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Lithogeochemistry of volcanic rocks associated
with volcanogenic massive sulfide (VMS)
deposits and applications to exploration

Chapter · January 2009


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Stephen Piercey
Memorial University of Newfoundland


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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)

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

Galley et al. in particular rift environ- 16 .g. 1999. Tl. 1986b. trace elements in lithogeochemical exploration. Piercey 500-2000 m hydrothermal plumes Mn. exploration for VMS deposits. these attributes provide key infor- times. Model for the setting and genesis of volcanogenic massive sulphide (VMS) deposits (from Galley. 2005. Of particular importance has been the determi. volatile metal species geochemical signatures provides powerful tools in the (e.. Similarly. mation on the heat flow and tectonic environment of nation of Th-Nb-Ta and the REE at ultra-low levels. VMS from the regional to local scale. 2007). 1993. Franklin et al. and The essential elements of the VMS system are pro- hydrothermal alteration attributes of the VMS system vided in Figure 3-1. attributes of volcanic rocks associated with VMS ing the high field strength elements (HFSE) and rare deposits. 1998. whereas they were not as easily accessible prior to ICP.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. key features for area selection. The combination of both primary and secondary litho- 2008. MASSIVE SULPHIDE DEPOSITS AND The paper initially presents the nature of the VMS THEIR CLASSIFICATION target: the geological and tectonic setting. tor elements (e. particularly important for discriminating the tectonic The latter provide information on the nature of fluid- environments of ancient VMS successions (e. and continue to form. In the prohibitively high costs and with low turn-around case of the former.. S. 2001b. except at of volcanic rocks associated with VMS systems. W) are also available now. followed by an overview of lithogeochemical earth elements (REE). Sb.g. includ.g. J. Mo. 1991. eralized zone and what part of a VMS system one is in. Piercey et al. As) and ultra-low level values for indica.. Piercey. Lentz. elements that were unavailable attributes associated with the hydrothermal alteration to explorationists in the 1970s and 1980s. Syme et al. 2007). THE TARGET: VOLCANOGENIC MS development. VMS deposit formation. Throughout Earth history.. Lesher rock interaction and whether one is proximal to a min- et al... 1993b. within exten- provides an overview of the primary lithogeochemical sional geodynamic regimes. The manuscript then deposits formed. Swinden. Barrie et al.

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

(1997). Jenner (1981) Piercey et al. V). can mobilize the HFSE . Piercey 1000 Pb. tectonic. When evaluating primary volcanic 1 lithogeochemical signatures. and mafic rocks are predominantly Boninitic rocks are associated with many ophiolite- sourced from asthenospheric mantle. In addition. Murphy and Hynes. environments. in subaqueous and 100 Alkalic variably altered volcanic sequences it is important to Rock / Primitive Mantle rely on immobile major and trace elements. 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. Jenner. Data from and Sun and McDonough (1989). LOTI = deposits is dependent on whether volcanism is associ- low-Ti island arc tholeiite. The last two groups are associated with evolved A environments dominated by continental crust or conti- nental crust-derived sedimentary rocks. Understanding the primary petrolog- Rock / Primitive Mantle ical processes affecting a volcanic belt is critical in pro- viding information on the thermal. Carbon dioxide- (CO2)-rich fluids.g. samples should have preserved textures. Betts Cove) and bimodal mafic sys- 18 . and petro- 10 logical history of a volcanic belt. BON = boninite. Kerrich and Wyman. and Mafic Geochemistry Kepezhinskas et al. 1996. Felsic rocks in these set. The deposits of the last two groups are notably Zn-Pb-Cu dominated. Sc. Hf. Stoltz et al. ated with juvenile or evolved substrates. and rare earth elements (REE) (e. mafic crust. it is critical that the fresh- IAT / LOTI BON est. deposits are preferentially associated with boninite and low-Ti tholeiite (LOTI) or mid-ocean continental crustal influence.1 secondary minerals. basalt). Abbreviations: BABB = back-arc basin basalt. N-MORB = normal mid-ocean ridge basalt. N-MORB 1 PRIMARY VOLCANIC LITHOGEOCHEMISTRY OF VOLCANOGENIC MASSIVE SULPHIDE- . 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. Oman. however. In juvenile gram and all others in this paper from Sun and McDonough (1989). 3-3.g. to understand primary igneous processes. the high BABB field strength elements (HFSE: Zr. Ewart et al. Nb. Ta. Y.1 and REE (e. Cyprus. CAB = calc-alkaline basalt. Felsic rocks in OIB (alkalic) 100 these environments are derived from melting of conti- Rock / Primitive Mantle nental crust or continental crust-derived rocks. (1990). E-MORB Mafic volcanism and plutonism associated with VMS (enriched mid-ocean ridge basalt). Namely. and (C) transitional (back-arc and arc rift-related strongly carbonate-altered rocks. ones that are not significantly mobilized during hydrothermal 10 alteration and metamorphism. ridge basalt (MORB) of both the normal (N-MORB) tings are derived primarily from melting of hydrated and enriched (E-MORB) varieties (Figs.g. S. 1997). Primitive mantle normalized plots: (A) non-arc basalt. IAT = island arc tholeiite. 3-4). and E-MORB mafic rocks commonly are derived from mantle 10 sources including both lithospheric and asthenospheric sources. including Al2O3 and TiO2. J. Primitive mantle values for this dia. (B) arc basalt. be free of veins and . Deposits in the hosted (mafic) VMS deposits (e. In addition. 1986) and this Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc should be taken into consideration when dealing with Figure 3-2. Turner- first three groups are enriched in Cu-Zn with very little Albright. (1994). (2004). least altered samples be taken.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. 1 Ti. and OIB = ocean island basalt. 3-2. key features that can be used to delineate potentially fertile versus barren volcanic basins.

