Journal of Geochemical Exploration 232 (2022) 106889

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/gexplo

Geology, alteration geochemistry, and exploration geochemical mapping of

the Ertsberg Cu-Au-Mo district in Papua, Indonesia
Utreck Rumbiak a, b, Chun-Kit Lai c, *, Reza Al Furqan a, Mega Rosana b, Euis Yuningsih b,
Basilios Tsikouras c, Elena Ifandi c, Amal Izzati Afiqah binti Abdul Malik c, Huayong Chen d
a
PT. Freeport Indonesia, Freeport-McMoran Copper and Gold, Tembagapura, Papua 99910, Indonesia
b
Faculty of Geological Engineering, Padjajaran University, Bandung, 40312, Indonesia
c
Geoscience Programme, Faculty of Science, Universiti Brunei Darussalam, Gadong, BE1410, Brunei Darussalam
d
Guangzhou Institute of Geochemistry, Chinese Academy of Science, Guangzhou 510640, China

A R T I C L E I N F O A B S T R A C T

Keywords: The Ertsberg-Grasberg district hosts the world’s largest Cu-Au(–Mo) skarn system. The mineralization is related
Ertsberg-Grasberg district to the Pliocene Ertsberg- and Grasberg intrusive complexes, which intruded the Jurassic-Cretaceous Kembe­
Porphyry-skarn mineralization langan Group siliciclastics and Cenozoic New Guinea Limestone Group. Despite previous studies, elemental
Alteration geochemistry
migration across the porphyry-skarn system and across the different ore stages is still unclear. Here, we attempt
Geochemical mapping
Indonesian Papua
to tackle this issue by integrating ore deposit geology, alteration/mineralization paragenesis, whole-rock
geochemistry of the Ertsberg granitoids and carbonate wallrocks, together with spatial mapping of hydrother­
mal minerals and target/pathfinder trace elements at the Deep Mill Level Zone of Ertsberg. Ores at Ertsberg are
mainly skarn-hosted, whose formation comprises five stages: (I) prograde skarn; (II) retrograde alteration; (III)
massive anhydrite replacement; (IV) late hydrothermal veining; (V) supergene alteration. Massive magnetite and
main Cu–Au mineralization occurred in Stage II and III, respectively, although minor Cu mineralization per­
sisted to Stage IV.
The Ertsberg granitoids have medium SiO2 and high Al2O3 contents, and consist mainly of (quartz-)monzonite
and minor (monzo)diorite. Least-altered samples have upper crust-normalized enrichments in certain large ion
lithophile elements (LILEs, e.g., U and K) and depletions in all high field strength elements (HFSEs, e.g., Ti, Y, and
Yb). The samples are fresh to moderately-altered, featured by garnet-diopside skarn and/or porphyry-style
(potassic, propylitic, phyllic) alterations and anhydrite replacement. Elemental mass balance calculation in­
dicates that the porphyry-style alteration zones are featured by feldspar destruction and the accompanying alkali
depletions, although the loss of K–Rb (in potassic and phyllic zones) and Ca-Ba-Sr (in propylitic zone) are
balanced by their respective capturing in secondary K-feldspar-mica and actinolite-epidote-anhydrite. Decar­
bonation of the dolomitic wallrocks likely released Mg-Ca-Sr, which facilitated the subsequent forsterite-diopside
exoskarn and anhydrite alteration. The enrichments of various ore-related target/pathfinder elements in these
altered samples are consistent with their mineralized nature, e.g., Fe–Mn (magnetite), Cu-Fe-Bi-Se-Te (bornite),
Mo–Re (molybdenite), Au-Ag-As-Bi-Te (auriferous pyrite/arsenopyrite), Zn-Fe-Mn-Sn-In (sphalerite), and Pb-
Ag-Bi (galena).
Alteration mineral and target/pathfinder elemental distribution patterns show that the ore fluids were likely
originated from the porphyry hydrothermal (potassic) centers near the Ertsberg pluton margin. The fluids then
spread out from the potassic centers, forming the surrounding propylitic zone, and migrated along the largely
NW-SE-oriented intrusive contact and fault zones. This formed the endoskarn in the Ertsberg pluton, the
forsterite-diopside exoskarn in the Waripi Formation dolomite, and the garnet-diopside exoskarn in the Ekmai
Formation limestone/calcareous sandstone-siltstone. As the hydrothermal system started to wane, the prograde
skarn formation is partially overprinted/enveloped by retrograde serpentine and actinolite/tremolite-epidote-
chlorite alterations, and then by magnetite mineralization and massive anhydrite replacement in the

* Corresponding author.
E-mail addresses: urumbiak@fmi.com (U. Rumbiak), chunkitl@utas.edu.au (C.-K. Lai), ralfurqa@fmi.com (R. Al Furqan), mega.fatimah.rosana@unpad.ac.id
(M. Rosana), e.tintin@unpad.ac.id (E. Yuningsih), basilios.tsikouras@ubd.edu.bn (B. Tsikouras), elena.ifandi@ubd.edu.bn (E. Ifandi), 16B2161@ubd.edu.bn
(A.I.A. binti Abdul Malik), huayongchen@gig.ac.cn (H. Chen).

https://doi.org/10.1016/j.gexplo.2021.106889
Received 18 April 2021; Received in revised form 25 July 2021; Accepted 29 August 2021
Available online 4 September 2021
0375-6742/© 2021 Elsevier B.V. All rights reserved.
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

carbonate wallrocks. The texturally-destructive skarn formation, and the dissolution of carbonate wallrocks and
hydrothermal anhydrite were likely pivotal in creating the highly-fractured Broken Zone, which served as a
structural trap for the high-grade Cu-Au-Mo ore deposition.

