LITHOGEOCHEMISTRY OF VOLCANIC ROCKS ASSOCIATED WITH

VOLCANOGENIC MASSIVE SULPHIDE DEPOSITS AND

APPLICATIONS TO EXPLORATION
Stephen J. Piercey
Stephen J. Piercey Geological Consulting, 11 First Avenue, St. John’s, Newfoundland A1B 1N3
(also Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, Newfoundland A1B 3X5)

ABSTRACT
Volcanic lithogeochemistry is a powerful tool in the exploration for volcanogenic massive sulphide
(VMS) deposits. Primary lithogeochemical signatures associated with volcanic rocks (petrochemical signa-
tures) provide critical information on the petrogenetic history and tectonic setting of volcanic rocks, which
in turn provide information on the thermal and geodynamic regime in which a belt has formed. Combined
with stratigraphic context, the geochemistry of mafic and felsic rocks can be used to outline petrochemical
assemblages, which delineate potentially fertile from less fertile volcanic basins on a regional scale.
Once fertile areas are delineated, alteration lithogeochemistry can be utilized to elucidate the superim-
posed effects of VMS-associated hydrothermal alteration. Recharge zones and semi-conformable alteration
zones distal from mineralized zones (i.e. kms to 10s of kms) are characterized by patchy alteration and asso-
ciated Mg-Na-Ca-Fe±(Si,CO2) enrichments and metal depletions. In contrast, areas proximal to upflow or
discharge zones (i.e. proximal or pipe-like alteration) are characterized by strong Na-Ca-depletions and vari-
able enrichments in Fe, Mg, Si, K, metals±(CO2). The utilization of lithogeochemical data coupled with
mass balance calculations, normative mineral plots, alteration indexes, and excellent geological and geo-
physical control can allow one to identify what part of the VMS alteration system one is in.

INTRODUCTION 1983; Watanabe and Sakai, 1983; Cumming and Krstic,

Volcanogenic massive sulphide (VMS) deposits have
been, and continue to be, important contributors to the
Canadian and global economy. Many of these VMS
camps have been significant producers for millennia
(e.g. Iberian Pyrite Belt), and in many cases have con-
tributed to the development of nations (e.g. Canadian
and Australian VMS camps). Since the 1970s, litho-
geochemistry has been an important tool in the explo-
ration for VMS deposits with the majority of the early
studies in the 1970s and 1980s focusing on alteration
lithogeochemistry to outline alteration zones associ-
ated with VMS mineralization (e.g. Ishikawa et al.,
1976; Spitz and Darling, 1978; Date et al., 1983;
Gibson et al., 1983; Campbell et al., 1984; Lesher et
al., 1986a; Kranidiotis and MacLean, 1987; MacLean
and Kranidiotis, 1987; MacLean, 1988; Saeki and
Date, 1980) and to discriminate prospective from less
prospective VMS belts (e.g. Lesher et al., 1986b;
Paradis et al., 1988; Swinden et al., 1989). Fewer stud-
ies have concentrated on sedimentary and exhalative
rocks (e.g. Kalogeropoulos and Scott, 1983), mineral
chemistry (e.g. Urabe and Scott, 1983; Urabe et al.,
1983), and stable and radiogenic isotopes to assist in
the understanding of alteration systems and fluid- and
metal-source tracing (e.g. Kowalik et al., 1981;
Spooner and Gale, 1982; Farrell and Holland, 1983;
Fehn et al., 1983; Franklin et al., 1983; Green et al.,
1987; Schiffman and Smith, 1988).
The development of analytical technology has lead
to major breakthroughs in lithogeochemistry since the
1990s. One of the key advances has been the develop-
ment of the inductively coupled plasma mass spec-
trometer (ICP-MS) and more recently high-resolution
ICP-MS (HR-ICP-MS). Once primarily a research tool
in universities and government laboratories, the ICP-
MS has become commonplace in most commercial lab
facilities providing the ability to obtain high-quality
analytical data for over forty trace elements with rapid
turn-around times on a variety of matrices (e.g. rocks,
soils, waters, and biological materials) (Jenner et al.,
1990; Eggins et al., 1997; Sylvester, 2001; Günther and
Hattendorf, 2005, and references therein). The ICP-MS
has revolutionized lithogeochemistry applied to VMS
exploration and has led to major advancements in vol-
canic lithogeochemistry (e.g. Swinden, 1991, 1996;
Barrie et al., 1993b; Syme and Bailes, 1993; Barrett
and Sherlock, 1996; Kerrich and Wyman, 1997; Lentz,
1998; Syme, 1998; Syme et al., 1999; Wyman et al.,
1999; Piercey et al., 2001a,b; Galley, 2003; Hart et al.,
2004), alteration lithogeochemistry (e.g. Huston, 1993;
Barrett and MacLean, 1994a,b, 1999; Large et al.,
2001a,b), and sedimentary rock lithogeochemistry (e.g.
Peter and Goodfellow, 1996; Davidson et al., 2001;
Goodfellow et al., 2003; Peter, 2003). Furthermore, the
ICP-MS has allowed the utilization of a wider range of

Piercey, S.J., 2009, Lithogeochemistry of volcanic rocks associated with volcanogenic massive sulphide deposits and applications to explo-
ration, in Submarine Volcanism and Mineralization: Modern through Ancient, (eds.) B. Cousens and S.J. Piercey; Geological Association of
Canada, Short Course 29-30 May 2008, Quebec City, Canada, p. 15-40.
 S. J. Piercey

500-2000 m

hydrothermal plumes Mn,Ba

Fe Si
Zn
300ºC +Mg
Cu +K 10s to
Cu
+SO4 100s of
metres
Mg-metasomatism H2O/rock >1

alteration/stringer zone
H2 O/rock >>1 fracture/fault zones

upper semiconformable 100s of

alteration zone metres -Si
-Na
spillitization recharge zone -Ca
+Si
1-3 km

silicification impermeable barrier +Mg

+CO2
reservoir zone
H2 O/rock <1 -Cu
-Zn
-Fe
lower semiconformable +Si
alteration zone +Ca
+Na

400ºC
subvolcanic intrusion
15-30 km

Figure 3-1. Model for the setting and genesis of volcanogenic massive sulphide (VMS) deposits (from Galley, 1993; Franklin et al., 2005; Galley
et al., 2007).

trace elements in lithogeochemical exploration, includ-
ing the high field strength elements (HFSE) and rare
earth elements (REE), elements that were unavailable
to explorationists in the 1970s and 1980s, except at
prohibitively high costs and with low turn-around
times. Of particular importance has been the determi-
nation of Th-Nb-Ta and the REE at ultra-low levels,
particularly important for discriminating the tectonic
environments of ancient VMS successions (e.g. Lesher
et al., 1986b; Swinden, 1991; Barrie et al., 1993b;
Lentz, 1998; Syme et al., 1999; Piercey et al., 2001b,
2008; Piercey, 2007). Similarly, volatile metal species
(e.g. Tl, Sb, As) and ultra-low level values for indica-
tor elements (e.g. Mo, W) are also available now,
whereas they were not as easily accessible prior to ICP-
MS development.
The paper initially presents the nature of the VMS
target: the geological and tectonic setting, and
hydrothermal alteration attributes of the VMS system
from the regional to local scale. The manuscript then
provides an overview of the primary lithogeochemical
attributes of volcanic rocks associated with VMS
deposits, followed by an overview of lithogeochemical
attributes associated with the hydrothermal alteration
of volcanic rocks associated with VMS systems. In the
case of the former, these attributes provide key infor-
mation on the heat flow and tectonic environment of
VMS deposit formation, key features for area selection.
The latter provide information on the nature of fluid-
rock interaction and whether one is proximal to a min-
eralized zone and what part of a VMS system one is in.
The combination of both primary and secondary litho-
geochemical signatures provides powerful tools in the
exploration for VMS deposits.
THE TARGET: VOLCANOGENIC
MASSIVE SULPHIDE DEPOSITS AND
THEIR CLASSIFICATION
The essential elements of the VMS system are pro-
vided in Figure 3-1. Throughout Earth history, VMS
deposits formed, and continue to form, within exten-
sional geodynamic regimes, in particular rift environ-