alkalic. Pearce et al.. Shasta MORB Fyre Lake BON Figure 3-3.e. Furthermore. Kidd Creek BON Tulsequah MORB #1 Josephine BON The high Nb values for West Shasta are likely erroneous. peralkaline. 2007). Fyre associated with the initiation of subduction (Brown and Lake) (Table 3-1).g. Bedard et al. alkalic HFSE-enriched rhyolite (A-type). and most boninite is associated with fore-arc extension more rarely in mafic-siliciclastic systems (e. East Pacific Table 3-1. peralkaline and calc- alkalic rhyolite (rarer) Felsic Siliciclastic MORB. Rambler). 1981. 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. Piercey et al. boninitic rhyolite Bimodal Felsic MORB. van der Laan et al. Snow Lake. Stern and Bloomer. Shasta LOTI Josephine MORB/BABB tems (e. E-MORB/OIB Flin Flon LOTI Rambler MORB Betts Cove LOTI including (A) boninite.. Proterozoic-Phanerozoic . Kidd Creek. 1992. preted to have formed from mantle sources that are 1998. Data Tulsequah MORB #2 sources are listed in Appendix 3-1. boninite.. and (D) Contaminated MORB ocean island basalt (OIB)-like. 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 .tholeiitic arc tholeiite present but rarer) rhyolite.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. Jenner. and modern mid-ocean ridges (e. low-Ti tholeiite (calc-alkalic and island Archean . boninite (rare) - Bimodal Mafic MORB. MORB - Mafic Siliciclastic MORB. alkalic HFSE-enriched rhyolite. 1992. 1981. with many mafic-hosted VMS deposits in ophiolite. the initiation of back-arc basin formation (Crawford et ultra-depleted mantle) that require very high tempera. 1989.. 1999) or with ultra-depleted in incompatible trace elements (i..FIII rhyolite. and calc-alkalic rhyolite (rarer) 19 . tures to melt (~1200-1500ºC) (Jenner. Wyman et al.. (C) mid-ocean Flin Flon MORB Noranda Troodos BON ridge basalt (MORB) and back-arc basin basalt (BABB).1 .1 . Boninitic-LOTI rocks are inter. Petrochemical assemblages of mafic and felsic rocks commonly associated with different VMS deposit classes (from Piercey. 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. 1992.g. 1999. 2001a). TAG. (B) low-Ti island arc tholeiite. 1989. VMS Deposit Class Mafic Felsic Mafic Boninite. Crawford Mid-ocean ridge basalts (MORB) are associated et al. 2000). low-Ti tholeiite.g. al. Kerrich et al... Falloon and Danyushevsky. Kutcho LOTI Josephine LOTI Kutcho LREE-IAT W.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 .

g. MORB. Oman) and back-arc basins (e. Escanaba Trough) (Table 3-1). Primitive mantle normalized plots for mafic rocks asso- Bransfield Strait IAT Lau Basin MORB ciated with volcanic massive sulphide deposits in modern oceans.g.. and (B) alkalic. Rambler. ocean Contaminated MORB island basalt-like mafic rocks. (Table 3-1). Semail).g. Lau Basin) boninite (e.g.g. 3-4). and Semail). S. Manus Basin MORB Axial Seamount MORB Guaymas MORB East Pacific Rise MORB Guaymas BABB Lau Basin IAT Rise. Lau Basin.1 . The high Nb data for Middle Contaminated MORB Escanaba Trough MORB Valley MORB are erroneous. Data sources are listed in Appendix 3- Tulsequah MORB 1. and Okinawa Trough (B) mid-ocean ridge basalt (MORB). Guaymas. MORB-like rocks with weak negative boninite (e. Troodos. typical of enriched-MORB).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. Windy Craggy.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 Mafic-Associated Figure 3-4. In mafic and bimodal-mafic systems (e.1 . are also present mafic-siliciclastic deposits in both the ancient record in many mafic-type VMS environments in modern and (e.and BABB- fore-arc or back-arc settings) the MORB-type rocks type rocks are interpreted to have formed from incom- commonly show an intimate relationship with boninitic patible element-depleted mantle with liquidus temper- and arc-tholeiitic rocks. 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 . Manus Basin. J.g. 3-3.g. Greens Creek) and modern sedi- ancient back-arc basins (e. Bransfield Strait MORB TAG MORB including (A) back-arc basin basalt and island arc tholeiite. mented ridges (e. or overlying and/or crosscutting (Figs. MORB-type rocks are also associated with called back-arc basin basalts (BABB). McKenzie and 1000 1000 A Alkalic. 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.g. Middle Valley. Data sources are listed in Appendix 3- Manus Basin BABB Middle Valley MORB 1. Ocean Island Basalt (OIB)-Like Mid-Ocean Ridge Basalt (MORB (enriched)) B 100 100 Rock / Primitive Mantle Rock / Primitive Mantle 10 10 1 1 . Turner-Albright) Nb anomalies on primitive mantle normalized plots. Tulsequah BABB Bathurst OIB 20 . with MORB either underlying atures of approximately 1200ºC (e.

