2012 Society of Economic Geologists, Inc.

Economic Geology, v. 107, pp. 15271538

Sources of Chalcophile and Siderophile Elements in Kermadec Arc Lavas*

CHRISTIAN TIMM,1, CORNEL E. J. DE RONDE,1 MATTHEW I. LEYBOURNE,1 DANIEL LAYTON-MATTHEWS,2 AND IAN J. GRAHAM1
1 Department of Marine Geosciences, GNS Science, PO Box 30-368, Lower Hutt 5040, New Zealand
2 Department of Geological Sciences and Geological Engineering, Queens University, Kingston, Ontario, Canada

Abstract
Volcanogenic massive sulfide (VMS) deposits typically contain significant proportions of magma-derived
chalcophile (Cu affinity) and siderophile (Fe affinity) elements such as Au, Cu, V, Zn, Mo, Bi, Sb, and As that
relate to the composition of associated (host) magmatic rocks. Here, we combine new and published trace
element data for lavas recovered from 15 volcanic centers along the Kermadec arc. The data show that mafic
back-arc and arc-front lavas are enriched in most of the chalcophile and siderophile elements when compared
with mid-ocean ridge basalts (MORB). Elevated (Cu, Zn, V, Mo, Pb)/Yb, Ba/La, As/Ce, and Sb/Pr ratios indi-
cate that the chalcophile and siderophile elements are either transported into the mantle wedge via hydrous
fluids derived from the subducting slab, or are liberated from residual mantle wedge sulfides that are oxidized
by hydrous fluids. Lower ratios of (Cu, Zn, Mo, Sb, and Pb)/(MREE, HREE) in basalts from the Kermadec
back arc (Havre Trough) when compared to the arc front suggests decreasing slab-related input into the man-
tle source away from the arc front. Unusually high contents of LILE, Ag, Sn, Mo, Th, LREE, MREE, Nb, Zr,
Hf, and positive trends in (Ag, Sn)/Yb with Th/Yb, Hf/Y, (La/Sm)N, but low Sr/Y, in dacites from the Brothers
volcanic center, southern Kermadec arc, indicate the additional transport of Ag and Sn via a solute-rich super-
critical fluid, or via a sediment-derived melt. Magmas generated through partial melting of a sub-arc mantle
metasomatized by hydrous melts thus appear to play an important role in the formation of Cu-Au-Agrich arc-
type VMS deposits.

Introduction
MINERALIZATION related to hydrothermal activity is associated
with volcanism and high heat flow at plate boundaries. In par-
ticular, large deposits of economically important metals (e.g.,
porphyry copper; Au-rich VMS) occur preferentially at con-
vergent plate boundaries (e.g., Sillitoe, 1973; Richards, 2003;
Stix et al., 2003; de Ronde et al., 2005, 2011). Compared with
mid-ocean ridge basalts (MORB), subduction-related mag-
mas commonly have elevated contents of Au, Ag, Cu, Mo, Bi,
Zn, V, Sb, As, Pb, and S, (e.g., Jochum and Verma, 1996; Noll
et al., 1996; Jochum and Hofmann, 1997; de Hoog et al.,
2001; Jenner et al., 2010; Richards, 2011) and are enriched in
fluid-mobile elements such as U, Ba, Pb, Rb, Sr, and K. Such
enrichment is attributed either to the addition of hydrous flu-
ids (melts) from the subducting slab (e.g., Elliot et al., 1997;
de Hoog et al., 2001), or to the liberation of chalcophile (S
affinity) and siderophile (Fe affinity) elements from the man-
tle wedge (e.g., Mungall, 2002). Whether this enrichment oc-
curs directly through the addition of fluids from the subduct-
ing slab, or is a function of more oxidizing mantle conditions
(high O2; low H2S) permitting greater Cu, Au, or Ag trans-
port (ultimately contributing to Cu-Au-Agrich VMS deposit
formation), is a matter of ongoing debate (e.g., Stolper and
Newman, 1994; Elliot et al., 1997; Sun et al., 2004; Jenner et
al., 2010).
Along the mid-southern Kermadec arc, hydrothermal vent-
ing has been detected at 76% of the volcanic centers (18 of
24; de Ronde et al., 2007). Three of these are known to host
sea-floor massive sulfides (VMS) i.e., Rumble II West, Broth-
ers and Clark volcanic centers (Leybourne et al., 2012; de
Corresponding author: e-mail, c.timm@gns.cri.nz
**A digital supplement to this paper is available at http://economicgeol
ogy.org/ and at http://econgeol.geoscienceworld.org/.
Ronde et al., 2003, 2005, 2011, in prep.), with Brothers host-
ing by far the most significant Cu-Au-Agrich mineralization
(with up to 90 ppm Au) discovered along the arc to date. A
magmatic fluid component in the mineralization at Brothers
has been identified (de Ronde et al., 2011), consistent with
the volcanic host rocks being enriched in these metals.
To determine the source of chalcophile and siderophile el-
ements involved in the formation of VMS deposits along the
Kermadec arc, we have analyzed 37 lava samples for their
trace element compositions (Supplementary Table 1; see
footnote), from seven arc-front volcanic centers between
Brothers in the southern Kermadec arc, to Monowai in the
northern Kermadec arc (Fig. 1). Kermadec arc volcanoes sit
on basaltic oceanic crust behind the Kermadec Ridge (the ex-
ceptions being Raoul and Macauley and Curtis Islands which
sit on the Kermadec Ridge itself), thus excluding the interac-
tion with continental crust to explain variations in lava com-
positions. Kermadec arc lavas, therefore, are ideal samples to
study sub-arc subduction-related mantle metasomatism, in-
cluding chalcophile and siderophile element enrichment.
Kermadec ArcGeologic Setting
The ~1,200-km-long submarine Kermadec arc makes up
the southern part of the ~2,500-km-long Tonga-Kermadec
arc and/or trench system northeast of New Zealand and
comprises 33 volcanic centers. East of the Kermadec arc, a
~200- (~25S) to >500-m (~36S)-thick sediment pile on
the Jurassic-Cretaceous Pacific Plate has been subducting
beneath the Australian Plate at a convergence rate of ~50
(around Clark) to ~70 mm yr1 (around Monowai; Fig. 1)
since late the Oligocene (e.g., Turner and Hawkesworth,
1997; Clift et al., 2001; Sutherland et al., 2010). The arc
front is accompanied by subparallel crustal extension in the
Havre Trough back arc.

0361-0128/12/4069/1527-12 1527
1528 TIMM ET AL.

176E 178E 180E 178W 176W 174W 172W atop the prominent cone volcano ~12 km south of the caldera
(e.g. Timm et al., 2011; Leybourne et al., 2012b).

ge
-23
AUSTRALIAN Here, we have combined new trace element data for

Rid
DSDP
-24 PLATE Site 204
Monowai, Hinepuia, Rakahore, Gamble, Putoto, Hinetapeka,

ga
69 and Brothers, with literature data for Monowai, Brothers,

Ton
-25
Monowai Raoul, Macauley, Curtis, Volcanolog, Sonne, LEsperance,
Osbourn
Hinepuia Trough
Rumble III, Rumble IV, Rumble V, Tangaroa, and Clark
-26 South (Gamble et al., 1997; Turner et al., 1997; Ewart et al., 1998;

Lo
Rakahore
Fiji Haase et al., 2002, 2006; Smith et al., 2009; Todd et al., 2011)

uis
-27 Gamble

v il
Basin to better understand the sources of chalcophile and/or

le
Putoto
siderophile elements along the Kermadec arc.