1. Introduction
The Ertsberg-Grasberg district (Papua, Indonesia) hosts a number of
(super)-giant skarn-/porphyry-type Cu-Au(–Mo) deposits, including
the Grasberg, Ertsberg East, and Kucing Liar, plus several smaller ones
such as the Big Gossan (Freeport-McMoran Inc., 2020; Leys et al., 2012).
These deposits are hosted in/around the Pliocene Ertsberg- and Grasberg
intrusive complexes, and in the exoskarn of the Cretaceous Kembe­
langan Group (Gp.) siliciclastics and Tertiary New Guinea Limestone Gp.
wallrocks (Fig. 1). The ore formation is generally interpreted to have
linked to a short burst of asthenospheric upwelling-related magmatism
(3.1–2.8 Ma; Wafforn, 2017), triggered by crustal delamination after the
collision of the northern-edge of Australian plate with an intra-oceanic
arc (Cloos et al., 2005). Despite many previous studies, it is still un­
clear how hydrothermal alteration at Ertsberg mobilized and trans­
ported the various ore-related elements, how such elemental transport
was influenced by the local lithologies and structures, and how that
contributed to the world-class skarn ore formation. In this study,
therefore, we aim to answer these questions through an integration of
ore deposit geology, alteration/mineralization paragenesis, whole-rock
geochemistry (pluton and carbonate wallrocks), and mineral/
elemental spatial distribution maps from Ertsberg. Using elemental mass
balance calculation, we further discuss the migration and deposition of
ore-forming materials across the pluton and wallrocks, which formed
the distinctive elemental/mineral zoning patterns we see today.
2. Geological background
2.1. Regional geology
The island of New Guinea is bordered by the Caroline and Bismarck
plates to the north and east, respectively, with the northern edge of the
Australian plate underthrust beneath the middle-southern part of the
island. The island is composed of four tectonic terranes, namely (from
south to north) the New Guinea foreland basin, the Central Range fold-
and-thrust belt, the Derewo (aka. Ruffaer) metamorphic belt, and the
Melanesian accreted oceanic arc-forearc complex (Fig. 1a) (Cloos et al.,
2005, and ref. therein). Formation of the Central Range, where the
Ertsberg-Grasberg district is located, was likely linked to the collision
between the Australian plate and the Melanesian arc. The collision had
likely jammed the subduction system, and caused rapid ENE-WSW-
directed (~070◦ ) crustal shortening and the Central Range uplift since
~13 Ma. The crustal shortening has also formed the Yellow Valley
Syncline, into which the Ertsberg and Grasberg intrusive complexes
were emplaced (Fig. 1b). The plutonism and the associated porphyry-
skarn mineralization are interpreted to have formed by post-collisional
crustal delamination and asthenospheric upwelling (Cloos et al., 2005;
Leys et al., 2012; Warren and Cloos, 2007).
The Central Range comprises Proterozoic to Upper Tertiary se­
quences. In the Ertsberg-Grasberg district, stratigraphy comprises the
predominantly-siliciclastic (minor calcareous) Kembelangan Group and
the New Guinea Limestone Group. The Kembelangan Group has four
formations, i.e., the Kopai (M. Jurassic to L. Cretaceous), Woniwogi (U.
Jurassic to L. Cretaceous), Piniya (L. to M. Cretaceous), and Ekmai (U.
Cretaceous-Paleocene). The Ekmai Formation comprises a lower sand­
stone, a middle limestone, and an upper shale member. The sandstone
member comprises mainly quartz arenite, with the upper 90 m con­
taining mixed mudstone and limestone, and capped by 20-m thick
calcareous mudstone. The overlying Tertiary New Guinea Limestone
Group has also four formations, i.e., the Waripi (Paleocene), Faumai
(Eocene), Sirga (L. Oligocene), and Kais (U. Oligocene to M. Miocene)
(Fig. 2) (Leys et al., 2012; McDowell et al., 1996). The Waripi Formation
comprises sucrosic (friable and vuggy) dolostone, crystalline dolomitic
limestone, and (minor) quartz arenite, and is capped by a < 2-m thick
nodular anhydrite bed. The Foumai Formation comprises well-sorted,
shallow-marine platform fossiliferous limestone and siliciclastic dolo­
stone: The lower part (thickness: ~ 100 m) contains quartz-bearing
dolomitic limestone with large benthic forams, whilst the upper part
(thickness: ~ 100–200 m) contains quartz-bearing limestone with
bryozoa and echinoderm fossils. Quartz is well-sorted and angular, and
is less abundant in the upper part than in the lower part. Sandstone beds
are present locally in the middle-lower parts of the formation. The Sirga
Formation comprises terrestrial to shallow-marine, thick-/cross-bedded
calcareous sandstone, whilst the Kais Formation is composed of massive
thick (>950 m) fossiliferous limestone. Lower part of the Kais Formation
is featured by benthic forams and glauconite (up to 20%, esp. in marl
beds), whilst the upper part contains mainly red algae and local inter­
bedded coal seams (10-to 30-cm-thick). The Kais Formation was inter­
preted to have deposited in a restricted shallow-marine carbonate
platform environment (Van Ufford, 1996).
2.2. Exploration history and geological setting of Ertsberg-Grasberg
district
Despite mineralization at Ertsberg was first documented by A. Colijn
and J.J. Dozy back in 1936, major exploration and mine development
did not occur until the early 1960s by Freeport. A series of orebodies
were discovered around the Ertsberg Intrusive Complex, which would
eventually constitute the East Ertsberg Skarn System. The Dom skarn
deposit was also discovered on the southern margin of the Intrusive
Complex in a limestone embayment. Subsequent drilling has discovered
the supergiant Grasberg (1988), the high-grade Big Gossan skarn (1991),
and the giant Kucing Liar skarn (1994) deposits (Leys et al., 2012;
Meinert et al., 1997; Pollard et al., 2005). A detailed account of the
exploration history has been given by Van Leeuwen (2018).
In the Ertsberg-Grasberg district, lithostratigraphy is dominated by
the New Guinea Limestone Group. Although all the four formations
(Waripi, Faumai, Sirga, and Kais) host high-grade Cu–Au skarn
mineralization, the lower part of the Waripi Formation (anhydrite
nodule-bearing dolomite, sandy dolostone with thin-bedded quartz
sandstone) represents the main ore host, particularly for skarn ores. The
depositional environment is interpreted as supratidal to shallow marine
shelf, reflecting the transition from the mainly siliciclastic Kembelangan
Gp. sedimentation into the New Guinea Limestone Gp. carbonate
deposition (Van Ufford, 1996). Beneath the Waripi Formation, all the
three members of the Ekmai Formation (Kembelangan Group) are pre­
sent. The shale (3–5 m thick) and limestone (≤100 m thick) members are
commonly hornfels-facies metamorphosed, and the limestone member is
also partially skarn-altered and hosts significant mineralization. The
sandstone member (~600 m thick) is arkosic and hosts disseminated-/
fracture-filled mineralization beneath the skarn orebodies. These sedi­
mentary units are intruded by various equigranular to porphyritic in­
trusions. Major local structures include the shallowly NW-plunging
Yellow Valley Syncline, and the NW-trending Wanagon, Ertsberg, and
Idenberg reverse faults (Gibbins, 2006; Mertig et al., 1994; Rubin and
Kyle, 1998). Many of these faults are crosscut by NE-trending sinistral
strike-slip faults, notably the Grasberg Fault (Fig. 1b). Based on cross­
cutting relations, McDowell et al. (1996) documented at least nine
intrusive bodies in the district, most of which are fine-grained porphy­
ritic dikes and sills. At Grasberg, three magmatic phases have been

2
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Journal of Geochemical Exploration 232 (2022) 106889

Fig. 1. (a) Tectonic map of the New Guinea island, showing the location of the Ertsberg-Grasberg district (after Cloos et al., 2005); (b) Geologic map of the Ertsberg-Grasberg district (after Wafforn, 2017). Abbre­
viations: BG – Big Gossan GB (E) – Gunung Bijih (Ertsberg); GBT (EESS) – Gunung Bijih Timur (East Ertsberg Skarn System); GIC – Grasberg Intrusive Complex; KL – Kucing Liar.
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

recognized, namely (from oldest to youngest) the Dalam Phase (diorite),
Main Grasberg Intrusion (MGI), and the early/late Kali dikes, among
which the MGI represents the main ore-forming phase and the Kali dikes
are post-mineralization. The magmatism lasted roughly from 3.1 to 2.8
Ma (Wafforn, 2017, and ref. therein). Ore-causative granitoids at Gras­
berg are mainly K-rich monzonitic to dioritic, and their emplacement are
clearly controlled by local structures. Porphyry-type mineralization is
mainly hosted within the MGI. Comparatively, the Ertsberg Intrusive
Complex is much less mineralized, and the skarn-type mineralization is
mainly hosted in the exoskarn of the Lower New Guinea Limestone
Group and Upper Kembelangan Gp. wallrocks (Gandler and Kyle, 2008;
Kyle et al., 2014; Leys et al., 2012; Pollard et al., 2005). Gibbins (2006)
identified four igneous rock types (the Hybrid Phase, the Ertsberg Dio­
rite, porphyry dikes, and (minor) aplite dikes) in the Ertsberg Intrusive
Complex, with the Hybrid Phase being a rind around the Ertsberg Diorite
that cooled faster. Zircon U–Pb dating on the Ertsberg Diorite yielded
2.97 ± 0.58 and 3.28 ± 0.3 Ma, and that on the porphyry dikes yielded
similar age of 2.98 ± 0.84 Ma (Gibbins, 2006).
2.3. East Ertsberg Skarn System
The East Ertsberg (Indonesian: Gunung Bijih Timur) Skarn System is
situated in the southern limb of the Yellow Valley Syncline (Fig. 1). The
system is a steeply-dipping continuous mineralized body that extends for
over 1.5 km deep, and can be divided into five mining zones according to
their depths, i.e., (top to bottom) the Gunung Bijih Timur, Intermediate
Ore Zone, Deep Ore Zone, Mill Level Zone, and Deep Mill Level Zone
(DMLZ) (e.g., Mertig et al., 1994) (Figs. 2–3). Mineralization remains
open to the northwest and at depth below the DMLZ. The deepest mining
zone DMLZ is investigated here because it is the least studied (among the
five mining zones) and the porphyry-skarn transition is well exposed in
this zone. Mineralization at the East Ertsberg Skarn System is predom­
inantly hosted by the Faumai (Gunung Bijih Timur and upper Interme­
diate Ore Zone) and Waripi (lower Intermediate Ore to Deep Mill Level
Zone) formations, and minor by the underlying Kembelangan Formation
(Fig. 2). Footwall of the East Ertsberg Skarn System comprises the
moderately-intensely endoskarn-altered Ertsberg granitoids, with
porphyry-style vein-type mineralization developed 50–150 m into the
pluton from the skarn zone. The hangingwall contact consists of hy­
drothermal breccia and massive sulfide mineralization, both in sharp
contact with the marbleized limestone wallrocks (Fig. 3) (Gandler,
2006; Gandler and Kyle, 2008; Kyle et al., 2014; Leys et al., 2012). The
rock package is intruded by a number of porphyry dikes in the potassic
alteration zone. Some of these dikes lack significant alteration (Gibbins,
2006) and may have been post-mineralized. Skarn alteration is strata­
bound and replaces the Ekmai and Waripi Fm. carbonate wallrocks.
Skarn mineralization at Ertsberg was molybdenite Re–Os dated to be
2.54 ± 0.02 Ma (Mathur et al., 2005) and phlogopite Ar–Ar dated to be
2.59 ± 0.15 Ma (Pollard et al., 2005), slightly younger than its Grasberg
(2.88 ± 0.02 Ma) and Kucing Liar (3.01 ± 0.02 Ma) counterparts

a Age Formation Thickness (m) Description

b
950+ Fossilferous limestone

25–40 Calcareous sandstone

217 Limestone, locally fossiliferous

Dolomite, limestone,
300 evaporite, sandstone,
siltstone
4 Calcareous shale
90 Sandy limestone

600 Quartz sandstone

Monzonite c
600 Mudstone, siltstone

Ekmai Fm. sandstone

950+ Sandstone, shale, siltstone

Monzonite d

Ekmai Fm. limestone (exoskarn)