Iberian Pyrite Belt..g. Okinawa Trough) and Eskay Creek ancient (e. 2004)..) Lake.. Langmuir 1000 A Panorama Dacite et al. 1988. 1986b. 1 FIV ible element-enriched OIB (Fig. Lentz. 2002. McKenzie and O’Nions. (C) Post-Archean volcanic massive post-Archean VMS-associated felsic rocks. 2002a. 3-2. or interaction 1 FIV with. continental crust are fundamentally different than 0 40 80 120 160 200 those associated with partial melting of a mafic sub. West Shasta Shinjo et al. 1986b. Lesher et al.g. restricted to post-Archean juvenile terranes. La/Ybn-Ybn with FI-FIII-affinity rhyolite discrimination signatures dependent on the VMS environment (Table diagrams (from Lesher et al. Panorama Rhyolite (Barren) ocean ridges or within back-arc basins (e. 3-6. Alkalic and La/Ybn Parys Mountain MORB-type basalts are associated with many bimodal. 2003). Ybn strate. 1991. or as flows that overlie felsic rocks and the 1000 B Finlayson Barren (calc-alkalic) associated mineralization (i. Felsic rocks in VMS environ- ments that form via partial melting of. Lesher et al. 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. 1992) and represent extension either at mid. Shinjo 100 Okinawa Trough Mount Read et al. Finlayson Barren (tholeiitic) Finlayson Deposit-Hosting date the main mineralization event).g. FI Sturgeon Lake 100 Blake River (Noranda) In evolved environments.... they commonly post.Barren) (e. Eskay Creek) geological record (Table 3-1).g. Finlayson FIIIa FIIIb Delta-Bonnifield (Mystic Ck.Barren) reflect a shift from rifting to true seafloor spreading C Flin Flon (Tholeiitic . (B) Post-Archean volcanic massive sulphide-associated and barren rhy- tures and assemblages that are somewhat different than olite from evolved environments. 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 . Bathurst. 1999.. (2004) Superior Province of Canada (Lesher et al. there Iberian Pyrite Belt is commonly a stratigraphic progression upwards from FI Bransfield Strait alkalic basalts to MORB (van Staal et al. Rogers and van Staal.. Bransfield Strait. (A) Archean 3-1). 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. Flin Flon (Mine Rhyolites) Rambler Barrett and Sherlock. The MORB-type and OIB-like rocks often occur as sills and dykes that 0 40 80 120 160 200 Ybn crosscut. the FIV suite that is largely Barrie et al.. Goodfellow et al. 1986b. to incompat. 1992. The I suite of felsic for VMS-associated and barren rhyolites in the rocks has low La/Ybn (and Zr/Y) ratios and high HFSE Superior Province — the FI to FIII suites of rhyolite. and (1986b) outlined a tripartite subdivision of felsic rocks expanded to a global database. van Staal et al. Hawkins.. Hart et al. and are interpreted to represent melts derived from lithos- 1 FIV pheric (alkalic) to asthenospheric (MORB) mantle sources. Langmuir Kidd Creek et al. 10 FII chemistry of felsic rocks associated with VMS systems (e. to include a fourth suite. Data sources are listed in Appendix 3-1. volcanic massive sulphide-associated and barren felsic rocks. Furthermore. Piercey et al. The FI 21 . to weakly incompatible element-enriched E-MORB. leading to different VMS-associated rhyolite Figure 3-6.. sulphide-associated and barren rhyolite from juvenile environments. Avoca Bathurst .Nepisguit Falls 10 FII modern (e. 1999. 1997. 1991.b)..Flat Landing Bk.g. felsic and felsic-siliciclastic settings from both the Bathurst .. 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. 1993. 1995).e. 1991. Piercey et al. Almodóvar et al.g.. FIIIb FIIIa 1998. contents (e. Hart et al. 3-5)..b. Barrie et al. Colpron et al. 3-7)... 2004). Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration Bickle. Furthermore.. 1996.. In Archean terrains much of our knowledge on fel- sic volcanic geochemistry is from research in the This classification was modified by Hart et al. 2004). Archean felsic rocks have signa. 1995. Zr>200 ppm) (Figs. FI 100 Kutcho 2002a. Hart et al. 1993a. 3-5).