16
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration
ments. These rift environments include mid-ocean
ridges, back-arc basins, intraoceanic arc rifts, and con-
tinental arc rifts (e.g. Swinden, 1991; Hannington et
al., 1995, 2005; Scott, 1997; Syme et al., 1999; Barrett
et al., 2001; Piercey et al., 2001b; Dusel-Bacon et al.,
2004). On a belt scale, VMS deposits are associated
with extensional grabens and calderas, synvolcanic and
synsedimentary faults, and significant variations in the
thickness of sedimentary and volcanic units proximal
to deposits (e.g. Gibson, 1989, 2005; Allen, 1992;
McPhie and Allen, 1992; Setterfield et al., 1995; Allen
et al., 1996; Gibson et al., 1999; Stix et al., 2003).
Synvolcanic and synsedimentary structures are com-
monly associated with felsic and mafic dyke swarms
that parallel the axis of the rift corridor (e.g. Gibson
and Watkinson, 1990; Setterfield et al., 1995; Gibson et
al., 1999) and are typically underlain by coeval synvol-
canic intrusive complexes (e.g. Campbell et al., 1981;
Galley, 1996, 2003). Dyke swarms and subvolcanic
intrusive complexes commonly have geochemical sig-
natures identical to the VMS-hosting volcanic
sequences (e.g. Galley, 1996, 2003; Barrett and
MacLean, 1999), and the subvolcanic intrusive com-
plexes are interpreted to be the heat pump that drove
hydrothermal circulation and potentially contributed
metals to the VMS hydrothermal system (e.g.
Campbell et al., 1981; Galley, 1996, 2003; Large et al.,
1996).
The generation of VMS deposits involves the draw-
down of cold seawater on the flanks of the rift axis, the
lateral transport of this fluid through the recharge zone
with progressive heating, the reduction of seawater sul-
phate to sulphide by fluid-rock interaction and/or sul-
phate loss owing to the retrograde solubility of anhy-
drite, the stripping of metals and sulphur from the wall
rocks, and the formation of semi-conformable alter-
ation (e.g. Franklin et al., 1981, 2005; Gibson et al.,
1983; Lydon, 1984; Large, 1992; Galley, 1993;
Skirrow and Franklin, 1994; Ohmoto, 1996).
Subsequent upwelling of fluids along synvolcanic and
synsedimentary structures through the discharge zone
results in the deposition of massive sulphide on the
seafloor or immediately beneath the rift, and below the
sulphides there is the formation of a high-temperature,
chlorite-(quartz)-rich alteration zone (Franklin et al.,
1981, 2005; Lydon, 1984; Large, 1992; Galley, 1993;
Ohmoto, 1996). In some VMS systems (e.g. Bathurst,
Finlayson Lake, Iberian Pyrite Belt), the fluids vent
into anoxic basins with abundant organic- and sulfur-
rich shale units, and these shale units record the anoxic
nature of the ambient environment of deposition (e.g.
Goodfellow and Peter, 1996; Goodfellow et al., 2003).
In other VMS districts (e.g. Bathurst, Noranda, Iberian
Pyrite Belt, Finlayson Lake, Windy Craggy), iron- and
metal-rich vent fluids exhaled onto the seafloor and
formed laterally extensive chemical sedimentary units
and iron formations (e.g. Kalogeropoulos and Scott,
1983; Duhig et al., 1992; Liaghat and MacLean, 1992;
Peter and Goodfellow, 1996; Leistel et al., 1997; Spry
et al., 2000; Davidson et al., 2001; Peter, 2003; Grenne
and Slack, 2005).
There are significant differences in the style and set-
ting of VMS deposits (e.g. Barrie and Hannington,
1999; Franklin et al., 2005; Galley et al., 2007) and this
has a significant influence on the primary lithogeo-
chemical signatures found in the VMS-associated vol-
canic rocks. Consequently, a brief note on VMS classi-
fication is warranted. Volcanogenic massive sulphide
deposits have been variously classified, but the most
robust, from a regional perspective, are non-genetic
and based on their host-rock assemblages (Barrie and
Hannington, 1999; Franklin et al., 2005; Galley et al.,
2007). These authors have classified VMS deposits
into the following five groups.
1) Mafic: deposits associated with mafic-dominated
assemblages, commonly ophiolitic. The deposits of
Cyprus, Oman, and ophiolite-hosted deposits in the
Newfoundland Appalachians are representative
districts/deposits of this group.
2) Bimodal-mafic: deposits associated with mafic-
dominated settings, but with up to 25% felsic
rocks; the latter commonly hosting the deposits.
The deposits of the Noranda Camp, Flin Flon-
Snow Lake, and Kidd Creek are representative dis-
tricts/deposits of this group.
3) Siliciclastic-mafic (or pelitic-mafic): these are
deposits associated with subequal proportions of
mafic and siliciclastic rocks; felsic rocks can be a
minor component; and mafic (and ultramafic)
intrusive rocks are common. The deposits of the
Besshi district in Japan and Windy Craggy, British
Columbia are representative districts/deposits of
this group.
4) Siliciclastic-felsic (or bimodal siliciclastic):
deposits in siliciclastic-dominated settings with
abundant felsic rocks and less than 10% mafic
material. These settings are commonly shale-rich
and the Bathurst District, Iberian Pyrite Belt, and
Finlayson Lake District are representative districts
of this group.
5) Bimodal-felsic: deposits associated with bimodal
sequences where felsic rocks are in greater abun-
dance than mafic rocks with only minor sedimen-
tary rocks. The deposits of the Kuroko, Buchans,
and Skellefte camps are representative districts of
this group.
The first three VMS groups are dominated by mafic
material and juvenile environments with very little
17
 S. J. Piercey

1000 Pb. The last two groups are associated with evolved
A environments dominated by continental crust or conti-
nental crust-derived sedimentary rocks. Felsic rocks in
OIB (alkalic)
100 these environments are derived from melting of conti-
Rock / Primitive Mantle

nental crust or continental crust-derived rocks, and

E-MORB
mafic rocks commonly are derived from mantle
10 sources including both lithospheric and asthenospheric
sources. The deposits of the last two groups are notably
Zn-Pb-Cu dominated.
N-MORB
1
PRIMARY VOLCANIC
LITHOGEOCHEMISTRY OF
VOLCANOGENIC MASSIVE SULPHIDE-
.1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc ASSOCIATED ROCKS
1000
B The primary volcanic lithogeochemical signatures of
volcanic suites provide significant insight into primary
CAB petrological processes involved in generating a vol-
100
canic assemblage. Understanding the primary petrolog-
Rock / Primitive Mantle

ical processes affecting a volcanic belt is critical in pro-

viding information on the thermal, tectonic, and petro-
10 logical history of a volcanic belt, key features that can
be used to delineate potentially fertile versus barren
volcanic basins. When evaluating primary volcanic
1 lithogeochemical signatures, it is critical that the fresh-
IAT / LOTI BON est, least altered samples be taken. Namely, samples
should have preserved textures, be free of veins and
.1 secondary minerals, and have known stratigraphic
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc
1000
position. In addition, spatial control in the field and in
C drill core can provide insight into important primary
lithogeochemical and petrological variations on a
regional to local scale. In addition, in subaqueous and
100 Alkalic
variably altered volcanic sequences it is important to
Rock / Primitive Mantle

rely on immobile major and trace elements, ones that

10
BABB
1 Ti, V), and rare earth elements (REE) (e.g. Jenner,
.1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al
Figure 3-2. Primitive mantle normalized plots: (A) non-arc basalt;
(B) arc basalt; and (C) transitional (back-arc and arc rift-related
basalt). Data from and Sun and McDonough (1989), Stoltz et al.
(1990), Jenner (1981) Piercey et al. (2004), Ewart et al. (1994), and
Kepezhinskas et al. (1997). Abbreviations: BABB = back-arc basin
basalt; BON = boninite; CAB = calc-alkaline basalt; E-MORB
(enriched mid-ocean ridge basalt); IAT = island arc tholeiite; LOTI =
low-Ti island arc tholeiite; N-MORB = normal mid-ocean ridge basalt;
and OIB = ocean island basalt. Primitive mantle values for this dia-
gram and all others in this paper from Sun and McDonough (1989).
continental crustal influence. Felsic rocks in these set-
tings are derived primarily from melting of hydrated
mafic crust, and mafic rocks are predominantly
sourced from asthenospheric mantle. Deposits in the
first three groups are enriched in Cu-Zn with very little
are not significantly mobilized during hydrothermal
alteration and metamorphism, to understand primary
igneous processes, including Al2O3 and TiO2, the high
field strength elements (HFSE: Zr, Hf, Nb, Ta, Y, Sc,
1996; Kerrich and Wyman, 1997). Carbon dioxide-
(CO2)-rich fluids, however, can mobilize the HFSE
and REE (e.g. Murphy and Hynes, 1986) and this
V Sc
should be taken into consideration when dealing with
strongly carbonate-altered rocks.
Mafic Geochemistry
Mafic volcanism and plutonism associated with VMS
deposits is dependent on whether volcanism is associ-
ated with juvenile or evolved substrates. In juvenile
environments, deposits are preferentially associated
with boninite and low-Ti tholeiite (LOTI) or mid-ocean
ridge basalt (MORB) of both the normal (N-MORB)
and enriched (E-MORB) varieties (Figs. 3-2, 3-3, 3-4).
Boninitic rocks are associated with many ophiolite-
hosted (mafic) VMS deposits (e.g. Cyprus, Turner-
Albright, Oman, Betts Cove) and bimodal mafic sys-

