple sources of apatite, the spatial distribution of apatite in till
does not suggest a unique association with mineralized rock
of the Pebble deposit (Kelley et al., 2011a). Rutile, identified
in drill core, was not detected in till samples, probably due to
its fine grain size and low overall abundance. In spite of its
abundance in the deposit, pyrite is rare, and other ore-related
sulfide minerals were not observed in till. This absence sug-
gests that processes such as preglacial supergene alteration of
the orebody and/or in situ weathering and oxidation of trans-
ported sulfide grains were active. Cinnabar is present in sev-
eral till samples and is interpreted to be related to Tertiary
epithermal deposits in the region (Eppinger et al., 2011; Kel-
ley et al., 2011a).
High abundances of andradite garnet have been identified
in the surficial sediments associated with nearly every por-
phyry Cu deposit tested for PCIMs, even if not identified in
associated bedrock (Averill, 2007). Results around the Pebble
deposit are consistent with these patterns. Andradite was not
observed in bedrock samples (Kelley et al., 2011a), yet it is
abundant in till samples (0.25- to 0.5-mm fraction). The high-
est andradite counts (>40 grains) occur in samples southwest
and down-ice of the Pebble deposit in close proximity to the
smaller 308 and 38 zones (both porphyries), and the 37 zone
(a skarn; Fig. 5A). The distribution of Mn epidote mimics that
of andradite (Kelley et al., 2011a, b). These minerals suggest
the presence of skarns associated with the porphyry deposits.
All till samples from the study, including those collected 8
to 10 km upice of the Pebble deposit, contain gold grains
(Fig. 5B), which suggests that multiple sources have con-
tributed gold to surficial deposits. However, tills immediately
adjacent to Pebble West contain 3 to 30 times the number of
gold grains than samples up- or downice, and the total num-
ber of grains decreases in the downice direction. The high
gold grain counts continue downice for many kilometers (Fig.
5B).
Abundant gold grains are also present in tills near the por-
phyry and skarn occurrences southwest of Pebble. The gold
grains range in size from 15 to 150 μm, with few larger grains.
Gold grain morphology (degree of rounding, polishing, and
flatness) may provide information about distance to the
source. All samples near Pebble contain at least 65% pristine
(primary shapes and surface textures) or modified (edges
damaged and grains striated) gold grains, whereas distal
samples contain mostly reshaped grains. Pristine grains re-
flect either a nearby bedrock source with little modification
during transport or liberation of gold grains from rock frag-
ments during in situ weathering of transported gold-bearing
sulfide grains (McClenaghan, 2005). Because most of the
gold in the deposit is contained in pyrite and chalcopyrite
(Lang et al., 2008, 2013; Gregory et al., 2013), the second op-
tion seems more likely, and it implies that postglacial till oxi-
dation was sulfide destructive. The presence of minor pyrite
but no chalcopyrite in tills is consistent with the greater sta-
bility of pyrite relative to chalcopyrite in the secondary weath-
ering environment.
The distribution of jarosite in till samples is more restricted
than that for gold (Fig. 5C). Jarosite is most abundant in
samples downice from Pebble and in samples close to the 37,
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 503

TABLE 2. Selected Element Concentration Means and Ranges for Near-Total Analyses of Major Drill Core Rock Units
from the Pebble Porphyry Cu-Mo-Au Deposit

Jurassic to Cretaceous Late Cretaceous to Eocene

Element1,2 Mudstone Andesitic mudstone/siltstone Mudstone and wacke Basalt Andesite

Map unit YW Y TY + TW TB TA
n=3 n=8 n=8 n=3 n=2

Median Range Median Range Median Range Median Range Median Range

Ag 1.32 1.25–1.56 1.49 0.60–7.69 0.14 0.09–0.25 0.06 0.05–0.08 0.135 0.13–0.14
As 25.2 19.9–37.6 20.3 2.3–116 33.4 18.6–68.2 3.4 3.0–3.5 7.35 5.0–9.7
Bi 0.24 0.18–0.28 0.375 0.18–0.86 1.05 0.13–1.8 0.02 0.02–0.03 0.06 0.03–0.09
Cd 0.74 <0.02–0.79 0.042 <0.02–0.88 0.285 0.18–0.37 0.32 0.10–0.83 0.125 0.10–0.15
Co 21.2 18.2–23 14 2.7–38.3 19.8 16.0–21.1 34.1 32.9–34.4 30.3 29.4–31.1
Cu 4,770 3,250–5,750 3,440 530–15,900 46 38.4–56.8 29.6 21.3–36.1 139 117–160
F 1,450 1,300–1,570 1,235 700–1,910 520 310–630 490 460–570 690 660–720
Fe % 3.3 3.02–3.39 4.39 2.58–12.3 4.79 4.64–5.73 8.77 8.65–9.0 7.94 7.47–8.4
Hg 0.04 <0.01–0.04 0.03 <0.01–0.05 0.23 0.14–0.85 <0.01 Not detected <0.01 Not detected
K% 6.47 6.02–7.02 5.57 3.85–6.35 1.44 0.92–1.58 0.76 0.60–0.90 0.835 0.55–1.12
Mn 168 154–204 136 69–453 918 861–1,110 1,560 1.420–1,690 1,280 1,250–1,320
Mo 178 140–393 251 79.6–500 2.54 1.96–5.96 0.86 0.80–0.86 1.59 1.42–1.76
Na % 1.84 1.21–2.13 1.04 0.20–2.5 1.31 1.22–1.43 1.97 1.92–2.26 3.3 2.82–3.78
Ni 31.5 31.4–39.3 23.9 11.5–39.3 25.5 23.2–30.7 38.5 37.7–39.7 41.8 41.0–42.5
Pb 7.2 7.1–8.4 12.3 4.8–21.7 16.8 11.9–21.9 20.3 13.5–27.7 15 14.3–15.7
Re 0.462 0.347–2.29 0.191 0.008–1.02 0.003 <0.002–0.011 0.002 0.002–0.003 0.003 0.002–0.003
S% 2.2 1.79–2.31 1.71 0.13–3.17 0.195 0.15–0.93 <0.01 <0.01–0.10 0.85 0.23–1.47
Sb 0.95 0.26–1.63 2.67 0.42–5.66 2.15 1.43–2.56 0.62 0.34–0.74 3.41 2.93–3.88
Th 3.81 3.68–3.91 3.09 1.98–3.72 5.62 4.65–6.36 2.7 2.61–2.73 5.14 5.0–5.27
Tl 1.38 1.09–1.53 0.965 0.74–1.47 1.04 0.58–1.71 0.11 0.08–0.13 0.205 0.14–0.27
U 1.5 1.4–1.5 1.4 0.40–2.0 2.7 2.4–3.4 0.8 0.60–1.0 2.05 2.0–2.1
V 241 223–259 245 176–350 159 133–168 187 184–190 249 247–250
W 8.5 8.4–15.4 8.2 6.0–22.8 1.2 1.0–1.6 0.6 0.60–0.70 1.7 1.6–1.8
Zn 76 20–88 26 14–821 101 89–113 195 177–238 138 130–146
ΣREE 95.2 69.3–128 96 66.9–167 93.4 77.3–102 171 168–180 185 182–188

Cretaceous

Element1,2 Monzodiorite Granodiorite in sills Granodiorite in plutons Diorite

Map unit N and N-p Gs Gp and G-p Db and D
n=5 n=9 n=9 n = 12

Median Range Median Range Median Range Median Range

Ag 1.62 0.31–2.18 1.59 0.20–3.26 1.73 1.18–2.78 2.64 1.32–4.74

As 12.5 0.30–35.9 15.1 3.6–344 7.1 2.1–10.3 12.9 3.7–203
Bi 0.19 0.15–0.41 0.34 0.15–1.69 0.31 0.14–3.84 0.415 0.10–1.35
Cd 0.2 <0.02–0.57 0.12 <0.02–4.52 0.06 <0.02–0.49 0.105 0.02–0.63
Co 17.1 14.8–40.1 13.6 2.5–25.4 13.3 3.4–18.9 38.8 22.3–57.1
Cu 4,670 894–7,100 5,090 104–9,970 12,100 2,620–17,000 6,620 3,950–16,500
F 2,150 2,120–2,890 1,260 860–1,770 1,000 500–1,590 2,220 2,030–3,020
Fe % 3.53 2.83–8.32 4.59 2.68–11.8 2.1 1.88–3.04 7.5 5.44–10.8
Hg 0.01 <0.01–0.09 0.01 <0.01–0.03 0.021 <0.01–0.03 0.03 <0.01–0.13
K% 5.99 3.61–6.75 5.6 1.15–6.31 5.35 5.16–6.4 5.03 3.92–6.16
Mn 228 197–820 120 14–174 46 23–255 550 294–1,420
Mo 253 90.7–633 161 78.6–4,550 336 159–1,380 180 67.1–866
Na % 1.38 0.72–1.9 0.28 0.14–1.07 0.22 0.15–1.57 0.88 0.25–1.66
Ni 22.2 19.1–27 13.1 2.1–24.6 10.3 5.0–19.4 27.3 15.2–43.4
Pb 6.4 4.8–8.4 8.8 5.8–19.7 15.6 5.6–24.6 6.35 3.2–19.7
Re 0.685 0.276–1.58 0.409 0.077–19.5 0.775 0.315–1.84 0.495 0.129–0.877
S% 1.8 1.4–2.58 2.57 1.22–15.1 1.77 1.46–2.46 3.12 1.01–5.86
Sb 1.18 0.34–3.5 0.85 0.37–2.17 0.59 0.24–1.69 0.84 0.43–15.5
Th 2.16 1.9–2.6 2.18 2.07–2.67 2.54 1.83–2.91 2.16 1.67–2.78
Tl 0.83 0.80–0.97 1.45 0.42–2.41 1.59 0.81–3.67 1.86 0.80–4.75
U 1.4 1.0–1.4 1 0.3–1.2 0.5 0.3–1.4 1.1 0.7–1.6
V 284 234–360 217 70–370 180 139–242 356 251–544
W 7.1 4.6–10.2 16.4 8.9–35.2 15.3 6.3–18.7 6.6 3.8–28.8
Zn 36 25–160 78 34–433 45 16–643 80.5 50–181
ΣREE 104 65.4–167 90.1 56.2–104 61.6 36.5–99.5 95.8 76–138

1 All analyses by 4-acid digestion followed by ICP-MS analysis except Hg (cold vapor atomic absorption spectrophotometry), F (specific ion electrode), and

ΣREE (38 element fusion ICP-MS); unpublished data from Northern Dynasty Minerals, analyses by ALS Minerals
2 Concentrations in parts per million, except as noted

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504 EPPINGER ET AL.

155°40'W 155°30'W 155°20'W 155°10'W

A: Andradite B: Gold C: Jarosite
Jarosite
A: Andradite < 10 grains < 8 grains < 3 grains
60°0'N
Groundhog
Mt. 10 - 20 grains 8 - 20 grains 4 - 47 grains
21 - 40 grains 21 - 46 grains 400 - 900 grains
41 - 125 grains 47 - 268 grains 901 - 2,500 grains
59°55'N
413 - 1,866 grains 269 - 590 grains
er
i Riv

ul Kaskanak Koktuli
For gold in figure
figurre B, heavy black line around symbol indicates
kt
N. Fork Ko Mt. Mt. wherre > 65% of the grains
samples where g arre pristine or modified
are
+ +
59°50'N
S. + Mineral occurr
occurrences
ences or zones (See
(See Fig. 1 for names)
Fo rk Koktuli R
. + + + k
.
C
++ ik Pebble 0.3 % Cu equivalent or
oree zone outline
ar
Tal
U pper

Pebble Limited Partnership main claim boundary

59°45'N
0 3 MI
Ice flow direction
direction
0 3 KM
Generalized moraines, dominantly rrelated
elated to the Kvichak Stade
155°40'W 155°30'W 155°20'W 155°10'W 155°40'W 155°30'W 155°20'W 155°10'W

B: Gold C: Jarosite
60°0'N 60°0'N
Groundhog Groundhog
Mt. Mt.

59°55'N 59°55'N
er

er
i Riv

i Riv

kt ul Kaskanak Koktuli kt ul Kaskanak Koktuli

N. Fork Ko Mt. Mt. N. Fork Ko Mt. Mt.
+ + + +
59°50'N 59°50'N
S. S.
Fo rk Koktuli R Fo rk Koktuli R
. + + + Ck
. + + + k
.

.
C
++ ik ++ ik
ar

ar
Tal

Tal
U pper

U pper
59°45'N 59°45'N
0 3 MI 0 3 MI

0 3 KM 0 3 KM

FIG. 5. Distribution of andradite garnet, gold, and jarosite in till samples (number of grains normalized to 10-kg sample).
A. Andradite. B. Gold. C. Jarosite. Glacial till polygons modified from Hamilton and Klieforth (2010) and Detterman and
Reed (1973). For base layer information, see Figure 1.