Barren) Flin Flon (Tholeiitic ..Nepisguit Falls Eskay Creek 100 Delta-Bonnifield (Mystic Ck. ate between the two groups (Figs.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 perature melts (T>900ºC) derived from melting of (Figs. 1986b. Diagram 100 after Leat et al. Bathurst . <10 km) felsic rocks (Fig. 3-7). (1986). 3-6.Flat Landing Bk. which are interpreted to have allowed these melts to rise to the surficial environment formed within Archean rift sequences from high-tem. Barrie et al.. (C) Post-Archean High Lake volcanic massive sulphide-associ- Zr > 200 ppm ated and barren rhyolite from juve- 200 nile environments. The formation at shallow depths (i. 3-6). 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 .) 10 1 10 100 1000 Nb 500 C Flin Flon (Calc-Alkalic . 1993. ity of Archean VMS deposits are hosted by FIII and FII 2004).. Data sources are listed in Appendix 3-1. S. 1995.e. thus. Barrie. 3-6. 22 . Piercey 700 A Panorama Dacite Figure 3-7. The FII suite has signatures intermedi. hydrated basaltic crust at shallow depths (Lesher et al. 3-7). (B) Post-Archean vol- canic massive sulphide-associated Zr South Bay and barren rhyolite from evolved Kamiskotia 300 environments. J. Zr-Nb diagram illustrat- (barren) Panorama Rhyolite ing HFSE variations in rhyolitic 600 rocks associated with volcanic Kidd Creek massive sulphide environments. without losing their heat of fusion (T>900ºC). 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). The major. Hart et al.

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

Massive Sulphide exploration tools for volcanic massive sulphide exploration. (A) Contoured Na2O contents for rhyolitic rocks of the Dacite Blake River Group. spillitized (Na-altered). 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. <0. the hydrothermal upflow zones are marked by strong depletions in Na2O due to feldspar and glass destruction.. (B) and for dacitic Zeolite rocks at the Fuzakawa mine. associated with the Ansil VMS deposit (from Galley. (A) Hughes (1973) diagram for outlining fresh. Kuroko district. Galley et al. Na-gains) versus pipe-like alteration (Na-depletions).. 2006). (B) Spitz-Darling index (Spitz and Darling. 1995. Montmorillonite 1983). Japan (from Date et al.4% Na2O 24 . 1978) (Al2O3/Na2O) versus Na2O plot for outlining fresh rocks versus those with Na-gains (spillitized) and losses (dia- gram from Ruks et al. Canada. Quebec. Chlorite-Sericite These zones of Na-depletion are extremely simple. yet effective.. 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. 1995). S. J. Data on the diagram are from Piercey (unpublished data). and keratophyric (K-altered) igneous rocks. These diagrams are useful for delineating semiconformable alteration (spillitization. In both cases.

Ternary plots of major elements and normative mineral ation types and pathways (Fig. 2005. Franklin et Lapillistone albite al. contouring of raw alkali and metal val- ues can be useful in delineating potential alteration zones (Fig. Franklin et al. Sericite Chlorite tify alteration zones. which are associated 20 with marked Na-depletions (Fig. 1990. 1978. simple contouring of 40 sericite Na2O values by Date et al. Ishikawa et al. Date et al. Strongly altered 1993. data is from Piercey. Bradshaw et al. Similarly.. Gemmell and Fulton. Franklin. (Fe+Mg) cation % als have also proved useful for outlining different alter. 1980. These proximal alteration zones have a well developed zonation in alteration minerals and phlogopite chemistry. B 1981.. Proximal A Al2O3 alteration zones represent hydrothermal upflow or dis- charge zones (e. Fig. Sebert et al. Utilization of major (and trace) C quartz 100 element data can be useful in identifying alteration. Large et al. Richards et al. 1992. Richards et al. MacDonald et al. 3-10) (e.. 2005). Extrem ely alte chlorite red rhy (1995) identified the proximal alteration zones beneath olite the Kuroko and Ansil deposits. 1991. from chlorite-(quartz)-rich cores to sericite- (quartz)-rich rims to quartz-sericite-rich envelope actinolite zones. 2001. Hashiguchi et al. Hodgson. 1993. clast muscovite like in impermeable strata (e. For example. 1996. Morton et al. 1992.g... flows) and can have Rhyolite 2 irregular shapes in impermeable volcaniclastic or sedi. 3-10) (Riverin and contents outlining volcanic massive sulphide-associated alteration. Gibson et al. 1993. Franklin. 2001a).b.. 2004. Gemmell and Large.. Riverin and Hodgson. chloritite Various lithogeochemical tools can be used to iden. 1993.. 1993). epidote ite Gemmell and Fulton.g. 3-9). 1980.g. 1976. Spitz and Darling.. (B) Cation 2004). Figure 3-10.. the alteration pipe is characterized by Ca-Na losses and Fe-Mg-K-Si-S- Silica leaching Moderately altered metal enrichments (e. Weakly altered bonate (Lydon. (A) MgO-Al2O3-(CaO+Na2O+K2O) plot (MacDonald et al. (1983) and Galley et al... Some precursor proximal alteration zones are also associated with car.. unpublished data). Knuckey et al. 2001). Spillitization versus K-metasomatism is important for delineating semiconformable versus pipe-like alter- 80 ation. Galley et al. 1980. 2005. 1992. 1996. Large. 2003. Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration typically less than a few hundred metres). 1989. 1981. 3-8A). MacLean and Barrett. lor biotite Least Altered ch Felsic Gibson. 1994a. 1982. Large et al.. Rhyolite 3 mentary strata (Riverin and Hodgson.. 2001. 1983. 1989. Rhyolite 1 Rhyolite 1 They have varying morphology but are typically pipe. Gemmell and Large. feeder zones to the deposits) and Qtz Porphyry form from high-temperature water-rock interaction.. 60 8B). 1980.g. 3. 1983. 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. Gemmell and Large. Squires et al. 1999. Lentz and sericitite Goodfellow.. as have normative mineral plots (both CIPW normative and (C) cation percentage plots illustrating various alter- and cation normative plots. 2001c. Huston. Sebert et al. Gemmell and Fulton. 1996. 1996. 25 ... Hudak et al. and can be done using the plot of Hughes (1973) Weakly to moderately altered rhyolite (Fig.. 3-9). 1992. 1984. Relative to background rocks. Barrett and ation minerals and alteration paths (from Barrett and MacLean. 1996. Barrett and MacLean. 2001. 1978) and Na2O contents (Fig. Ternary plots of 0 10 20 30 40 50 major elements with various potential alteration miner. Spillitization versus Na-losses can also be Si cation % precursor delineated using the Spitz-Darling index (Al2O3/Na2O) (Spitz and Darling. 2008).