18
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration

1000 1000
Boninites A Low Ti-Tholeiites (LOTI) B

100 100
Rock / Primitive Mantle

Rock / Primitive Mantle

10 10

1 1

.1 .1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc

1000 1000
MORB and BABB C OIB-like D

100 100

Rock / Primitive Mantle

Rock / Primitive Mantle

10 10

1 1

.1 .1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc

Snow Lake BON Kutcho MORB W. Shasta MORB Fyre Lake BON Figure 3-3. Primitive mantle normalized plots for mafic rocks asso-
Snow Lake LOTI Rambler BON Betts Cove BON Windy Craggy ciated with VMS deposits in mafic-dominated VMS environments,
E-MORB/OIB
Flin Flon LOTI Rambler MORB Betts Cove LOTI including (A) boninite; (B) low-Ti island arc tholeiite; (C) mid-ocean
Flin Flon MORB Noranda Troodos BON ridge basalt (MORB) and back-arc basin basalt (BABB); and (D)
Contaminated MORB ocean island basalt (OIB)-like. The low Eu values in the Josephine
Kamiskotia Troodos LOTI
Contaminated MORB Noranda MORB
Troodos LOTI LOTI data are likely due to Eu loss during hydrothermal alteration.
Kidd Creek BON Tulsequah MORB #1
Josephine BON
The high Nb values for West Shasta are likely erroneous. Data
Tulsequah MORB #2 sources are listed in Appendix 3-1.
Kutcho LOTI Josephine LOTI
Kutcho LREE-IAT W. Shasta LOTI Josephine MORB/BABB

tems (e.g. Kidd Creek, Snow Lake, Rambler), and most boninite is associated with fore-arc extension
more rarely in mafic-siliciclastic systems (e.g. Fyre associated with the initiation of subduction (Brown and
Lake) (Table 3-1). Boninitic-LOTI rocks are inter- Jenner, 1989; Stern and Bloomer, 1992; Kerrich et al.,
preted to have formed from mantle sources that are 1998; Bedard et al., 1999; Wyman et al., 1999) or with
ultra-depleted in incompatible trace elements (i.e. the initiation of back-arc basin formation (Crawford et
ultra-depleted mantle) that require very high tempera- al., 1981; Piercey et al., 2001a).
tures to melt (~1200-1500ºC) (Jenner, 1981; Crawford Mid-ocean ridge basalts (MORB) are associated
et al., 1989; Pearce et al., 1992; van der Laan et al., with many mafic-hosted VMS deposits in ophiolite,
1992; Falloon and Danyushevsky, 2000). Furthermore, and modern mid-ocean ridges (e.g. TAG, East Pacific
Table 3-1. Petrochemical assemblages of mafic and felsic rocks commonly associated with different VMS deposit classes (from Piercey, 2007).
VMS Deposit Class Mafic Felsic
Mafic Boninite, low-Ti tholeiite, MORB -
Mafic Siliciclastic MORB, alkalic, boninite (rare) -
Bimodal Mafic MORB, boninite, low-Ti tholeiite (calc-alkalic and island Archean - FIII rhyolite. Proterozoic-Phanerozoic - tholeiitic
arc tholeiite present but rarer) rhyolite, boninitic rhyolite
Bimodal Felsic MORB, alkalic HFSE-enriched rhyolite (A-type), peralkaline and calc-
alkalic rhyolite (rarer)
Felsic Siliciclastic MORB, alkalic HFSE-enriched rhyolite, peralkaline, and calc-alkalic
rhyolite (rarer)

19
 S. J. Piercey

1000 1000
A Back-Arc Basin Basalts (BABB) B Mid-Ocean Ridge Basalts (MORB)
and Island Arc Tholeiites (IAT)

Rock / Primitive Mantle

Rock / Primitive Mantle

100 100

10 10

1 1

.1 .1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc

Continental
Crust-Associated
Bransfield Strait IAT
Bransfield Strait MORB
Okinawa Trough
Contaminated MORB
Manus Basin BABB
Manus Basin MORB
Guaymas MORB
Guaymas BABB
Mafic-Associated
Lau Basin MORB
TAG MORB
Escanaba Trough MORB
Middle Valley MORB
Axial Seamount MORB
East Pacific Rise MORB
Lau Basin IAT
Figure 3-4. Primitive mantle normalized plots for mafic rocks asso-
ciated with volcanic massive sulphide deposits in modern oceans,
including (A) back-arc basin basalt and island arc tholeiite, and
(B) mid-ocean ridge basalt (MORB). The high Nb data for Middle
Valley MORB are erroneous. Data sources are listed in Appendix 3-
1.

Rise, Oman) and back-arc basins (e.g. Lau Basin)
(Figs. 3-3, 3-4). MORB-like rocks with weak negative
Nb anomalies on primitive mantle normalized plots,
called back-arc basin basalts (BABB), are also present
in many mafic-type VMS environments in modern and
ancient back-arc basins (e.g., Lau Basin, Manus Basin,
Semail). In mafic and bimodal-mafic systems (e.g.
fore-arc or back-arc settings) the MORB-type rocks
commonly show an intimate relationship with boninitic
and arc-tholeiitic rocks, with MORB either underlying
1000
A Alkalic, Ocean Island Basalt (OIB)-Like
Mid-Ocean Ridge Basalt (MORB (enriched))
boninite (e.g. Semail), or overlying and/or crosscutting
boninite (e.g. Troodos, Rambler, Turner-Albright)
(Table 3-1). MORB-type rocks are also associated with
mafic-siliciclastic deposits in both the ancient record
(e.g. Windy Craggy, Greens Creek) and modern sedi-
mented ridges (e.g. Middle Valley, Guaymas, and
Escanaba Trough) (Table 3-1). MORB- and BABB-
type rocks are interpreted to have formed from incom-
patible element-depleted mantle with liquidus temper-
atures of approximately 1200ºC (e.g. McKenzie and
1000
B

100 100
Rock / Primitive Mantle

Rock / Primitive Mantle

10 10

1 1

.1 .1
Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc

Avoca MORB Delta/Bonnifield OIB

Iberian Pyrite Belt Figure 3-5. Primitive mantle normalized plots for mafic rocks asso-
Eskay Creek MORB ciated with VMS deposits associated with continental crust including
Contaminated MORB
Kudz Ze Kayah OIB Iberian Pyrite Belt MORB (A) mid-ocean ridge basalt (MORB) (note the enrichment in incom-
Parys Mountain Iberian Pyrite Belt OIB patible elements, typical of enriched-MORB), and (B) alkalic, ocean
Contaminated MORB island basalt-like mafic rocks. Data sources are listed in Appendix 3-
Tulsequah MORB 1.
Tulsequah BABB
Bathurst OIB

20
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration

Bickle, 1988; McKenzie and O’Nions, 1991; Langmuir 1000

A Panorama Dacite
et al., 1992) and represent extension either at mid- Panorama Rhyolite
(Barren)
ocean ridges or within back-arc basins (e.g. Langmuir Kidd Creek
et al., 1992; Hawkins, 1995). FI
Sturgeon Lake
100 Blake River (Noranda)
In evolved environments, deposits are preferentially
Blake River (Regional)
associated with mafic rocks that have MORB and alka-

La/Ybn
South Bay
lic (or within-plate or ocean island basalt (OIB)) signa-
Kamiskotia
tures (Figs. 3-2, 3-5). The MORB present in the 10 FII High Lake
evolved environments is commonly of E-MORB affin-
ity and often there is a complete range of mafic rocks FIIIa FIIIb
from incompatible element-depleted MORB, to weakly
incompatible element-enriched E-MORB, to incompat- 1 FIV
ible element-enriched OIB (Fig. 3-5). The MORB-type
and OIB-like rocks often occur as sills and dykes that 0 40 80 120 160 200
Ybn
crosscut, or as flows that overlie felsic rocks and the 1000
B
Finlayson Barren (calc-alkalic)
associated mineralization (i.e. they commonly post- Finlayson Barren (tholeiitic)
Finlayson Deposit-Hosting
date the main mineralization event). Furthermore, there Iberian Pyrite Belt

is commonly a stratigraphic progression upwards from FI

Bransfield Strait

alkalic basalts to MORB (van Staal et al., 1991; Shinjo 100 Okinawa Trough
Mount Read
et al., 1999; Piercey et al., 2002a,b). Alkalic and
La/Ybn
Parys Mountain

MORB-type basalts are associated with many bimodal- Avoca

Bathurst - Flat Landing Bk.
felsic and felsic-siliciclastic settings from both the Bathurst - Nepisguit Falls
10 FII
modern (e.g. Bransfield Strait, Okinawa Trough) and Eskay Creek

ancient (e.g. Bathurst, Iberian Pyrite Belt, Finlayson FIIIa FIIIb

Delta-Bonnifield (Mystic Ck.)