52, and 308 zones. Most grains are variably worn, suggesting
that jarosite formed prior to glaciation during supergene en-
richment of the upper part of Pebble West. Jarosite grains as-
sociated with the Pebble deposit and nearby occurrences are
among the first ever identified in PCIM studies of till samples
(Stu Averill, pers. commun., 2008). Their unique presence
and preservation at Pebble probably reflect two main factors:
(1) many deposits never develop a supergene enrichment
zone; and (2) in glaciated areas the level of bedrock erosion is
typically below the oxide cap development zone (i.e. below
the jarosite zone) so jarosite is not available for incorporation
into the till. Since a supergene cap developed at Pebble West
(Lang et al., 2008, 2013), the presence of jarosite in till
samples suggests that the deposit was not deeply eroded.
Water
Lower determination limits for cations analyzed by HR-
ICP-MS, a relatively new technique available commercially
since around 2005, are commonly two and perhaps three or-
ders of magnitude below those by standard ICP-MS. As a
consequence, the resulting dataset is robust and has few
highly censored elements (i.e., those with “less than” values),
an unusual feature for water analyses. The lower determina-
tion limits for elements analyzed by HR-ICP-MS allow ob-
servation of element patterns at exceedingly low concentra-
tion ranges. Basic statistics for selected variables in 168
surface waters (ponds, streams, and springs) are given in Fig-
ure 6. The elements Au, Hg, Pt, and Se were nearly 100%
censored and are not discussed further.
Surface waters in the greater surrounding area are all cir-
cumneutral (median pH 6.47; maximum pH 8.16). Regionally,
surface waters are generally dilute with specific conductance
values commonly in the low tens of microsiemens per cen-
timeter (μS/cm, median 41.4 μS/cm). Samples with specific
conductance above 65.2 μS/cm (upper quartile) are all from
surface waters within or close to the deposit area. Calcium is

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 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 505

9
1000 Median
25th and 75th percentiles
Minimum and maximum concentrations
100 ICP-MS lower determination limit 8
na Not available in standard ICP-MS suite

n = 168
10
7

1
Concentration

0.1

5
0.01

4
0.001

0.0001 na na 3

0.00001
2
Cond μS/cm

Cl- mg/L

F- mg/L
Ca mg/L

Cd μg/L
SO42- mg/L

Co μg/L
DOC mg/L

Fe mg/L

Cu μg/L
K mg/L

Pb μg/L

Sb μg/L
Zn μg/L

Re μg/L
Alk mg/L

U μg/L
Na mg/L

ΣREE μg/L

Th μg/L

Ag μg/L
Ba μg/L

Tl μg/L
V μg/L
As μg/L

Mo μg/L

Bi μg/L
Mn μg/L

Ni μg/L

In μg/L
W μg/L

pH
Cations, anions, and field parameters
FIG. 6. Box and whisker plots showing summary statistics for selected ions and field parameters in 168 spring, stream, and
pond water samples. All analyses by HR-ICP-MS except pH, Cond, Alk, DOC, SO42–, Cl−, and F−. Lower determination lim-
its for traditional ICP-MS are indicated by dotted line for comparison. ΣREE = sum of rare earth elements, Cond = specific
conductance, Alk = alkalinity, DOC = dissolved organic carbon.

the major cation in the waters and major anion compositions
range from bicarbonate to sulfate dominant, with the highest
SO42– and F− concentrations from low pH ponds and springs in
the Pebble West zone (Eppinger et al., 2012). Springs have
the highest major ion concentrations and generally higher
specific conductance values. Dissolved organic carbon con-
centrations are highest in ponds in the deposit area (Eppinger
et al., 2012).
Geochemical results for the surface waters reveal two
anomalous groups of samples within the deposit area that
uniquely reflect their respective local geologic settings. In the
Pebble West zone, water samples are highly anomalous in
several elements and they have coincident lower pH values
that reflect locally exposed and near-surface sulfide-bearing
mineralized rocks under shallow cover. In contrast, geochem-
ical anomalies over the deeply concealed Pebble East zone
are more subtle and water samples are circumneutral in pH.
Beyond the Pebble deposit area, water samples from some of
the other exploration zones are also anomalous in one or
more elements.
Pebble West zone: Samples with the lowest pH values, rang-
ing from 3.6 to 4.8, are from four ponds in the Pebble West
zone, in proximity to sulfide- and related ferrihydroxide-bear-
ing rubble crop that is exposed or under thin cover (Fig. 2A).
All but ten of the 44 sites with pH values below 6.0 (lower
quartile) are from surface water samples in and adjacent to
the Pebble deposit, the majority in samples from Pebble West
(Eppinger et al., 2012). Trace element chemistry in waters is
closely related to pH, with several cations (e.g., Cu; Fig.7A)
having highest concentrations in the low pH pond and spring
waters at Pebble West. These metalliferous, low pH ponds
and springs lie along the trace of a NW-trending fault identi-
fied in drill core (Eppinger et al., 2012). The cluster of
samples with highly anomalous Cu concentrations (hundreds
of μg/l) is flanked to the west and south by seeps and ponds
with lower level anomalous Cu concentrations (tens of μg/l).
Together, these anomalous samples comprise nearly the en-
tire upper quartile of Cu concentrations in the dataset. Other
cations that show similar robust patterns to Cu include the
rare earth elements (REE), Ni, Cd, Re, Tl, Zn, and K. Con-
centrations for Re and Tl in particular range from the ones to
tens of ng/l, and these elements would not have been de-
tected using traditional ICP-MS (Eppinger et al., 2012).
Pebble East and Pebble West zones: A broad, 4-km-wide
area encompassing both Pebble West and the deeper Pebble
East zones contains numerous spring and pond samples that
are circumneutral in pH and have attendant anomalous con-
centrations in elements that are commonly mobile at higher

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506 EPPINGER ET AL.

155°40'W 155°20'W 155°W

60°N

A: Cu, μg/L
A: Cu, μg/L V
V
Cu, μg/L
V Pond Seep Stream Percentile
V
V VV
ND (0.01)
< 75th 0.01 < x ” 1.74
VV
V

O PW V VOVV PE 75 - 90th 1.74 < x ” 7.21

V
VV
O V
Q
Q VV
V
V
V
VV
V
V
V
VO V
V
V
O
O
V
V
V
V
V
VO
V
OO VV O
V
V
V Q
OO
Q
V
VV
Q 90 - 95th 7.21 < x ” 82.4
O V VVV
VV VV V
VV
VV Q
V Q
V 95 - 97.5th 82.4 < x ” 337
O VV VVQ
r

O V V
V VV
R iv e

Kaskanak Q O Q > 97.5th 337 < x ” 661

i Koktuli
t ul Mtn. O +
N . F o r k K ok Q Mtn.
+Q
59°50'N

Q Q Q
O O
Frying Pan Q
Q Q
S. F O
Lake
ork Q
K o k tu li R.

.
Ck
QO
+
OO
V +Q +
Q
+O O
OO O OOV O
O OO
VV Q+
O O
Q OQ Q Q
ri k
Tal a
V Q Sharp Mtn.
0 3MI
V V
V
0 3KM V
U.

B: Mo, μg/L
60°N

B: Mo, μg/L V
V
V
Pond Seep Stream Percentile Mo, μg/L
V
V VV
ND (0.004)
< 75th 0.004 < x ” 0.369
VV
V

O PW V VOVV PE 75 - 90th 0.369 < x ” 0.640

V
VVV
O V VV
V
V V
VVVV V Q
Q 90 - 95th 0.640 < x ” 1.37
VVO
Q
Q VVV
VVOOO
V
V V
V
V
VV
OO
O QO
V V
V V
O
O V VV
V V V
V VV V
V V VV
Q
V
V
VV
VV Q
V Q
V 95 - 97.5th 1.37 < x ” 2.10
r

O
R iv e

VV
O Q
V
Kaskanak Q > 97.5th 2.10 < x ” 3.13
t ul i Mtn. +
N . F o r k K ok QOQ
Q
Koktuli Mtn.
+Q
59°50'N

Q Q
O O
Frying Pan Q
Q Q Q
S. F O
Lake
Q
ork
K o k tu li R.
VQO +
.
Ck

+
O +
OOV
O
O
Q
+
OO O O
Q
OO O O
ri k

VV +
QO OOQ
Q Q
Tal a

V Q Q Sharp Mtn.
0 3MI
V V
V V
0 3KM
U.
60°N

C: Ag, ng/L
C: Ag, ng/L V
V
V
Pond Seep Stream Percentile Ag, ng/L
V
V VV
ND (2.00)
< 75th 2.00 < x ” 2.07
VV
V
75 - 90th 2.07 < x ” 4.03
V PE
V
O V VOV
PW
VVV
Q 90 - 95th 4.03 < x ” 5.73
O OV
Q
V VV V
V
Q VVV
O VVVV
V
VV
VOVV
O
V
V
V
V
Q VO
V
V
V
V
V
VVQO
V
OQ
O
V
VOV
VV Q 95 - 97.5th 5.73 < x ” 9.27
O
V VV
VV Q V
V
VV
V
VV Q
V V
r

O VV
R iv e

VV
V
Kaskanak Q O Q > 97.5th 9.27 < x ” 13.1
i Koktuli
t ul Mtn. O
+
N . F o r k K ok QQ
Q Q
Mtn.
+
59°50'N

Q Q
O
Q
O Pebble Limited Partnership claim boundary
Frying Pan Q Q
S. F O Q
Lake + Mineral occurrences or zones
ork
K o k tu li R.
.
Ck

QO
+ (See Fig. 1 for names)
OO +
V
OO
Q O Q +
OV
O O
O +
OOQOOOOOQ
ri k

VV +
Q
Pebble 0.3% Cu eq. ore zone outline
QQ
Tal a

V Q Sharp Mtn.
0 3MI Arbitrary line indicating the West (PW) and
V V
V East (PE) Zones of the Pebble ore body
V
0 3KM
U.

Fault

FIG. 7. Copper, molybdenum, and silver in filtered and acidified water samples, determined by HR-ICP-MS. A. Copper.
B. Molybdenum. C. Silver. ND = not detected at indicated lower limit. For base layer information, see Figure 1.