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

g. Petrochemical assemblages are nity. Windy Craggy) or boninite (e. Madeisky. 1 or 2001a). The PER approach has not been Petrochemical assemblages are an attempt to link these utilized extensively by workers in the VMS commu.g.g. the potential to host VMS mineralization (Fig. between mafic and felsic rocks and associated ples that deviate from the primary trend are affected by sedimentary rocks or their chemostratigraphy. 2004) or mafic (e. Lesher et al. fields areas.g. O’Connor-Parsons and Stanley.g..g.7 ppm massive ore 10 Figure 3-12. Guaymas. Hart et al. Newfoundland. ratios are chosen to remove the ous studies on the primary lithogeochemistry of vol- potential effects of closure and mass change on the canic rocks in VMS belts have either focused on felsic absolute concentrations of elements (Stanley and (e. Piercey. Swinden.. 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 .. are commonly associated with MORB (e. it has been applied very successfully in chemostratigraphic assemblages of mafic and felsic gold exploration (e.g. alteration (Fig. however. or more rarely OIB (e.1 canic belt. (C) Hg/Na2O-Ba/Sr plot of Collins (1989) for delineating proximal versus barren alteration from the Tally Pond vol- . Most previ- element (e. sam.. 3-c14. Al or Zr).. Canada. 27 . Piercey et al. Ba/Sr structed using molar ratios of potentially mobile ele. ( A) Tl-Sb volatile element plot outlining the fields for Barren background through to proximal alteration zones (from Large et al.. 3-13).. deposits is the identification of fertile ground in green.1 . 1994). spond to primary geological process (e. The diagrams have slopes that corre.or A Regional Area Selection Tool BABB-type rocks. Data in (A) and (B) are from .1 1 10 100 1000 Piercey (unpublished data). 2007. Swinden. Middle Valley). Fyre Lake). 2007). Swinden et al. with less emphasis on the relationships crystallization) and secondary alteration minerals. fractional 1991) rocks. provide key information on the tectonic setting and ments to a conserved denominator that is an immobile heat flow of a given volcanic assemblage. 1989. 1997. indicative of fore-arc rifting or ini- One of the key challenges in the exploration for VMS tiation of back-arc spreading (Fig. In mafic-siliciclastic environments. Lentz. ration tool in VMS systems. boninite DISCUSSION and/or LOTI commonly host the VMS deposits but are Petrochemical Assemblages: commonly overlain (or underlain) by MORB. 2001.. and are a predictive tool to identify environments with suggesting that it has considerable promise as an explo. 1986b. Table 3-1. 3-c14) (e. (B) Diagrams outlining the extent of volatile element halos distal volcanic rocks around some Australian volcanic massive sulphide deposits (from Large et al. Primary lithogeochemical signatures of 1999).g. 1991. as these signatures Trough.1 1 10 100 1000 Sb 200 m 1000 C Thalanga 100 Duck Pond and 100 m Boundary Horizons Hg/Na2O Tl > 0. different data sets. 2007). 2001c).g. 1998. Escanaba ing potentially prospective belts. Murphy and rocks that indicate a specific geodynamic environment Stanley. the deposits mafic and felsic rocks have been utilized for identify. Eilu et al. Bedard et al. In mafic-dominated VMS environments.