Lake, Eskay Creek) geological record (Table 3-1), and

are interpreted to represent melts derived from lithos-
1 FIV
pheric (alkalic) to asthenospheric (MORB) mantle
sources; the associated stratigraphic progression from 0 40 80 120 160 200
alkalic basalt to MORB is commonly interpreted to Ybn
1000
Flin Flon (Calc-Alkalic - Barren)
reflect a shift from rifting to true seafloor spreading C Flin Flon (Tholeiitic - Barren)
(e.g. van Staal et al., 1991; Goodfellow et al., 1995; Flin Flon (Mine Rhyolites)
Rambler
Barrett and Sherlock, 1996; Almodóvar et al., 1997; West Shasta
Shinjo et al., 1999; Colpron et al., 2002; Piercey et al., FI
100 Kutcho

2002a,b; Rogers and van Staal, 2003). Snow Lake (Primitive Arc)
La/Ybn

Snow Lake (Mature Arc)

Snow Lake (Mature Arc-
Felsic Geochemistry Powderhouse Dacite)

Considerable research has been undertaken on the geo- 10 FII

chemistry of felsic rocks associated with VMS systems
(e.g. Lesher et al., 1986b; Barrie et al., 1993a; Lentz,
1998; Hart et al., 2004). Felsic rocks in VMS environ-
ments that form via partial melting of, or interaction
with, continental crust are fundamentally different than
those associated with partial melting of a mafic sub-
strate, leading to different VMS-associated rhyolite
signatures dependent on the VMS environment (Table
3-1). Furthermore, Archean felsic rocks have signa-
tures and assemblages that are somewhat different than
post-Archean VMS-associated felsic rocks.
In Archean terrains much of our knowledge on fel-
sic volcanic geochemistry is from research in the
Superior Province of Canada (Lesher et al., 1986b;
Barrie et al., 1993; Hart et al., 2004). Lesher et al.
(1986b) outlined a tripartite subdivision of felsic rocks
for VMS-associated and barren rhyolites in the
Superior Province — the FI to FIII suites of rhyolite.
FIIIb
FIIIa
1 FIV
0 40 80 120 160 200
Ybn
Figure 3-6. La/Ybn-Ybn with FI-FIII-affinity rhyolite discrimination
diagrams (from Lesher et al., 1986b; Hart et al., 2004). (A) Archean
volcanic massive sulphide-associated and barren felsic rocks. (B)
Post-Archean volcanic massive sulphide-associated and barren rhy-
olite from evolved environments. (C) Post-Archean volcanic massive
sulphide-associated and barren rhyolite from juvenile environments.
Data sources are listed in Appendix 3-1.
This classification was modified by Hart et al. (2004)
to include a fourth suite, the FIV suite that is largely
restricted to post-Archean juvenile terranes, and
expanded to a global database. The I suite of felsic
rocks has low La/Ybn (and Zr/Y) ratios and high HFSE
contents (e.g. Zr>200 ppm) (Figs. 3-6, 3-7). The FI
21
 S. J. Piercey

700
A Panorama Dacite
Figure 3-7. Zr-Nb diagram illustrat-
(barren)
Panorama Rhyolite ing HFSE variations in rhyolitic
600
rocks associated with volcanic
Kidd Creek
massive sulphide environments.
500
Sturgeon Lake (A) Archean volcanic massive sul-
Blake River (Noranda) phide-associated and barren felsic
rocks (South Bay Nb data are likely
Blake River (Regional)
400 erroneous). (B) Post-Archean vol-
canic massive sulphide-associated
Zr

South Bay
and barren rhyolite from evolved
Kamiskotia
300 environments. (C) Post-Archean
High Lake volcanic massive sulphide-associ-
Zr > 200 ppm ated and barren rhyolite from juve-
200 nile environments. Data sources
are listed in Appendix 3-1. Diagram
100 after Leat et al. (1986).

0
0 10 20 30 40 50
Nb
10000
B Finlayson Barren (calc-alkalic)
Finlayson Barren (tholeiitic)
Finlayson Deposit-hosting
Iberian Pyrite Belt
Bransfield Strait
Okinawa Trough
1000 Mount Read
Peralkaline Parys Mountain
Avoca
Zr

Zr>200 ppm Bathurst - Flat Landing Bk.

Bathurst - Nepisguit Falls
Eskay Creek
100
Delta-Bonnifield (Mystic Ck.)

10
1 10 100 1000
Nb
500
C Flin Flon (Calc-Alkalic - Barren)
Flin Flon (Tholeiitic - Barren)
Flin Flon (Mine Rhyolites)
Rambler
400
West Shasta
Kutcho
Snow Lake (Primitive Arc)
300 Snow Lake (Mature Arc)
Snow Lake (Mature Arc-
Zr

Powderhouse Dacite)

Zr>200 ppm
200

100

0
0 10 20 30 40 50 60
Nb

suite has high La/Ybn ratios and lower HFSE contents
(Figs. 3-6, 3-7). The FII suite has signatures intermedi-
ate between the two groups (Figs. 3-6, 3-7). The major-
ity of Archean VMS deposits are hosted by FIII and FII
felsic rocks (Fig. 3-6), which are interpreted to have
formed within Archean rift sequences from high-tem-
perature melts (T>900ºC) derived from melting of
hydrated basaltic crust at shallow depths (Lesher et al.,
1986b; Barrie et al., 1993; Barrie, 1995; Hart et al.,
2004). The formation at shallow depths (i.e. <10 km)
allowed these melts to rise to the surficial environment
without losing their heat of fusion (T>900ºC), thus,

22
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration
giving them greater ability to drive long-lived
hydrothermal systems (e.g. Barrie et al., 1999). In con-
trast, the other suites are interpreted to have formed
from lower temperature melts (<900ºC) at deeper lev-
els in the crust (>10 km) (Lesher et al., 1986b; Barrie,
1995; Hart et al., 2004). These melts have less poten-
tial to drive hydrothermal systems due to their lower
temperatures of fusion and loss of heat upon transport
to the surface of the Earth from depth.
In Proterozoic and Phanerozoic terrains, the litho-
geochemical signatures of felsic rocks are dependent
on whether the felsic rocks are associated with juvenile
or evolved environments. In post-Archean evolved
environments felsic rocks have a range of signatures,
but most VMS deposits are associated with rhyolite
that has elevated HFSE and REE contents (Fig. 3-7)
and FIII to FII signatures (Fig. 3-6); there is a tendency
for rocks in these settings to have FII affinities, how-
ever (Fig. 3-6) (Lentz, 1998; Hart et al., 2004; Piercey
et al., 2001b, 2008). Some rocks in these evolved set-
tings, particularly those associated with continental rift
or continental back-arc rifts (e.g. Delta-Bonnifield,
Avoca), have rhyolite with extremely elevated HFSE
content that is peralkalic in composition (e.g. Zr>500
ppm; Fig. 3-7) (e.g. Mortensen and Godwin, 1982;
McConnell, 1991; Dusel-Bacon et al., 2004). Like their
Archean equivalents, felsic rocks associated with
evolved settings represent high-temperature (>900ºC)
melting of crust within rift environments (e.g. conti-
nental arc and back-arc rifts) (Lentz, 1998; Piercey et
al., 2001b, in press).
In post-Archean juvenile environments, felsic rocks
are unlike both Archean and evolved post-Archean set-
tings. The rhyolite in juvenile environments typically
mirror the petrology of associated mafic rocks and have
tholeiitic to boninitic affinities with low Zr/Y (<4) and
La/Ybn ration (Fig. 3-6), and depletions in HFSE and
REE (e.g., Zr<50-100 ppm) (Fig. 3-7). In addition, the
rhyolite typically has flat REE profiles (not shown) and
FIV affinities (Fig. 3-6). The rhyolite typically forms
the partial melting of mafic (to andesitic) substrates dur-
ing fore-arc rifting, intra-arc rifting, or rifting during the
initiation of back-arc basin activity (e.g. Shukuno et al.
2006). Their low overall trace element contents are
likely because of the low trace element compositions of
their mafic source rocks (e.g. boninite and arc tholeiite).
ALTERATION LITHOGEOCHEMISTRY
Whereas petrochemistry provides indicators of the right
type of geodynamic environment, alteration lithogeo-
chemistry provides insight into the existence of a poten-
tial VMS hydrothermal system. Sampling to understand
alteration is fundamentally different than petrochem-
istry. In the latter we are interested in primary lithogeo-
chemical attributes of rocks, whereas alteration litho-
geochemistry involves understanding the distribution
of mobile elements. Sampling for alteration involves a
number of steps. The first step is to collect a suite of
representative least altered samples. The samples could
be the same samples used for petrochemistry and pro-
vide the background to which all other samples are
compared. Altered samples then should be sampled as a
function of alteration mineralogy (quartz, chlorite,
sericite, carbonate, etc.) and alteration intensity (e.g.
strong, moderate, weak). If possible, end members of
alteration types should be chosen such that samples
with mixed alteration assemblages can be compared. In
outlining alteration zones, it is important to have spatial
distribution of samples. This can be achieved through
sampling traverses on properties or on a regional scale,
or via detailed sampling in drill core. In both surface
and drill core, sampling should be done at discrete
intervals (e.g. every n boxes of drill core or every n
kilometres in the field) where there are fundamental
changes in lithology or where there are significant
changes in alteration type or intensity.
Alteration in VMS systems can be divided into two
types: semiconformable alteration, and proximal or
pipe-like alteration. These types of alteration are
broadly associated with zones of hydrothermal
recharge and discharge, respectively (e.g. Alt, 1995,
1999). During hydrothermal recharge, lateral fluid flow
results in the formation of semiconformable alteration,
generally at lower temperatures, and involves the
leaching of metals from permeable zones within a foot-
wall substrate (Galley, 1993, and references therein).
Lateral fluid flow results in zoning of alteration miner-
als, mineral chemistry, and lithogeochemistry in a ver-
tical manner, due to the geothermal gradient, with
accompanying spillitization, silicification, epidote-
quartz, and carbonization±potassic alteration
(MacGeehan and MacLean, 1980; Munhá and Kerrich,
1980; Munhá et al., 1980; Galley, 1993; Gibson et al.,
1983; Morton et al., 1990; Skirrow and Franklin, 1994;
Alt, 1995). The associated alteration products result in
varying gains of Si, Ca, Fe, Na, Mg, CO2±K
(MacGeehan and MacLean, 1980; Munhá and Kerrich,
1980; Munhá et al., 1980; Morton et al., 1990; Galley,
1993; Gibson et al., 1983; Skirrow and Franklin, 1994)
and significant depletions in metals (Gibson et al.,
1983; Richardson et al., 1987; Galley, 1993; Skirrow
and Franklin, 1994; Alt, 1995, 1999). These semicon-
formable alteration zones have significant lateral extent
(e.g. 10s-100s of km; Galley, 1993) and alteration is
commonly patchy (rather than pervasive) in nature,
with Mg-K enrichments in the uppermost parts of the
crust, and enrichments in Na-Mg, Na, and Ca-Fe with
depth (Galley, 1993).
Proximal, or pipe-like, alteration is discordant to
stratigraphy and has a much smaller lateral extent (e.g.
23
 S. J. Piercey