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 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT
pH. For example, numerous samples containing anomalous
Mo concentrations (0.369−3.13 μg/l) lie within this area (Fig.
7B). Other cations with similar distributions include V, As,
and Mn, at concentration ranges generally amenable to stan-
dard ICP-MS. However, anomalous concentrations of Ag, In,
Sb, Th, U, and W fall in the exceedingly low ng/l concentra-
tion ranges discernible only with the HR-ICP-MS method
(Eppinger et al., 2012). These cations (e.g., Ag; Fig. 7C) de-
lineate a broad area surrounding the Pebble West and East
zones. Although measured Ag concentrations are close to the
lower determination limit of 2 ng/l, HR-ICP-MS is a particu-
larly rigorous technique for Ag (Paul Lamothe, personal com-
mun., 2010). Possible low-level dispersion of Ag is evident
along Upper Talarik Creek (Fig. 7C). A similar possible dis-
persion pattern for Th and U (not shown) was also observed.
Antimony concentrations (not shown) decrease with distance
along both Upper Talarik Creek and the South Fork of the
Koktuli River (Eppinger et al., 2012). Anomalous concentra-
tions of all of these elements are also common in samples
from springs and ponds overlying or adjacent to major NE-
and NW-trending faults in the Pebble East zone (Fig. 7; Ep-
pinger et al., 2012).
Other occurrences: West and southwest of the Pebble de-
posit area are several concealed, undisturbed porphyry and
skarn occurrences (Fig. 1). There has been minor helicopter-
supported drilling on the 25, 37, 38, 308, 52, 65, and Sill
zones. Surface waters from areas surrounding these occur-
rences are generally circumneutral in pH. Several elements
occur at low level, but anomalous concentrations around the
occurrences, particularly in the vicinity of the 52, 37, 308, and
38 zones. These include the cations Ag (Fig. 7C), As, Cd, Cu
(Fig. 7A), Mo (Fig. 7B), Re, the REE, Sb, Th, Tl, Re, V, W,
and the anion SO42– (Eppinger et al., 2012). Molybdenum con-
centrations in particular target these occurrences, with a
spring immediately northeast of the 52 zone that contains the
highest Mo concentration in the entire study (3.1 μg/l Mo),
and an adjacent highly anomalous stream. Samples just north
of the Sill zone also have high Mo concentrations. The low-
level multielement anomalies in surface waters surrounding
these occurrences are easily discerned using HR-ICP-MS,
but most would not have been detected using traditional ICP-
MS (Fig. 6).
Bedload stream and basal pond sediments
Bedload stream and basal pond sediments are commonly
collected in reconnaissance surveys because their chemistry is
representative of the watershed from which they are col-
lected. The distribution of pond and stream sediment
samples in the study area is uneven, with greater density over
the Pebble deposit area than the surrounding region. Few
ponds and streams are present in the vicinity of the outlying
mineral occurrences, and sediment sampling there was lim-
ited to the 38 and Sill zones (Fig. 1). The sediment in ponds
is likely composed predominantly of the glacial material in
which the ponds are located.
Sediment input to many of the ponds is limited and there-
fore sediment is sparse. Summary statistics for selected ele-
ments in combined stream and pond sediments are provided
in Figure 8. High concentrations and variations spanning
three orders of magnitude characterize Au, Cu, and Mo,
0361-0128/98/000/000-00 $6.00
507
whereas concentration ranges are narrower for other ele-
ments. Although maximums are not extreme, median con-
centrations of As and Sb are an order of magnitude higher
than crustal abundance values for intermediate to felsic rocks
(Fig. 8). In contrast, median concentrations for Hg and Pb are
slightly lower than crustal abundance values for intermediate
to felsic rocks. Mercury concentrations in sediments are all
less than 0.32 ppm (median 0.03 ppm).
Anomalous elements in the Pebble deposit area: There are
two clusters of samples with concentrations of Cu, Mo, and Au
that are greater than the 90th percentile (Fig. 9, areas 1 and
2). Both clusters overlie the Pebble West zone. A NW-trend-
ing moraine (= the till ridge of Fig. 2A), part of the Iliamna
stade of the Brooks Lake glaciation (Hamilton and Klieforth,
2010), bisects the area and forms a local surface drainage di-
vide between Upper Talarik Creek to the north and the South
Fork of the Koktuli River to the south (Fig. 9). Ponds to the
northeast of this divide do not contain anomalous metal con-
centrations. Anomalous element concentrations are not found
in samples from ponds in the Pebble East zone.
The highest Cu concentrations in the study (high hundreds
to thousands of parts per million), are in pond sediments in
area 1, about 900 m east of the discovery outcrop, where
sparse iron-stained rubble crop and surface efflorescent salts
are present locally (Figs. 2A, 9A). Sporadic rubble crop sug-
gests that glacial cover is thin, but there are a variety of glacial
deposits. The ponds containing highly anomalous Cu in sedi-
ment are the same ponds described earlier that are charac-
terized by low pH, high specific conductance, and high metal
content in water. Sediment samples from area 1 also contain
elevated concentrations of S, Fe, Mo, and REE (90th per-
centile and above).
Area 2 is southwest of the discovery outcrop, is offset to the
west and south of the 0.3% Cu equivalent orebody (Fig. 9), is
devoid of rubble crop, and is completely covered by glacial
deposits of the Kvichak stade (Hamilton and Klieforth, 2010).
Area 2 contains a cluster of samples with Cu concentrations
that fall in the 75th to 95th percentile range (Fig. 9A). The ab-
solute Cu concentrations in these samples (hundreds of ppm)
are highly anomalous when compared to rocks of intermedi-
ate to felsic composition (Fig. 8; Levinson, 1980). If the
highly skewed samples from area 1 (thousands of ppm) are re-
moved from the dataset, then Cu concentrations in several
samples from area 2 fall above the 90th percentile range. Both
the highest Au concentrations (70−254 parts per billion
(ppb); Fig. 9B) and highest Mo concentrations (9−22 ppm;
Fig. 9C) are in the same area 2 pond sediment samples as the
elevated Cu concentrations. Other elements that have anom-
alous concentrations in sediment from area 2 include W, Sb,
Tl, F, K, Rb, and low-level Pb.
Anomalous elements distal to the Pebble deposit area: Only
two pond and four stream sediment sites distal to and not
downstream of the Pebble deposit area contain anomalous
Cu, Au, or Mo concentrations (<75th percentile, Fig. 10). Sed-
iment from a pond 8 km east of Groundhog Mountain con-
tains anomalous Au (60 ppb) and W concentrations. Anom-
alous Au concentrations (123 ppb) are also present in a pond
about 6 km southwest of Sharp Mountain.
A stream-sediment sample collected from a drainage cross-
ing the 38 zone contains anomalous concentrations of Cu
507
508 EPPINGER ET AL.

1000

100
Concentration

10

0.1

Median
25th and 75th percentiles
0.01 Minimum and maximum concentrations
Average abundance values for felsic to
intermediate igneous rocks
n = 99
ΣREE ppm

Org. C pct
Rb ppm

Cu ppm

Pb ppm

Sb ppm

Hg ppm
F ppm

Zn ppm

U ppm
Au ppb

Mo ppm
V ppm

As ppm

W ppm
Fe pct

K pct

S pct
Elements
FIG. 8. Box and whisker plots showing summary statistics for selected elements in 99 pond and stream-sediment samples,
analyzed by total or near-total techniques. ΣREE = sum of rare earth elements. Average abundance values are from Levin-
son (1980) and Rose et al. (1979).

(170 ppm) and Mo (9.5 ppm), and elevated Au (15 ppb). A of 21 ppm (Fig. 8). Gold reveals a similar pattern with an el-
sediment sample collected immediately below quartz stock- evated concentration of 26 ppb within a kilometer of the de-
work related to the epithermal Sill zone contains 701 ppb Au, posit, decreasing to 6 ppb at the site 12 km downstream.
the highest concentration in sediment from the study. Fine Molybdenum concentrations range from 4 to 9.5 ppm in the
gold flecks and iron-oxide pseudomorphs after pyrite were stream sediments. Other anomalous elements in these five
observed in panned stream sediment from this site; other samples include As, F, Fe, K, Mo, Sb, and W. This dispersion
anomalous metals include As, Mo, Sb, W, and ΣREE. Distal train is not strong and may not have stood out in a regional
from known mineral occurrences, stream sediments from two study done prior to the discovery of Pebble. There are no sim-
sites along the south end of Koktuli Mountain contain anom- ilar dispersion patterns for Au, Cu, and Mo from interval sed-
alous Cu and/or Mo concentrations (Fig. 10); one of these iment samples collected along Upper Talarik Creek, which
also contains anomalous W concentrations. Anomalous con- drains the deeply concealed Pebble East zone (Fig. 10). Gold
centrations of Cs, K, and Rb (>90th percentile) are present in is not detected and Cu and Mo concentrations are below the
all three sediment samples draining the south end of Koktuli median value. However, concentrations of F, U, and V are el-
Mountain. evated (all >90th percentile) in the five sediment samples col-
Stream-sediment samples collected for 12 km at about 2.5- lected along Upper Talarik Creek.
km intervals along the South Fork of the Koktuli River reveal
natural metal dispersion downstream of the thinly covered Pond sediment cores
and partially exposed Pebble West zone (Fig. 10). This dis- Pond core sediments were collected to determine if changes
persion is best observed for Au, Cu, and Mo. Copper con- in sedimentation rates and variations in element concentra-
centrations are as high as 199 ppm within 1 km of the deposit tions with depth in the ponds could be determined to better
but gradually decrease with distance (66 ppm Cu at a site 12 understand processes of metal input. Four pond cores were
km downstream). These concentrations are not strongly collected within or adjacent to the Pebble West zone: two
anomalous but are well above the median Cu concentration (sites 255 and 256) from the naturally acidic, metalliferous

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 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 509

155°22'W 155°20'W 155°18'W 155°16'W 155°14'W 155°12'W 155°10'W

A: Cu, ppm
59°55'N

A: Cu, ppm 3.20 - 65.1 ppm (<75th %ile)

Upper
65.2 - 198 ppm (75 - 90th %ile)
AREA 1
59°54'N

Ta
199 - 448 ppm (90 - 95th %ile)

lar
+

ik
449 - 744 ppm (95 - 97.5th %ile)

Cre
ek
745- 2,400 ppm (>97.5th %ile)
59°53'N

AREA 2
59°52'N

Frying Koktuli
Pan Mountain
Lake
0 2MI
59°51'N

+
S. Fork
0 2KM Koktuli
River
59°55'N

B: Au, ppm
B: Au, ppm
Not Detected (at 0.005 ppm)
Upper
0.005 - 0.012 ppm (<75th %ile)
AREA 1
59°54'N

Ta

0.013 - 0.032 ppm (75 - 90th %ile)

la
rik

+
0.033 - 0.068 ppm (90 - 95th %ile)
Cre
ek

0.069 - 0.253 ppm (95 - 97.5th %ile)

59°53'N

AREA 2 0.254 - 0.701 ppm (>97.5th %ile)

59°52'N

Frying Koktuli
Pan Mountain
Lake
0 2MI
59°51'N

+
S. Fork
0 2KM Koktuli
River

C: Mo, ppm
59°55'N

C: Mo, ppm
0.57 - 3.85 ppm (<75th %ile)
Upper
3.86 - 6.82 ppm (75 - 90th %ile)
AREA 1
59°54'N

Ta

6.83 - 9.21 ppm (90 - 95th %ile)

la
rik

+
9.22 - 12.6 ppm (95 - 97.5th %ile)
Cre
ek

12.7 - 22.3 ppm (>97.5th %ile)

59°53'N

AREA 2
Pebble 0.3% Cu eq. ore zone outline
59°52'N

Arbitrary line indicating the West and

Frying Koktuli East Zones of the Pebble ore body
Pan Mountain
Fault
Lake
0 2MI + Sill
59°51'N

+
S. Fork + Discovery outcrop
0 2KM Koktuli
River Approximate trace of surface drainage divide

FIG. 9. Distribution of copper (A), gold (B), and molybdenum (C) in pond and stream-sediment samples in the Pebble
deposit area, determined by ICP-MS following four-acid digestion (Cu and Mo) and atomic absorption spectrophotometry
following a fire assay preconcentration (Au). For base layer information, see Figure 1.

0361-0128/98/000/000-00 $6.00 509

510 EPPINGER ET AL.

155°40'W 155°30'W 155°20'W 155°10'W 155°0'W

Site distal from Pebble deposit with anomalous
O
O
O
O
Groundhog
elements listed (S = stream, P = pond)
O
O
O
Mountain
P Au O Stream sediment samples collected at
intervals along South Fork Koktuli River and
59°55'N

+
O O
Upper Talarik Creek
O O
O O
OO
O

O O
O OOO
OO

OO
O O
O
O
Pond or stream sediment site
OOO OO
O OO
O
O OO O
O O O O O
OO O
O O O OO OO O
O
O
Cu, Au, MoO
OO
OO
O
O
OO
O
O
OO
O Pebble Limited Partnership claim boundary
OO O O
Koktuli O
O

Cu, AuO F.P. Lake Mt. O

r
ve

i Pebble 0.3% Cu eq. ore zone outline

u li R
North Fork Kokt + Sill zone+
59°50'N

Mo O S Au
S + Mineral occurrences or zones
S Mo
Mo O O O
O
So u
th Fo rk Koktuli Ri O
(See Fig. 1 for names not listed)
ver O Cu, Mo
Cu, Mo
+ S Cu, Au, Mo +
+ k
+ 38 zone ree Percentile
C
O O
+
arik

O
Sharp 75th 90th
Mountain
er Tak

Cu 65.1 198 ppm

59°45'N

0 5 MI
O O
Au 12 32 ppb
Up p

P Au O

0 5KM
Mo 3.85 6.82 ppm

FIG. 10. Copper, gold, and molybdenum concentrations above the 75th percentile in pond and stream sediments in
samples distal to the Pebble deposit. For base layer information, see Figure 1.