se
-28 Hinetapeka

am
Methods and Results

ou
Raoul group

nt
-29 Macauley Island 62
New geochemical data presented (Supplementary Table 1)
Curtis Island in this paper includes analysis of samples containing <5% of

ch
-30

ain
Volcanolog alteration minerals (based on quantitative petrographical ex-
ge

-31 amination; Graham et al., 2008). For major element analysis,

LEsperance
Rid

dried powders were mixed with lithium tetraborate and am-

Rid lville

monium nitrate, fused to a homogeneous glass bead, and an-

dec

-32
ugh
ge

Tro vre

alyzed at the University of Auckland, calibrated against Geo-

ma
Co

Ha

-33 55 logical Survey of Japan rock standards JB-2 and JA-1. Loss on
Ker

ignition (LOI) was determined by the weight loss incurred

Sonne
-34
Brothers
-35 Rumble III PACIFIC
Rumble IV PLATE
Rumble V
-36 Clark Tangaroa 49
Hikurangi
-37
Plateau
NEW ZEALAND
-38
FIG. 1. Tonga-Kermadec and Lau-Colville arcback-arc system. Arrows
with numbers (in mm yr1) represent the relative Pacific-Australian plate
convergence rates (after DeMets et al., 1994). Black stars represent the lo-
cations of the volcanic centers with new data presented in this study, whereas
the white stars represent other volcanic centers for which literature data has
been used.
Volcanoes of the Kermadec arc sit on 10- to 18-km-thick
oceanic crust of Eocene age (Duncan and Clague, 1985), 110
to 140 km west of the trench and ~120 km above the sub-
ducting slab (e.g., Isacks and Barazangi, 1977; Wiens et al.,
2008). The northern part of the Kermadec arc (i.e., between
2529S) comprises six volcanic centers (Hinetapeka,
Putoto, Rakahore, Gamble, Hinepuia, and Monowai; Fig. 1),
each dominated by a single volcano that was sampled during
the 2004 NZAPLUME III expedition of the R/V Tangaroa.
Samples from Brothers were obtained during manned sub-
mersible dives in 2004 with the Shinkai 6500 and in 2005 with
the Pisces V as part of the New Zealand American Ring of
Fire expedition.
Hydrothermal activity of varying degrees has been detected
at the majority of the Kermadec arc volcanic centers (e.g., de
Ronde et al., 2001, 2007; Graham et al., 2008), with Clark (de
Ronde et al., 2003), Brothers (de Ronde et al., 2005, 2011),
and Rumble II West (de Ronde, 2006; Leybourne et al.,
2012a) being host to VMS mineralization. Monowai is the
most volcanically active center and hosts the most extensive
hydrothermal activity in the northern Kermadec arc, with a
system associated with the large caldera volcano and another
from a 3-g sample of powder heated to 1,000C for 4 h in a
silica crucible. Trace elements were laser ablated on Li borate
fused sample glass disks at the Australian National University,
using an EXCIMER laser ablation system coupled with a
HP7500 Agilent ICP-MS, following the methods of Eggins et
al. (1998). The JB-2 and JA-1 standard reference material was
run in parallel with the samples as a primary standard. Re-
peated sample analysis provided a precision of <7% relative
standard deviation (RSD; except for U, La, Pb, Er, and Cr,
which were 89%).
For analysis of Ag, Mo, Sb, Sn, As, Bi, Li, and Tl, ~100 mg
of powdered sample was digested in a microwave vessel using
6 ml of 28.9 M HF and 4 ml of 15.8 M HNO3. A 60-min
ramped heat program was run to 220C at a maximum of 40
bars. After completing the heating program, the vessels were
cooled to room temperature and carefully vented in a fume
hood. After confirming complete sample digestion by visual
inspection, evaporation was performed in two steps. The con-
tents of each microwave vessel were quantitatively trans-
ferred to a Savillex digestion vessel, transferred to a 70C
hotplate, and dried to incipient dryness to evaporate most of
the HF and prevent fluoride formation. These vessels were
allowed to cool, then 2 mL of 12.1 M HCl was added to each
which was then capped and heated to 150C on a hotplate for
24 h. The vessels were then allowed to cool, were uncapped,
and returned to a 70C hotplate to evaporate to incipient dry-
ness. Finally, the residue was dissolved in 10 mL of 2 wt %
HNO3 containing 1 ppb In (internal standard) and made up
to a final volume of 50 mL. Clear solutions were obtained in
all cases and procedural blank solutions were also prepared.
The solutions were analyzed at the Queens Facility for Iso-
tope Research, Kingston, Ontario, using an Element XR,
high-resolution ICP-MS. Standard analyses are given as sup-
plementary Table 2.
Geochemical characteristics
The selected Kermadec arc lavas, normalized to 100%
volatile free, range in composition from basalt (tholeiite) to

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 SOURCES OF CHALCOPHILE AND SIDEROPHILE ELEMENTS IN KERMADEC ARC LAVAS 1529

rhyolite (4873 wt % SiO2; Fig. 2). The majority of the lavas 1,000
show normal mid-ocean ridge basalt (N-MORB)-like high
field strength element (HFSE) ratios, such as (La/Sm)N enriched
100
1.2; Zr/Y 3.0; Hf/Yb 0.95 (not shown) with typical arc-
type negative anomalies for Nb and enrichments of large ion

Sample/MORB
lithophile elements (LILE) such as Cs, Rb, Ba, K (Fig. 3). 10
The concentrations of chalcophile and siderophile elements
in the basaltic lavas range from depleted (e.g., Ag, Sn; Fig. 4)
1
through similar (e.g., Zn, V, Mo) to enriched (e.g., Sb, As, Cu,
Pb), when compared with N-MORB (Fig. 4a-j). Copper, V,
and Zn concentrations increase with SiO2 concentrations up 0.1
to ~55 wt % SiO2 and then decrease, whereas Ag, Sn, Mo, As,
Pb and Bi, generally increase with increasing SiO2. depleted
0.01

Mo
Nb

Nd

Gd
Discussion

Pb

Sb

Yb
Rb

Cu
Cs

Zn
Dy
La

Ag
Th

Eu
Zr

Y
Er
Ce

Sm

Ho
Tm
Ba

Tb
Sn
Hf
U

Pr
Sr

Lu
P

Bi
K

Ti
Tl

Behavior of chalcophile and siderophile elements
during subduction zone magmatism
Because of the sulfur affinity of chalcophile and siderophile
elements the presence of sulfur strongly influences their be-
havior in subduction zone systems. In the absence of an S-
bearing phase and/or melt, Pb, Sb, Sn, Ag, Bi, As, Mo, and Tl
behave as incompatible elements. Gold, Cu, Zn, Ag, and V
also behave incompatibly during fractional crystallization
until the onset of Fe-Ti oxide fractionation at ~55 wt % SiO2
(Togashi and Terashima, 1997; Jenner et al., 2010). Titano-
magnetite fractionation changes the redox state of the magma
by removing FeOtotal (including Fe3+) and together with the
subsequent reduction of SO2 4 to S , results in the formation
2 Bi, Pb, and Mo, however, generally increase with increasing
of Au and Cu-H2S complexes which can partition into high-
temperature hydrous supercritical fluids (Sun et al., 2004; Za-
jacz et al., 2011).
10
8 fractionating crystal phases olivine, orthopyroxene, clinopy-
Na2O+K2O wt%
V
Li
FIG. 3. MORB-normalized (after Sun and McDonough, 1989; Jenner et
al., 2010; for Cu and Ag) multitrace element diagram for the Kermadec arc
mafic lavas (SiO2 <55 wt %), showing element enrichments and depletions
relative to N-MORB. Symbols are as in Figure 2.
A decrease in Cu, Zn, and V (and FeOtotal, MnO; not
shown) contents (Fig. 4) at ~55 wt % SiO2 in the Kermadec
lavas argues for removal of these metals into an immiscible
sulfide phase or magmatic brine phase, following sulfate re-
duction induced by crystallization of titanomagnetite and py-
roxene in the Kermadec lavas. The contents of Ag, Sn, Sb, As,
wt % SiO2 that argues against their partitioning into the crys-
tallizing phases in the magma reservoir. These elements,
therefore, appear moderately incompatible during fractional
crystallization. At lower silica contentsbefore the onset of
magnetite crystallization, and irrespective of how these ele-
ments are incorporated into crystals or sulfidesthe process
of fractional crystallization passively enriches them in the
melt owing to the incompatibility of these metals in the major

Rhyolite
roxene, plagioclase (amphibole and mica, e.g., Sun and Mc-
6 BAB Donough, 1989; Blundy and Wood, 2003).
Evidence for sulfur enrichment in the mantle wedge above
4 a subducting slab comes from melt-inclusion studies, such as
the one done on olivines from mantle xenoliths and basaltic
2 rocks from Batan Island of the Luzon arc (Mtrich et al.,
Bas- 1999). The presence of a hydrous S-rich silicate melt, sulfide
Basalt And And Dacite globules, H2O-S-rich vapor and some anhydrite in these sam-
45 50 55 60 65 70 75 80 ples demonstrates different sulfide carriers and different O2
and S2 conditions, resulting in variable sulfur contents in the
SiO2 wt% respective lavas. Other evidence for slab-derived S addition to
the mantle wedge was identified in lavas from the Mariana
Monowai Gamble Brothers LEsperance* Rumble IV*
Monowai Putoto Raoul group Volcanolog* Rumble V* arc (Woodhead et al., 1987; Alt et al., 1993), while Albarede
Hinepuia
Rakahore
Hinetapeka Macauley Sonne Smt* Tangaroa and Michard (1986) have proposed reinjection of S into the
Brothers Curtis Island Rumble III* Clark* arc mantle via hydrothermal fluids. Due to their strong sulfur
FIG. 2. Silica vs. total alkalis for Kermadec arc lavas, following the rock
affinity, chalcophile and siderophile elements are likely to ac-
classification of Le Maitre et al. (2002). Field for the southern Lau Basin and company S transfer from the slab to the mantle wedge
Havre Trough basalts (BAB = back-arc basalts) are added for comparison. (Stolper and Newman, 1994; Noll et al., 1996; de Hoog et al.,
Data obtained from the literature (marked by an asterisk in the legend) are 2001).
from Turner et al. (1997), Haase et al. (2002, 2006), Ewart et al. (1998), It has long been recognized that the chalcophile elements
Smith et al. (2009), and Todd et al. (2011). The two different symbols for
each of Monowai and Brothers represent new data (colored) and literature Pb, Sb, As, and Tl (together with Ba, Cs, Rb, U, K, and Sr) are
data (white and gray), respectively. highly fluid-soluble and thus mobile under oxidizing mantle

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1530 TIMM ET AL.