crosscut and overlain by MORB-type basaltic rocks Barrett and Sherlock. 2004).g. 1999).. 3-c14) (e. 1999. Hart et al. 1999. Bailey. The occurrence of MORB and alkalic basalt in any fel- ing centres (e. 1998. Noranda. 2002). Piercey et al. 1994. 2001b.05 0. some cases..25Ba 100Mn Madeisky. ated. 5 10C 0. Hot spot the preexisting mafic-dominated substrate via mantle magmatism may have been significant in the case of upwelling during the rift event (e.. van Staal et al. Wyman et al. 1999. and overlain by OIB-like alkalic basalt Boninite/LOTI and associated rhyolite are commonly and/or MORB-type basalt (e. al. crosscut. Syme... Rambler. sic-dominated setting is indicative of rifting and the mal arc volcanism to back-arc-related magmatic activ- 28 . Rogers and van Staal. Stakes and Franklin... Various mass balance plots for VMS- 45 20S associated alteration systems.g. Dusel-Bacon et al. The felsic rocks are typically spatially associ- 1999. Davis et al.. 2003).g.. Piercey A 50 Figure 3-13. 1999. S.05 -4 plagioclase chloritization involving destruction mass addtion of Fe+Mg -6 ) icit e (ser -8 1/ 3 m= m . the absent and the rhyolite has normal. C14) (Piercey et al. (B) Δ(CaO+Na2O) versus Co 0. Almodóvar et al. HFSE. 2004). Bailey.5Ce 100P La feldspar fractionation) and various alteration phases.. Prior et al.0 (chlorite) (X-axis) -10 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.b. In most cases. the felsic imented back-arc rifts (Fig. Noranda) or via a transition from nor. Zr/Y>7 but with Zr<200 ppm and volcanic-arc lying mafic rocks are MORB in affinity (e.4 Mass Gain 30U Ma 1986) for altered basalt from the Windy Craggy deposit nt 40 n sta (Peter and Scott. Piercey et al.and REE-enriched rhyolite is 2002). 1998. calc-alkalic affinity deposits are hosted by FII-FIII rhyolite yet the under. Kerrich et al.. rocks that occur within these mafic-dominated envi- 1982. 1999).10 0.. Syme et al.00 -20 0 20 0. 1994. felsic rocks having calc-alkalic to within-plate (A-type) nite-like or tholeiitic rhyolite. In all these crosscut and/or overlain by OIB and/or MORB-type cases. Flin Flon). 1994). 1999. 20 20Zr 0. 1999). ity (e.15 Δ(Fe2O3+MgO) Molar Al/Zr indicative of formation within sedimented rifts or sed. affinity on discrimination plots). Dusel-Bacon et al.. 1991. 1996. the stratigraphic sequences are indicative of for. with the rhyolite hosting to peralkalic affinities (e. 1997. Wyman et al. ronments mark the rift episode and reflect melting of Peter and Scott. Si 0.. mation within rift environments..e. Bailes and Galley. 1997.. 1995. 2001a).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. 1999.. J. Piercey et al. Barrie et al. Bailes and Galley. 1992a. the OIB-type rocks at Windy Craggy (Peter and Scott. Lentz. Syme et al. McConnell et mineralization (Fig. 1983.b. 3-c14) (Saunders et al.1Cr 30Eu 15 4Mg Samples that lie off the primary trend are altered.00 0. either via true spread. 1993. 1993). 1991.e. (A) Isocon plot (Grant. (i. In bimodal felsic and felsic-siliciclastic environ- In bimodal-mafic environments. In 1999. 2002a. and Y Nd the greater the deviation from the trend indicates 10Hf 10 20Ti greater alteration intensity (from Stanley and Al Nb 6Ca 0. (Fig. felsic rocks predominate over mafic rocks with are commonly spatially associated with depleted boni.1Sr 0. (C) Pearce 25 Mass Loss Element Ratio (PER) diagram outlining various slopes 10Th Fe3+ Sc 50Tb corresponding to a primary igneous process (i.g.. boninite and LOTI ments. but these rocks are Lafleche et al. In some bimodal mafic environments.g.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. 2004).g. ss C h lo r itiz e d B a s a lt W C U 9 0 .g. Meijer.. mafic rocks (Stolz..