ponds from area 1 described above, and two (sites 371 and S, and Hg are dissimilar with more extreme concentration
372) from area 2. Another core was collected from Frying Pan ranges in mineralized cores. Copper concentrations are an
Lake about 6 km downstream of the deposit. Background order of magnitude higher in pond cores from the deposit area
cores were collected from a pond in an adjacent drainage compared to the background ponds, and Mo concentrations are
about 2.2 km west of the West zone (375), from a pond about also much higher in samples from mineralized ponds. Boxplots
8.5 km north (374), and from a pond about 15 km northwest for the Frying Pan Lake sediment core samples show distrib-
(373) of Pebble (Fig. 1). No pond cores were collected from utions similar to those for background sediment core samples.
ponds over the deeply buried Pebble East zone. The highest Cu concentration (782 ppm) is in mineralized
Except for Frying Pan Lake, all sampled ponds are closed- core 256 (Fig. 12), collected from a low pH pond with coinci-
system kettles without inlet or outlet. The eight pond sedi- dent high Cu concentrations. Copper concentrations in min-
ment cores are short, around 50 cm or less, implying limited eralized pond cores 371 and 372 are greater than 250 ppm,
sediment input over time. Stratification or laminations sug- whereas those in core 255 are less than 200 ppm. Despite the
gesting varves are absent in the pond sediment cores, and at- variability, Cu concentrations in these cores are an order of
tempts at dating the sediments in two cores in the deposit magnitude higher than those in background (373, 374, and
area by 137Cs and 210Pb were inconclusive. Therefore, the sed- 375) or Frying Pan Lake cores (medians of 30 and 50 ppm,
iment cores cannot be used to provide a chronological history respectively; Fig. 12).
of sediment input. There are changes in elemental concen- The variation in Cu concentration with depth is not consis-
trations as a function of depth, but obvious element trends tent among cores (Fig. 12). A significant decrease in Cu con-
between cores are not discernible. centration from surface to 52-cm depth characterizes miner-
The Frying Pan Lake core contains fine- to medium-sand- alized core 256, but other mineralized cores show overall
sized sediment, including what is likely volcanic ash and sparse increases in Cu concentration or remain relatively constant
wood and fine-grained organic detritus. Cores from the Peb- with depth. The Frying Pan Lake core has higher concentra-
ble West zone contain subangular to subrounded, very-fine- tions in the upper 10 cm (Fig. 12) and has a slightly higher
to medium-sand-size sediment, with local pebbles up to 25 median Cu concentration compared to background cores, in-
mm across. There are sporadic clots of hematite and some dicating probable transport of Cu from the deposit area by
weak orange staining. The descriptions of the background the South Fork of the Koktuli River into the lake. Downhole
cores taken farther away from the deposit area are similar. Mo concentrations in sediment cores (not shown) generally
To contrast mineralized from background pond sediment range from 1 to 2 ppm, with the exception of mineralized
cores, basic statistics are shown for selected elements in Figure cores 371 and 372, where the range of Mo concentrations is 8
11, which includes the four ponds in the Pebble deposit area to 23 ppm. Samples from these latter two cores control the
and the three background ponds. The pond core from Frying skewness to high concentrations evident in the Mo mineral-
Pan Lake, downstream of the deposit and therefore neither ized boxplot (Fig. 11).
background nor mineralized, is not shown in the figure. Distri- A previous study by Munk et al. (2010) on trace element ac-
butions and median values for the elements Zn, Rb, Pb, Sb, and cumulation in the region showed that sediment cores from
U are similar for the background and mineralized pond core Lake Clark and Kontrashibuna Lake, located northeast of the
sediments. However, distributions of Cu, As, Mo, W, organic C, Pebble deposit, contained average concentrations of 63 and

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 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 511

1,000

100

10
Concentration

1.0

0.10
Median Mineralized, n = 80
25%-75%
Min-Max Background, n = 43

0.010

Org. C pct

Hg ppm
Cu ppm

Rb ppm

Pb ppm

Sb ppm
Zn ppm

U ppm
As ppm

W ppm
Mo ppm

S pct
Element
FIG. 11. Box and whisker plots showing summary statistics for selected elements in pond sediment core samples. Four
cores are from mineralized ponds in the Pebble deposit area and three cores are from proximal and distal background pond
sites; core from Frying Pan Lake excluded from plot. For sediment core locations, see Figure 1.

0
Core 255M Core 371M
Core 373B Core 372M
10
Core 374B
Core 256M

20
Depth, cm

30 Core 255M
Core 256M
Core 371M
40 Core 372M
Core 373B
Core 375B Core 374B
50
Frying Pan Lake core Core 375B
FP Lake

60
0 100 200 300 400 500 600 700 800

Copper concentration, ppm

FIG. 12. Downhole plots for copper concentrations in eight pond sediment core samples, including four from mineral-
ized ponds in the Pebble deposit area (M suffix), three from background ponds (B suffix), and one from Frying Pan Lake
just downstream of the deposit. Copper determined by ICP-MS following four-acid digestion.

0361-0128/98/000/000-00 $6.00 511

512 EPPINGER ET AL.
33 ppm Cu, respectively, and cores from south of the Pebble
deposit contained average concentrations of 14 ppm (Naknek
Lake), 9 ppm (Brooks Lake), and 3 ppm (Idavain Lake). The
range of Cu concentrations in the background pond sediment
cores from the Pebble study overlap the range of Cu concen-
trations from these regionally located lakes, but sediment
cores collected over the deposit area exceed these concentra-
tions by as much as an order of magnitude at the high end of
the concentration range.
Soils
Soil pH values range from 3.2 to 7.0 (median pH 5.23).
Most of the soil samples with pH <5 are from sites overlying
the Pebble deposit. However, four of eight regional back-
ground samples also have pH <5 values. Some of the low pH
soils are spatially associated with the acidic ponds and seeps
overlying the Pebble West zone. However, the large range of
values and the sporadic distribution of acidic samples suggest
that multiple processes are controlling soil pH. Hamilton
(2007) noted that the amount of soil saturation can cause pH
to vary and that both strongly acidic and strongly alkaline pH
values can be associated with mineral deposits, depending on
the height of the water table. Soil pH can influence the re-
sults of weak partial leach methods (Smee, 2003; Hamilton,
2007), a factor that may explain some of the variability in the
results from the different partial leach analyses used on soils.
Extractions of varying strengths release pathfinder ele-
ments from different target phases within the soil: ion-ex-
changeable phases, oxide coatings, carbonates, sulfides, or
biogenically derived phases (Chao, 1984; Mann, 2010). The
contrasts in element concentrations resulting from these
leaches may better reflect concealed mineral deposits at
depth, whereas those derived from the total and near-total di-
gestions of soils commonly reflect only exposed or near-sur-
face mineralized and associated altered rock.
Single elements: The use of several multielement analytical
methods quickly generates a large amount of geochemical
data and a systematic approach is necessary for effective in-
terpretation (Grunsky, 2010). Discussion of single elements
here is focused dominantly on Au, Cu, and Mo because most
of the elemental variation that is associated with mineralized
rock in this soil dataset can be expressed by the behavior of
these three elements. Additional plots of single-element data
are available in Anderson et al. (2011).
Strong digestions (sinter, four-acid, aqua regia; Table 1) in-
dicate the thinly covered to locally exposed Pebble West
zone, as shown with the distribution of Au concentrations
following aqua regia digestion (Fig. 13A). Anomalous Au is
conspicuously absent over the deeper Pebble East zone
where cover is much thicker (Fig. 4), corresponding well
with the results for Au concentrations in pond sediments and
PCIM gold grains in tills. Copper distributions following
near-total four-acid digestion are similar to those of Au (Fig.
13B). There is a close correspondence between the Cu
anomaly in soil and the underlying, nearly exposed mineral-
ization at Pebble West but an absence of a Cu anomaly in soil
over the deeply concealed Pebble East zone. Single-element
maps of the data from aqua regia, near-total, and total diges-
tion methods for the elements Ag, As, Bi, Fe, Sb, Te, Tl, V,
and W reveal distribution patterns similar to those for Au
0361-0128/98/000/000-00 $6.00 512
and Cu. The distribution of Mo as determined by total and
near-total methods like four-acid digestion (Fig. 13C) is also
similar to that of Au and Cu but includes a small low-level
anomalous response over the Pebble East zone.
Partial leach techniques that target weakly held elements in
the soil matrix (Table 1) indicate the shallow Pebble West
zone, but also commonly identify the deeper Pebble East
zone. This is well illustrated by the distribution of Mo con-
centrations (Fig. 14A) from Enzyme Leach analyses. Similar
distribution patterns are observed in single-element plots for
Mo, As, Sb, and V concentrations using the BioLeach, Ionic
Leach, Mobile Metal Ions (MMI®) leach, sodium pyrophos-
phate leach, TerraSol Leach, and, to a lesser extent, deionized
water leach techniques. The distribution of U in samples an-
alyzed following TerraSol Leach (Fig. 14B) shows almost the
same distribution pattern as Mo (Fig. 14A). The U enrich-
ment over the Pebble East zone is evident on soil maps for
every analytical method used in this study. The lithologies
from drill core with the highest U concentrations are post-
mineral mudstones and wackes (2.4−3.4 ppm U) or andesites
(2.0−2.1 ppm U) whereas mineralized Cretaceous granodior-
ite sills and plutons contain low U concentrations (0.3−1.4
ppm; Table 2). The distribution of Cu by Ionic Leach (Fig.
14C) is similar to the patterns for Cu determined by total and
near-total digestion techniques (e.g., Fig. 13B) except for a
slight enrichment over the Pebble East zone. Most of the
other partial leach techniques also indicate slight Cu enrich-
ment over Pebble East.
Multielement principal component analysis: Although pat-
terns are discerned from single-element plots, there is a
wealth of information recognizable only when multielement
statistical data interpretation methods, such as principal com-
ponent analysis, are applied. These techniques aid in recog-
nizing geochemical processes reflected by the data (Grunsky
et al., 2009; Grunsky, 2010). The results of principal compo-
nent analysis, observed in scree plot and biplot diagrams,
quantify variability and highlight interelement relationships
that are used to discern geochemical processes. Mapping the
principal component scores reveals patterns that show ele-
ment associations that can be related to geologic features and
mineralization. A description of the principal component
analysis constraints used in this study is provided in Appendix
1, but a complete discussion of the principal component
analysis analysis for each set of digestions is beyond the scope
of this paper. A method-by-method summary of the principal
components deemed most significant is provided in Table A1.
Described below are the principal component analysis results
for two representative analytical methods, four-acid digestion,
and Enzyme Leach.
Four-acid digestion data from 131 samples collected along
the east-west and north-south soil transects (Fig. 1A) were
evaluated after Ag, Cs, and P results were removed from the
dataset (variability too low and concentrations too close to
analytical lower reporting limits). The principal component
analysis was done on the remaining 39 elements (Table A1).
Figure 15A shows a scree plot of the ordered eigenvalues
that were obtained from the principal component analysis.
The steep slope of the first three eigenvalues in the scree
plot indicates that most of the data variation is contained in
these three components, accounting for 36, 14, and 10% of
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 513

155°20'W 155°18'W 155°16'W 155°14'W

A: Au, ppb, by Aqua Regia digestion
A: Au, ppb
59°55'N

U <0.50 (not detected) - 11.5 ppb (<75th %ile)

pp
er
11.6 - 54.2 ppb (75 - 90th %ile)

k 54.3 - 109 ppb (90 - 95th %ile)

Ta ee
larik Cr
110 - 226 ppb (95 - 97.5th %ile)
227 - 640 ppb (>97.5th %ile)
59°54'N

B +

0 1MILE B’
59°53'N

Koktuli
0 1KILOMETER Mountain
0 500 100015002000

B: Cu, ppm, by 4-acid ICP–AES/MS

B: Cu, ppm
Cu (ppm)
West East

B B’ Subsurface ore body limits

+ Ground surface Drill hole trace
1000 ft / 305 m

Inferred normal fault

Sea Level
Cu (ppm) in drill core
-1000 ft / 305 m
43 1,030 2,040 2,850 3,840 5,050 7,340
-2000 ft / 610 m

-3000 ft / 915 m
Vertical Exageration = 1.5x
-4000 ft / 1220 m

155°20'W 155°18'W 155°16'W 155°14'W

155°20'W 155°18'W 155°16'W 155°14'W
C: Mo, ppm, by 4-acid ICP–AES/MS
C: Mo, ppm
59°55'N

U 0.59 - 3.68 ppm (<75th %ile)

pp
er
3.69 - 9.37 ppm (75 - 90th %ile)

k 9.38 - 15.2 ppm (90 - 95th %ile)

Ta ee
larik Cr
15.3 - 21.1 ppm (95 - 97.5th %ile)
21.2 - 60.7 ppm (>97.5th %ile)
59°54'N

+ Discovery outcrop

Pebble 0.3% Cu eq. ore zone outline

0 1MILE
59°53'N

Arbitrary line indicating the West and

Koktuli
Mountain East Zones of the Pebble ore body
0 1KILOMETER
Fault

FIG. 13. Maps for gold and molybdenum, and profile for copper concentrations in soil samples analyzed following aqua
regia and four-acid digestion techniques. A. Distribution of gold after an aqua regia digestion. B. East-west profile showing
copper in soils following a four-acid digestion, plotted over a cross section of copper concentrations in exploratory drill holes.
Cross section is along east-west (with jog to southeast) soil line B-B shown in Figure 13A. The solid line in the cross section
represents the approximate ground surface. The dashed line is the surface of the subcropping mineralized porphyry system.
Drill core copper data from Northern Dynasty Minerals. C. Distribution of molybdenum following a four-acid digestion.