A 12 B 50 Qtz Porphyry
Rhyolite 1
Igneous Spectrum
Spillite Rhyolite 1
10 (Na Metasomatism) (Weakly Altered) clast
40 Rhyolite 2

Keratophyre Rhyolite 3
8 (K-Metasomatism) Lapillistone

Al2O3/Na2O
K2O+Na2O

30
Na Loss
6
20 Fresh to Weakly Na Altered
4 Alterated

10
2

0 0
0 20 40 60 80 100 0 1 2 3 4 5 6 7
100*K2O/Na2O+K2O Na2O
Figure 3-8. (A) Hughes (1973) diagram for outlining fresh, spillitized (Na-altered), and keratophyric (K-altered) igneous rocks. (B) Spitz-Darling
index (Spitz and Darling, 1978) (Al2O3/Na2O) versus Na2O plot for outlining fresh rocks versus those with Na-gains (spillitized) and losses (dia-
gram from Ruks et al., 2006). These diagrams are useful for delineating semiconformable alteration (spillitization, Na-gains) versus pipe-like
alteration (Na-depletions). Data on the diagram are from Piercey (unpublished data).

Lower Amulet Rhyolite

A

Rusty Ridge Formation

Upper contact Upper contact
of of
Northwest Fm Rusty Ridge Fm

Northwest Formation

Flavrian
Pluton

2-3% Na2O
Flavrian Formation
1-2% Na2O
Ansil QFP

0-1% Na2O
Outline
of
Ansil Deposit B
0 400 m

0 1 km
Fukazawa Mine
D3
Figure 3-9. (A) Contoured Na2O contents for rhyolitic rocks of the Dacite
Blake River Group, Quebec, Canada, associated with the Ansil VMS
deposit (from Galley, 1995; Galley et al., 1995), (B) and for dacitic Zeolite
rocks at the Fuzakawa mine, Kuroko district, Japan (from Date et al., Montmorillonite
1983). In both cases, the hydrothermal upflow zones are marked by
strong depletions in Na2O due to feldspar and glass destruction. Chlorite-Sericite
These zones of Na-depletion are extremely simple, yet effective, Massive Sulphide
exploration tools for volcanic massive sulphide exploration.
<0.4% Na2O

24
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration

typically less than a few hundred metres). Proximal A Al2O3

alteration zones represent hydrothermal upflow or dis-
charge zones (e.g. feeder zones to the deposits) and Qtz Porphyry
form from high-temperature water-rock interaction. Rhyolite 1
Rhyolite 1
They have varying morphology but are typically pipe- clast
muscovite

like in impermeable strata (e.g. flows) and can have Rhyolite 2

irregular shapes in impermeable volcaniclastic or sedi- Rhyolite 3
mentary strata (Riverin and Hodgson, 1980; Franklin et Lapillistone
albite
al., 1981, 2005; Gemmell and Large, 1992; Large,
1992; Franklin, 1993, 1996; Gibson et al., 1999; epidote

ite
Gemmell and Fulton, 2001; Large et al., 2001c;

lor
biotite Least Altered

ch
Felsic
Gibson, 2005). These proximal alteration zones have a
well developed zonation in alteration minerals and phlogopite
chemistry, from chlorite-(quartz)-rich cores to sericite-
(quartz)-rich rims to quartz-sericite-rich envelope actinolite

zones, reflecting increasing temperature of hydrother-

MgO tremolite CaO+Na2O+K2O
mal fluid-rock interaction from rim to core of the alter-
Quartz
ation pipe (Riverin and Hodgson, 1980; Franklin et al., B
1981, 2005; Knuckey et al., 1982; Richards et al.,
1989; Gemmell and Large, 1992; Franklin, 1993, 1996;
Gemmell and Fulton, 2001; Large et al., 2001a). Some precursor
proximal alteration zones are also associated with car- Weakly altered
bonate (Lydon, 1984; Morton et al., 1990; Squires et
al., 2001; Hudak et al., 2003; Bradshaw et al., 2008).
Relative to background rocks, the alteration pipe is
characterized by Ca-Na losses and Fe-Mg-K-Si-S-
Silica leaching

Moderately altered
metal enrichments (e.g. Ishikawa et al., 1976; Spitz and
Darling, 1978; Riverin and Hodgson, 1980; Date et al.,
1983; Hashiguchi et al., 1983; Richards et al., 1989;
Gemmell and Large, 1992; Galley et al., 1993; Huston,
Strongly altered
1993; Barrett and MacLean, 1994a,b; Lentz and
sericitite
Goodfellow, 1996; Gemmell and Fulton, 2001). chloritite

Various lithogeochemical tools can be used to iden- Sericite Chlorite

tify alteration zones. Utilization of major (and trace) C quartz
100
element data can be useful in identifying alteration.
Spillitization versus K-metasomatism is important
for delineating semiconformable versus pipe-like alter-
80
ation, and can be done using the plot of Hughes (1973) Weakly to moderately
altered rhyolite
(Fig. 3-8A). Spillitization versus Na-losses can also be
Si cation %

precursor
delineated using the Spitz-Darling index (Al2O3/Na2O)
(Spitz and Darling, 1978) and Na2O contents (Fig. 3- 60
8B). Similarly, contouring of raw alkali and metal val-
ues can be useful in delineating potential alteration
zones (Fig. 3-9). For example, simple contouring of 40 sericite
Na2O values by Date et al. (1983) and Galley et al. Extrem
ely alte
chlorite
red rhy
(1995) identified the proximal alteration zones beneath olite

the Kuroko and Ansil deposits, which are associated 20

with marked Na-depletions (Fig. 3-9). Ternary plots of
major elements with various potential alteration miner-
als have also proved useful for outlining different alter-
ation types and pathways (Fig. 3-10) (Riverin and
Hodgson, 1980; MacDonald et al., 1996; Sebert et al.,
2004), as have normative mineral plots (both CIPW
and cation normative plots; Fig. 3-10) (e.g. Barrett and
0 10 20 30 40 50
(Fe+Mg) cation %
Figure 3-10. Ternary plots of major elements and normative mineral
contents outlining volcanic massive sulphide-associated alteration.
(A) MgO-Al2O3-(CaO+Na2O+K2O) plot (MacDonald et al., 1996;
Sebert et al., 2004; data is from Piercey, unpublished data). (B) Cation
normative and (C) cation percentage plots illustrating various alter-
ation minerals and alteration paths (from Barrett and MacLean,
1991; MacLean and Barrett, 1993).