300
Onset of magnetite Onset of magnetite
a) f)
250 crystallization crystallization
0.4

Cu (ppm)

Sb (ppm)
200
0.3
150
0.2
100

50 0.1
HTB

b) g)
3
400
V (ppm)

Mo (ppm)
300 2
200
1
100 MORB

c) h)
200 0.07
Zn (ppm)

Bi (ppm)
150 0.05

100
0.03
50
0.01

0.09 d) i) 7
6
0.07
Ag (ppm)

As (ppm)
0.05 4
3
0.03
2
0.01 1

3 e) j)
Sn (ppm)

10
Pb (ppm)

1 5

45 50 55 60 65 70 75 50 55 60 65 70 75 80
SiO2 wt% SiO2 wt%
Monowai Gamble Brothers LEsperance* Rumble IV*
Monowai Putoto Raoul group Volcanolog* Rumble V*
Hinepuia Hinetapeka Macauley Sonne Smt* Tangaroa
Rakahore Brothers Curtis Island Rumble III* Clark*

FIG. 4. Select elements vs. SiO2 (wt %). (a) Cu, (b) V, (c) Zn, (d) Ag, (e) Sn, (f) Sb, (g) Mo, (h) Bi, (i) As, and (j) Pb ppm.
The dark gray field represents MORB, whereas the white field represents back-arc basalts (BAB; Haase et al., 2002; Todd
et al., 2011). The dotted line marks the onset of magnetite crystallization.