0361-0128/98/000/000-00 $6.00 513

514 EPPINGER ET AL.

155°20'W 155°18'W 155°16'W 155°14'W

A: Mo, ppb, by Enzyme Leach
A: Mo, ppb
59°55'N

U 0.02 - 7.11 ppb (<75th %ile)

pp
er
7.12 - 52.4 ppb (75 - 90th %ile)

k 52.5 - 111 ppb (90 - 95th %ile)

Ta ee
larik Cr
112 - 116 ppb (95 - 97.5th %ile)
117 - 705 ppb (>97.5th %ile)
59°54'N

0 1MILE
59°53'N

Koktuli
0 1KILOMETER Mountain

B: U, ppb, by TerraSol Leach

B: U, ppb
59°55'N

U 1.72 - 23.8 ppb (<75th %ile)

pp
er
23.9 - 83.1 ppb (75 - 90th %ile)

k 83.2 - 278 ppb (90 - 95th %ile)

Ta ee
larik Cr
279 - 809 ppb (95 - 97.5th %ile)
809 - 1,780 ppb (>97.5th %ile)
59°54'N

0 1MILE
59°53'N

Koktuli
0 1KILOMETER Mountain

C: Cu, ppb, by Ionic Leach

C: Cu, ppb
59°55'N

U 5 - 873 ppb (<75th %ile)

pp
er
874 - 4,700 ppb (75 - 90th %ile)

k 4,710 - 8,880 ppb (90 - 95th %ile)

Ta ee
larik Cr
8,890 - 12,600 ppb (95 - 97.5th %ile)
12,600 - 82,800 ppb (>97.5th %ile)
59°54'N

+ Discovery outcrop

Pebble 0.3% Cu eq. ore zone outline

0 1MILE
59°53'N

Arbitrary line indicating the West and

Koktuli
Mountain East Zones of the Pebble ore body
0 1KILOMETER
Fault

FIG. 14. Maps for molybdenum, uranium, and copper in soils leached and analyzed by partial leach techniques. A. Dis-
tribution of molybdenum after Enzyme Leach. B. Distribution of uranium after TerraSol Leach. C. Distribution of copper
after Ionic Leach. Sample gaps in north-south and east-west traverse lines for Ionic Leach due to insufficient sample re-
maining for analysis.

0361-0128/98/000/000-00 $6.00 514

 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 515

14
A B Ba
Al La
Y Sr
Na Ca
Ce

12
Mg
U

0.4
Li Th Sc
Ga
10 Ti Be Cr
Zn Sn
Pb
In
Ni
K Nb
Eigenvalue

0.0
Mn Co
8

Rb

PC 2
S
Cd
6

Fe

-0.4
4

SbTl Mo

W
2

Bi As Te

-0.8
Cu
0

0 5 10 15 20 25 30 35 40 -0.8 -0.4 0.0 0.4 0.8 1.2

Ordered Eigenvalue PC 1
155°20'W 155°18'W 155°16'W 155°14'W
C: 4-acid Principal Component 1
C: 4-acid PC1+ Positive Scores (see biplot in B above)
59°55'N

U
pp
er [Mo-Cd-S-Ca-U-Sr]
<0.00
k
Ta ee 0.001 – 0.200
la rik Cr
0.201 – 0.400
0.401 – 0.600
59°54'N

0.601 – 0.800
+
>0.800

0 1MILE
59°53'N

Koktuli
0 1KILOMETER Mountain

D: 4-acid Principal Component 2

D: 4-acid PC2- Negative Scores (see biplot in B above)
59°55'N

U
pp
er [Cu-Bi-Te-As-W-Mo-Sb-Tl]
<-0.800
k
Ta ee -0.799 – -0.600
larik Cr
-0.599 – -0.400
-0.399 – -0.200
59°54'N

-0.199 – 0.00
+
>0.00
+ Discovery outcrop

Pebble 0.3% Cu eq. ore zone outline

0 1MILE
59°53'N

Arbitrary line indicating the West and

Koktuli
Mountain East Zones of the Pebble ore body
0 1KILOMETER
Fault

FIG. 15. Principal component analysis of log-centered, four-acid digestion soil data. A. Scree plot of eigenvalues from the
principal component analysis. B. Biplot showing sample scores (circles) and element scores (element name) from the first
two principal components. Bolded elements are discussed in text. C. Map of rotated first principal component positive scores
highlighting the Mo-Cd-S-Ca-U-Sr association in the Pebble East zone. D. Map of rotated second principal component neg-
ative scores delineating the Cu-Bi-Te-As-W-Mo-Sb-Tl association over the Pebble West zone.

0361-0128/98/000/000-00 $6.00 515

516 EPPINGER ET AL.
the variability of the data respectively, for a total variability of
60%. A biplot of the first two principal components (Fig. 15B)
reveals that these components account for the variability as-
sociated with Cu-Mo deposits. In order to simplify the inter-
pretation, the component scores were rotated 45° clockwise.
The rotated first component (PC1) shows an element group-
ing of Mo-Cd-S-Ca-U-Sr associated with the positive compo-
nent scores. Negative scores of PC1 are associated with an
array of elements related to major rock-forming minerals,
most likely feldspars, hornblendes, pyroxenes and clays. The
rotated negative PC2 axis shows an association of Cu-Bi-Te-
As-W-Mo-Sb-Tl, also reflecting mineralized rock. Similar to
PC1, this grouping is inversely associated with the elements
interpreted as rock-forming minerals. A map of the scores of
the rotated first component is shown in Figure 15C. The ele-
vated positive values of PC1 reflect relative Mo-Cd-S-Ca-U-
Sr enrichment in sample traverses over the Pebble East zone.
The Ca-Sr component of PC1 may be related to the circum-
neutral pH of pond and spring waters observed in this area;
Mo, Cd, S, and U are all mobile under circumneutral pH con-
ditions. Figure 15D shows a map of the scores of the second
principal component (PC2). The strong negative scores of
PC2 represent relative Cu-Bi-As-Te-W-Sb-Tl-Mo enrich-
ment over the thinly concealed Pebble West zone, where
variable pH waters are present.
Enzyme Leach data on 158 samples collected along the same
soil transects were evaluated after Bi, Os, Pt, and Ru were re-
moved from the dataset for reasons described above, resulting
in 64 variables (Table A1). The principal component analysis
scree plot reveals that the first three components account for
more than 55% of the overall variability (Fig. 16A). Principal
component 2 shows an inverse association between Au (posi-
tive) and Mo (negative; Fig. 16B). The fifth principal compo-
nent accounts for 51% of the total Cu variability, and the bi-
plot of PC2 versus PC5 (Fig. 16B) shows that Cu variability is
independent of Au and Mo. Copper is associated with Mn, Co,
and Cr, possibly indicating a mafic signature, although, since
PC5 is dominated by Cu, mineralization is another possibility.
Molybdenum is associated with Ca-Sb-V-Mg-As-Sr-Na-Ge
(PC2). Scores for elements associated with PC5 (Cu-Mn-Co-
Cr-Cd-Ag) in samples over the Pebble deposit are shown in
Figure 16C. Samples highest in the Cu-dominant PC5 are
present over both the Pebble West and East zones. Interest-
ingly, a single-element plot of Cu by enzyme leach (Anderson
et al., 2011) does not delineate samples over the East zone be-
cause extremely high Cu concentrations over the West zone
overwhelm the Cu signal; the multielement PC5 suite over-
comes this outlier effect and reveals the East zone anomaly.
Also interesting, samples along the north-south traverse over
Pebble East are not indicated in the PC5 map. However, a
map of scores for the more complex PC2 association that con-
tains Mo (Fig. 16D) strongly highlights the Pebble East zone
and is similar to the single-element distribution of Mo shown
in Figure 14A. As described above for the four-acid digestion
PC1, the presence of Ca and Sr in this association may reflect
the circumneutral pH in pond and spring waters; several of
the other components in the association (Sb, V, As, and U) are
mobile under circumneutral pH conditions. Described ear-
lier in the water results, these elements are present in anom-
alous concentrations in water samples from the East zone.
0361-0128/98/000/000-00 $6.00
Discussion
Optimal geochemical methods for exploration of
concealed deposits
Porphyry deposits typically occur in clusters within mag-
matic belts (Sillitoe, 1972; Seedorff et al., 2005, and references
therein) and the likelihood for additional occurrences of por-
phyry deposits in southwest Alaska is considered high. How-
ever, traditional exploration methods may not work well be-
cause more than 70% of the land area up to 200 km southwest
of Pebble comprises post-Pebble-age Tertiary to Quaternary
cover rocks and sediments. A high level of importance should
therefore be placed on development of exploration tools that
can detect concealed deposits. In choosing optimal geochem-
ical tools, factors such as scale of surveys, multimedia and
multielement interpretation, unconventional pathfinder ele-
ments, and newer highly sensitive analytical techniques should
be considered.
The importance of scale in choosing sample media: The pur-
pose of geochemical surveys changes with scale (Theobald et
al., 1991). Results summarized here show that shallow till
sampling and PCIM analyses, pond sediment sampling,
spring/pond/stream water sampling combined with analysis
by highly sensitive HR-ICP-MS, and soil sampling have the
potential to be effective regional-to-local methods of explo-
ration in southwest Alaska (Kelley et al., 2011a; Eppinger et
al., 2012). These techniques have had minimal use previously
in the region.
Dispersal trains for PCIMs are long at Pebble. The gold
grain dispersal train in till extends for many kilometers down-
ice of the Pebble deposit (Fig. 5B). If gold grain abundances
are used in conjunction with andradite garnet (Fig. 5A) and
epidote abundances, most of the length of the South Fork
Koktuli River (nearly 25 km distance) is considered anom-
alous for its PCIM content. The significant size of this anom-
aly indicates that the PCIM method is an effective regional
exploration tool.
Pond sediment sampling is also effective but with poten-
tially smaller dispersion patterns than for PCIMs (Kelley et
al., 2011a). Pond distributions on the landscape might inhibit
uniform sampling coverage; some areas in the Pebble region
contain numerous pond-filled kettles, whereas ponds were
sparse in other areas. Stream-sediment sampling in glacial
drift-covered areas can be problematic because of develop-
ment of modern drainage networks that cut across the grain
of glacially sculpted landscapes, making follow-up of anom-
alies more difficult.
Spring/pond/stream water sampling combined with analysis
by highly sensitive HR-ICP-MS is a highly effective regional
exploration tool. The combined pond, seep, and stream sites
sampled in the study area are fairly evenly distributed over
~1,200 km2 (Fig. 7). The Pebble deposit and smaller occur-
rences to the southwest are distinguished by anomalous Cu,
Mo, and Ag concentrations in proximal waters (Fig. 7). The
use of the HR-ICP-MS technique is a major reason for the
success of hydrogeochemistry in regional exploration in the
study area. Several anomalous elements (As, Cu, K, Mn, Mo,
Ni, REE, V, and Zn) with concentrations in the μg/l and mg/l
ranges could have been detected using standard ICP-MS.
However, because concentrations are near the lower end of
516
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 517

Cu
A B

0.6
18

0.4
Mn Co
Cr Cd
14 Ag
U

0.2
Rb
Eigenvalue

Re
Mo Cs

PC 5
MgAs Zn Tl Pb
S Cl Eu
10

0.0
Ca Lu TmYb YHo Fe KI Pd
Sb Sr DyGd InBr SnBe TeTh
Na ScPrLi Ce
Er W Sm
8

Ge Tb Nd La Se Ni Au

-0.2
V Al
Zr Ba
6

Hf Ga

-0.4
4

Hg
Nb
2

Ta

-0.6
0

Ti

0 5 10 20 30 40 50 60 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8

Ordered Eigenvalue PC 2
155°20'W 155°18'W 155°16'W 155°14'W
C: Enzyme Leach Principal Component 5
C: Enzyme Leach PC5+ Positive Scores (see biplot in B above)
59°55'N

U
pp
er [Cu-Mn-Co-Cr-Cd-Ag]
<0.00
k
Ta ee 0.001 – 0.100
la rik Cr
0.101 – 0.200
0.201 – 0.250
59°54'N

0.251 – 0.300
+
>0.300

0 1MILE
59°53'N

Koktuli
0 1KILOMETER Mountain

D: Enzyme Leach Principal Component 2

D: Enzyme Leach PC2- Negative Scores (see biplot in B above)
59°55'N

U
pp
er [Ca-Sb-V-Mg-Mo-As-Sr-Na-Ge]
<-0.400
k
Ta ee -0.399 – -0.300
larik Cr
-0.299 – -0.200
-0.199 – -0.100
59°54'N

-0.099 – 0.00
+
>0.00
+ Discovery outcrop

Pebble 0.3% Cu eq. ore zone outline

0 1MILE
59°53'N

Arbitrary line indicating the West and

Koktuli
Mountain East Zones of the Pebble ore body
0 1KILOMETER
Fault

FIG. 16. Principal component analysis of log-centered, Enzyme Leach soil data. A. Scree plot of eigenvalues from the
principal component analysis. B. Biplot showing sample scores (circles) and element scores (element name) from the second
and fifth principal components. Bolded elements are discussed in text. C. Map of principal component five positive scores
highlighting the Cu-Mn-Co-Cr-Cd-Ag association. D. Map of principal component two negative scores portraying the Ca-
Sb-V-Mg-Mo-As-Sr-Na-Ge association over the Pebble East zone.