Sandstone, conglomerate,
800+ limestone, mudstone Waripi Fm. limy dolomite e

Forsterite-diopside skarn

Sample location Massive magnete ore

Fig. 2. (a) Lithostratigraphic column (after Van Ufford, 1996) with sampling depths (red dots) and (b) geologic cross-section of the Ertsberg Cu skarn district; (c-e)
Drill-core photos showing the contact relations (white dotted-line) between: (c) biotite-epidote-chlorite-altered monzonite and garnet-epidote ± magnetite-altered
Ekmai Fm. calcareous sandstone. Both rock types cut by anhydrite-quartz and chalcopyrite-pyrite ± galena veins; (d) weakly biotite-chlorite-altered monzonite and
(dark-)green exoskarn-altered Ekmai Fm. limestone with magnetite mineralization. Both rock types cut by anhydrite-quartz ± sulfide veins and sericite selvages.
Chalcopyrite-pyrite patches also occur in the exoskarn; (e) Waripi Fm. limey dolomite, (dark-)greenish forsterite-diopside exoskarn, and massive magnetite ore.
Abbreviations: Te (Ertsberg pluton); Tw (Waripi Fm. dolomite); Ekmai Formation: Kkeh (shale), Kkel (limestone), Kkes (calcareous sandstone-siltstone). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

736600 E 737000 E 737400 E 737800 E

LEGEND

Ertsberg Diorite

Waripi Fm

Ekmai Fm. –
Shale Member
954 9400 N
Ekmai Fm. –
Limestone Member
Ekmai Fm. –
Sandstone Member

Hornfels

Exoskarn

Broken Zone
954 900 N

Sheeted Vein Zone

954 8600 N

Fig. 3. Geologic map of the Deep Mill Level Zone (DMLZ) at 2600 L.

(Mathur et al., 2000, 2005), and probably also younger than minerali­ Stage IV (Fig. 4h). Metallic minerals include mainly chalcopyrite,
zation at Big Gossan (phlogopite 40Ar/39Ar: 2.82 ± 0.04 Ma) (Pre­ bornite, and pyrite, with minor native gold, electrum, gold(‑silver)
ndergast, 2003). telluride, molybdenite, sphalerite, galena, pyrrhotite, marcasite, covel­
lite, digenite, and chalcocite (Fig. 6). Spatial distribution of the alter­
ation/mineralization zones delineated through alteration mineral
2.4. Alteration/mineralization paragenesis and veining at Deep Mill Level
mapping will be presented in Section 5.
Zone
At the DMLZ, skarn-type veining is well developed in/around the
pluton, and consists of eight types (Type 1 to 8), i.e., (1) Stage I garnet-
At the DMLZ, Cu–Au mineralization is mainly (>75%) hosted in the
diopside skarn veins (1–5 cm wide) in the endoskarn zone in contact
skarn-style altered rocks (esp. magnetite-/anhydrite-altered Lower
with the siliciclastic/carbonate wallrocks; (2) Stage II epidote-chlorite-
Waripi Formation) and minor in the porphyry-style altered (quartz-)
quartz ± serpentine veinlets (0.1–4 mm) with magnetite alteration
monzonite (Fig. 4a–c). Porphyry-style alterations include mainly
halo; (3) Stage II sinuous magnetite-amphibole veinlets (0.5–1 mm) in
potassic, minor propylitic, and locally phyllic. These alterations are best
the skarn and potassic/propylitic alteration zones (Fig. 4c); (4) Stage III
developed toward the intrusive contact and are rarely texture-
sinuous, greyish-white “A”-type barren quartz veins (0.5–10 mm)
destructive. Potassic alteration occurs as selective replacement of
(Fig. 4d). These veins are well-developed in the skarn and potassic zone
hornblende by biotite, and the formation of pinkish K-feldspar. Potassic-
and crosscut skarn veins; (5) Stage III “B”- and “AB”-type quartz-
altered rocks are locally overprinted by propylitic (actinolite/tremolite-
anhydrite veins/veinlets (Fig. 4e): the former is straight (0.5–25.0 mm
epidote-chlorite) alteration, e.g., the alteration of hydrothermal biotite
wide), whilst the latter is transitional between A- and B-type. These
into chlorite (Figs. 4d–e and 5a). Phyllic alteration (Fig. 5b–c) is limited
veins are commonly Cu mineralized with spotty/blebby bornite, chal­
to selvages of quartz-sericite-pyrite veins in highly-fractured area, for
copyrite, molybdenite, and pyrite, and are best developed in the
instance the area between the NE22 and NE32 faults in northwestern
potassic-propylitic and skarn zones. Anhydrite is present is some A-, B-
DMLZ (Fig. 3). Potassic and propylitic alterations likely took place
and AB-type veins at 2600–3000 L (meter elevation level); (6) Stage III-
before prograde-skarn alteration, as evidenced by the alteration of
IV chalcopyrite veins are irregular (0.3–5 mm wide), and contain also
potassic- and propylitic-altered monzonite by the texturally-destructive
minor pyrite and quartz/anhydrite (Fig. 4d). These veins/veinlets are
garnet endoskarn (Fig. 5d–e). Porphyry-style mineralization occurs
found cutting AB-/B-veins in the Ertsberg pluton, hornfels, and the
mainly as sulfide (chalcopyrite-pyrite ± bornite)-quartz-anhydrite veins
dolomite exoskarn. Type-5/-6 veins account for the main copper
and stockwork. In this study, we focused mainly on the skarn-style
endowment at Ertsberg; (7) early-Stage IV pyrite and D-type pyrite-
alteration as it is spatially more widespread and economically more
quartz-sericite veins (0.3–10 mm) with pyrite centerline (Figs. 4f and
important. According to mineral paragenesis and crosscutting relations,
6). The veining crosscut the potassic-/propylitic-altered rocks, and is
the skarn-style alteration/mineralization can be divided into five stages
also found in hornfels zone and locally in the dolomite exoskarn with
(Fig. 7), namely (I) prograde skarn; (II) early-retrograde alteration; (III)
minor sphalerite and galena, and rare chalcopyrite; (8) late-Stage IV
late-retrograde alteration with massive anhydrite replacement; (IV) late
calcite-anhydrite veins (0.5–1 cm) are ore-barren and crosscut older
hydrothermal veining; (V) supergene alteration. Massive magnetite
vein generations (Fig. 5f).
mineralization occurred in Stage II. The main Cu–Au mineralization
occurred in Stage III, although minor Cu mineralization is also found in

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U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

a 1m b 1m

c d

e f

g h

Fig. 4. (a–b) Mine-tunnel and (c-h) drill-core photos from the DMLZ in Ertsberg: (a) Contact between exoskarn (Fo-Di-Gt-Mag-Anh) and Waripi Fm. dolomitic
marble. Inset photo shows anhydrite nodule clusters; (b) Potassic (Kfds-Bt-Hbl)-altered Ertsberg quartz monzonite cut by quartz ± anhydrite-pyrite stockwork; (c)
Intensely and pervasively endoskarn-altered Ertsberg monzonite. Endoskarn garnet alteration partially replaced by patchy retrograde chlorite-epidote alteration,
which is in turn overprinted by semi-massive or Type-3 magnetite vein mineralization, and eventually by densely-disseminated or vein-type chalcopyrite miner­
alization; (d) Ertsberg monzonite is potassic and then propylitic (Act-Epi-Chl) altered with disseminated chalcopyrite-pyrite mineralization. Altered rocks are cut
firstly by Type-4 quartz A-veins and then by Type-6 chalcopyrite veins; (e) Hornfelzed Ekmai Fm. shale brecciated by Type-5 quartz-gypsum vein that contains pyrite
and rare molybdenite; (f) Potassic (with weak overprinting propylitic)-altered Ertsberg monzonite intruded by Type-7 D-vein (qtz-ser) with pyrite centerline and
alteration halo; (g) Anhydrite-altered Waripi Fm. dolomite with patchy/Type-3 wavy-veinlet magnetite and densely-disseminated/Type-5 veinlet bornite-covellite-
chalcopyrite mineralization; (h) Massive magnetite mineralization overprinted by densely-disseminated bornite-covellite and (tarnished) chalcopyrite mineraliza­
tion. Abbreviations: Act (Actinolite); Anh (Anhydrite); Bio (Biotite); Bn (Bornite); Ch (Chlorite); Cpy (Chalcopyrite); Cv (Covellite); Di (Diopside); Ep (Epidote); Feld
(Feldspar); Fo (Forsterite); Gyp (Gypsum); Hbx (Hornblende); Kfds (K-feldspar); (Mag) Magnetite; Mo (Molybdenite); Qtz (Quartz); Serp (Serpentine).