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 SOURCES OF CHALCOPHILE AND SIDEROPHILE ELEMENTS IN KERMADEC ARC LAVAS
conditions prevalent in the mantle above a dehydrating sub-
ducting slab (e.g., Hofmann et al., 1986; Jochum and Verma,
1996; Noll et al., 1996; Jochum and Hofmann, 1997). Hy-
drous fluids are the predominant carrier of these elements,
transporting them from the subducting slab (consisting of
sedimentary cover, altered oceanic crust, and serpentinized
ultramafics) to the overlying mantle wedge (e.g., Stolper and
Newman, 1994; Elliot et al., 1997; Plank and Langmuir, 1998;
Hattori and Guillot, 2003, 2007; Ruepke et al., 2004; Span-
dler et al., 2004). Copper (and Au) is also considered mobile
during dehydration of a subducting slab, especially in the
presence of Cl or S (e.g., Hamlyn et al., 1985; Noll et al.,
1996). To what extent Cu and Au are transferred to the man-
tle wedge remains equivocal, although we know arc tholeiites
and calc-alkaline magmas formed through partial melting of
the metasomatized mantle wedge are enriched in these ele-
ments (e.g., Jochum and Verma, 1996; Noll et al., 1996;
Jochum and Hofmann, 1997). Regelous et al. (2010) have
shown that 42 to 90% of the Pb in lavas from the Tafahi and
Niuatoputapu volcanoes of the northern Tonga arc has been
added to the mantle wedge via subduction zone fluids derived
from dehydration of altered oceanic crust. By contrast, volca-
noes along the southern Kermadec arc appear to have a
greater influence from subducted Pacific sediment (Gamble
et al., 1996; Haase et al., 2002; Regelous et al., 2010). Molyb-
denum and Sn (and W) are considered less mobile during de-
hydration of the subducting slab (Noll et al., 1996).
The enrichment of mobile metals in arc hydrothermal flu-
ids is strongly dependent on the oxidation state of the mantle
wedge, the S content of the mantle, and therefore the oxida-
tion state and S content in the resulting magma (Hamlyn et
al., 1985; Mungall, 2002). Arc magmas are typically more ox-
idized (up to 2*log O2) above the quartz-fayalite-magnetite
buffer (QFM) than are MOR lavas. This leads to the dissolu-
tion of S as SO24 (e.g., Carroll and Rutherford, 1985) and the
retention of chalcophile elements in the magma since they
are incompatible during fractional crystallization of olivine,
pyroxene, and plagioclase (e.g., Hamlyn et al., 1985). Mungall
(2002) associated Au and Cu deposits in arc environments to
an affinity with high oxygen fugacities (QFM >1) and adakitic,
sodic-alkaline, or potassic lava compositions that enable Cu
and Au to be liberated from the metasomatized mantle wedge
and partitioned into magmas.
In laboratory rock dehydration experiments, Cu is seen to
behave as a fluid-mobile element during the dehydration of
altered oceanic crust (as represented by amphibolite) at
upper mantle pressures and temperatures (i.e., 5.5 GPa and
900C; Kogiso et al., 1997), whereas Zn and V are less fluid-
mobile. For example, Cu contents were reduced by up to
50% in the starting amphibolite after the dehydration experi-
ment that argues for their removal by a hydrous fluid upon
amphibole breakdown. By contrast, Zn and V were only de-
creased by 3.8 and 7.1%, respectively.
Direct evidence of Au and Cu enrichments in the mantle
wedge above arc volcanoes occurs in the metasomatized peri-
dotite mantle xenoliths from Tubaf seamount (Lihir Island
group of the Tabar-Lihir-Tanga-Feni island arc, Papua New
Guinea) that contains Au-enriched vein minerals precipitated
from slab-derived oxidizing S-rich fluids (McInnes et al.,
1999; Grgoire et al., 2001). High platinum group and Au
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1531
concentrations in ultramafic mantle xenoliths (i.e., peridotites
and pyroxenites) from the Kamchatka arc further support en-
richment of siderophile elements in the sub-arc mantle
(Kepezhinskas et al., 2002). High Au and low HFSE contents
in the xenoliths are consistent with the addition of Au to the
mantle wedge from the slab via hydrous fluids, rather than via
melts. Such occurrences, however, do not in themselves
prove that the chalcophile and siderophile elements were
added from the subducting slab, rather than being redistrib-
uted within the metasomatized mantle wedge.
In the following section we therefore focus on two hy-
potheses regarding the derivation of chalcophile and
siderophile elements in the Kermadec arc lavas. The inter-
pretations are based on geochemical tracers sensitive to the
addition of hydrous fluids, or hydrous melts derived from a
subducting slab to a depleted mantle wedge.
A rock perspective on chalcophile and siderophile
elements in Kermadec arc lavas
A number of variables, including mantle source composi-
tion, oxygen and sulfur fugacity, degree of partial melting,
fractional crystallization, and late-stage contamination and/or
alteration all play a role in the abundance and behavior of
chalcophile and siderophile elements in arc lavas. Our selec-
tion of fresh lavas excludes late-stage contamination and/or
seawater and/or hydrothermal alteration as variables in the
observed range of compositions. The slight increase in con-
centration of chalcophile and siderophile elements during
fractional crystallization (in the absence of a sulfide and/or a
metal phase) observed in the Kermadec arc lavas (Fig. 3) has
only a minor effect on incompatible element ratios such as
La/SmN, Sb/Pr, As/Ce, Ag/Yb, Mo/Yb, and (Cu, Zn, V)/Yb
with SiO2 <~55 wt %. Similar, or higher concentrations of Cu,
V, Zn, and Mo with SiO2 <~55 wt % when compared with
MORB, coupled with generally higher (Cu, Zn, V, Mo)/Yb
values cannot therefore be explained by fractional crystalliza-
tion.
Copper, Zn, V, and Mo contents are generally higher in arc-
front lavas than in the back-arc lavas resulting in higher (Cu,
Zn, V, Mo)/(Yb, Y, Zr) values. Given that Cu, Zn, V, and Mo
are incompatible with olivine, pyroxene, and plagioclase in
magmas with SiO2 <~55 wt % (and therefore preferentially
partition into the melt), and that the mantle beneath the arc
front is more depleted than that beneath the back arc (via a
mechanism of previous melt extraction in the back arc; e.g.,
Haase et al., 2002; Timm et al., 2011), some of these elements
either must have already been removed during partial melt-
ing and melt extraction in the back arc in order to form back-
arc basalts or remain in the mantle wedge. For example, in an
oxidized mantle wedge containing no residual sulfides Cu is
moderately incompatible and Yb mildly incompatible during
mantle melting and the difference in the degree of partial
melting beneath the more enriched back arc (~5%; Haase et
al., 2002) and the depleted arc front (~1020%, Haase et al.,
2002; Timm et al., 2011) would result in similar, or higher
Cu/Yb values in the back-arc lavas compared with the arc-
front lavas. This is contrary to what is observed. On the other
hand, residual sulfides are present in the mantle wedge, higher
Cu/Yb values in the arc-front lavas can be explained through
different oxidation states and related differences in silicate
1532 TIMM ET AL.
melt/sulfide ratio beneath the back and arc fronts (e.g.,
Richards, 2011).
Another process that can control the content of chalcophile
and siderophile element content is the dissolution of residual
sulfides in the mantle source. For example, Rehkaemper et
al. (1999) suggested that for dry mantle regimes, such as be-
neath MORs, sulfide dissolution and the related liberation of
platinum group elements (PGE) occurs at <20% partial melting
of the mantle assuming a columnar melting regime. Although
few Kermadec arc lavas are formed through ~20% melting,
most are formed by significantly lower degrees of partial
melting (i.e., ~1018%; Haase et al., 2002; Timm et al., 2011).
This argues against total sulfur consumption from the mantle
wedge beneath most of the Kermadec arc front. Similar and
even higher (Cu, Zn, V, Mo)/REE values in the arc-front
lavas, when compared with back-arc lavas and MORB, there-
fore suggest either an increase in enrichment of these ele-
ments in the mantle wedge from the back to the arc front, or
more oxidizing conditions in the arc front leading to increased
mass transfer from sulfide phases to the silicate melt.
Given the limited mobility of Zn and V in hydrous fluids,
these elements are likely to be released from the mantle
wedge. The most plausible mechanism controlling the vary-
ing enrichments in Zn and V elements in arc-front and back-
arc lavas (other than direct slab-related input) therefore, is
the different oxidation states of the parental mantle, which is
commonly lower in the back-arc than the arc-front mantle
(Jugo, 2009; Kelley and Cottrell, 2009; Wallace and Edmonts,
2011). Recent sulfur speciation melt inclusion data from the
southern Kermadec arc-front and Havre Trough back-arc
lavas show that olivine-hosted melt inclusions have similar
(Rumble II West, Rumble III, and Rumble IV) to higher
(Rumble II East) proportions of S6+ in lavas from the arc front
(~3090% S6+) compared to the back arc (~3055% S6+;
Wysoczanski et al., 2012), consistent with a similar to more
oxidized mantle beneath the arc front.
Most Kermadec arc basalts have high (Cu, V, Zn, Mo)/Yb
values and high ratios of highly fluid mobile to fluid-immobile
elements (e.g., Ba/La, Pb/Yb; Figs. 5, 6), but consistently low
ratios of fluid-immobile incompatible elements (e.g., Th/Yb;
La/(Sm,Yb)N; Nb/Zr; Figs. 57.). High Ba/La and Pb/Yb val-
ues have been attributed to predominantly slab-derived Ba
and Pb being added to the mantle wedge, via hydrous fluids
(e.g., Elliot et al., 1997; Kessel et al., 2005). Possible sources
of these chalcophile and siderophile elements within the slab
are sediment, altered oceanic crust, and serpentenized up-
permost lithosphere.
Sediments sampled from DSDP Site 204 (west of the
southern Tonga trench; Turner et al., 1997; Fig. 1) and sea-
water-altered Cretaceous oceanic crust sampled from the
Osbourn trough (Worthington et al., 2006; Fig. 1) have Cu
and Zn contents up to 374 and 651 ppm, respectively, sug-
gesting a possible source for these elements in addition to
the sub-arc mantle wedge. However, the Cu and Zn content
of subducted sediment notably decreases southward along
the arc due to the increasing input of silica-rich, continen-
tally derived sediment from New Zealand (Gamble et al.,
1996). For example, the relatively low Cu and Zn contents of
sediments sampled between 30 and 38S (<121 ppm; Gam-
ble et al., 1996) suggests that enrichment of these elements
0361-0128/98/000/000-00 $6.00
in the mantle source is not directly related to their concen-
tration in the slab.
The chalcophile elements As, Sb, Tl, and Bi are strongly
mobile in hydrous fluids under oxidizing mantle conditions
(e.g., Jochum and Verma, 1996; Noll et al., 1996; Jochum and
Hofmann, 1997). All are enriched in pelagic sediments (e.g.,
Maher, 1984; Rouxel et al., 2003; Rehkaemper et al., 2004),
seawater-altered MORB (Jochum and Verma, 1996), serpen-
tinites (Hattori and Guillot, 2003, 2007) and peridotites that
have experienced subduction-related metasomatism (e.g.,
Ishimaru and Arai, 2008). Higher ratios of fluid-mobile to fluid-
immobile elements (e.g. Ba/La, Pb/Yb, Sr/Nd (not shown),
Sb/Pr, As/Ce, Tl/La (not shown); Fig. 5; and Bi/Nd; Fig. 6) in
Kermadec arc lavas when compared with MORB are consis-
tent with the addition of largely fluid-transported chalcophile
elements such as Pb, Sr, Sb, As, Bi, and Tl from the slab to the
melting region beneath the arc front. Ratios of Ba/La, Sb/Pr,
As/Ce, Bi/Nd, and Pb/Yb for moderately mafic lavas (i.e., MgO
>4 wt %) vary along the arc, suggesting slightly varied fluid
activity and/or slab composition, as previously recognized by
Haase et al. (2002). The more evolved lavas (i.e., SiO2 >70 wt
%) trend toward higher fluid-mobile/fluid-immobile ratios that
likely also reflect an increase in incompatible chalcophile and
siderophile elements during fractional crystallization. Mafic
lavas (i.e., MgO > 5 wt %) of the southern Tonga-Kermadec arc
have concentrations of Sn and Ag (see Fig. 4) and the HFSE
(e.g., REE, Zr, Y, Hf) that overlap with MORB. Sn/Yb is lower
than MORB and Ag/Yb (Fig. 6) is generally similar to MORB,
suggesting little or no transport of slab-derived Sn and Ag into
the mafic arc-front lavas (Fig. 6). Hydrous fluids therefore ap-
pear to have little or no influence on Ag and Sn being released
from residual mantle wedge sulfides beneath the Kermadec arc.
Chemically anomalous Brothers volcanic center dacites
Brothers dacites have anomalous trace element composi-
tions when compared with other Kermadec lavas; they have
significantly higher concentrations of highly to moderately in-
compatible elements such as K, Pb, Th, Tl, Ba, U, Rb, Ag, Be,
LREE, Hf, Nb, Zr and to a lesser extent Na, Bi, Cs, Li, Mo,
Pb, and MREE. This in turn means that Brothers dacites
have relatively elevated ratios of highly to moderately incom-
patible elements (e.g. Nb/Zr, Ba/La, Th/Yb, Mo/Yb, Bi/Nd,
La/Sm). Haase et al. (2006) attributed this enrichment to ex-
treme fractional crystallization of a parental basaltic magma,
rather than remelting of lower crustal amphibolite. However,
the higher Rb/Sr, Nb/Zr, Ba/La, K/Rb, La/Sm, Sm/Yb, and
Th/Yb values can also be explained through partial melting of
amphibole/phlogopiterich hydrous veins/cumulates in the
mantle and/or lower crust. Amphiboles are rich in Rb, Nb, Ba,
and K and may also act as a sponge for other elements (e.g.
Ionov et al., 1996; Tiepolo et al., 2007). Irrespective of magma
formation beneath Brothers, the strong enrichment of highly
to moderately incompatible elements requires either input of
these elements into the sub-arc mantle or the presence of an
enriched component in the ambient mantle or crust beneath
this volcanic center. Hydrous fluids have limited ability to
transport LREE, but cannot mobilize HFSE such as Nb, Zr,
MREE, and Th. These elements are more effectively trans-
ported via hydrous melts, supercritical fluids, or added
through bulk mixing. Partial melting of altered oceanic crust
1532
 SOURCES OF CHALCOPHILE AND SIDEROPHILE ELEMENTS IN KERMADEC ARC LAVAS 1533