25

Figure 3-11. Alteration box plot with the 100
Hashimoto alteration index (AI) (Ishikawa et al.,
1976) versus the chlorite-carbonate-pyrite index
(CCPI) (CCPI and diagram from Large et al.,
2001b). This diagram contains least altered fields
for various volcanic rocks and nodes for different
alteration minerals. Arrays on this diagram can be
used to outline different alteration types, and dia-
genetic (i.e. semiconformable) versus hydrother-
mal (i.e. proximal or pipe-like) alteration. Data are
CCPI
from Piercey (unpublished data).
MacLean, 1991; MacLean and Barrett, 1993; Liaghat and
MacLean, 1995).
Most previous alteration diagrams are based on the
loss of Ca-Na during the alteration process, followed by
subsequent gains in K (sericite), Fe-Mg (chlorite, car-
bonate), and Si (quartz). This elemental behaviour is the
premise behind many alteration indexes, whereby ele-
ments gained during the alteration process are normal-
ized against elements lost during the process with the
index number increasing with greater intensity of alter-
ation and proximity to mineralization (Ishikawa et al.,
1976; Saeki and Date, 1980; Gemmell and Large, 1992;
Gemmell and Fulton, 2001; Large et al., 2001b). A
novel approach to alteration indexes is the combination
of the Hashimoto alteration index (AI) and the chlorite-
carbonate-pyrite index (CCPI) in the alteration box plot
by Large et al. (2001b) (Fig. 3-11). This diagram con-
tains a box for least altered samples and respective
nodes for alteration minerals (Fig. 3-11). Unaltered
rocks lie within the least altered box, with varying alter-
ation types forming trends towards the alteration nodes
(Fig. 3-11).
Large et al. (2001a,c) recently illustrated that the
volatile elements Tl and Sb, once difficult to analyze,
have very large dispersal halos (e.g. 100s of metres)
around Zn-rich Australian VMS deposits (Fig. 3-12). A
similar volatile element enrichment is observed in the
Duck Pond and Boundary massive sulphide systems in
the Newfoundland Appalachians, where the alteration
system is characterized by elevated Hg, Hg/Na2O, and
Ba/Sr ratios (Fig. 3-12) (Collins, 1989).
Previous methods involve data uncorrected for mass
variations during alteration. More rigorous quantifica-
26
S. J. Piercey
epidote chlorite
calcite dolomite/ankerite pyrite
Basalt
80 and
Andesite
Least Altered Box
Alteration Field
60
Dacite
40 Qtz Porphyry
Rhyolite 1
Rhyolite
Rhyolite 1 sericite
clast
20 Rhyolite 2
Rhyolite 3
Diagenetic Field
albite Lapillistone
K-feldspar
0
0 20 40 60 80 100
Hashimoto Index (AI)
AI = 100*(K2O+MgO)/(K2O+MgO+CaO+Na2O)
CCPI = 100*(Fe2O3T+MgO)/( Fe2O3T+MgO+K2 O +Na2O)
tion of mass variance and elemental gains and losses
during alteration has been the focus of considerable
research. Gresens (1967) provided one of the first
methods to quantify mass and volume change during
alteration and metamorphism, and this method has
been utilized in VMS alteration studies by some work-
ers (e.g. Gibson et al., 1983; Lesher et al., 1986a; Lentz
and Goodfellow, 1993). Grant (1986) provided a
graphical alternative to Gresens (1967), whereby the
elemental concentrations in an altered rock are plotted
against those in a fresh rock on an X-Y plot (Fig. 3-13)
(see also Huston, 1993 and Baumgartner and Olsen,
1995). Immobile elements in these diagrams form a lin-
ear array (the isocon), the slope of which provides an
indicator of the net mass gain or loss during alteration;
elements that have been gained during the alteration
process lie above the isocon and those that have been
lost during the alteration process lie below the isocon.
MacLean and Barrett (MacLean, 1990; MacLean and
Barrett, 1993; Barrett and MacLean, 1994a,b, 1999)
devised a mass balance method that measured mass
changes relative to igneous fractionation trends. Once
various igneous populations are identified, the altered
rocks are compared to the least altered rocks using
immobile elements to obtain a mass-change factor (the
enrichment factor). This factor is then utilized to mass
correct the altered samples, which are then compared to
the least altered suite to calculate elemental changes.
This method provides a means of dealing with large
data sets quickly and provides an easy method for visu-
alizing absolute mass changes (Fig. 3-13).
Stanley and Madeisky (1994) have utilized Pearce
Element Ratios (PER) to quantify metasomatism (see
also Robinson et al., 1996). PER diagrams are con-
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration

1000
B Rosebery
A
Ore Proximal

100

pe
elo
100 m

nv
eE
Tl

10
Or Qtz Porphyry Hellyer
Rhyolite 1
Sb > 3 ppm Tl + Sb
Background Rhyolite 1
1 Clast
Rhyolite 2
Rhyolite 3
Lapillistone
.1
.1 1 10 100 1000
Sb 200 m
1000
C
Thalanga

100
Duck Pond and
100 m
Boundary Horizons
Hg/Na2O

Tl > 0.7 ppm massive ore

10

Figure 3-12. ( A) Tl-Sb volatile element plot outlining the fields for
Barren background through to proximal alteration zones (from Large et al.,
1 or 2001a). (B) Diagrams outlining the extent of volatile element halos
distal volcanic rocks around some Australian volcanic massive sulphide deposits (from
Large et al., 2001c). (C) Hg/Na2O-Ba/Sr plot of Collins (1989) for
delineating proximal versus barren alteration from the Tally Pond vol-
.1 canic belt, Newfoundland, Canada. Data in (A) and (B) are from
.1 1 10 100 1000 Piercey (unpublished data).
Ba/Sr

structed using molar ratios of potentially mobile ele-
ments to a conserved denominator that is an immobile
element (e.g. Al or Zr); ratios are chosen to remove the
potential effects of closure and mass change on the
absolute concentrations of elements (Stanley and
Madeisky, 1994). The diagrams have slopes that corre-
spond to primary geological process (e.g. fractional
crystallization) and secondary alteration minerals; sam-
ples that deviate from the primary trend are affected by
alteration (Fig. 3-13). The PER approach has not been
utilized extensively by workers in the VMS commu-
nity; however, it has been applied very successfully in
gold exploration (e.g. Eilu et al., 2001; Murphy and
Stanley, 2007; O’Connor-Parsons and Stanley, 2007),
suggesting that it has considerable promise as an explo-
ration tool in VMS systems.
DISCUSSION
Petrochemical Assemblages:
A Regional Area Selection Tool
One of the key challenges in the exploration for VMS
deposits is the identification of fertile ground in green-
fields areas. Primary lithogeochemical signatures of
mafic and felsic rocks have been utilized for identify-
ing potentially prospective belts, as these signatures
provide key information on the tectonic setting and
heat flow of a given volcanic assemblage. Most previ-
ous studies on the primary lithogeochemistry of vol-
canic rocks in VMS belts have either focused on felsic
(e.g. Lesher et al., 1986b; Lentz, 1998; Hart et al.,
2004) or mafic (e.g. Swinden et al., 1989; Swinden,
1991) rocks, with less emphasis on the relationships
between mafic and felsic rocks and associated
sedimentary rocks or their chemostratigraphy.
Petrochemical assemblages are an attempt to link these
different data sets. Petrochemical assemblages are
chemostratigraphic assemblages of mafic and felsic
rocks that indicate a specific geodynamic environment
and are a predictive tool to identify environments with
the potential to host VMS mineralization (Fig. 3-c14;
Table 3-1; Piercey, 2007).
In mafic-dominated VMS environments, boninite
and/or LOTI commonly host the VMS deposits but are
commonly overlain (or underlain) by MORB- or
BABB-type rocks, indicative of fore-arc rifting or ini-
tiation of back-arc spreading (Fig. 3-c14) (e.g.
Swinden, 1991; Piercey et al., 1997; Bedard et al.,
1999). In mafic-siliciclastic environments, the deposits
are commonly associated with MORB (e.g. Escanaba
Trough, Guaymas, Middle Valley), or more rarely OIB
(e.g. Windy Craggy) or boninite (e.g. Fyre Lake),
27
 S. J. Piercey

A 50
Figure 3-13. Various mass balance plots for VMS-
45 20S
associated alteration systems. (A) Isocon plot (Grant,
ss
C h lo r itiz e d B a s a lt W C U 9 0 - 4

Mass Gain
30U Ma 1986) for altered basalt from the Windy Craggy deposit
nt
40 n sta (Peter and Scott, 1999). (B) Δ(CaO+Na2O) versus
Co
0.2Co Δ(Fe2O3+MgO) variations for volcanic rocks from the
35
20Yb 10Sm Noranda camp illustrating the absolute elemental
30 5Au gains and losses and the associated alteration paths
20Ta 100Lu (from MacLean and Barrett, 1993). (C) Pearce
25 Mass Loss Element Ratio (PER) diagram outlining various slopes
10Th
Fe3+ Sc 50Tb corresponding to a primary igneous process (i.e.
20 20Zr 0.5Ce
100P La feldspar fractionation) and various alteration phases.
Si 0.1Cr 30Eu
15 4Mg Samples that lie off the primary trend are altered, and
Y Nd the greater the deviation from the trend indicates
10Hf
10 20Ti greater alteration intensity (from Stanley and
Al Nb 6Ca 0.1Sr 0.25Ba
100Mn Madeisky, 1994).
5 10C 0.1Ni
Rb 100K 10Na
0
0 5 10 15 20 25 30 35 40 45 50
Least altered basalt (average of 5)
B 6
Flavrian andesite
C 0.10
Qtz Porphyry

n)
t io
Northwest rhyolite Rhyolite 1

na
4

io
Rhyolite dykes Rhyolite 1

ct
ra
clast

f
ar
sp
2 Rhyolite 2

ld
fe
1(
Rhyolite 3

=
Molar (Na+K)/Zr

m
Δ (CaO+Na2O)