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U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

Fig. 5. Thin-section photomicrographs (XPL) of the Ertsberg (quartz-)monzonite and (meta-)sedimentary wallrocks: (a) Weakly epidote-altered monzonite; (b)
Intensely sericite- and anhydrite-altered monzonite with rare least-altered igneous feldspar grains preserved; (c) Intensely biotite- and anhydrite-altered monzonite
cut by quartz vein. Hydrothermal biotite occurs as fine-grained aggregates; (d) Texturally-destructive, garnet-phlogopite endoskarn-altered monzonite cut by
anhydrite vein; (e) Epidote-chlorite-altered monzonite with plagioclase partially preserved; (f) Magmatic texture of monzonite completely obliterated by garnet
endoskarn alteration. Rock cut by late calcite vein; (g) Hornfelzed Ekmai Fm. shale with microcrystalline quartz, epidote-altered; (h) Hornfelzed and epidote-altered
Ekmai Formation with porphyroblastic quartz aggregate; (i) Ekmai Fm. meta-sandstone with recrystallized irregular quartz grain margin and subgrain texture,
epidote-altered; (j) Waripi Fm. dolomitic marble with phlogopite and semi-massive sulfide ore; (k) Phlogopite exoskarn-altered and sulfide-mineralized Ekmai Fm.
sandy limestone with occasional quartz and feldspar grains preserved. Abbreviations as in Fig. 4 and Bi (Biotite); Cal (Calcite); Grt (Garnet); Mu (Muscovite); Opq
(Opaque); Phl (Phlogopite); Plg (Plagioclase); Qtz (Quartz); Rt (Rutile); Ser (Sericite); Sul (Sulfide).

3. Samples and methods
3.1. Sample descriptions
In this study, a total of 51 samples were collected from the DMLZ drill
cores, including those from the Ertsberg pluton (n = 13), Waripi Fm.
dolomite (n = 30), and Ekmai Fm. limestone (n = 6), and calcareous fine
sandstone-siltstone (n = 2). These samples range from unaltered to
moderately-altered to reveal the alteration impact on the whole-rock
geochemistry. Petrographic thin sections were prepared and observed
under transmitted/reflected light microscopy for their lithology, alter­
ation/mineralization features, and mineral paragenesis.
Ertsberg granitoids: The granitoids are often also called the Ertsberg
Diorite, but available geochemical data (Section 4.1) indicate that these
rocks are mostly (quartz-)monzonitic. The samples are medium-grained,
and have mainly plagioclase (55–60 vol%) and alkali feldspars (35–40
vol%), and minor quartz (<10 vol%), igneous hornblende (<10 vol%)
and augite (<5 vol%) (Fig. 5a). Secondary minerals (5–40 vol%) include
mainly hydrothermal actinolite (fibrous or rims around augite), patchy
epidote and chlorite, veined microcrystalline quartz, and calcite and
sericite in plagioclase hair-like cracks or pseudomorphs (Fig. 5f). For the
altered samples, their alteration styles include diopside-forsterite-garnet
endoskarn (n = 1), potassic (n = 4), propylitic (n = 3), and sericite (n =
2).
Endoskarn-altered (quartz-)monzonite contains mainly prograde
diopside, forsterite, and brownish andradite/grossular garnet. Intensely-
altered samples have their primary igneous texture obliterated. For­
sterite is locally retrograde-altered to serpentine and talc, whilst diop­
side to actinolite/tremolite, epidote, chlorite, and phlogopite. Primary
hornblende and augite are largely altered, whereas feldspar grains are
still locally preserved. Late calcite veins are common. Our endoskarn
samples contain disseminated chalcopyrite-pyrite, minor molybdenite,
sphalerite and galena, and rare electrum (Figs. 4c and 5d).
The potassic-altered samples show selective, texturally non-
destructive alteration of augite-biotite-plagioclase/alkali feldspar by
hydrothermal K-feldspar-amphibole-biotite. Potassic alteration is over­
printed locally by weak propylitic and anhydrite alterations (Figs. 4d
and 5c). Mineralization consists of chalcopyrite (as quartz-chalcopyrite
veins or fracture-infill), veined pyrite, trace molybdenite (as blebs in
quartz-anhydrite veins), and rare bornite and sphalerite (Fig. 6).
The propylitic-altered samples are greenish-grey and only weakly-
altered. Alteration minerals include mainly actinolite, epidote and
chlorite, whilst minor quartz and trace residual hornblende and biotite
were also observed. Augite is partially altered into actinolite, epidote
and chlorite, biotite to chlorite, and plagioclase feldspars to epidote and
chlorite. Weak disseminated chalcopyrite-molybdenite-pyrite minerali­
zation is cut by anhydrite-quartz veins/veinlets (Fig. 5).
The phyllic-altered samples are mainly featured by sericite(-biotite)
selvages and the associated pyrite veining. Apart from pyrite, minor
galena and molybdenite, and trace chalcopyrite and sphalerite are also

7
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

Fig. 6. Laser-mount photos and photomicrographs (reflected and transmitted light) of the Ertsberg Type-7 ore veins: (a) laser mount photo, showing the vein with
pyrite centerline; (b–c) Pyrite and chalcopyrite with quartz; (d–e) Very fine-grained electrum in quartz; (f) laser-mount photo, showing the vein with alteration halo;
(g–h) Sphalerite rimmed by pyrite in quartz vein; (i–j) Disseminated chalcopyrite, bornite, and covellite with quartz; (k–l) Disseminated pyrite, chalcopyrite, and
sphalerite with quartz. Abbreviations as in Figs. 4 to 5 and Apy (Arsenopyrite); Bo (Bornite); El (Electrum); Sph (Sphalerite).

Composion
Mid-retrograde + massive Late-retrograde + late hydrothermal Supergene
Prograde skarn (I) Early-retrograde (II)
anhydrite replacement (III) veining (IV) alteraon
Mineralizaon Fe Cu-Au Cu-Au(Pb-Zn)
Forsterite
Diopside
Garnet
Scapolite
Magnete
Anhydrite
Quartz
Mica
Serpenne
Tremolite – Acnolite
Phlogopite
Talc
Chlorite
Chalcedony
Epidote
Calcite
Bornite
Chalcopyrite
Gold
Molybdenite
Pyrite
Galena
Sphalerite
Pyrrhote
Marcasite
Electrum
Covellite
Arsenopyrite

Fig. 7. Summary diagram of the skarn-style alteration/mineralization paragenesis at Ertsberg.

present (Fig. 5).
Ekmai Fm. limestone (Kkel), calcareous fine-sandstone-siltstone
(Kkes) and shale (Kkeh): Similar to the dolomite samples, the lime­
stone samples are variably marbleized, and consist of calcite (70–80 vol
%), quartz (<10 vol%), mica (<10 vol%), and minor (<5 vol% each)
chlorite and scapolite. The fine-sandstone-siltstone samples are sub­
rounded and moderately sorted, and have mainly quartz (>75 vol%),
muscovite (<10 vol%), and minor (<5 vol% each) epidote, opaque
minerals and calcite cement. Some sandstones are deformed and meta­
morphosed, as shown by the irregular boundary, and the subgrain and
undulatory extinction textures of quartz. Many siliciclastic (Kkes and
Kkeh) samples are hornfelzed with local weak exoskarn alteration.
These hornfelzed samples comprise predominantly microcrystalline
quartz (>85 vol%) plus minor (<5 vol% each) mica, epidote, chlorite,
and opaque minerals. The altered samples contain disseminated pyrite
and Fe–Ti oxides, and trace galena and sphalerite (Figs. 4e and 5g–i,k).

8
U. Rumbiak et al.
Fig. 8. Harker-type diagrams for the Ertsberg granitoids.
Waripi Fm. dolomite: The rocks are variably metamorphosed/
recrystallized into medium-grained dolomitic marble. The dolomite is
sucrosic, well-sorted, vuggy (from foraminifera dissolution), and with
occasional fossil remnants (e.g., bryozoa, coral, ooids, and peliods). The
unaltered samples (n = 9) contain mainly dolomite ± calcite (70–90 vol
%), quartz (10–20 vol%), plus minor (<5 vol%) feldspar and glauconite.
Some moderately to intensely exoskarn-altered samples (n = 20) are also
anhydrite-altered (n = 10) and magnetite-mineralized (n = 8). Alter­
ation minerals include prograde (forsterite, diopside, garnet) and
retrograde (serpentine, tremolite, phlogopite, talc) ones and anhydrite.
Chalcopyrite, pyrite, molybdenite, sphalerite, and (minor) galena are
present in the skarn-altered samples, whilst trace (arseno)pyrite,
sphalerite, and galena are locally found in the unaltered samples
(Figs. 4g and 5j).
3.2. Whole-rock geochemical analysis and mass balance calculation
Both whole-rock major and trace element compositions were
analyzed at the ALS Lab (Australia). The samples were subjected to
lithium borate fusion and then acid dissolved before analysis by ICP-MS.
This provides the most quantitative analytical approach for a broad
elemental suite, and a total of 54 elements were analyzed. To increase
the representativeness of our whole-rock geochemical dataset, pub­
lished Ertsberg granitoid data by McMahon (1994) and Gibbins (2006)
were also compiled for comparison. As the rock samples are variably
altered and have different loss of ignition (LOI), major element oxides
were normalized to 100 wt% excluding volatiles. Geochemical data
treatment and discrimination diagram plotting were performed with
ioGAS (version 7.3) software. Mass balance calculation for the elemental
gain/loss (in different lithologies under different alteration styles) were
performed with the isocon method suggested by Gresens (1967) and
modified by Grant (1986). Aluminum (Al2O3) is used as an immobile
element. The calculation results are illustrated by isocon diagrams, with
the isocon line gradient defined by the mass of the fresh samples against
that of the altered ones (M◦ /Ma). Elements fall above and below the
reference isocon denote the elements gained and lost during alteration,
9
Journal of Geochemical Exploration 232 (2022) 106889
respectively. Detailed calculation procedures are similar to those out­
lined by Ulrich and Heinrich (2001). Calculated elemental gain/loss of
the granitoid samples (of a particular alteration style) are shown with
their average value, whereas those of the meta-sedimentary wallrock
samples are shown with their individual value due to their wider
compositional ranges.
3.3. Distribution maps of target/pathfinder elements and minerals
To reveal the spatial mineral-geochemical change caused by alter­
ation and its possible lithologic/structural links, various spatial
elemental/mineral maps were constructed at 2600 L. Further analytical
details are confidential and not disclosed here. Spatial elemental maps
were constructed on the target elements (Cu, Au, Mo, As, Ag, Pb, Zn),
and alteration-sensitive pathfinder elements and their ratios (Bi, Te, Sb,
Co, Ti/Sr, (Cs + Rb)/Th). Mineral maps were made on the major ore
(chalcopyrite) and alteration minerals, including porphyry-type (biotite,
chlorite, and sericite) and skarn-type (diopside, forsterite, garnet,
magnetite, and serpentine) ones and anhydrite. The Cu, Au, and Ag
elemental maps are not disclosed due to confidentiality reason. Thus, the
chalcopyrite & Mo and As maps are used as a proxy for Cu and Au,
respectively, although the spatial distribution patterns between Cu–Au
and their proxies are not without difference.
4. Results
4.1. Whole-rock geochemistry of the Ertsberg granitoids
Among the 13 granitoid samples analyzed, 3 are unaltered/least-
altered and 10 are variably-altered (4 potassic, 3 propylitic, 2 sericite,
and 1 endoskarn). The LOI of most samples (new and published) in the
dataset are ≤3 wt%, and the LOI shows little correlation with immobile
element contents (e.g., P, Zr, REEs) and their ratios (e.g., Zr/Y, (La/
Sm)N) (Supplementary Fig. 1; Supplementary Table 1). Therefore,
immobile element geochemistry of our compiled dataset can be used for
the following petrogenetic discussion.
 U. Rumbiak et al.
10