Peter.. zones are associated with zones of 18O depletion vide critical information on the geochemical signatures (δ18O<6-8). and hydrothermal circulation (Cathles. Cathles. 1980. 1993. dote.. mal system or what part of a VMS system one might be Davidson et al.. Rift environments are under extension for significant gains in Na-Mg.. Alt.. 1998. Large Alteration Lithogeochemistry: Identifying the et al. exhibit 18O isotope enrichments (i. Paradis et al. 1981. 2003b). 1983. Galley et al. Galley. 1980. Schiffman and Smith. 1993. 1992. 1990. The overall elevated geothermal gradient Riverin and Hodgson. Alt. are associated 2006).. 1980. faults for upwelling fluids in the discharge zone 1995.. 1983. 1994. in many cases. 1993. often on the kilometres to tens nated substrate.. 1980. Semiconformable alter. 1980. relatively low water-rock ratios (e. 1993. Munhá and Kerrich. eruption of Mn-Mg-poor carbonate (e. Hannington et al. regardless of Munhá et al. 1996. deposit type. 1995. Kalogeropoulos and tifying potentially prospective environments. Gemmell and Fulton.. Lydon. In addition. 1999). Gibson et al. Cathles. Chlorite ation zones are notably patchy in their distribution but from proximal zones is Fe-rich (i. 1993. Gemmell and Fulton. semiconformable alteration within the Schiffman and Smith. These two ingredients 1995. 2000. high Fe/Al epi- basalt (e. and elevated Tl-Sb. Skirrow and Franklin. and Na-rich mica (e. indicative of high-temperature water-rock imposed on a volcanic unit by hydrothermal activity. ments create void space at the base of the crust.. 1994. Santaguida. 1999. McPhie and Allen.g. Munhá and Kerrich.g. metals. 1999. typically have elevated temperatures and are characterized by significant gains in Fe-Mg-K- (>~900ºC for felsic rocks and >~1200ºC for mafic Si. Alt. McCaig et al.. 2001). 1999.e. 1989. which 1988. 1992. 2001a). Gibson et al. Munhá et al..g. Liaghat and they do not predict whether one is in a VMS hydrother. 1983. high-temperature magmatism. Hannington allows for the upwelling of mantle. 1980. Furthermore. Richardson et al. Urabe and Scott. tion) versus proximal. Hoy et al. 3-c15) (e. Gibson. and in some cases Ca-Fe enrichment (MacGeehan and fracturing. 2005. 1999.. Furthermore. silicifica- much of their history resulting in extensional faulting tion. Barrett and MacLean. Skirrow and Franklin. at the base of the crust leads to an elevated geothermal Saccocia et al. 1988. 1980. mal (versus detrital) origin (e. Gemmell and hydrothermal circulation. are regionally extensive. Huston et al. Franklin et al.. ing the conduits for fluid flow in the recharge zone and 1987. semiconformable alteration zones are associated with ronment. Proximal alteration in. 1988. associated with upwelling hydrothermal fluids Barrie et al. 2007. the et al. in some cases CO2. Galley. 1991. Large et al. partial melting. lower temperature (<250ºC) water-rock interaction at Allen et al. Regional are critical for the formation of a productive VMS envi. 1983. Gillis 1995). 1992. Huston et al. rift environ. the discharge or upflow zones. pipe-like alteration representing 1993. 1983. 1992.. Munhá et al. losses in metals. 1993. 1995. 1988. in contrast.. 1994a..e. 1999.. gradient in the rift environment (McKenzie and Bickle. which are key in driving and maintaining along with high Ba/Sr.. MacLean. including both the mafic zones are generally tens to hundreds of metres in scale. 1993. McKenzie and Bickle. hydrothermal recharge zone (i.. Proximal alteration zones are also asso- Volcanogenic Massuve Sulphide Plumbing ciated with hydrothermal sedimentary rocks with System chemical signatures indicating a dominantly hydrother- Petrochemical assemblages provide the means of iden. 3-12. the magmatic and Large. 1983. AI. 1984. and felsic suites.g. namely. Duhig et al. 2001. This elevated gradient results in crustal partial with pervasive alteration that is at higher water-rock melting and the formation of the rhyolite that hosts ratios and generally at higher temperatures that are mineralization in the bimodal VMS environments (e. The upwelling of mantle and ponding of basalt and Thompson. Setterfield et al. distal to mineraliza. and. S.e. 1999). Lithogeochemistry of Volcanic Rocks Associated with VMS Deposits and Applications to Exploration upwelling of mantle beneath a continental crust-domi. Large. CCPI.g. These products from partial melting. 2003b). 2007). 1999). 2005.. Saeki and Date. 2003. Green et al.b... δ18O>6-8) due to 1992. Hyndman et al. 3-10. Richardson et al.. 1994). semiconformable alter- generation of basaltic magmas. rocks).g. Semiconformable alteration zones also (Gibson and Watkinson. 2003). in contrast. using alteration lithogeochemistry it is critical to iden. 1985. tify regional. 2001. calcite). In all petrochemical assemblages. Prior et al. Fe- the base of the crust.. 3-9.. 1993. McPhie et al. Gibson et al. Kerrich. In interaction at high water-rock ratios (e.. Gemmell Piercey et al. Currie and Hyndman. Peter and Goodfellow. of the rift will also contribute to the maintenance of Date et al. high Fe/Mg ratio) 29 . 3-13. 1981.g. Alteration lithogeochemistry. Hashiguchi et al. Barrett and MacLean. there is the association of 1) rifting and 2) 1993. Huston and Taylor.. Hawkins. 1983. 1995. 1996. ponding of this basalt at ation zones are associated with Mg-rich chlorite.. however. 1994. Barrie S/Na2O values (Figs. 1987. Scott. Paradis et al.. Proximal alteration zones. 1995.. Taylor and South. (Franklin et al... provid... 2005. 1980. Hg/Na2O. providing the permeability necessary and MacLean. 1998. of kilometres scale (MacGeehan and MacLean. et al. 1981. 2001a. 1980. can pro. 1983. 1980. Alt and Teagle. 2001b). Lentz. Saccocia and Seyfried.g. Munhá and for focusing hydrothermal fluid flow.