0.05
a) d)
0.9
BAB 0.04

+ sediment
0.7 MORB

melt
0.03
Th/Yb

Nb/Zr
0.5
BAB 0.02
0.3
0.01
0.1 MORB

b) e) Potutu
As/Cemax = 1.6 0.7

100
0.5
+ hydrous

+ hydrous
Ba/La

As/Ce
fluid

fluid
0.3
50

0.1

c) f)
4
0.3
+hydrous
fluid or
melt

+ hydrous

Sb/Pr
fluid
Pb/Yb

0.2
2

0.1
1

0 0
20 25 30 35 25 30 35 40
Latitude (S) Latitude (S)
Monowai Gamble Brothers LEsperance* Rumble IV*
Monowai Putoto Raoul group Volcanolog* Rumble V*
Hinepuia Hinetapeka Macauley Sonne Smt* Tangaroa
Rakahore Brothers Curtis Island Rumble III* Clark*

FIG. 5. Along arc variation of (a) Th/Yb, (b) Ba/La, (c) Pb/Yb, (d) Nb/Zr, (e) As/Ce, and (f) Sb/Pr. The gray dotted line
marks average MORB composition (Sun and McDonough, 1989; Noll et al., 1996; Jochum and Hofmann, 1997), whereas
the solid gray line marks the average composition of southern Lau Basin/Havre Trough back-arc basalts (BAB; Haase et al.,
2002; Todd et al., 2011).

commonly results in elevated (LREE, MREE)/HREE) and
Sr/Y, as well as high concentrations of Al (e.g., Martin, 1999;
Bindemann et al., 2005; Condie, 2005) that are not observed
in the Brothers dacites. Of note are the sulfide Cu, Pb, and
Zn data for Brothers and Clark volcanoes which plot in the
field for continental crust-derived VMS deposits (cf. the
field for oceanic crust-derived deposits, which might have
been expected), consistent with the inferred continental sig-
nature of the sediments subducted beneath the southern Ker-
madec arc (de Ronde et al., 2005).

0361-0128/98/000/000-00 $6.00 1533

1534 TIMM ET AL.

150
a) d) 1.4

1.2

100 1.0
Cu/Yb

0.8

Mo/Yb
0.6
50
BAB 0.4

0.2
MORB

b) e) Hinepuia
Ag/Ybmax = 0.022
250

0.01

Ag/Yb
V/Yb

150

0.005

50

c) f)
50 0.4

0.3
Zn/Yb

Bi/Nd*100
30 0.2

0.1

10 0
20 25 30 35 25 30 35 40
Latitude (S) Latitude (S)
Monowai Gamble Brothers LEsperance* Rumble IV*
Monowai Putoto Raoul group Volcanolog* Rumble V*
Hinepuia Hinetapeka Macauley Sonne Smt* Tangaroa
Rakahore Brothers Curtis Island Rumble III* Clark*

FIG. 6. Along arc variations of (a) Cu/Yb, (b) V/Yb, (c) Zn/Yb, (d) Mo/Yb, (e) Ag/Yb, and (f) Bi/Nd*100. The gray dotted
line marks the average composition of MORB (Hertogen et al., 1980; Sun and McDonough, 1989; Yi et al., 2000; Jenner et
al, 2010), whereas the solid gray line marks the average composition of southern Lau Basin/Havre Trough back-arc basalts
(BAB; Haase et al., 2002). Yb and Nd values used for Ag/Yb, Cu/Yb, and Bi/Nd ratios represent average Pacific MORB de-
rived from the PetDB and Georoc databases (where MgO >5 wt %). Note that Cu/Yb, Zn/Yb, and V/Yb values are not shown
for SiO2 >55 wt % to avoid the effect of magnetite crystallization.

It has been suggested that Th can only be mobilized in hy- addition of Th-rich sedimentary components to the mantle
drous melts and supercritical fluids (e.g., Elliot et al., 1997; wedge. In addition, high Ag (0.3 ppm) and Mo (67 ppm)
Kessel et al., 2005) and therefore is a sensitive tracer for the concentrations have been observed in Pacific Ocean pelagic

0361-0128/98/000/000-00 $6.00 1534

 SOURCES OF CHALCOPHILE AND SIDEROPHILE ELEMENTS IN KERMADEC ARC LAVAS 1535

3
a) d)

+hydrous
70

fluids
Marine Sediments
2

La/SmN
Sr/Nd
50 BAB

BAB
30
+sediment +sediment 1

s
iment
10 e Sed
MORB Marin MORB

+hydrous fluids b) e) Marine Sediments

(Avg. Ag/Yb = 0.09)

100 0.01
Cu/Yb

Ag/Yb
FC

+sediment

50 0.005
Marine Sediments
+sediment
MORB

1.5
c) f) Marine Sediments
250 (Avg. Mo/Yb = 5.04)
+hydrous
+hydrous

FC

fluids?

200 +sediment 1.0

fluids
V/Yb

Mo/Yb
150

100 0.5
Marine Sediments
+sediment
50
BAB

0
0.0 0.5 1.0 1.5 0.5 1.0 1.5 2.0
Th/Yb Th/Yb
Monowai Gamble Brothers LEsperance* Rumble IV*
Monowai Putoto Raoul group Volcanolog* Rumble V*
Hinepuia Hinetapeka Macauley Sonne Smt* Tangaroa
Rakahore Brothers Curtis Island Rumble III* Clark*

FIG. 7. Variations of (a) Sr/Nd, (b) Cu/Yb, (c) V/Yb, (d) La/SmN, (e) Ag/Yb, and (f) Mo/Yb. Gray and white fields repre-
sent MORB (Hertogen et al., 1980; Sun and McDonough, 1989; Yi et al., 2000; Jenner et al, 2010) and Havre Trough basalt
(BAB; Haase et al., 2002) data, respectively. The field bound by the dotted line is for marine sediments (Turner et al., 1997;
DSDP Site 204; Gamble et al., 1996). Marine sediment data (averages) are from Koide et al. (1986; Ag) and Turner et al.
(1997; Mo); average Yb is after Turner et al. (1997). FC = fractional crystallization. Hydrous fluid addition does not affect
the Th/Yb value. FC vector is based on decreasing Sr, Cu, and V at SiO2 >55 wt %.

sediments (Koide et al., 1986; Turner et al., 1997). As the
Brothers dacites have significantly higher Th/Yb, Ag/Yb, and
Mo/Yb, together with high La/SmN and Sn/Yb, the most likely
candidate for the high Ag-Mo-Th-LREEbearing end mem-
ber at Brothers is, therefore, subducted sediment. A sedi-
mentary influence on the mantle source beneath Brothers is
supported by glass analyses of recently discovered basaltic-
andesite dikes which show significantly higher La/SmN and
Th/Yb values and HFSE, K, Pb, Cu, V, and Mo concentra-
tions than other basaltic andesites from the Kermadec arc.
Despite the high concentrations of Pb, Sn, Mo, Ag, and Bi
in Brothers dacites, concentrations of Cu, Zn, and V are sig-
nificantly lower than in mafic lavas elsewhere along the arc.
However, limited melt inclusions studies of plagioclase from
Brothers lavas show glass and/or melt concentrations of ~1%
H2O, ~550 ppm F, ~5,000 ppm Cl, and ~70 ppm S, with some