Journal of Geochemical Exploration 232 (2022) 106889

Fig. 9. Geochemical classification diagrams for the Ertsberg granitoids: (a) TAS (after Middlemost, 1994); (b) ASI vs. SiO2 (after Frost and Frost, 2008); (c) Sr/Y vs. SiO2 (after Richards et al., 2012); (d) Alteration box
plot (after Large et al., 2001); (e) Na/Al vs. K/Al (molar) (after Davies and Whitehead, 2006).
U. Rumbiak et al.
Fig. 10. (a) Chondrite-normalized REE patterns and (b) upper continental crust
(UCC)-normalized multi-element spidergram for the Ertsberg granitoids.
Chondrite- and UCC-normalizing values are from Sun and McDonough (1989)
and Taylor et al. (1981), respectively.
After normalizing the whole-rock geochemical data to 100 wt%
excluding volatile components, most samples fall into narrow ranges of
SiO2 (61.40–63.29 wt%), TiO2 (0.75–0.90 wt%), and Al2O3
(15.32–16.20 wt%) (Supplementary Table 1). Unaltered samples are
high-K, metaluminous-peraluminous (ASI: molar [Al/(Ca - 1.67P + Na
+ K)] = 1.0–1.4), and cluster inside the (quartz-)monzonite fields in the
TAS diagram (Fig. 9a–b). In the Harker-type diagrams, most published
data (Gibbins, 2006; McMahon, 1994) also fall on the same fractionation
trends as our DMLZ samples, in which SiO2 correlates positively with
K2O, Na2O, Zr, Zr/Y, and (La/Sm)N, but negatively with TiO2, MgO, CaO
(and Sr), FeOT, and P2O5 (Fig. 8). The negative SiO2 vs. P2O5 correlation
is suggestive of I-type affinity, as also indicated by the absence of per­
aluminous minerals such as cordierite and muscovite. The rocks have
similar chondrite-normalized REE patterns, featured by LREE/MREE
enrichments and flat HREE patterns (Fig. 10a). When normalized to the
upper continental crust (Taylor et al., 1981), the rocks are enriched in
certain large ion lithophile elements (LILEs, e.g., Rb, U, K), but depleted
in all high field strength elements (HFSEs, e.g., Y and Yb) (Fig. 10b). The
granitoid samples have generally elevated Sr/Y (mostly >40) and low Y
(<20 ppm), indicative of adakitic affinity (Fig. 9c). In the Chlorite-
Carbonate-Pyrite Index (CCPI) vs. Alteration Index (AI) alteration box
plot (Ishikawa et al., 1976; Large et al., 2001), the DMLZ samples trend
toward the chlorite-pyrite alteration end-member. Data from McMahon
(1994) and Gibbins (2006) are more scattered, with some trending to­
ward the albite and epidote-calcite alteration end-members (Fig. 9d). In
the Na/Al vs. K/Al (molar) plot (Davies and Whitehead, 2006), the
Ertsberg granitoid data fall on/close to the plagioclase-K-feldspar (bio­
tite) trend, mainly toward K-feldspar-muscovite alteration and minor
toward clay alteration (Fig. 9e).
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Journal of Geochemical Exploration 232 (2022) 106889
4.2. Mineral and elemental distribution maps of DMLZ
4.2.1. Mineral distribution maps
In these maps, porphyry-/skarn-type indicator minerals are used as a
proxy for their respective alteration/mineralization styles, i.e., potassic
(biotite), propylitic (chlorite), phyllic (sericite), anhydrite (anhydrite),
prograde-skarn (forsterite-diopside-garnet), retrograde (serpentine,
chlorite), magnetite (Fe-oxide mineralization), and chalcopyrite
(Cu–Au mineralization). At the DMLZ, all the porphyry-style alteration
is best developed along the intrusive contact with the Waripi Formation,
and weakens away from it. Two potassic alteration centers (biotite >6
vol%) are present in the NW part (between the EW22–EW25 faults) and
in the central part (at the South–EW27–NE26 fault intersection) of the
intrusive contact (Fig. 11a), whilst propylitic alteration is the strongest
(chlorite >6 vol%) between the NE22 and NE24 faults (Fig. 11b). Phyllic
alteration is best developed (sericite >15 vol%) in the highly-fractured
area between the NE24 and NE32–NW6 faults (Fig. 11c). Anhydrite
alteration is widespread both within and outside the pluton, but is best
developed (anhydrite >10 vol%) adjacent to the potassic center (around
the NE26 fault) along the South Fault, as well as in the Waripi Fm.
anhydrite nodule-bearing dolomite along an ESE-trend on both sides of
the Ertsberg 1 and EW19A-B faults (Fig. 11d).
Skarn-style alteration is developed mainly in the exocontact and
minor in the endocontact, with prograde skarn alteration occurring close
to the intrusive contact and being partially replaced and enveloped by
retrograde alteration. Forsterite alteration is developed predominantly
in the NW-part of the Waripi Fm. exoskarn zone, and is the strongest
(forsterite >10 vol%) along the NE30 and EW19A-B faults (Fig. 12a).
The diopside alteration center (diopside >15 vol%) is developed to the
southeast of its forsterite counterpart, along the Ertsberg 1 Fault and
between the NE30 and EW27 faults. The alteration extends into the
pluton around the EW27 and South faults. Another weaker diopside
alteration zone (diopside: 10–15 vol%) is located in the hornfelzed
Ekmai Formation, bounded by the intrusive contact and the EW13A-B
faults (Fig. 12b). This alteration zone in the Ekmai Formation overlaps
partially with an andradite/grossular garnet alteration center (garnet
>6 vol%). Two other garnet alteration centers are present in the endo­
skarn zone around the NE21–EW20 and NE36–South fault intersections
(Fig. 12c). Distribution of the major retrograde serpentine alteration
(serpentine >4 vol%) appears to have enveloped the prograde forsterite
alteration, and is particularly well developed along the EW23 Fault,
between the NE21 and NE 25 faults, and between the EW15 and EW19B
faults (Fig. 12d).
Magnetite alteration is only locally developed. The main occurrence
(magnetite >10 vol%) is centered in the southeastern Ertsberg pluton
(northeast of the NW4A Fault), developed with well-concentric zoning.
Minor occurrences are also present in the endoskarn zone between the
South Fault and the intrusive contact, as well as in the Waripi Fm.
exoskarn zone between the NE30, EW15, and Ertsberg 1 faults
(Fig. 12e). Distribution of the chalcopyrite-highs (chalcopyrite >1 vol%)
is concentrated mainly in the NW-part of the area between the NE21 and
NE32 faults, as well as in the SE-part of the pluton west of the EW1B
Fault (Fig. 11e).
4.2.2. Elemental distribution maps
As for the target elements (Mo, As, Pb, Zn), spatial distribution of Mo
bear more resemblance with Cu than that of chalcopyrite, probably
because Cu is also hosted in other Cu minerals such as bornite and
(minor) covellite, chalcocite, and digenite. The Mo-highs (>0.02%) in­
side the pluton are located in the SE-part of the area between the EW13B
and NW40 faults, whilst those outside the pluton are located mainly in
the Broken Zone (defined as Rock Quality Designation (RQD) <25%)
around the intersections of the Ertsberg 1–EW6 faults and NE30–NS2B
faults, and minor between the East Ertsberg Skarn System (EESS) W and
NE32 faults (Fig. 13a).
Distribution of As is widespread and shares certain similarities with
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

Fig. 11. Spatial distribution maps for porphyry-style alteration mineral contents (%) at DMLZ 2600 L (a: biotite; b: chlorite; c: sericite), (d) anhydrite, and (e)
chalcopyrite.