Bergslagen region. 21 degrees N. P. 2001). Geology and genesis of the Areas that exhibit these characteristics are prospective Aznalcóllar massive sulfide deposits. 1992. J. Zierenberg et al. greenfields area selection Piercey’s research is funded by Discovery Grant from versus brownfields near-mine exploration) different the Natural Sciences and Engineering Research techniques will be utilized. Sáez. Council (NSERC) of Canada. Relvas et and have engaged in many fruitful discussions that al. Suzanne Paradis. regions for further detailed. sulfide and Fe oxide deposits. v. Society of Economic blages and these various alteration lithogeochemical Geologists. hydrothermal systems. volcanic. and Almodóvar. Petrology and chemistry of lavas from seamounts flanking the East SUMMARY Pacific Rise axis.C. R. They have freely shared their ideas and thoughts and Ba-rich with low Na (Large et al. Proximal epidotes have low Fe/Al Wayne Goodfellow. Chemical. 1988. prospective v. While field-based B. 1996. p. Relvas et al.. Batiza.. lithogeochemistry has become sedimentary setting of strongly deformed Zn-Cu massive a common tool in exploration in both greenfields and sulfide deposits at Benambra. geochemistry... Mark Hannington.L. focus hydrothermal fluid recharge and discharge. Memorial associated with dolomite (Squires et al. Boehlert. J. Seyfried. R.. in Seafloor Hydrothermal Systems: rily at identifying parts of the VMS hydrothermal sys. 2008). and Geological tem. and M. techniques. Urabe et al.. significantly. Monograph 91. Interactions. p. Alan Galley. R. 1987. M. and Jan Hannington et al. 1993. 2006). R.H. and carbonate is typ. Iberian Pyrite Belt. and Greg Dunning. p. 1993. v. I. Saccocia and deposits: Jim Franklin. 1989. Humphris. Batiza. nor. (eds. American Geophysical Union. 1983. Mineralium Deposita. and Atolls.. in particular the VMS environment... Kranidiotis and intrusive. Thorough and thoughtful ration petrochemistry and reconnaissance alteration reviews by Matt Leybourne and Brian Cousens are lithogeochemistry will be utilized more commonly. matism provide the crustal permeability required to Economic Geology. Barrie. Reviews in Economic Geology. 2001a) when I thank my colleagues whom I have had numerous dis- the chlorite coprecipitates with pyrite or other Fe-bear. 1994. Dave Lentz. 1999.. brownfields areas. Maestre. and ration for VMS deposit. 2003a. Bradshaw et al. belt-scale exploration. American Geophysical Union. Reconstruction of the tectonic. Tom Hart.. G.g. 2008).. Economic Geology. sedimentary. cussions with regarding lithogeochemistry and VMS ing phases (Saccocia et al. Petrochemical assem. Alt.. Pons. Harold Gibson. E.D. John Hanchar. whereas in other it is Mg-rich (Urabe and Scott..M. 1998. Rift zones and high-temperature mag. semiconformable Volcanic-Associated Massive Sulfide Deposits: Processes (recharge-zone) alteration from proximal. Richards et mineralogical. 825-854. al.. Mike Lesher. Probing the TAG hydrothermal drill-core research documenting volcanic. 1994). p. Toscano.F. S.. Physical. P. Depending on the stage of the Derek Wilton. muscovite is typically K. in Seamounts.. pipe-like and Examples in Modern and Ancient Environments. Peter. VMS belts are associated with petrochemical assem. and alteration facies. oxygen-isotopic profiles from deep 30 . combined with geological mapping and Alt. 87.H. p. 2006. implications concerning the mantle source composition for both seamount and adja- Volcanogenic massive sulphide (VMS) deposits remain cent EPR lavas.. Combining petrochemistry and alteration lithogeo. J. Facies analysis of a 1 9 Ga. Steve exploration program (e. REFERENCES istry) will be utilized. mound and stockwork. 2001a. methods and geophysics are critical tools in Mn-rich (Large et al. back-arc. 1981. 91.L.E. Allan... Allen. and processes. blages that are indicative of rifting and high-tempera. 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OIB = ocean island basalt. . BON = boninite.FII V V V V V (HFSE enriched to V V BON/THOL V V MORB/BON calc-alkalic to rhyolites FIII . LOTI = low-Ti island arc tholeiite. MORB = mid-ocean ridge basalt. MORB BON (+/-LOTI) MORB Fe-Ti V V V or OIB Icelandite V V V V OIB.FII-FIV V V FIII . see text for a discus- sion of FII and FIII rhyolite. Based on concepts presented herein and Piercey (2007). IAT = island arc tholeiite.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-c14.156 Mafic Mafic Bimodal Bimodal Felsic Fe-Ti Siliciclastic Mafic Felsic Siliciclastic Icelandite MORB MORB or BON (+/-LOTI) MORB MORB OIB. MORB V MORB (+/-BON) V V V V VV FIII . Petrochemical assemblages for various volcanogenic massive sulphide deposit environments and deposit types. HFSE = high field strength elements.

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. and their bases are about 1 km in diameter. A 200 m diameter cone on the floor of Axial Seamount submarine east rift zone of Haleakala Volcano. cone. This cone subsequent figures are slope-shaded bathymetry. 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.. Slope-shading is a technique that shades depending on the slope of the surface rather than illuminating from one direction. CCPI = chlorite-carbonate-pyrite index. on the Juan de Fuca Ridge (Thomas et al. 2001c). 1990). the only one sampled is constructed of alkalic lavas. 157 View publication stats . 200 kHz bathymetric data was collected with the autonomous The 30 kHz bathymetric data are gridded at 30 m (MBARI Mapping MBARI mapping vehicle (AUV) D. This and most of the data are gridded at 1 m and shown with 10 m contours. The cone has a 2000b). most of the data was previously imaged by side-scan sonar (Embley et al. Allan B... The lumpy terrain on the western flank may be constructional Unlike their subaerial counterparts.18. flying at 50 m altitude. was collected with hull-mounted multibeam systems. The Team. 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. these submarine cones lack or may be slump deposits from a collapse of part of the cone. the Figure 4-c6. 2006). Cluster of steep-sided cones on the Hana Ridge. heights of deep crater reaching almost to the regional depth surrounding the several hundred metres. The summit craters.. The cones have aspect ratios averaging 0. 2000) and shown with 200 m contours. Hawaii (Clague et al.