0361-0128/98/000/000-00 $6.00 1535

1536 TIMM ET AL.
inclusions significantly enriched in Cu, up to 45 to 60 ppm
(de Ronde et al., 2011). The irregular distribution of Cu in
the melt inclusions, when combined with this element having
the greatest variability of all the trace elements analyzed
(57%), points to the mobility of Cu in the Brothers magma
phenocrysts. Thus, the higher contents of most chalcophile
and siderophile elements in the Brothers dacites, if compared
to other dacites along the arc, may indicate a preferential loss
of Cu in magmatic fluids exsolved through degassing of
dacitic melts prior to eruption (de Ronde et al., 2011). This
may be an important mechanism for the transfer of Cu and
other chalcophile and siderophile elements from the melt to
the seafloor and ultimately the formation of Cu-Au VMS de-
posits. Basaltic-andesitic dikes that underlie the main edifice
at Brothers could provide additional Cu, Mo (+Au) and V
(Zn) and heat aiding in the formation of VMS mineraliza-
tion; a possible deep-seated basaltic magma reservoir has
been identified at Brothers from gases dissolved in vent fluids
(de Ronde et al., 2011). Irrespective, the anomalously high
contents of chalcophile and siderophile elements in the
Brothers dacites require significant input from the subducting
slab, with transport most likely via hydrous sediment melts
and/or high-temperature supercritical fluids in addition to the
usual hydrous fluid-related sub-arc mantle enrichments.
Conclusions
Lavas from seven volcanic centers along the Kermadec arc
show Cu, V, Zn, Mo, Sb, As, and Bi enrichment, with Ag and
Sn depletion, when compared with MORB. High fluid-mo-
bile to fluid-immobile element ratios (e.g., Pb/Yb, Ba/La,
As/Ce, Sb/Pr) in mafic lavas (MgO >5 wt %) from the arc
front, together with high (Cu, Zn, V and Mo)/Yb values, sug-
gest a mantle source region metasomatized and oxidized via
fluid input from the subducting slab. Fluid-mobile to fluid-
immobile element ratios and (Cu, Zn, V, Mo)/Yb values higher
than MORB increase between back-arc (i.e., Havre Trough)
and Kermadec arc-front mafic lavas, consistent with either in-
creasing slab input of Cu, Zn, V, and Mo (and As, Sb, Tl Bi)
or more oxidizing conditions in the melt source region.
Dacites from the Brothers volcanic center of the southern
Kermadec arc show much higher concentrations of fluid im-
mobile chalcophile and siderophile elements (e.g., Th,
LREE, MREE, Sn, Ag, Mo, Nb, Zr, Y, Hf) and higher values
of, for example, Hf/Yb, LREE/(MREE,HREE), and Th/Yb
than do other dacites along the arc. These trace element char-
acteristics are best explained by the input of hydrous sedi-
ment melt into the mantle source beneath Brothers. We con-
clude, therefore, that Cu (and Au), Zn, V, and Mo (+Sb, As,
Bi, Tl) are added to the mantle wedge in hydrous fluids from
subducted sediment and/or altered oceanic crust, whereas Ag
and Sn are mobilized via sediment partial melting, bulk mix-
ing between the slab and the mantle wedge, or by solute-rich
supercritical fluids.
Acknowledgments
J. E. Mungall and I. E. M. Smith are thanked for thorough
and constructive reviews that helped improve the manuscript.
D. A. Butterfield is also thanked for editorial handling and ad-
ditional very helpful comments. This research is supported by
Mineral Wealth Core Science Area funding at GNS Science
0361-0128/98/000/000-00 $6.00 1536
via the New Zealand Ministry for Science and Innovation
(MSI).
REFERENCES
Albarade, F., and Michard, A., 1986, Transfer of continental Mg, S, O, and U,
to the mantle through hydrothermal alteration of the oceanic crust: Chem-
ical Geology, v. 57, p. 115.
Alt, J., C., Shanks, W.C., III, and Jackson, M.C., 1993, Cycling of sulfur in
subduction zones: The geochemistry of sulfur in the Mariana Island arc and
back-arc through: Earth and Planetary Science Letters, v. 119, p. 477494.
Bindeman, I.N., Eiler, J.M., Yogodzinski, G.M., Tatsumi, Y., Stern, C.R.,
Grove, T.L., Portnyagin, M., Hoernle, K., and Danyushevsky, L.V., 2005,
Oxygen isotope evidence for slab melting in modem and ancient subduc-
tion zones: Earth and Planetary Science Letters, v. 235, p. 480496.
Blundy, J., and Wood, B., 2003, Partitioning of trace elements between crys-
tals and melts: Earth and Planetary Science Letters, v. 210, p. 383397.
Carroll, M.R., and Rutherford, M.J., 1985, Sulfide and sulfate saturation in
hydrous silicate melts: Journal of Geophysical Research, v. 90, p. 601612.
Clift, P.D., Rose E.F., Shimizu, N., Layne, G.D., Draut, A.E., and Regelous,
M., 2001, Tracing the evolving flux from the subducting plate in the Tonga-
Kermadec arc system using boron in volcanic glass: Geochimica et Cos-
mochimica Acta, v. 65, p. 33473364, doi:10.1016/S0016-7037(01)00670-6
Condie, K., 2005, TTGs and adakites: Are they both slab melts?: Lithos, v. 80,
p. 3344, doi:10.1016/j.lithos.2003.11.001
de Hoog, J.C.M., Mason, P.R.D., and Van Bergen, M.J., 2001, Sulfur and
chalcophile elements in subduction zones: Constraints from a laser ablation
ICP-MS study of melt inclusions from Galunggung Volcano, Indonesia:
Geochimica et Cosmochimica Acta, v. 65, p. 31473164.
DeMets, C., Gordon, R.G., Argus, D.F., and Stein, S., 1994, Effect of recent
revisions to the geomagnetic reversal time scale and estimates of current
plate motions: Geophysical Research Letters, v. 21, p. 21912194, doi:
10.1029/94GL02118
de Ronde, C.E.J., 2006, Mineralization associated with submarine volcanoes
of the southern Kermadec arc, New Zealand: Australasian Institute of Min-
ing and Metallurgy Monograph 25, p. 333338.
de Ronde, C.E.J., Baker, E.T., Massoth, G.J., Lupton, J.E., Wright, I.C.,
Feely, R.A., and Greene, R.R., 2001, Intra-oceanic subduction-related
hydrothermal venting, Kermadec volcanic arc, New Zealand: Earth and
Planetary Science Letters, v. 193, p. 359369.
de Ronde, C.E.J., Faure, K., Bray, C.J., Chappell, A., and Wright, I. C., 2003,
Hydrothermal fluids associated with seafloor mineralization at two south-
ern Kermadec arc volcanoes, offshore New Zealand: Mineralium Deposita,
v. 38, p. 217233.
de Ronde, C.E.J., Hannington, M.D., Stoffers, P., Wright, I.C., Ditchburn,
R.G., Reyes, A.G., Baker, E.T., Massoth, G.J., Lupton, J.E., Walker, S.L.,
Greene, R.R. Soong, C.W.R., Ishibashi, J., Lebon, G.T., Bray, C.J., and
Resing, J.A., 2005, Evolution of a submarine magmatic-hydrothermal sys-
tem: Brothers Volcano, southern Kermadec arc, New Zealand: ECONOMIC
GEOLOGY, v. 100, p. 10971133.
de Ronde, C.E.J., Baker, E.T., Massoth, G.J., Lupton, J.E., Wright, I.C.,
Sparks, R.J., Bannister, S.C., Reyners, M.E., Walker, S.L., Greene, R.R.,
Ishibashi, J., Faure, K., Resing, J.A., and Lebon, G.T., 2007, Submarine
hydrothermal activity along the mid-Kermadec arc, New Zealand: Large-
scale effects on venting: Geochemistry, Geophysics, Geosystems, v. 8,
Q07007, doi:10.1029/2006GC001495.
de Ronde, C.E.J., Massoth, G.J., Butterfield, D.A., Christenson, B.W.,
Ishibasi, J., Ditchburn, R.G., Hannington, M.D., Brathwaite, R.L., Lupton,
J.E., Kamenetsky, V.S., Graham, I.J., Zellmer, G.F., Dziak, R.P., Embley,
R.W., Dekov, L.J., Munnik, F., Lahr, J., Evans, L.J., and Takai, K., 2011,
Submarine hydrothermal activity and gold-rich mineralization at Brothers
Volcanoe, Kermadec arc, New Zealand: Mineralium Deposita, doi
10.1007/s00126-011-0345-8.
Duncan, R.A., and Clague, D.A., 1985, Pacific Plate motion recorded by