12
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

Fig. 12. Spatial distribution maps for skarn-style alteration mineral contents (%) at DMLZ 2600 L: (a) forsterite; (b) diopside; (c) garnet; (d) serpentine,
(e) magnetite.

13
U. Rumbiak et al.
Fig. 13. Spatial distribution maps for target element contents (ppm) and major structures at DMLZ 2600 L: (a) Mo; (b) As; (c) Zn; (d) Pb.
that of Au. The As-highs (>100 ppm) are mainly developed in the
Broken Zone in the Waripi Formation (between the EW15–NE30 faults),
in the hornfelzed Ekmai Formation (between the Ertsberg 1–EW13
faults), as well as in the exoskarn zone (between the NE26–NS2B faults).
Minor As-highs are also found in the NW-part of the pluton (between the
NE22–NE32 faults) near the potassic center. Proximal skarn (forsterite)
and anhydrite zones, e.g., between the EW15 Fault and intrusive con­
tact, has distinctly low As content (<10 ppm) (Fig. 13b). Local Pb-/Zn-
highs (>0.3%) are scattered in the Waripi Formation away from (north
of) the skarn zone. The Pb and Zn contents in the pluton, Ekmai For­
mation, and forsterite and anhydrite zones are commonly very low
(<0.05%) (Fig. 13c–d).
As for the pathfinder elements (Bi, Te, Sb, Co) and ratios (Ti/Sr, (Cs
+ Rb)/Th), the two major Bi-highs (>20 ppm) are both adjacent to the
potassic centers (Fig. 14a): The one at the NW-part of the pluton (be­
tween the NE21–NE32 faults) coincides with the phyllic center and the
sole Te-high (>15 ppm), whilst the one near the skarn–hornfels
boundary (along the EW27 Fault) coincides with the Ag-high. The latter
high-Bi area also contains medium Te content (5–10 ppm), away from
which the Te content is all low (<5 ppm) (Fig. 14b). Antimony content is
mostly low (<5 ppm) across the DMLZ, except very locally (Sb: 5–25
ppm) in the Ekmai Fm. sandstone between the EW1A and EW3A faults
(Fig. 14c).
Titanium and Sr are temperature-sensitive elements, and increasing
Ti/Sr ratio generally reflects higher hydrothermal temperature. At the
DMLZ, one high-Ti/Sr (>25) zone occurs in the NW-part of the pluton
(between the NE32–EW16 faults) around the potassic center; whilst the
other Ti/Sr-high occurs in the Ekmai Fm. hornfels between the EW1B
and NE16A faults, overlapping with the garnet-diopside exoskarn cen­
ter. Two intermediate Ti/Sr (5–10) zones overlap spatially with the
sheeted vein zone and potassic center at the South–EW13A fault inter­
section (Fig. 14e). The Ti/Sr highs generally correspond well with the Co
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Journal of Geochemical Exploration 232 (2022) 106889
highs (>20 ppm) (Fig. 14d), and they both correspond well with the
Au–Cu highs. The primitive mantle-normalized ((Cs + Rb)/Th)N ratio is
an alkali alteration index (Cs and Rb are mobile under alteration
whereas Th is not), and has been used as gold fertility discrimination
(Heath and Campbell, 2004). At the DMLZ, distributions of the ((Cs +
Rb)/Th)N highs (>30) correspond spatially with the potassic alteration
in the pluton, and there are also some isolated highs in the exoskarn
zone, e.g., between the NE21–NE23 faults coinciding with the As–Bi
(and Cu–Au) highs (Fig. 14f).
5. Discussion
5.1. Elemental enrichment and depletion across the Ertsberg mineral
system
5.1.1. Ertsberg granitoids
From the mass-balance calculation, potassic-altered samples (n = 4)
show distinct K–Rb gains (c.f. unaltered samples, n = 3), consistent
with the formation of secondary K-feldspar and biotite (Fleet et al.,
2003). The hydrothermal biotite formation is also demonstrated by the
K-Ti-Ni-V-Sn gains (Fleet et al., 2003), whilst the mild overall Fe–Mg
loss can be explained by the primary hornblende break-down. The slight
Ca-Ba-Sr gains are likely caused by the overprinting carbonate veining.
Since the samples are sulfide mineralized, elements that can substitute
into metal sulfides (due to the similar ionic mass-to-charge ratios to
sulfur and ore metals), notably Se for S and Sn–Zn for Fe in chalcopyrite
(George et al., 2018), Bi-Se-Te in bornite (Cook et al., 2011a), Re for Mo
in molybdenite (Voudouris et al., 2009), Fe-Sn-In for Zn in sphalerite (e.
g., 2Zn2+ ↔ Cu+ + In3+) (Cook et al., 2009, 2011b; Di Benedetto et al.,
2005), and Bi–Ag for Pb in galena (2Pb2+ ↔ Bi3+ + Ag+) (Foord and
Shawe, 1989) are also more enriched in the potassic-altered samples
(Fig. 15a; Supplementary Tables 2–3).
U. Rumbiak et al.
Fig. 14. Spatial distribution maps for pathfinder element contents (ppm) and ratios at DMLZ 2600 L: (a) Bi; (b) Te; (c) Sb; (d) Co; (e) Ti/Sr; (f) (Cs + Rb)/Th.
The weakly propylitic-altered (actinolite-epidote-chlorite) samples
(n = 3) show Ca-Fe-Ti-Ni-Co-V gains and Na-Ba-Sr-Eu loss, signifying
actinolite-epidote-chlorite formation and feldspar destruction, respec­
tively. Calcium was likely also released during feldspar destruction, but
was then consumed by the actinolite-epidote formation, yielding even
slight Ca gain (possibly from magma replenishment). The samples are
molybdenite, chalcopyrite, and gold mineralized, as reflected by the
Mo–Re, Cu-Zn-Sn, and Au-Ag-Bi-Te gains, respectively (Fig. 15b; Sup­
plementary Tables 2–3).
The mildly phyllic-altered samples (n = 2) display gains in K-Rb-Cs-
LREEs and Fe-S-Ti-As-Sb-Te, reflecting sericite (muscovite)-clay and
pyrite alteration, respectively. The polymetallic mineralization is re­
flected in the enrichments in Pb-Ag-Bi (galena), Mo–Re (molybdenite),
and to a lesser extent sphalerite (Zn-Cu-In) and gold (Au-As-Bi-Sb-Te).
Sodic/calcite feldspar destruction is reflected in the distinct loss in Ca-
Na-Ba-Be-Sr-Eu. The Ca removal from the sericite-altered rocks may
15
Journal of Geochemical Exploration 232 (2022) 106889
have achieved through sulfation of anorthite (magmatic anorthite or an
intermediate phase of garnet-diopside sulfation), a chemisorption re­
action critical to Stage III anhydrite replacement and reduced sulfur
formation Eq. (1), and the eventual sulfide deposition Eq. (2) (Henley
et al., 2015, 2017):
3CaAl2 Si2 O8 + 4SO2 (g) + H2 O(g) →3CaSO4 + 3Al2 SiO5 + 3SiO2 + H2S(g)
(1)
CuCl2 (g) + FeCl2 (g) + 2H2 S(g) →CuFeS2 + 4HCl(g) (2)
The Ca released may have also contributed to Stage IV calcite veining
that is prevalent in the potassic/propylitic zones (Fig. 15c; Supplemen­
tary Table 1).
The endoskarn-altered sample (n = 1) has distinct Fe-Mg-Mn-Ca-Ti
gains, consistent with the garnet and diopside formation. The exten­
sive feldspar destruction is consistent with the loss of K–Na (Ca-loss
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

100 100
Er Er
Sr TiO₂
TiO₂ Tb
80 80
Altered rock (wt%/ppm)

Altered rock (wt%/ppm)

SiO₂Rb
Ba Hf
Gd Sr
Tb Rb
P₂O₅ Gd P₂O₅ Dy SiO₂
60 60 Mo La
As Ba
Al₂O₃
Tm Dy Hf Al₂O₃
K₂O La Se Nd
Se Bi S Sm Tm
Cs
40 Fe₂O₃ Nd 40 Fe₂O₃ K₂O
Ce
YbZr Sm
Cs
Zn BeYbZr
Lu S Lu Ce
Cu MgO Be Cu
20 Bi MoZn 20 Te Eu
Pb Pr MgO
Ho CaO EuAs Potassic Na₂O Propylitic
Te Ho
Pr CaO
Na₂O
0 Pb 0
0 20 40 60 80 100 0 20 40 60 80 100
Unaltered/Fresh rock (wt%/ppm) Unaltered/Fresh rock (wt%/ppm)