0361-0128/98/000/000-00 $6.00 517

518
the ICP-MS analytical working range for some of these (As,
Cu, Mo, Ni, and V; Fig. 6), results could be nondetects and
the Pebble deposit and especially the smaller occurrences to
the southwest might not be indicated. Anomalous Ag, In, Re,
Sb, Th, Tl, U, and W, with concentrations in the ng/l range,
would not be detected at all by standard ICP-MS and there-
fore no distinct pattern over Pebble and other mineralized
areas would have been revealed.
Soil sampling and partial leach techniques are more useful
as one approaches the local deposit scale. With some excep-
tions in glaciated areas due to displacements by glacial drift,
soil geochemistry typically reflects the underlying geologic
materials.
The importance of multimedia and/or multiple element in-
terpretation of results: Multimedia sampling allows for more
thorough anomaly characterization. If conducting blind ex-
ploration in the Pebble area before discovery of the deposit,
anomalous concentrations of elements like Cu, Mo, and Au in
multiple sample media would increase confidence in the in-
terpretation of a significant mineralized source. However,
there are numerous possibilities for the mineralized source of
anomalous Au and Cu concentrations in pond sediment,
stream sediment, and water samples in the study area be-
cause skarn, placer, epithermal, and porphyry deposits are
common throughout southwest Alaska. Combining miner-
alogical and geochemical techniques improves understanding
of geochemical dispersion pathways and exploration models
(Anand and Robertson, 2012). Indicator mineral identifica-
tions provide a mineralogical connection to these geochemi-
cal anomalies, thereby increasing the confidence of correct
interpretation of deposit type for a given geochemical anom-
aly. For example, gold grain abundance together with grain
count abundances of andradite garnet, epidote, and jarosite in
till are good indicators of porphyry and/or skarn deposits.
Gold grain morphology may also indicate proximity to sources.
Pristine or modified morphologies of the grains suggest short
transport of grains or in situ weathering of gold-bearing sul-
fide minerals in till samples. The presence of jarosite in till
100 200 300
South
0
1000 ft / 305 m
Sea Level
-1000 ft / 305 m
-2000 ft / 610 m
-3000 ft / 915 m
59°53’N 59°54’N
FIG. 17. North-south profile contrasting Enzyme Leach molybdenum concentrations in soils with the ratio of Enzyme
Leach molybdenum to total organic carbon concentrations in soils, plotted over a cross section of molybdenum concentra-
tions in exploratory drill holes in the Pebble East zone. Cross section is along the north-south (with jog to southeast) soil line
shown in Figure 1A.The solid line in the cross section represents the approximate ground surface. The dashed line is the sur-
face of the subcropping mineralized porphyry system. Drill core molybdenum data from Northern Dynasty Minerals.
0361-0128/98/000/000-00 $6.00
EPPINGER ET AL.
may be indicative of supergene development of a mineralized
porphyry system and its level of erosion (Kelley et al., 2011a),
both important in exploration of porphyry deposits.
Multielement interpretation may also help determine the
nature of the source of anomalous metal concentrations. This
is particularly evident with the soil geochemistry from Peb-
ble. Regardless of the method, anomalous Au almost exclu-
sively coincides with the shallow Pebble West zone. Copper
anomalies are also strong over Pebble West but, in some of
the weaker leaches, Cu appears in principal component
analysis associations over the Pebble East zone. This differs
from single-element Cu results like those in Figure 13B and
various single-element maps of Cu (e.g., Cu by Enzyme
Leach) shown in Anderson et al. (2011), where the extreme
Cu concentrations over Pebble West overwhelm any response
over Pebble East. The principal component analysis is able to
overcome this outlier effect for elements and reveals the
more subtle anomaly over Pebble East, as shown in Figure
16C for Cu. Molybdenum is found in different element asso-
ciations over both the Pebble West and East zones, similar to
its presence in circumneutral water samples from both areas.
Ratios of elements are also a powerful tool. Unlike the Peb-
ble West zone, a large number of soil samples from traverses
over the Pebble East zone were collected in peat bogs or
highly organic soils. This raises the question of whether the
oxyanion anomalies are due to the mineralization at depth, or
to a natural sink for elements transported in groundwaters
into the eastern area from the more exposed Pebble West
zone. To test this idea, the concentrations of Mo, as deter-
mined by the Enzyme Leach method, were divided by the
total organic carbon (TOC) concentration determined for
each sample. Figure 17 contrasts the concentrations of Mo by
Enzyme Leach with the ratio Mo/TOC in profile form along
the north-south soil traverse over a cross section of Mo con-
centrations and faults/fractures in exploratory drill holes
(Northern Dynasty Minerals, unpub. data). This traverse only
crosses the deeply concealed portion of the Pebble East
zone. When compared to Mo by Enzyme Leach alone, the
North Mo in soil (ppm), by Enzyme Leach ICP–MS
Mo (ppm)
Mo:TOC ratio (x5)
Ground surface Subsurface ore body
Drill hole trace
Inferred normal fault
Mo (ppm) in drill core
1 5 50 100 150 220 350
Vertical Exageration = 1x
59°55’N
518
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT
Mo/TOC ratio profile indicates that the majority of the Mo
soil anomaly over the Pebble East zone is likely due to sorp-
tion on organic matter. However, the strong Mo/TOC anom-
aly to the south is spatially correlated with underlying miner-
alized bedrock that is cut by graben-bounding and related
faults. This suggests the migration of metalliferous ground-
water upward along major faults and accumulation of Mo by
sorption to reduced organic matter in the soils.
Copper, Au, F, Mo, Sb, Tl, and W, all anomalous in pond
and stream sediments from the vicinity of the Pebble deposit,
are elements that are indicative of porphyry Cu deposits (Cox,
1986; John, 2010). Similarly, elevated Rb concentrations in
rocks have been used as a guide to detect potassically altered
rocks around porphyry copper deposits in Chile (Armbrust et
al., 1977). Anomalous K and Rb in several pond sediments
and anomalous K in waters in the Pebble West zone likely re-
flect underlying potassium-silicate altered rocks that are
widespread in the Pebble deposit (Eppinger et al., 2011,
2012; Gregory et al., 2013).
Unconventional elements: Several of the elements present in
anomalous concentrations in water samples from the Pebble
area are not traditional pathfinder elements used in explo-
ration for porphyry deposits. These include U, In, Re, and V.
Low-level anomalous U concentrations (14.5−125 ng/l) are
present in ponds, springs, and streams in the deposit area,
particularly over Pebble East, dispersing downstream along
Upper Talarik Creek (Eppinger et al., 2012). Anomalous U
also characterizes soil leachates from this area (e.g., TerraSol
Leach; Fig. 14B). In contrast, none of the water samples from
surrounding mineral occurrences contain high U. Whole-rock
geochemical analyses indicate that the highest U concentra-
tions are in the Tertiary volcanic and volcaniclastic rocks that
unconformably overly the deposit at depth over Pebble East
(units TY, TW, TA, Table 2). Therefore, the low-level anom-
alous U concentrations in water and organic-rich soil are
likely derived from the Tertiary units rather than the underly-
ing porphyry orebody.
Low-level anomalous concentrations of In (0.31−3.1 ng/l),
Re (15.6−158 ng/l), and V (357−3,420 ng/l) are present in
water samples that cluster around the Pebble deposit and one
or more of the outlying mineral occurrences in the Pebble re-
gion (Eppinger et al., 2012). Rhenium, a trace element in
molybdenite, and In, a trace element in chalcopyrite, are po-
tentially important pathfinder elements. Vanadium is present
in unusually high concentrations (>300 ppm) in ores from
Pebble (Table 2; Kelley et al., 2010); black rutile in drill core
samples from Pebble contains high V concentrations (avg 6.3
wt %, Kelley et al., 2010). The anomalous V concentrations in
water samples, as well as high V content in soils, appear to re-
flect the unusually high V signature at Pebble. The nontradi-
tional pathfinder elements In, Re, and V may complement
the traditional pathfinders Cu, Mo, REE, Sb, SO42–, Tl, W, and
precious metals for the assessment of similar porphyry de-
posits in the region.
New techniques: The relatively new, ultrasensitive HR-
ICP-MS technique used on water samples in this study re-
veals low-level (ng/l) anomalous concentrations for several el-
ements. Anomalous distributions of Ag, In, Mo, Re, Sb, Th,
Tl, U, V, and W were found over Pebble and/or over other
mineral occurrences in the district, at concentrations
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519
amenable only by ultrasensitive techniques. Low-level, but
nevertheless anomalous element concentrations were com-
mon in water samples collected from springs and ponds prox-
imal to faults cutting the Pebble orebody at depth. Water
sample analysis by HR-ICP-MS has great potential for delin-
eating low-level element anomalies in concealed terranes.
While common in northern Canada, few studies involving
the use of indicator minerals have been undertaken in Alaska.
The relatively new PCIM method was successful in delineat-
ing long dispersion trains for gold, andradite garnet, and epi-
dote at Pebble and other occurrences in the district. Gold
grains with relatively pristine morphologies and jarosite grains
were restricted to areas close to Pebble. The PCIMs identi-
fied aided in discerning geochemical processes and, in the
case of jarosite, provided clues to degree of deposit preserva-
tion and supergene enrichment. The PCIM method holds
promise in similar glaciated terranes of southwestern Alaska.
A natural extension to indicator mineral studies is trace ele-
ment determination within individual grains, utilizing rela-
tively new QEMSCAN (underway) or MLA techniques.
Other new exploration geochemical techniques employed
at Pebble include stable and radiogenic isotope studies.
Mathur et al. (2013) determined that δ65Cu is enriched in
mineralized versus unmineralized rocks and found that this
trend persists in groundwater samples, even at low Cu con-
centrations. Less definitive was a radiogenic isotope (Pb, Sr,
and Nd) study by Ayuso et al. (2013). Isotope compositions in
pond sediments and soils were compared with those from
mineralized and/or altered and postmineralization rocks in an
attempt to discern a mineralization signal in cover materials.
Processes of metal mobility and migration
The utility of geochemistry in exploring for deeply buried
mineral deposits depends on an understanding of the
processes by which ore-associated species migrate through
overburden. Without this understanding, geochemical anom-
alies are difficult to interpret in areas that lack subsurface
control. The eastward tilt of the Pebble orebody, the varying
depth of cover over the orebody, and later glacial processes
profoundly affect the geochemical responses in the various
sample media. Four processes are described:
1. In the Pebble West zone, thin cover and local exposure
of the orebody has facilitated the oxidation of pyrite and other
sulfides, along with associated ferrous-ferric iron reactions.
These reactions release H+ (Plumlee and Logsdon, 1999) into
surficial waters, resulting in the local natural acidification of
ponds and associated high metal concentrations in waters,
sediments, and soils.
2. In contrast, the East zone is concealed by both Late
Cretaceous to Eocene volcanic/volcaniclastic rocks and over-
lying glacial deposits, precluding the oxidation of sulfides in
the underlying orebody. Low-level geochemical anomalies in
spring and pond waters reflect the circumneutral nature of
the waters in the East zone. Partial leaches of soils over the
East zone reveal geochemical anomalies in a similar suite of
elements that are mobile in circumneutral conditions.
3. The indicator minerals gold, jarosite, and pyrite in till re-
veal a displaced pattern to the west and south of the outline
of the Pebble orebody, as ore-related minerals were scraped
520 EPPINGER ET AL.
off of the orebody and deposited in downice till. Sediment
and water samples collected from ponds occupying glacial
kettles in till reveal geochemical anomalies that are attributed
to the displaced ore-related minerals contained in the till.
4. Finally, electrochemical processes might be involved in
the movement of elements, particularly in the Pebble West
area.
Pebble West zone (waters, sediments, and soils). At Pebble
West, the four low pH ponds (3.6−4.8) with associated high
metal and sulfate contents reflect an undisturbed naturally
acidic and metalliferous local ecosystem, common in mineral-
ized areas where sulfide- and/or related ferrihydroxide-bearing
minerals in bedrock interact with water and oxygen (Eppinger
et al., 2000, 2007; Eppinger and Fuge, 2009). Mineralized
bedrock is under shallow cover in this area (Fig. 2A) and the
low pH ponds straddle NW-trending faults identified in drill
core. These faults likely provide a conduit for groundwater
passage through and interaction with the underlying shallow
mineralized bedrock. Subsequent upwelling of ferrous iron-
rich groundwater may cause Fe hydroxide and hydroxysulfate
precipitation at the pond bottom, releasing H+ in the process
(Nordstrom and Alpers, 1999; Smith, 1999), a hypothesis dis-
cussed in greater detail in Eppinger et al. (2012). Anomalous
concentrations of Cu, Cd, F-, K, Ni, Re, REE, SO42–, Tl, and
Zn from these low pH ponds and adjacent springs are also
likely derived from these upwelling waters (Eppinger et al.,
2012). In agreement, Cu concentrations in basal pond sedi-
ment from this area are extremely high (area 1, Fig. 9A) and
Cu analyses of low pH-pond sediment core sample 256 reveal
that the highest trace element concentrations are in the upper
~15 cm of core (Fig. 12), likely due to remobilization within
the sediment pile and sorption onto the precipitating iron
oxide grains. In general, Cu concentrations show a positive
relationship to Fe and organic C throughout the sediment
cores, likely indicating complexation of Cu by Fe hydroxides
and oxides as well as organics in the system. High to ex-
tremely high Cu concentrations along the entire 30- to 50-cm
lengths of the sediment cores from the deposit area suggest
that natural metal accumulation processes are long-lived, al-
though precise dating attempts of the cores were unsuccess-
ful. Iron-rich orange, sandy sediment is also present in springs
east of the 52 zone and north of Kaskanak Mountain (Fig. 1)
and likely reflects the same processes. Black “moss” mats at-
tached to cobbles and small boulders are distinctive along the
shorelines of acidic ponds at Pebble West. Similar-looking
black moss was observed in naturally acidic waters at Red
Mountain, Alaska (Eppinger et al., 2007), where further study
identified the moss as Gymnocolea inflata, an unusual acid-
and metal-tolerant liverwort (Gough et al., 2006). Recogni-
tion of this plant in the region may be useful in identifying
possible ore deposit-related low pH conditions.
Results from the total and near-total soil digestion methods
show that the soils over the same portion of the Pebble West
zone are variably enriched in Cu, Au, Ag, As, Bi, Fe, Mo, Sb,
Te, Tl, V, and W. Because these digestions dissolve (nearly)
the entire soil matrix, we interpret the anomalous elemental
concentrations and associations to be the signature of miner-
als derived from the near-surface porphyry Cu-Au-Mo de-
posits of the Pebble West zone.
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Pebble East zone (waters and soils): In the more deeply
buried Pebble East zone, waters have circumneutral pH val-
ues and contain anomalous concentrations of Ag, As, In, Mn,
Mo, Sb, Th, U, and V (Eppinger et al., 2012). These elements
display various degrees of mobility under circumneutral pH
(Smith and Huyck, 1999). Anomalous concentrations of many
of these same elements characterize rare circumneutral drill
hole seeps that likely tap the deeper groundwater system and
the unoxidized orebody at depth (Eppinger et al., 2012). The
majority of the low-level metal anomalies would not have
been detected using traditional ICP-MS techniques but are
easily revealed at concentrations well within the dynamic
range of HR-ICP-MS (Fig. 6).
The results from the partial leach analyses of Pebble area
soils show an enrichment of weakly bound As, Cr, Mo, S, Sb,
U, V, and W over the Pebble East zone (e.g., Fig. 14). This is
largely the same suite of anomalous elements in waters from
the area. These elements commonly form oxyanions (molyb-
date, tungstate, vanadate, antimonate, arsenate, sulfate, and
chromate) or other complexes (e.g., carbonate for U) that are
generally mobile in circumneutral-pH, oxygenated waters.
Oxyanions commonly complex with natural organic matter
and become concentrated in reduced clays and organic-rich
soils (Smith et al., 1997; Smith and Huyck, 1999), both of
which are common in the Pebble East zone.
Several of the ponds and springs in the Pebble East zone
overlie or are adjacent to NE-trending graben-bounding and
NW-trending faults identified in drill core. Soil transects
cross directly over the graben-bounding fault system and nu-
merous other faults identified in drill core. We hypothesize
that the faults serve as conduits for the upward migration of
water initially in contact with the orebody at depth. Up-
welling alone might account for the metal suite in springs and
ponds, but the presence of these metals in soil samples com-
monly collected distal to water sources is more problematic.
Although speculative, migration of the deep groundwater to
the surface, mixing with shallow waters, and local flooding of
soil profiles could be facilitated by seismic pumping or frac-
ture dilation, possible consequences of the common low-level
seismic activity related to the active subduction zone located
about 500 km to the southeast (U.S. Geological Survey,
2011c). Similar processes have been proposed for the migra-
tion of metals in Chile (Cameron et al., 2002; Kelley et al.,
2006).
Displaced anomaly (waters, sediments, and indicator min-
erals): The ponds just south of and along the western edge of
Pebble West have pH values between 5.0 and 6.0, low-level
anomalous concentrations (up to 90th percentile) of Tl, Re,
and the REE, and even higher concentrations (above 95th per-
centile) of Ag, Mo, V, and W in water (Eppinger et al., 2012).
Springs were not observed in the area. Associated basal pond
sediments have the highest Au concentrations (up to 254 ppb;
area 2, Fig. 9), highest Mo concentrations (up to 22 ppm), high
Cu concentrations (second only to the low pH ponds), and
anomalous concentrations of F, K, and Rb, Sb, Tl, and W. Pond
sediment cores from the area (371 and 372, Fig. 12) have Cu
concentrations above 250 ppm throughout their lengths and
have the highest Mo concentrations (up to 23 ppm).