linear volcanic chains, in Nairn, A.E.M., Stehli, F.G., and Uyeda, S., eds.,
The ocean basins and margins, 7A: The Pacific: New York, Plenum, p.
89121.
Eggins, S.M., Rudnick, R.L., and McDonough, W.F., 1998, The composition
of peridotites and their minerals: A laser-ablation ICP-MS study: Earth and
Planetary Science Letters, v. 154, p. 5371.
Elliot, T., Plank, T., Zindler, A., White, W., and Bourdon, B., 1997, Element
transport from slab to volcanic front at the Mariana arc: Journal of Geo-
physical Research, v. 102, p. 14,99115,019.
 SOURCES OF CHALCOPHILE AND SIDEROPHILE ELEMENTS IN KERMADEC ARC LAVAS
Ewart, A., Collerson, K.D., Regelous, M., Wendt, J.I., and Niu, Y., 1998,
Geochemical evolution within the Tonga-Kermadec-Lau arc-back-arc sys-
tems: The role of varying mantle wedge composition in space and time:
Journal of Petrology, v. 39, p. 331368.
Gamble, J., Woodhead, J., Wright, I., and Smith, I., 1996, Basalt and sedi-
ment geochemistry and magma petrogenesis in a transect from oceanic is-
land arc to rifted continental margin arc: The Kermadec-Hikurangi margin,
SW Pacific: Journal of Petrology, v. 37, p. 15231546.
Gamble, J.A., Christie, R.H.K., Wright, I.C., and Wysoczanski, R.J., 1997, Prim-
itive K-rich magmas from Clark Volcano, southern Kermadec arc: A para-
dox in the K-depth relationship: Canadian Mineralogist, v. 35, p. 275290.
Graham, I.J., Reyes, A.G., Wright, I.C., Peckett, K.M., Smith, I.E.M., and
Arculus, R.J., 2008, Structure and petrology of newly discovered volcanic
centers in the northern Kermadec-southern Tofua arc, South Pacific Ocean:
Journal of Geophysical Research, v. 113, B08S02, doi:10.1029/2007JB005453.
Grgoire, M., McInnes, B.I.A., and OReilly, S.Y., 2001, Hydrous metasoma-
tism of oceanic sub-arc mantle, Lihir, Papua New Guinea, Part 2. Trace el-
ement characteristics of slab-derived fluids: Lithos, v. 59, p. 91108.
Haase, K.M., Worthington, T.J., Stoffers, P., Garbe-Schoenberg, D., and
Wright, I., 2002, Mantle dynamics, element recycling, and magma genesis
beneath the Kermadec arc-Havre Trough: Geochemistry, Geophysics,
Geosystems, v. 3, 1071, doi:10.1029/2002GC000335
Haase, K.M., Stroncik, N., Garbe-Schoenberg, D., and Stoffers, P., 2006,
Formation of island arc dacite magmas by extreme crystal fractionation: An
example from Brothers Seamount, Kermadec island arc (SW Pacific): Jour-
nal of Volcanology and Geothermal Research, v. 152, p. 316330.
Hamlyn, P.R., Keays, R.R., Cameron, W.E., Crawford, A.J., and Waldron,
H.M., 1985, Precious metals in magneian low-Ti lavas: Implications for
metallogenesis and sulfur saturation in primary magmas: Geochimica et
Cosmochimica Acta, v. 49, p. 17971811.
Hattori, K.H., and Guillot, S., 2003, Volcanic fronts form as a consequence of ser-
pentine dehydration in the forearc mantle wedge: Geology, v. 31, p. 525528.
2007, Geochemical character of serpentines associated with high- to ul-
trahigh-pressure metamorphic rocks in the Alps, Cuba, and the Himalayas:
Recycling of elements in subduction zones: Geochemistry, Geophysics,
Geosystems, v. 8, p. 127.
Hertogen, J., Janssens, M.-J., and Palme, H., 1980, Trace elements in ocean
ridge basalt glasses: Implications for fractionations during mantle evolution
and petrogenesis: Geochimica et Cosmochimica Acta, v. 44, p. 21252143.
Hofmann, A.W., Jochum, K.P., Seufert, M., and White, W.M., 1986, Nb and
Pb in oceanic basalts: New constraints on mantle evolution: Earth and
Planetary Science Letters, v. 79, p. 3345.
Ionov, D.A., Griffin, W.L., and OReilley, S.Y., 1996, Volatile-bearing miner-
als and lithosphile trace elements in the upper mantle: Chemical Geology,
v. 141, p. 153184.
Isacks, B.L., and Barazangi, M., 1977, Geometry of Benioff zones: Lateral seg-
mentation and downwards bending of the subducted lithosphere, in Taiwani,
M., and PitmanW.C., III, eds., Island arcs deep sea trenches and back-arc
basins, Maurice Ewing Series, vol. 1: Washington, C.C., AGU, p. 99114.
Ishimaru, S., and Arai, S., 2008, Arsenide in a metasomatized peridotite
xenolith as a consequence on arsenic behavior in the mantle wedge: Amer-
ican Mineralogist, v. 93, p. 10611065.
Jenner, F.E., ONeill, H.C.S., Arculus, R.J., and Mavrogenes, J.A., 2010, The
magnetite crisis in the evolution of arc-related magmas and the initial con-
centration of Au, Ag and Cu: Journal of Petrology, v. 51, p. 24452464.
Jochum, K.P., and Hofmann, A.W., 1997, Constraints on earth evolution from
antimony in mantle-derived rocks: Chemical Geology, v. 139, p. 3949.
Jochum, K.P., and Verma, S.P., 1996, Extreme enrichment of Sb, Tl and other
trace elements in altered MORB: Chemical Geology, v. 130, p. 289299.
Jugo, P.J., 2009, Sulfur content at sulfur saturation in oxidized magmas: Ge-
ology, v. 37, p. 415418.
Kelley, K.A., and Cottrell, E., 2009, Water and the oxidation state of subduc-
tion zone magmas: Science, v. 325, p. 605607.
Kepezhinskas, P., Defant, M, and Widom, E., 2002, Abundance and distrib-
ution of PGE and Au in the island-arc mantle: Implications for sub-arc
metasomatism: Lithos, v. 60, p. 113128.
Kessel, R., Schmidt, M.W., Ulmer, P., and Pettke, T., 2005, Trace element
signature of subduction-zone fluids, melts and supercritical liquids at
120180 km depth: Nature, v. 437, p. 724727.
Kogiso, T., Tatsumi, Y., and Nakano, S., 1997, Trace element transport dur-
ing dehydration processes in the subducted oceanic crust.1. Experiments
and implications for the origin of ocean island basalts: Earth and Planetary
Science Letters, v. 148, p. 193205.
0361-0128/98/000/000-00 $6.00
1537
Koide, M., Hodge, V.F., Yang, J.S., Stallard, M., Goldberg, E.G., Calhoun, J.,
and Bertine, K.K., 1986, Some comparative marine chemistries of rhenium,
gold, silver and molybdenum: Applied Geochemistry, v. 1, p. 705714.
Leybourne, M.I., Schwarz-Schampera, U., de Ronde, C.E.J., Baker, E.T.,
Faure, K., Walker, S.L., Butterfield, D.A., Resing, J.A., Lupton, J.E., Han-
nington, M.D., Gibson, H.L., Massoth, G.J., Embley, R.W., Chadwick, Jr.,
W.W., Clark, M.R., Timm, C., Graham, I.J., and Wright, I.C., 2012, Sub-
marine magmatic-hydrothermal systems at the Monowai volcanic center,
Kermadec arc: ECONOMIC GEOLOGY, v. 107, p. 16691694.
Leybourne, M.I., de Ronde, C.E.J., Wysoczanski, R.J., Walker, S.L., Timm,
C., Gibson, H.L., Layton-Matthews, D., Baker, E.T., Clark, M.R., Caratori
Tontini, F., Faure, K., Lupton, J.E., Fornari, D.J., Soule, S.A., and Massoth,
G.J., 2012, Geology, hydrothermal activity, and sea-floor massive sulfide
mineralization at the Rumble II west mafic caldera: ECONOMIC GEOLOGY,
v. 107, p. 16491668.
Le Maitre, R.W., ed., Streckeisen, A., Zanettin, B., Le Bas, M.J., Bonin, B.,
Bateman, P., Bellieni, G., Dudek, A., Efremova, S., Keller, J., Lamere, J.,
Sabine, P.A., Schmid, R., Srensen, H., and Woolley, A.R., 2002, in Igneous
rocks: A classification and glossary of terms, recommendations of the In-
ternational Union of Geological Sciences, Subcommission of the Systemat-
ics of Igneous Rocks, 2nd ed.: Cambridge, U.K., New York, Cambridge Uni-
versity Press, 236 p.
Maher, W.A., 1984, Mode and occurrence and speciation of arsenic in some
pelagic and estuarine sediments: Chemical Geology, v. 47, p. 333345.
Martin, H., 1999, Adakitic magmas: Modern analogues of Archaean grani-
toids: Lithos, v. 46, p. 411429.
McInnes, B.I.A., McBride, J.S., Evans, N.J., Lambert, D.D., and Andrew,