100 Rb 100
TiO₂ Se
Pb
Er TiO₂
80 80
Altered rock (wt%/ppm)

Altered rock (wt%/ppm)

SiO₂ Gd La
Cs
S Se Tb Hf SiO₂
Dy
La
60 Hf Sr 60 Er
Bi K₂O Al₂O₃
Tm Ba Cu Tm Gd Tb
Nd P₂O₅ Dy Sr
Zn Fe₂O₃ Nd
Fe₂O₃ Al₂O₃ P₂O₅
40 Mo
Ce 40 Bi S Sm
Cu Mo MgO Ce Rb
Sm Zn Zr Ba
Te CaO K₂O
Eu Zr Lu
20 Te Pr Lu Be
Yb 20 Pr
Pb Yb Cs
Ho MgO Endoskarn
Phyllic Na₂O Eu As
CaO Be
0 Na₂O Ho
0
0 20 40 60 80 100 0 20 40 60 80 100
Unaltered/Fresh rock (wt%/ppm) Unaltered/Fresh rock (wt%/ppm)

Fig. 15. Elemental mass balance plots (isocon method) of the Ertsberg (quartz)monzonite of different alteration styles: (a) Potassic; (c) Propylitic; (c) Phyllic;
(d) Endoskarn.

likely compensated by garnet-diopside formation), and the trace ele­ The distinct Mg-S-gains in the magnetite-anhydrite-altered samples
ments that substitute for K (Rb-Cs-Tl) and Na–Ca (Ba-Be-Sr-Eu) in likely reflect anhydrite formation, and their lower Ca content may have
feldspars (Bédard, 2006). The Cu–Au polymetallic mineralized nature been relative, caused by the sharp Fe-Mn-Mg increase due to massive
of the samples is reflected in the gains in metals (e.g., Au, Cu, Mo, Ag, Pb, magnetite mineralization. The diopside-quartz alteration has caused
Zn, Co, Ni, Sn, W) and the elements that substitute into the metal sul­ mass loss (− 18%), whereas the magnetite-anhydrite alteration has led to
fides, notably Bi-Se-Te in bornite and Re in molybdenite (Fig. 15d; substantial mass gain (avg. +59.82%). Except for the stronger Si but
Supplementary Table 2). weaker Fe-Ni-Cr-V gains, the diopside-anhydrite-altered samples (n = 3)
Average mass changes caused by porphyry-style alterations are all have generally similar elemental gain/loss to the magnetite-anhydrite-
very minor (potassic: +2.5%, propylitic: +1.8%, phyllic: +0.8%) altered samples. The stronger Si gain is likely caused by the residual
compared with that caused by endoskarn alteration (+14.6%). diopside in these samples, whilst the lower Fe-Ni-Cr-V contents are
consistent the weaker magnetite mineralization in these samples (Sup­
5.1.2. Waripi Fm. dolomite plementary Table 4).
As for the prograde exoskarn alteration (Stage I), the prograde
exoskarn-altered samples (n = 2) display strong Fe–Mg gains compared 5.1.3. Ekmai Fm. limestone and calcareous siltstone
with the unaltered samples (n = 9), with the diopside-altered sample (n As for the hornfelization and exoskarn alteration (Stage I), most
= 1) being considerably more Fe-rich and the diopside-forsterite-altered exoskarn-altered hornfelzed limestone samples (n = 5) are featured by
sample (n = 1) more Mg-Ni-rich, consistent with the diopside and for­ strong-moderate gains in Ca-Mn-Ni-Cr-Sr, reflecting the formation of
sterite chemical compositions, respectively. The formation of diopside garnet, diopside, epidote, and anhydrite. The major loss in Fe-K-Si may
± forsterite ± amphibole (actinolite-tremolite) is also evidenced by the have attributed to glauconite destruction, and that in mobile elements
strong-moderate Si-Mn-Cr gains. The Mg-gain may have sourced from (K-Na-Ba-Be-Rb-Cs-U) to carbonate-clay mineral destruction during
the dolomite destruction, whilst the concomitant Ca-Be-Ba-Sr release hornfelization. As described in Section 3.1, the samples are weakly
was likely taken up by the calc-silicate formation in the Ekmai Forma­ Pb–Zn mineralized but not (or trace) Cu-Mo-Au mineralized, resulting
tion to the southeast along the fluid pathway (Section 5.2), as well as to in the Pb-Zn-Ni-Cr gains (Fig. 17a–b; Supplementary Table 5).
Stage III anhydrite replacement and/or Stage IV calcite veining. As a The exoskarn-altered hornfelzed calcareous siltstone sample (n = 1)
major ore host, the prograde-exoskarn samples are magnetite-, gold-, shows similar elemental gain/loss to the five limestone samples, except
and Cu-Mo-Zn sulfide-mineralized, consistent with the elevated Fe-V-Ni- for the lack of metal (Pb-Zn-Ni-Cr) gain due to its largely unmineralized
Cr (hydrothermal magnetite) (Deditius et al., 2018; Nadoll et al., 2015), nature (Fig. 17c–d; Supplementary Table 5).
Au-Ag-As-Bi-Te (gold), Cu-Fe-Zn-Sn-S-As-Se (chalcopyrite), Mo-Re-S The hornfelization and exoskarn alteration have altogether caused a
(molybdenite), and Zn-Fe-Mn-Sn-In-S (sphalerite) contents. The pro­ significant mass loss to both the Ekmai Fm. limestone (− 26.86 to
grade exoskarn alteration is marked by strong mass gain of +10.81% − 50.71%, avg. − 42.94%) and calcareous siltstone (− 70.13%). We
(diopside) and +20.59% (diopside-forsterite), averaging +15.70% would argue that such major mass loss was likely critical to provide the
(Fig. 16a–b; Supplementary Table 3). rock permeability required for ore fluid circulation and later ore
As for the retrograde and anhydrite alterations (Stage II), the deposition.
diopside-quartz-altered (n = 1) and magnetite-anhydrite-altered (n = 2)
samples all display marked Ca ± Mg loss, reflecting further decarbon­
ation, whilst their respective gains in Si and Fe-Mn-Cr-Ni are consistent
with the hydrothermal quartz and magnetite deposition (Fig. 16c–f).

16
U. Rumbiak et al. Journal of Geochemical Exploration 232 (2022) 106889

Fig. 16. Elemental mass balance plots (isocon method) of the altered Waripi Fm. dolomite: (a–b) Stage I diopside(-forsterite) alteration; (c–d) Stage II diopside-
quartz alteration; (e–f) Stage II magnetite-anhydrite alteration; (g–h) Stage II diopside-anhydrite alteration.

5.2. Spatial elemental/mineral zoning pattern, fluid migration, and ore hydrothermal centers were present at/around the potassic alteration
precipitation centers. This is evidenced by the high-intermediate Ti/Sr (thus elevated
hydrothermal temperature) there, and the propylitic alteration (chlo­
From the elemental and mineral maps, we postulate that two rite: 4–8 vol%) around both potassic centers. The Ti/Sr highs in the