0 Lapillistone

-2 0.05

-4
plagioclase chloritization involving
destruction mass addtion of Fe+Mg
-6
)
icit e
(ser
-8 1/ 3
m=
m - 0 (chlorite) (X-axis)
-10 0.00
-20 0 20 0.00 0.05 0.10 0.15
Δ(Fe2O3+MgO) Molar Al/Zr

indicative of formation within sedimented rifts or sed- ity (e.g. Rambler, Flin Flon). In most cases, the felsic
imented back-arc rifts (Fig. 3-c14) (Saunders et al., rocks that occur within these mafic-dominated envi-
1982; Davis et al., 1994; Stakes and Franklin, 1994; ronments mark the rift episode and reflect melting of
Peter and Scott, 1999; Piercey et al., 2001a). Hot spot the preexisting mafic-dominated substrate via mantle
magmatism may have been significant in the case of upwelling during the rift event (e.g. Meijer, 1983;
the OIB-type rocks at Windy Craggy (Peter and Scott, Barrie et al., 1993; Prior et al., 1999).
1999). In bimodal felsic and felsic-siliciclastic environ-
In bimodal-mafic environments, boninite and LOTI ments, felsic rocks predominate over mafic rocks with
are commonly spatially associated with depleted boni- felsic rocks having calc-alkalic to within-plate (A-type)
nite-like or tholeiitic rhyolite, with the rhyolite hosting to peralkalic affinities (e.g. Lentz, 1999; McConnell et
mineralization (Fig. 3-c14) (e.g. Bailes and Galley, al., 1991; Piercey et al., 2001b; Dusel-Bacon et al.,
1999; Kerrich et al., 1998; Syme, 1998; Syme et al., 2004). The felsic rocks are typically spatially associ-
1999; Wyman et al., 1999; Bailey, 2002). ated, crosscut, and overlain by OIB-like alkalic basalt
Boninite/LOTI and associated rhyolite are commonly and/or MORB-type basalt (e.g. van Staal et al., 1991;
crosscut and overlain by MORB-type basaltic rocks Barrett and Sherlock, 1996; Almodóvar et al., 1997;
(Fig. C14) (Piercey et al., 1997; Bailes and Galley, Piercey et al., 2002a,b; Rogers and van Staal, 2003). In
1999; Syme et al., 1999; Wyman et al., 1999; Bailey, some cases, HFSE- and REE-enriched rhyolite is
2002). In some bimodal mafic environments, the absent and the rhyolite has normal, calc-alkalic affinity
deposits are hosted by FII-FIII rhyolite yet the under- (i.e. Zr/Y>7 but with Zr<200 ppm and volcanic-arc
lying mafic rocks are MORB in affinity (e.g. Noranda; affinity on discrimination plots), but these rocks are
Lafleche et al., 1992a,b; Hart et al., 2004). In all these crosscut and/or overlain by OIB and/or MORB-type
cases, the stratigraphic sequences are indicative of for- mafic rocks (Stolz, 1995; Dusel-Bacon et al., 2004).
mation within rift environments, either via true spread- The occurrence of MORB and alkalic basalt in any fel-
ing centres (e.g. Noranda) or via a transition from nor- sic-dominated setting is indicative of rifting and the
mal arc volcanism to back-arc-related magmatic activ-
28
 Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration
upwelling of mantle beneath a continental crust-domi-
nated substrate.
In all petrochemical assemblages, regardless of
deposit type, there is the association of 1) rifting and 2)
high-temperature magmatism. These two ingredients
are critical for the formation of a productive VMS envi-
ronment. Rift environments are under extension for
much of their history resulting in extensional faulting
and fracturing, providing the permeability necessary
for focusing hydrothermal fluid flow, namely, provid-
ing the conduits for fluid flow in the recharge zone and
faults for upwelling fluids in the discharge zone
(Gibson and Watkinson, 1990; McPhie and Allen,
1992; McPhie et al., 1993; Setterfield et al., 1995;
Allen et al., 1996; Gibson et al., 1999, 2007; Gibson,
2005; McCaig et al., 2007). In addition, rift environ-
ments create void space at the base of the crust, which
allows for the upwelling of mantle, partial melting, the
generation of basaltic magmas, ponding of this basalt at
the base of the crust, and, in many cases, eruption of
basalt (e.g. McKenzie and Bickle, 1988; Hawkins,
1995). The upwelling of mantle and ponding of basalt
at the base of the crust leads to an elevated geothermal
gradient in the rift environment (McKenzie and Bickle,
1988; Hyndman et al., 2005; Currie and Hyndman,
2006). This elevated gradient results in crustal partial
melting and the formation of the rhyolite that hosts
mineralization in the bimodal VMS environments (e.g.
Barrie et al., 1993; Lentz, 1998; Prior et al., 1999;
Piercey et al., 2001b). Furthermore, the magmatic
products from partial melting, including both the mafic
and felsic suites, typically have elevated temperatures
(>~900ºC for felsic rocks and >~1200ºC for mafic
rocks), which are key in driving and maintaining
hydrothermal circulation (Cathles, 1981, 1983; Barrie
et al., 1999). The overall elevated geothermal gradient
of the rift will also contribute to the maintenance of
hydrothermal circulation.
Alteration Lithogeochemistry: Identifying the
Volcanogenic Massuve Sulphide Plumbing
System
Petrochemical assemblages provide the means of iden-
tifying potentially prospective environments; however,
they do not predict whether one is in a VMS hydrother-
mal system or what part of a VMS system one might be
in. Alteration lithogeochemistry, in contrast, can pro-
vide critical information on the geochemical signatures
imposed on a volcanic unit by hydrothermal activity. In
using alteration lithogeochemistry it is critical to iden-
tify regional, semiconformable alteration within the
hydrothermal recharge zone (i.e. distal to mineraliza-
tion) versus proximal, pipe-like alteration representing
the discharge or upflow zones. Semiconformable alter-
ation zones are notably patchy in their distribution but
are regionally extensive, often on the kilometres to tens
of kilometres scale (MacGeehan and MacLean, 1980;
Munhá et al., 1980; Munhá and Kerrich, 1980; Galley,
1993; Gibson et al., 1983; Richardson et al., 1987; Alt,
1995, 1999; Skirrow and Franklin, 1994). Regional
semiconformable alteration zones are associated with
significant gains in Na-Mg, losses in metals, silicifica-
tion, and in some cases Ca-Fe enrichment (MacGeehan
and MacLean, 1980; Munhá et al., 1980; Munhá and
Kerrich, 1980; Gibson et al., 1983; Richardson et al.,
1987; Galley, 1993; Skirrow and Franklin, 1994; Alt,
1995, 1999). Semiconformable alteration zones also
exhibit 18O isotope enrichments (i.e. δ18O>6-8) due to
lower temperature (<250ºC) water-rock interaction at
relatively low water-rock ratios (e.g. Munhá et al.,
1980; Munhá and Kerrich, 1980; Schiffman and Smith,
1988; Cathles, 1993; Paradis et al., 1993; Hannington
et al., 2003b). Furthermore, semiconformable alter-
ation zones are associated with Mg-rich chlorite, Fe-
Mn-Mg-poor carbonate (e.g. calcite), high Fe/Al epi-
dote, and Na-rich mica (e.g. Franklin et al., 1981; Gillis
and Thompson, 1993; Saccocia and Seyfried, 1994;
Saccocia et al., 1994; Alt, 1995; Santaguida, 2000;
Large et al., 2001a; Hannington et al., 2003b).
Proximal alteration zones, in contrast, are associated
with pervasive alteration that is at higher water-rock
ratios and generally at higher temperatures that are
associated with upwelling hydrothermal fluids
(Franklin et al., 1981, 2005; Lydon, 1984; Gemmell
and Large, 1992; Gemmell and Fulton, 2001). These
zones are generally tens to hundreds of metres in scale,
and are characterized by significant gains in Fe-Mg-K-
Si, metals, S, in some cases CO2, and elevated Tl-Sb,
along with high Ba/Sr, AI, CCPI, Hg/Na2O, and
S/Na2O values (Figs. 3-9, 3-10, 3-12, 3-13, 3-c15) (e.g.
Riverin and Hodgson, 1980; Saeki and Date, 1980;
Date et al., 1983; Hashiguchi et al., 1983; Gemmell and
Large, 1992; Barrett and MacLean, 1994a,b, 1999;
Galley et al., 1995; Gemmell and Fulton, 2001; Large
et al., 2001a). Proximal alteration zones are also asso-
ciated with hydrothermal sedimentary rocks with
chemical signatures indicating a dominantly hydrother-
mal (versus detrital) origin (e.g. Kalogeropoulos and
Scott, 1983, 1989; Duhig et al., 1992; Liaghat and
MacLean, 1992; Peter and Goodfellow, 1996, 2003;
Davidson et al., 2001; Peter, 2003). Proximal alteration
zones are associated with zones of 18O depletion
(δ18O<6-8), indicative of high-temperature water-rock
interaction at high water-rock ratios (e.g. Green et al.,
1983; Urabe and Scott, 1983; Taylor and South, 1985;
Schiffman and Smith, 1988; Barrett and MacLean,
1991; Cathles, 1993; Hoy et al., 1993; Paradis et al.,
1993; Huston et al., 1995; Alt and Teagle, 1998;
Huston and Taylor, 1999; Huston et al., 1999). Chlorite
from proximal zones is Fe-rich (i.e. high Fe/Mg ratio)
29
 S. J. Piercey
in some cases (Franklin et al., 1981; Kranidiotis and
MacLean, 1987; Zierenberg et al., 1988; Richards et
al., 1989; Lentz and Goodfellow, 1993; Hannington et
al., 2003b; Relvas et al., 2006), whereas in other it is
Mg-rich (Urabe and Scott, 1983; Urabe et al., 1983;
Gemmell and Fulton, 2001; Large et al., 2001a) when
the chlorite coprecipitates with pyrite or other Fe-bear-
ing phases (Saccocia et al., 1994; Saccocia and
Seyfried, 1994). Proximal epidotes have low Fe/Al
ratios (Gillis and Thompson, 1993; Santaguida, 2000;
Hannington et al., 2003b), muscovite is typically K-
and Ba-rich with low Na (Large et al., 2001a; Relvas et
al., 2006; Bradshaw et al., 2008), and carbonate is typ-
ically Fe- to Mn-rich (Large et al., 2001a; Hannington
et al., 2003a; Bradshaw et al., 2008); some deposits are
associated with dolomite (Squires et al., 2001).
Combining petrochemistry and alteration lithogeo-
chemistry provides a powerful tool for understanding
the VMS environment. Depending on the stage of the
exploration program (e.g. greenfields area selection
versus brownfields near-mine exploration) different
techniques will be utilized. In the early stages of explo-
ration petrochemistry and reconnaissance alteration
lithogeochemistry will be utilized more commonly,
whereas in more advanced stages of exploration alter-
ation lithogeochemistry and more refined alteration
identification methods (e.g. isotopes, mineral chem-
istry) will be utilized.
SUMMARY
Volcanogenic massive sulphide (VMS) deposits remain
attractive targets for exploration. While field-based
methods and geophysics are critical tools in explo-
ration for VMS deposit, lithogeochemistry has become
a common tool in exploration in both greenfields and
brownfields areas. In greenfields areas, prospective
VMS belts are associated with petrochemical assem-
blages that are indicative of rifting and high-tempera-
ture magmatism. Rift zones and high-temperature mag-
matism provide the crustal permeability required to
focus hydrothermal fluid recharge and discharge, and
heat to drive hydrothermal circulation, respectively.
Areas that exhibit these characteristics are prospective
regions for further detailed, belt-scale exploration.
Belt-scale lithogeochemical tools are aimed prima-
rily at identifying parts of the VMS hydrothermal sys-
tem. The utilization of raw lithogeochemical data, nor-
mative mineral plots, cation plots, alteration indexes,
and various mass balance methods provide powerful
tools in delineating regional, semiconformable
(recharge-zone) alteration from proximal, pipe-like
(discharge-zone) alteration. Petrochemical assem-
blages and these various alteration lithogeochemical
techniques, combined with geological mapping and
drill-core research documenting volcanic, sedimentary,
30
intrusive, and alteration facies, and other geophysical,
mineralogical, and isotopic methods can lead to robust
genetic and exploration models for VMS systems.
ACKNOWLEDGEMENTS
I thank my colleagues whom I have had numerous dis-
cussions with regarding lithogeochemistry and VMS
deposits: Jim Franklin, Alan Galley, Harold Gibson,
Wayne Goodfellow, Mark Hannington, Tom Hart,
Dave Lentz, Mike Lesher, Suzanne Paradis, and Jan
Peter. They have freely shared their ideas and thoughts
and have engaged in many fruitful discussions that
have focused my ideas and arguments. This paper was
written while Steve Piercey was a sabbatical visitor in
the Department of Earth Sciences, Memorial
University of Newfoundland and Labrador (MUN).
The faculty and staff at MUN are thanked for their hos-
pitality and for numerous discussions, in particular
Derek Wilton, John Hanchar, and Greg Dunning. Steve
Piercey’s research is funded by Discovery Grant from
the Natural Sciences and Engineering Research
Council (NSERC) of Canada. Thorough and thoughtful
reviews by Matt Leybourne and Brian Cousens are
greatly appreciated and have improved this manuscript
significantly.
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156
Mafic Mafic Bimodal Bimodal Felsic
Fe-Ti Siliciclastic Mafic Felsic Siliciclastic
Icelandite