The ponds fill glacial kettles in till deposited by the Pleis-
tocene Brooks Lake glaciation that swept generally southward
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT
across the deposit area from the northeast and north (Hamil-
ton and Klieforth 2010). PCIMs gold and jarosite are abun-
dant in several till samples in this area and to the south, be-
yond the area of water and pond sediment sampling (Fig. 5).
Gold grain counts are in the hundreds and grains commonly
exhibit pristine to slightly modified morphologies, whereas
jarosite counts are as high as 1,500 grains (Kelley et al.,
2011a). Gold and jarosite grain counts diminish downice from
around Frying Pan Lake, where one of several terminal
moraines is present (Hamilton and Klieforth 2010). The pris-
tine gold and high grain counts of gold and jarosite in till,
proximal to but not directly over the Pebble deposit, repre-
sent an offset PCIM anomaly immediately downice of the de-
posit. The water and pond chemistries in the kettles most
likely reflect dissolution of ore-related and secondary miner-
als in the enclosing till, rather than hydromorphic processes
as described in (1) and (2) above. Rebagliatti and Lang (2009)
also documented downice dispersion to the west and south of
the Pebble orebody for Cu and Au concentrations in soils.
Distal from Pebble, widespread dispersion of gold in surfi-
cial materials is demonstrated by minor gold grains counts
common in till samples (Kelley et al., 2011a). Sporadic
cinnabar is present locally in tills from the Pebble area and
beyond (Kelley et al., 2011a). Low-level concentrations of
both gold and cinnabar are widespread and well-documented
in surficial materials throughout southwest Alaska and are
commonly related to Late Cretaceous to Tertiary epithermal
activity (Eppinger, 1993; Gray et al., 2000; Gray and Bailey,
2003). Low-level concentrations of Au and Hg in pond and
stream sediments probably reflect displaced anomalies from
gold and cinnabar grains entrained in tills underlying the
ponds and streams. Supporting this hypothesis, Hg concen-
trations are inherently low in mineralization-related diorite,
monzodiorite, and granodiorite (median 0.01−0.03 ppm,
Table 2). Thus, near Pebble, Hg in sediments and cinnabar in
till are probably attributable to unidentified Tertiary epither-
mal deposits on and around Koktuli Mountain (Kelley et al.,
2011a; Eppinger et al., 2011).
Electrochemical transport (soils): Hamilton (1998, 2000)
showed that many weak selective leach anomalies in the soil
are due to the upward electrochemical transport of elements
over an oxidizing sulfide orebody. These conditions com-
monly produce geochemical “rabbit ear” anomalies associated
with geophysical self-potential (SP) anomalies. The role of
electrochemical transport of elements was investigated using
the geophysical self-potential technique along the soil profiles
over the Pebble deposit to test whether a “geobattery” was
present over the mineralized zone within the Earth’s natural
redox field (Minsley et al., 2008). Several large SP anomalies,
on the order of −600 mV and nearly 1 km in diameter, locally
coincident with geochemical anomalies, were revealed in the
Pebble West zone where cover is shallow. The SP anomalies
are consistent with the presence of a subsurface electro-
chemical cell. Local geochemical anomalies in soil flank
strong SP lows, consistent with rabbit ear geochemical anom-
alies surrounding reduced zones above ore bodies (Hamilton,
1998, 2000). Locally high Fe2+:Fe3+ ratios in waters (Ep-
pinger et al., 2012) and the presence of both anaerobic and
iron-oxidizing bacteria in soils (M. Stanton, pers. commun.)
indicate reduced areas at Pebble West. These features may
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521
facilitate the migration and fixation of metals in the shallow
Pebble West zone. Similar anomalies were not observed over
the deeper Pebble East zone, likely due to the much deeper
cover. Continued research on this topic is underway.
Conclusions
This orientation study demonstrates the strong control of
local geologic and geochemical features on the effectiveness
of different traditional and newer reconnaissance geochemi-
cal exploration techniques and thus has important implica-
tions for exploration. On the basis of these results, we conclude
that PCIM analyses of till and highly sensitive HR-ICP-MS
analyses of spring and pond water samples may be particu-
larly useful in exploration for porphyry Cu deposits in glacial-
till covered areas in southwest Alaska. The several kilometer-
long dispersion trains of gold and jarosite and the nearly
25-km-long train, if combined with andradite garnet and Mn-
rich epidote, indicate the applicability of this method on a re-
gional scale. Mineralogical information aids in the interpreta-
tion of geochemical anomalies and helps determine deposit
type. In contrast, while high concentrations and wide varia-
tions are found for Au, Cu, and Mo in pond and stream sedi-
ment samples within the Pebble West zone, only weak dis-
persion persists downstream and no geochemical anomalies
were observed in sediment samples from Pebble East.
Surface-water sampling coupled with HR-ICP-MS analysis
is applicable at both regional and local scales, but caution
should be used when interpreting water chemistry because
local subsurface and surface conditions can lead to contrast-
ing geochemical signatures, even over different parts of the
same orebody. For example, anomalous elements in lower pH
waters at Pebble West include the cations Cu, Cd, K, Ni, Re,
the REE, and Tl; and the anions F– and SO42–, whereas lower
level anomalous element concentrations in circumneutral
surface waters at Pebble East and outlying mineral occur-
rences include Ag, As, In, Mn, Mo, Sb, Th, U, V, and W. Pond
sediment can be a useful sample medium at both regional and
local scales, if pond distribution is adequate.
This study highlights the limitations of conventional total
and near-total analysis of soil samples in extensively covered
terrane. These techniques were effective in identifying shal-
lowly buried to exposed altered and mineralized rock at Peb-
ble West (Ag, As, Au, Bi, Cu, Fe, Sb, Te, Tl, V, and W) but in-
effective at identifying the higher grade, but deeply buried
Pebble East zone. Several partial leach extractions that attack
labile elements weakly bound to grains in soils are effective at
delineating underlying mineralized rock at Pebble East (As,
Mo, Sb, and V), particularly when multivariate statistical tech-
niques like principal component analysis are used.
The multimedia approach aids in identifying possible
processes that caused the significant geochemical variations
within and among the various media. In the Pebble West zone,
thin cover, local exposure of the orebody, and underlying faults
have facilitated the oxidation of pyrite and other sulfides, and
associated ferrous-ferric iron reactions—both processes that
release H+ into surficial waters, resulting in local natural acid-
ification of ponds and promoting element mobility and devel-
opment of metal anomalies in waters, sediments, and soils. In
the deeply buried Pebble East zone, thick cover precluded
oxidation of sulfides in the underlying orebody, concomitant
522 EPPINGER ET AL.
acid generation, and large-scale metal mobility. Low-level
geochemical oxyanion anomalies in spring and pond waters
and in soil partial leach samples from Pebble East reflect the
circumneutral nature of the waters that may have migrated
from depth to the surface along graben-bounding and associ-
ated faults that cut an unoxidized portion of the orebody at
depth. Although speculative, regional low-level seismicity re-
lated to the active subduction zone to the southeast could fa-
cilitate the water movement, mixing, element migration to
shallow levels, and metal emplacement in organic-rich soils.
Analyses from various sample media collected in this study
have applicability beyond exploration. Samples were collected
prior to surface disturbance in the deposit area and include
background samples well beyond the mineralized area. High
Cu concentrations (hundreds of ppm) in entire pond sediment
core intervals from natural low pH ponds at Pebble West sug-
gest long-lived natural metal accumulation processes. The in-
tegrated dataset resulting from this study serves as a rigorous
baseline for the region. Data from the multiple partial leach
techniques provide geochemical information on soil phases
that extend beyond the data typically collected in baseline
studies. The highly sensitive analytical techniques used on
water samples are also atypical of baseline studies.
Acknowledgments
We are grateful to the Pebble Limited Partnership (PLP)
for access, logistical support, datasets, and scientific support
for this research effort. In particular, we thank Mark Re-
bagliati (Geological Consulting), Lena Brommeland (North-
ern Dynasty Minerals), Jim Lang (Lang Geoscience, Inc.),
Robin Smith (PLP), and Gernot Wober (PLP) for facilitating
logistics and providing geologic insight. For field assistance,
we thank Crystal Chung, Cassady Harraden, Lindsey Klep-
pin, Brian McNulty, Miguel Ricardo, and Nicola Struyk (all
from PLP); Megan Cardenas (University of Alaska), and
Déne Tarkyth (Anglo American). We are also thankful to the
following commercial analytical laboratories and associated
individuals for contributing analytical support: John Gravel,
Acme Analytical Laboratories, Ltd. (www.acmelab.com), Eric
Hoffman, Activation Laboratories, Ltd. (www.actlabs.com),
Mary Doherty and Brenda Caughlin, ALS Minerals (www.
alsglobal.com), Pierrette Prince, SGS Minerals Services
(www.sgs.com), and J. Robert Clark, Skyline Assayers and
Laboratories (www.skylinelab.com). We also thank the fol-
lowing USGS analysts: Monique Adams, Michael Anthony,
Zoe Ann Brown, Phil Hageman, Richard O’Leary, Mark Stan-
ton, and Todor Todorov. Economic Geology reviewers Chris
Benn and Garth Graham provided constructive comments
that helped improve the manuscript. John Chapman also pro-
vided helpful comments. This is Geological Survey of Canada
ESS contribution no. 20120332. The use of trade, product, or
firm names in this article is for descriptive purposes only and
does not imply endorsement by the U.S. Government.
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 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT
APPENDIX 1
Principal components analysis of the soil leach geochemistry
The objective of principal components analysis is to reduce
the number of variables necessary to describe the observed
variation within a set of data. This is achieved by forming lin-
ear combinations of the variables derived from some measure
of association (i.e., correlation or covariance). The linear com-
binations are formed so that the maximum amount of vari-
ability within the data defines the first principal component.
Successive components account for decreasing variability and
are constrained to be mathematically orthogonal to each
other. The data to be evaluated by principal component
analysis are commonly adjusted using either log-centered
transformations (Aitchison, 1983, 1986) or isometric log ratios
(Egozcue et al., 2003). In this study, a log-centered transfor-
mation was applied as it allows use of the entire suite of avail-
able geochemical elements available for each analytical
method (Buccianti et al., 2006; Grunsky, 2010). For each
method, the few elements with the majority of concentrations
consistently below the lower determination limit were re-
moved from the dataset. There are many variants of principal
component analysis and the variant used here is simultaneous
RQ-mode principal component analysis (Zhou et al., 1983).
This method has the advantage of presenting the principal
component scores of the observations and the variables (ele-
ments) at the same scale and on a diagram know as a biplot
(e.g., Fig. 15B). This method is similar to the biplot method
of Gabriel (1971).
Observations from the principal component analysis evalu-
ation of the various soil digestions in Table A1 are as follows:
1. A significant amount of Cu-Au-Mo variability is gener-
ally present in the first few principal components derived
from each analytical method. This demonstrates that the fin-
gerprint of mineralization is well represented in the sample
population.
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2. The scree plots of the various principal component
analyses are all “steep,” meaning that the first few compo-
nents (<4) account for greater than 65% of the overall vari-
ability of the data. This supports the interpretation that the
first few components generally represent geochemical
processes and/or events that are tied to the underlying geol-
ogy and subsequent modification of the landscape. Therefore,
these components can be a useful tool for interpreting the
geochemical responses and building an exploration model.
3. The total and near-total digestions (sodium peroxide sin-
ter, four-acid, aqua regia) tend to highlight the Cu-Au-Mo
mineralization in the first two components, whereas the
weaker leaches delineate mineralization in the lesser compo-
nents (PC2-PC5).
4. At least one mineralization-related component targets
the Pebble West zone in every one of the digestion methods
and most of the methods also give some response over the
deeply buried mineralization in the Pebble East zone. The
commonly used aqua regia digestion was one of the few
methods that did not have a response over Pebble East. In
the case of the four-acid digestion, the east and west portions
of the deposit show up as separate principal components, a
reflection of the different element associations and perhaps
indicating the different post-deposit–formation processes
that occurred.
526
Number of
Digestion method samples1
Deionized Water Leach
BioLeach
Enzyme Leach
TerraSol Leach
Mobile Metal Ion
(MMI®) Leach
Ionic Leach
Cold Hydroxylamine
HCl Leach
Sodium Pyrophosphate
Leach
Aqua Regia Digestion
Four Acid Digestion
Sodium Peroxide Sinter
Digestion
Note: — = not applicable
1 Although samples were collected from 142 sites, not every fraction could be collected at every site; Enzyme and TerraSol Leach methods exceed 142
samples since the collection protocol required paired samples under specified conditions (Anderson et al., 2011)
2 Elements were excluded from the principal components analysis because of low analytical variability, too many samples with concentrations close to or
below detection limit, or because elements reported by lab varied across years
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TABLE A1. Summary of Mineralization-Related Element Associations Determined by Principal Components
Elements included in PCA
77 Al, As, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs,
Cu, Dy, Er, Eu, Fe, Gd, Ho, K, La, Li,
Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Pr,
Rb, Sc, SiO2, Sm, SO4, Sr, Ta, Tb, Ti,
Tl, Tm, U, V, Y, Yb, Zn, Zr
77 Ag, As, Au, Ba, Be, Bi, Br, Cd, Ce,
Co, Cr, Cs, Cu, Er, Eu, Ga, Gd, Ge,
Hf, Ho, I, In, La, Li, Lu, Mn, Mo, Nb,
Nd, Ni, Pb, Rb, Sb, Sc, Se, Sr, Ta, Tb,
Th, Tl, U, V, W, Zn, Zr
158 Ag, Al, As, Au, Ba, Be, Br, Ca, Cd, Ce,
Cl, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe,
Ga, Gd, Ge, Hf, Hg, Ho, I, In, K, La,
Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni,
Pb, Pd, Pr, Rb, Re, S, Sb, Sc, Se, Sm,
Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U,
V, W, Y, Yb, Zn, Zr
158 Ag, Al, As, Au, Ba, Be, Bi, Ca, Cd,
Ce, Cl, Co, Cr, Cs, Cu, Dy, Er, Eu,
Fe, Ga, Gd, Ge, Hf, Hg, Ho, In, K,
La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd,
Ni, Pb, Pd, Pr, Pt, Rb, Re, S, Sb, Sc,
Se, Sm, Sn, Sr, Ta, Th, Ti, Tl, Tm, U,
V, W, Y, Yb, Zn, Zr
77 Ag, Al, As, Au, Ba, Ca, Cd, Ce, Co, Cu,
Dy, Er, Eu, Fe, Gd, La, Li, Mg, Mo,
Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Sm,
Sr, Tb, Th, Ti, Tl, U, W, Y, Yb, Zn, Zr
113 Ag, As, Au, Ba, Be, Br, Ca, Cd, Ce,
Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga,
Gd, Ge, Hf, Hg, Ho, I, In, La, Li, Lu,
Mg, Mn, Mo, Nb, Nd, Ni, Pb, Pd, Pr,
Rb, Re, Sb, Se, Sm, Sn, Sr, Tb, Th, Ti,
Tl, Tm, U, W, Y, Yb, Zn, Zr
131 Ag, Al, As, Ba, Be, Br, Ca, Cd, Ce,
Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga,
Gd, Hf, Ho, I, In, K, La, Li, Lu,
Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb,
Pr, Rb, Re, Sb, Sm, Sr, Tb, Th, Ti,
Tl, Tm, U, V, W, Y, Yb, Zn, Zr
77 Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce,
Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga,
Gd, Hf, Hg, Ho, I, In, K, La, Li, Lu,
Mg, Mn, Mo, Nb, Nd, Ni, Pb, Pr,
Rb, Sb, Se, Sm, Sn, Sr, Ta, Tb, Th,
Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr
123 Ag, Al, As, Au, B, Ba, Bi, Ca, Cd, Co,
Cr, Cu, Fe, Ga, Hg, K, La, Mg, Mn,
Mo, Na, Ni, P, Pb, S, Sb, Sc, Se, Sr,
Th, Ti, Tl, U, V, W, Zn
131 Al, As, Ba, Be, Bi, Ca, Cd, Ce, Co,
Cr, Cu, Fe, Ga, In, K, La, Li, Mg,
Mn, Mo, Na, Nb, Ni, Pb, Rb, S, Sb,
Sc, Sn, Sr, Te, Th, Ti, Tl, U, V, W, Y, Zn
130 Ag, Al, As, Ba, Be, Bi, Ca, Cd, Ce,
Co, Cr, Cs, Cu, Er, Eu, Fe, Ga, Gd,
K, La, Li, Lu, Mg, Mn, Mo, Nb, Ni,
P, Pb, Rb, Sb, Sc, Sm, Sn, Sr, Ta,
Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr
526
Elements
excluded2 Comments
Ag, Bi, Ga, Ge, 80% of the data variability is accounted for by
Lu, Nb, Sb, Se, the first five components; a 30° clockwise
Th, W rotation of PC3-PC5 highlights Cu enrichment
and accounts for 58% of Cu variability
Dy, Hg, Os, 75% of total variability is accounted for in
Pd, Pr, Pt, Re, the first four components; the Cu-Au-Mo
Ru, Sm, Te, response is shared between the two
Tm, Y, Yb components; alternatively these components
could have been rotated
Bi, Os, Pt, Ru 55% of total variability is accounted for in
the first three components; variability of Au,
Cu, and Mo appear to be independent from
each other; Cu appears to have a mafic
association and Au, a felsic association
Ir, Os, Rh, 64% of total variability is accounted for in the
Ru, Te first three components; significant variability
of Cu is spread over PCs 1, 2, 4, 5 and 6;
most of the Au variability is contained in
PCs 5 and 6 and most of the Mo variability
is accounted for in PCs 1 and 2
Bi, Cr, Pd, Pt, 76% of total variability is accounted for in the
Sn, Ta, Te first three components
Bi, Ta, Te 74% of total variability is accounted for in the
first three components
Au, B, Bi, Ge, 76% of total variability is accounted for in the
Hg, Se, Sn, first four components; PC4 accounts for 41%
Ta, Te of Cu variability; PC3 accounts for 18.5% of
Cu variability
Au, Br, B, 56% of the total variability is accounted for in
Ge, Re, Te the first two components
Be, Ce, Cs, Ge, 57% of total variability is accounted for in the
Hf, In, Li, Nb, first three components; 76% of Cu variability
Pd, Pt, Rb, Re, explained in the first two components
Sn, Ta
Ag, Cs, P 60% of total variability is accounted for in the
first three components; PC2 is inversely
associated with elements likely related to
major rock-forming minerals
Dy, Ge, Hf, Ho, 57% of total variability is accounted for in the
In, Nd, Pr, Tb first three components; over 70% of Cu
variability is accounted for by components 2
and 3; over 75% of the variability of Mo is
accounted for by components 1 and 3
 GEOCHEMICAL & MINERALOGICAL STUDIES, PEBBLE PORPHYRY Cu-Au-Mo DEPOSIT 527