A.S., 1999, Osmium isotope constraints on ore metal recycling in subduc-
tion zones: Science, v. 286, p. 512516.
Mtrich, N., Schiano, P., Clocchiatti, R., and Maury, R.C., 1999, Transfer
of sulfur in subduction settings: An example from Batan Island (Luzon
volcanic arc, Phillipines): Earth and Planetary Science Letters, v. 167, p.
114.
Mungall, J.E., 2002. Roasting the mantle: Slab melting and the genesis of
major Au and Au-rich Cu deposits: Geology, v. 30, p. 915918.
Noll, P.D.J., Newsom, H.E., Leeman, W.P., and Ryan, J.G., 1996, The role of
hydrothermal fluids in the production of subduction zone magmas: Evi-
dence from siderophile and chalcophile trace elements and boron:
Geochimica et Cosmochimica Acta, v. 60, p. 587611.
Plank, T., and Langmuir, C.H., 1998, The chemical composition of subduct-
ing sediment and its consequences for the crust and mantle: Chemical Ge-
ology, v. 145, p. 325394.
Regelous, M., Gamble, J.A., and Turner, S.P., 2010, Mechanism and timing
of Pb transport from subducted oceanic crust and sediment to the mantle
source of arc lavas: Chemical Geology, v. 273, p. 4654.
Rehkaemper, M., Halliday, A.N., Fitton, J.G., Lee, D.-C., Wieneke, M., and
Arndt, N., 1999, Ir, Ru, Pt, and Pd in basalts and komatiites: New con-
straints for geochemical of platinum group elements in the mantle:
Geochimica et Cosmochimica Acta, v. 63, p. 39153934.
Rehkaemper, M., Frank, M., Hein, J.R., and Halliday, A.N., 2004, Cenozoic
marine geochemistry of thallium deduced from isotopic studies of ferro-
manganese crusts and pelagic sediments: Earth and Planetary Science Let-
ters, v. 219, p. 7791.
Richards, J.P., 2003, Tectono-magmatic precursors for porphyry Cu-(Mo-Au)
deposit formation: ECONOMIC GEOLOGY, v. 98, p. 15151533.
2011, Magmatic to hydrothermal metal fluxes in convergent and col-
lided margins: Ore Geology Reviews, v. 40, p. 126.
Rouxel, O., Ludden, J., and Fouquet, Y., 2003, Antimony isotope variations
in natural systems and implications for their use as geochemical tracers:
Chemical Geology, v. 200, p. 2540.
Ruepke, L.H., Morgan, J.P., Hort, M., and Connolly, J.A.D., 2004, Serpen-
tine and the subduction zone water cycle: Earth and Planetary Science Let-
ters, v. 223, p. 1734.
Sillitoe, R.H., 1973, The tops and bottoms of porphyry copper deposits: ECO-
NOMIC GEOLOGY v. 68, p. 799815.
Smith, I.E.M., Price, R.C., Stewart, R.B., and Worthington, T.J., 2009, An as-
sessment of the mantle and slab components in the magmas of an oceanic
arc volcano: Raoul Volcano, Kermadec arc: Journal of Volcanology and
Geothermal Research, v. 184, p. 437450.
Spandler, C., Hermann, J., Arculus, R., and Mavrogenes, J., 2004, Geochem-
ical heterogeneity and element mobility in deeply subducted oceanic crust:
Insights from high-pressure mafic rocks from New Caledonia: Chemical
Geology, v. 206, p. 2142.
1537
1538 TIMM ET AL.
Stix, J., Kennedy, B., Hannington, M., Gibson, H., Fiske, R., Mueller, W., and
Franklin, J., 2003, Caldera-forming processes and the origin of submarine
volcanogenetic massive sulfide deposits: Geology, v. 31, p. 375378.
Stolper, E., and Newman, S., 1994, The role of water in the petrogenesis of
Mariana trough magmas: Earth and Planetary Science Letters, v. 121, p.
293325.
Sun, S.S., and McDonough, W.F., 1989, Chemical and isotopic systematics of
ocean basalts: Implications for mantle composition and processes, in Saun-
der, A.D., and Norry, M.J., eds., Magmatism in the ocean basins: Geologi-
cal Society of London, p. 313345.
Sun, W., Arculus, R.J., Kamenetsky, V.S., and Binns, R.A., 2004, Release of
gold-bearing fluids in convergent margin magmas prompted by magnetite
crystallization: Nature, v. 431, p. 975978.
Sutherland, R., Collot, J., Lafoy, Y., Logan, G.A., Hackney, R., Stagpoole, V.,
Uruski, C., Hashimoto, T., Higgins, K., Herzer, R.H., Wood, R., Mortimer,
N., and Rollet, N., 2010, Lithospheric delamination with foundering of
lower crust and mantle caused permanent subsidence of New Caledonia
trough and transient uplift of Lord Howe Rise during Eocene and
Oligocene initiation of Tonga-Kermadec subduction, western Pacific: Tec-
tonics, v. 29, p. 16.
Tiepolo, M., Oberti, R., Zanetti, A., Vannucci, R., and Foley, S.F., 2007,
Trace-element partitioning between amphibole and silicate melts: Annual
Reviews in Mineralogy and Geochemistry, v. 67, p. 417452.
Timm, C., Graham, I.J., de Ronde, C.E.J., Leybourne, M.I., and Woodhead,
J., 2011, Geochemical evolution of Monowai: New insights into the north-
ern Kermadec arc subduction system, SW Pacific: Geochemistry, Geo-
physics, Geosystems, v. 12, Q0AF01, doi:10.1029/2011GC003654
Todd, E., Gill, J.B., Wysoczanski, R.J., Hergt, J., Wright, I.C., Leybourne,
M.I., and Mortimer, N., 2011, Hf isotopic evidence for small-scale hetero-
geneity in the mode of mantle wedge enrichment: Southern Havre Trough
and South Fiji Basin back arcs: Geochemistry, Geophysics, Geosystems, v.
12, Q09011, doi:10.1029/2011GC003683
Togashi, S., and Terashima, S., 1997, The behavior of gold in unaltered island
arc tholeiitic rocks from Izu-Oshima, Fuji, and Osoreyama volcanic areas,
Japan: Geochimica et Cosmochimica Acta, v. 61, p. 543554.
0361-0128/98/000/000-00 $6.00 1538
Turner, S., and Hawkesworth, C., 1997, Constraints on flux rates and mantle
dynamics beneath island arcs from Tonga-Kermadec lava geochemistry:
Nature, v. 389, p. 568573.
Turner S., Hawkesworth C., Rogers N., Bartlett J., Worthington T., Hergt, J.,
Pearce, J, and Smith I.E.M. 1997, 238U-230Th disequilibria, magma petro-
genesis and flux rates along the depleted Tonga-Kermadec island arc:
Geochimica et Cosmochimica Acta, v. 61, p. 48554884.
Wallace, P.J., and Edmonts, M., 2011, The sulfur budget of magmas: Evi-
dence from melt inclusions, submarine glasses, and volcanic emissions: Re-
views in Mineralogy and Geochemistry, v. 73, p. 215246.
Wiens, D.A., Conder, J.A., and Fault, U.H., 2008. The seismic structure and
dynamics of the mantle wedge: Annual Review of Earth and Planetary Sci-
ences, v. 36, p. 421455.
Woodhead, J.D., Harmon, R.S., Fraser, D.G, 1987, O, S, Sr, and Pb isotope
variations in volcanic rocks from the Northern Mariana Islands: Implica-
tions for crustal recycling in intra-oceanic arcs: Earth and Planetary Science
Letters, v. 83, p. 3952.
Worthington, T.J., Hekinian, R., Stoffers, P., Kuhn, T., and Hauff, F., 2006,
Osbourn trough: Structure, geochemistry and implications of a mid-Creta-
ceous paleospreading ridge in the South Pacific: Earth and Planetary Sci-
ence Letters, v. 245, p. 685701.
Wysoczanski, R.J., Handler, M.R., Schipper, C.I., Leybourne, M.I., Creech,
J., Rotella, M.D., Nichols, A.R.L., Wilson, C.J.N., and Stewart R.B., 2012,
The tectonomagmatic source of ore metals and volatile elements in the
southern Kermadec arc: ECONOMIC GEOLOGY, v. 107, p. 15391556.
Yi, W., Halliday, A.N., Alt, J.C., Lee, D.-C., Rehkaemper, M., Garcia, M.O.,
Langmuir, C.H., and Su, L., 2000, Cadmium, indium, tin, tellurium, and
sulfur, in ocean basalt: Implications for chalcophile element fractionation in
the Earth: Journal of Geophysical Research, v. 105, p. B18,927B18,948.
Zajacz, Z., Seo, J.H., Candela, P.A., Piccoli, P.M., and Tossell, J.A., 2011, The
solubility of copper in high-temperature magmatic vapors: A quest for the
significance of various chloride and sulfide complexes: Geochimica et Cos-
mochimica Acta, v. 75, p. 28112827.