MORB MORB
or
BON (+/-LOTI)

MORB
MORB

OIB, MORB
BON (+/-LOTI) MORB Fe-Ti V V
V
or OIB Icelandite V V V V
OIB, MORB V
MORB (+/-BON) V V
V
V VV
FIII - FII-FIV V V FIII - FII
V V V V V
(HFSE enriched to V V
BON/THOL V V
MORB/BON calc-alkalic to
rhyolites FIII - FII
(HFSE enriched to peralkalic)
calc-alkalic to felsic
MORB IAT/LOTI peralkalic)
(+/-BON) BON felsic
MORB
KOM
BON

Cyprus Besshi Noranda Kuroko Bathurst

Oman Windy Craggy Flin Flon Buchans Iberian Pyrite Belt
Bay of Islands Fyre Lake Kidd Creek Mount Read Finlayson Lake
Slide Mountain Outokumpu Rambler Eskay Creek

Ultramafic rocks Sedimentary rocks Felsic intrusion (deep seated)

Gabbro Icelandite Felsic intrusion (high level)

Sheeted mafic dykes MORB Massive sulphide deposit

Submarine Volcanism and Mineralization: Modern through Ancient

V V
Basalt V
V V Felsic volcanic rocks

Figure 3-c14. Petrochemical assemblages for various volcanogenic massive sulphide deposit environments and deposit types. Based on concepts presented herein and Piercey (2007). BON
= boninite; HFSE = high field strength elements; IAT = island arc tholeiite; LOTI = low-Ti island arc tholeiite; OIB = ocean island basalt; MORB = mid-ocean ridge basalt; see text for a discus-
sion of FII and FIII rhyolite.
 Colour Figures

Increase in Eu/Eu* Limit of Tl halo

of Fe-Si cherts Tl+Sb increases
Ba/Sr increases

Mn content of carbonate increases

S/Na2O increases
δ18 O decreases CCPI increases

Limit of Na depletion AI increases

Hanging-wall volcanic rocks Chlorite alteration Quartz alteration

Massive sulphide Sericite alteration

Exhalites (ore-equivalent horizon) Carbonate alteration

Footwall volcanic rocks

Albite alteration

Figure 3-c15. Model of alteration zonation associated with Zn-rich polymetallic volcanogenic hydrothermal massive sulphide deposits and alter-
ation vectors useful for exploration (from Large et al., 2001c). CCPI = chlorite-carbonate-pyrite index.

130º1'50"W 130º1'45"W
155º56'0"W 155º54'0"W
0 1 2
20º46'0"N

45º58'40"N
kilometres

4 0
-40
0 -15
-1
53

45º58'35"N
0

-40
-600

0
20º44'0"N

-155
0
-400

00 0
-6 0
-8 -1570
45º58'30"N

0 100 200

metres

Figure 4-c5. Cluster of steep-sided cones on the Hana Ridge, the
submarine east rift zone of Haleakala Volcano, Hawaii (Clague et al.,
2000b). The cones have aspect ratios averaging 0.18, heights of
several hundred metres, and their bases are about 1 km in diameter.
Unlike their subaerial counterparts, these submarine cones lack
summit craters; the only one sampled is constructed of alkalic lavas.
The 30 kHz bathymetric data are gridded at 30 m (MBARI Mapping
Team, 2000) and shown with 200 m contours. This and most of the
subsequent figures are slope-shaded bathymetry; most of the data
was collected with hull-mounted multibeam systems. Slope-shading
is a technique that shades depending on the slope of the surface
rather than illuminating from one direction.
Figure 4-c6. A 200 m diameter cone on the floor of Axial Seamount
on the Juan de Fuca Ridge (Thomas et al., 2006). The cone has a
deep crater reaching almost to the regional depth surrounding the
cone. The lumpy terrain on the western flank may be constructional
or may be slump deposits from a collapse of part of the cone. The
200 kHz bathymetric data was collected with the autonomous
MBARI mapping vehicle (AUV) D. Allan B. flying at 50 m altitude. The
data are gridded at 1 m and shown with 10 m contours. This cone
was previously imaged by side-scan sonar (Embley et al., 1990).

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