17
U. Rumbiak et al.
Fig. 17. Elemental mass balance plots (isocon method) of the Stage I hornfelzed and exoskarn altered (a–b) Ekmai Fm. limestone; (c–d) Ekmai Fm. calcar­
eous siltstone.
hornfelzed Ekmai Fm. calcareous rocks may not be genuinely
temperature-related, as they can also be associated with decarbonation-
related Sr loss. Occurrence of hydrothermal center in these two localities
are further supported by the adjacent Bi-highs, which are common in­
dicator of high-temperature conditions (e.g., Cook and Ciobanu, 2004;
Marcoux et al., 1996). The coexisting high-Te in these places agrees well
with the alkali-rich (monzonitic) nature of the Ertsberg ore-forming
magmas (Section 4.1), since the higher pH fluids in these magmas are
more capable to transport Te and Au than near-neutral pH ones
(Grundler et al., 2013; McPhail, 1995; Smith et al., 2017). Such feature
is also widely reported in other alkaline-hosted mineral systems (e.g.,
Jensen and Barton, 2000). The occurrence of high-Bi also coincides with
the phyllic alteration and highs of Au and As. Spatial coupling of Bi and
Au is commonly attributed to the effective scavenging of gold by Bi-
bearing fluids (e.g., Schlöglova et al., 2017). It is possible that these
ore-related target/pathfinder elements (Au-As-Bi-Te) and fluid (and/or
gas; Henley et al., 2017; Sieber et al., 2020) were originated from the
porphyry hydrothermal center through the highly-fractured zone in NW-
part of the pluton (Fig. 18a–b).
Distribution of the subsequent skarn-related (prograde, retrograde,
magnetite) and anhydrite alterations follows a similar NW-SE-trending
corridor bounded by the Ertsberg 1 fault and the intrusive contact.
The prograde forsterite alteration appears to have originated from (and
enveloping) the propylitic alteration center (around the intrusive con­
tact–NE21-22 fault intersection) and the potassic alteration center
further SE (around the South–EW27 fault intersection). The hydrother­
mal fluids may have then propagated along the major faults around the
pluton, especially along the EW (18, 19A-B) and NE (26, 29, 30) faults,
as demonstrated by the intensive alteration (forsterite >10 vol%) there.
The forsterite alteration appears to have bounded to the SE by the EW27
Fault, whereas the diopside and garnet alterations likely continued
successively further SE, with the latter being distinctly controlled by the
lithologic change from predominantly dolomitic to calcic. Rock volume
18
Journal of Geochemical Exploration 232 (2022) 106889
change during the carbonate dissolution and the calc-silicate formation
may have increased the rock porosity in the exoskarn zone, which laid
the pathways for the subsequent retrograde, magnetite, and anhydrite
alterations (Fig. 18b).
The retrograde serpentine and chlorite alterations were mainly
developed within/around the prograde forsterite and diopside-garnet
alterations, respectively, reflecting the continuous expansion of the
fluid-rock reaction regime. Magnetite mineralization is developed close
to the serpentine alteration (between the NE30–EW15 faults), whilst
anhydrite alteration encompasses and extends further away from most
areas affected by the previous prograde endo/exoskarn (forsterite-
diopside ± garnet) and retrograde serpentine-chlorite alterations. As
abovementioned, chemosorption reaction of anhydrite would lead to
rapid disproportionation of SO2 into anhydrite and reduced sulfur, the
latter of which would combine with the ore metals in metal chloride
complexes and precipitated (Henley et al., 2015, 2017). Dissolution of
the highly-soluble anhydrite (Blounot and Dickson, 1969) was inter­
preted to have formed the Broken Zone, which greatly increased the rock
porosity for the subsequent Cu-Au-Ag-Mo sulfide ore precipitation
(Hughes and Wiwoho, 2005). This is reflected by the distinct highs in Mo
(and the unpublished Cu-Au-Ag) and in Co–As (proxies for auriferous
pyrite) in/around the anhydrite zone. The ore fluids likely cooled down
as they travelled further north/northeast from the hydrothermal center,
during which they would have reacted with the wallrocks, and mixed
with the formation water in the latter. This would likely cause the pre­
cipitation of low-temperature, distal-skarn Pb–Zn sulfides (e.g., sphal­
erite and galena) along/around the northern segments of EW15 and NE
(22 and 30) faults and their inferred northern/north-eastern continua­
tion (Fig. 18c).
As shown in Fig. 18d, Our model of lateral fluid migration from a
porphyry-style hydrothermal center (potassic alteration) ➔ propylitic
and phyllic zones (the latter in the highly-fractured NW part of the
pluton) ➔ prograde endoskarn along/near the intrusive contact ➔
 U. Rumbiak et al.
19

Journal of Geochemical Exploration 232 (2022) 106889

Fig. 18. Schematic alteration model for the Ertsberg DMLZ 2600 L, showing the fluid-rock reaction pathways and migration of various ore-related elements: (a) potassic and propylitic alterations; (b) phyllic and
prograde skarn alterations; (c) retrograde and anhydrite alterations; (d) magnetite and Cu–Au (with As–Mo as proxies) and Pb–Zn skarn mineralization.
U. Rumbiak et al.
prograde forsterite exoskarn in Waripi Fm. dolomite ➔ prograde
diopside-garnet skarn in Ekmai Fm. limestone/calcareous sandstone-
siltstone ± Waripi Fm. dolomite ➔ retrograde serpentine and chlorite
alterations within/enveloping the prograde skarn zone ➔ magnetite
mineralization ± anhydrite replacement in the Waripi and Ekmai Fm.
carbonates ➔ Cu-Au-Ag-Mo sulfide mineralization ± anhydrite
replacement in the Waripi and Ekmai Fm. carbonates (esp. Broken
Zone) ➔ distal Pb–Zn sulfide mineralization in Waripi Fm. dolomite
(north of the Cu-Au-Ag-Mo orebody), is well consistent with the results
of our whole-rock geochemical data and elemental mass balanced
calculation. The alkalic Ertsberg (quartz-)monzonite has likely supplied
the K–Rb (for potassic and phyllic) and other magma-derived elements
(Ni-V-Sn) (for propylitic) for the porphyry-style alterations. The hy­
drothermal fluids, which are already rich in the alkalis by the porphyry-
style and endoskarn alterations (notably through feldspar destruction),
are further enriched in these elements by the dissolution of Waripi Fm.
dolomitic carbonates, although the Mg released was likely conserved by
the Mg-silicate (forsterite-diopside-tremolite) deposition. The resultant
fluids may have promoted the diopside-garnet formation in the Ekmai
Formation (esp. in its siliciclastic member), as reflected by their strong
Ca-Mg-Mn-Th-U-Sc-Y gains. The strong Si-Fe-Mn-Ni-Cr gains in the
exoskarn-altered Waripi/Ekmai Fm. samples reflect substantial fluid and
elemental supply from the pluton, consistent with the more magmatic S-
isotope signature over time for the sulfide/anhydrite in hydrothermal
veins (Gibbins, 2006). Such fluid/elemental supply may have been
maintained by the more-mafic magma recharge into the pluton, as evi­
denced by the higher MgO and Sc-V-Ni-Cr contents for the younger
granitoid phases in the intrusive complex (Makis et al., 2018). After the
skarn alteration, the garnet-diopside and residual magmatic anorthite in
the fluids may have triggered the aforementioned sulfation of garnet-
diopside-anorthite, leading to Stage III massive anhydrite replacement
and reduced sulfur formation (Henley et al., 2015, 2017). The anhydrite
may have also oxidized the Fe2+ liberated from the alteration of
igneous/prograde-skarn mafic minerals (e.g., amphibole and biotite),
promoting magnetite and sulfide mineralization (Sulaksono et al.,
2021). The reaction/dissolution of hydrothermal anhydrite and calcite
likely provided also the open-space architecture for high-grade Cu–Au
mineralization.
6. Conclusions
In this study, we have better elucidated the porphyry- and skarn-style
alteration/mineralization processes at the Deep Mill Level Zone of
Ertsberg, and how they were brought about by elemental migration
across different lithologies and structures.
(1) At Ertsberg, skarn-style alteration/mineralization occurred after
its porphyry-style counterpart and comprises five major stages: (I) pro­
grade skarn; (II) retrograde alteration + main-stage magnetite miner­
alization; (III) massive anhydrite replacement + main-stage Cu–Au
mineralization; (IV) late hydrothermal veining; (V) supergene alter­
ation. The Ertsberg granitoids consist mainly of (quartz-)monzonite and
minor (monzo)diorite. Altered samples are featured by garnet-diopside
endoskarn and/or porphyry-style (potassic, propylitic, phyllic) alter­
ations and anhydrite replacement.
(2) Elemental mass balance calculation indicates that the porphyry-
style altered samples are featured by alkali depletions caused by feldspar
destruction. Decarbonation of the Waripi and Ekmai Fm. wallrocks
likely provided part of the Mg-Ca-Sr for the following forsterite-diopside
exoskarn and anhydrite formation. Enrichments of various ore-related
target/pathfinder elements in these altered samples are consistent
with their mineralized nature, e.g., Fe–Mn (magnetite), Cu-Fe-Bi-Se-Te
(bornite), Mo–Re (molybdenite), Au-Ag-As-Bi-Te (auriferous pyrite/
arsenopyrite), Zn-Fe-Mn-Sn-In (sphalerite), and Pb-Ag-Bi (galena).
(3) Alteration mineral and target/pathfinder elemental zoning pat­
terns show that the ore fluids were likely originated from the pluton,
which then outflowed from the potassic centers, through the
20
Journal of Geochemical Exploration 232 (2022) 106889
surrounding propylitic zone, to the intrusive contact to form the endo­
skarn. From there the fluids continued to travel along the largely SE-
trending intrusive contact and SE-/NE-trending fault zones into the
wallrocks, forming the forsterite-diopside (Waripi Fm. dolomite) and
garnet-diopside (Ekmai Fm. limestone/calcareous sandstone-siltstone)
exoskarn. Exoskarn alteration was followed by retrograde (serpentine-
amphibole-epidote-chlorite) alterations, and then by magnetite miner­
alization and massive anhydrite replacement. This created the open-
space Broken Zone around the pluton for the subsequent high-grade
Cu-Au-Mo skarn ore deposition.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.gexplo.2021.106889.
CRediT authorship contribution statement
Utreck Rumbiak: Data collection, Petrography. Chun-Kit Lai: Inves­
tigation, Writing. Reza Al Furqan: Map production, Reviewing. Mega
Rosana: Supervision. Euis Yuningsih: Supervision. Basilios Tsikouras:
Data processing, Reviewing. Elena Ifandi: Editing. Amal binti Abdul
Malik: Figure production. Huayong Chen: Academic advice.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We thank PT. Freeport Indonesia for providing the data and
permission to publish the work, as part of the first author’s MSc project.
Christiani Aloysius, Dhani Aulia Haflil, Dr. Clyde Leys, and other col­
leagues of the first author are thanked for their continuous support. Our
thanks go also to members of the UBD Economic Geology Research Team
(project grant number [UBD/RSCH/1.4/FICBF(b)/2020/027]) for
helping with the data analysis and manuscript editing. The Editor-in-
Chief Prof. Stefano Albanese, Assistant Editor Pooria Ebrahimi, and
two anonymous reviewers are thanked for their insightful review and
comments.
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