Analyses of Soil Results from Eleven Different Partial Leach and Total Digestion Analytical Techniques

First Mineralization-Related Principal Component (PC) Second Mineralization-Related Principal Component (PC)

Component and Explained Component and Explained

element association variability Spatial distribution element association variability Spatial distribution

PC5 rotated: Cu-K-Li-Na3,5 4.9% Pebble West with a minor — — —

response over Pebble East

PC4: Cu-Au-Mo3 8.1% Pebble West PC6: Ag-W3 3.3% Highlights Pebble West and a
couple of sites over Pebble East

PC2: Ca-Sb-V-Mg-Mo- 16% Pebble East PC5: Cu-Mn-Co-Cr-Cd-Ag3 4.8% Highest scores along the
As-Sr-Na-Ge-U4 east-west transect over both the
Pebble West and Pebble East

PC6 rotated: Cu-Au- 3.3% Pebble West — — —

Ag-Mo3,6

PC2: Ca-Sr-Mg-Cu-Ba- 30% Pebble West and a minor PC6: Cu-Au4 3.0% Strongly highlights Pebble West
Au-Ag4 response over Pebble East but also shows some enrichment
over Pebble East

PC2: Mg-Ni-Ca-Sr-Cd- 19% Pebble West and Pebble East PC4: Hg-Au-Ag-Cu4 6.4% Pebble West
Mo-Zn-Ba-Cu-Ga4

PC3: Cu-K-Pb-Tl-Cs-Zn3 5.9% Pebble West only PC4: Cu-Mo-Fe-Tl3 5.0% Pebble West and a minor
response over Pebble East

PC2: Mo-Zn-Mg-Cd- 13% Pebble East PC4: Cu-Rb-Cs-Co- 6.4% Pebble West only
As-Sr-Ca4 Ni-Ag-Li3

PC2 rotated: Cu-Au- 18% Pebble West — — —

Mo-Ag-Tl3,6

PC1 rotated: Mo-Cd-S3,6 36% Highest scores over Pebble PC2 rotated: Cu-Bi-As- 14% Highest scores over
East; moderately high scores Te-W-Sb-Tl-Mo4,6 Pebble West
over Pebble West

PC2: Fe-Cu-W-Bi-Sb- 15% Relative Fe-Cu enrichment PC3: Cu-Mo-W4 8.3% Pebble West
Rb-Cs-K3 over Pebble East

3 Positivescores
4 Negative scores
5 Rotated 30° clockwise
6 Rotated 45° clockwise

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