Hydrothermal alteration and lithogeochemistry of the ... · ARTICLE Hydrothermalalterationandlithogeochemistryofthe Boundaryvolcanogenicmassivesulphidedeposit,central Newfoundland,Canada

ARTICLE

Hydrothermal alteration and lithogeochemistry of theBoundary volcanogenic massive sulphide deposit, centralNewfoundland, CanadaMichael J. Buschette and Stephen J. Piercey

Abstract: The Boundary volcanogenic massive sulphide deposit (0.50 Mt at 3.5% Cu, 4.0% Zn, and 1.0% Pb, 34 g/t Ag) is hosted bythe Tally Pond group (�510 Ma), Victoria Lake supergroup, central Newfoundland, Canada, and represents a subseafloorreplacement-style massive sulphide deposit. The deposit is hosted by rhyolitic lapilli tuff of the Bindons Pond formation. Therhyolites have immobile element signatures consistent with the formation of felsic rocks through the melting of juvenile-weaklyevolved crust within an extensional rift environment (rifted peri-continental arc). The host rocks of the Boundary deposit containelevated alteration indices, including high Ba/Sr, Hg/Na2O, chlorite–carbonate–pyrite index, and Ishikawa alteration index values. Themobile element geochemistry effectively differentiates between three distinct hydrothermal alteration styles: intense chlorite,chlorite-sericite, and quartz-sericite. Intense chlorite alteration exhibits mass gains in MgO and Cu and depletions in K2O and Ba.Chlorite-sericite alteration contains variable gains and losses of SiO2, K2O, Ba, MgO, and Fe2O3 depending on the dominantmatrix mineral phase (i.e., chlorite vs. sericite). The quartz-sericite assemblage has mass gains in SiO2, K2O, Ba, and Fe2O3.Short-wave infrared spectroscopic data, particularly AlOH and FeOH absorption hulls, differentiate alteration styles and corre-late with lithogeochemical results: AlOH absorption features increase in length (>2208 nm) proximal to Zn mineralization andwavelength variations correspond to relative abundances of sericite and chlorite. Electron probe microanalyses indicate thatincreasing short-wave infrared wavelengths correlate with increasing Mg–Fe and Fe contents in sericite and chlorite, respec-tively. Collectively, these data have been used to develop a three-dimensional alteration model of the Boundary deposit.

Résumé : Le gisement de sulfures massifs volcanogènes Boundray (0,50 Mt contenant 3,5 % Cu, 4,0 % Zn, 1,0 % Pb, 34 g/t Ag) estencaissé dans le Groupe de Tally Pond (�510 Ma) du Supergroupe de Victoria Lake dans le centre de Terre-Neuve, Canada; il s’agitd’un gisement de sulfures massifs de style remplacement sous le plancher océanique. Le gisement est encaissé dans un tufrhyolitique a lapilli de la Formation de Bindons Pond. Les rhyolites ont des signatures d’éléments immobiles qui concordent avecla formation de roches felsiques par la fusion d’une croûte juvénile peu évoluée dans un environnement de rift d’extension (unarc péricontinental distendu). Les roches encaissant le gisement Boundary ont des indices d’altération élevés, incluant desrapports Ba/Sr, Hg/Na2O élevés, un indice chlorite–carbonate–pyrite élevé et des valeurs élevées de l’indice d’altérationd’Ishikawa. La géochimie des éléments mobiles permet de distinguer trois styles distincts d’altération hydrothermale : unealtération intense en chlorite, en chlorite-séricite et en quartz-séricite. L’altération intense en chlorite montre des gains mas-siques en MgO et en Cu et des pertes en K2O et Ba. L’altération en chlorite-séricite montre des gains et des pertes variables en SiO2,K2O, Ba, MgO et Fe2O3 selon la phase minérale dominante de la matrice (c.-a-d. chlorite par rapport a séricite). L’assemblagequartz-séricite a accru sa masse en SiO2, K2O, Ba et Fe2O3. Les données spectrométriques d’infrarouge de courte longueur d’onde(SWIR), surtout les enveloppes d’absorption d’AlOH et de FeOH, différencient les styles d’altération et concordent avec lesrésultats lithogéochimiques : les caractéristiques d’absorption d’AlOH augmentent de longueur (>2208 nm) a proximité de laminéralisation en zinc et les variations de longueur d’onde correspondent a des abondances relatives de séricite et de chlorite.Des microanalyses électroniques indiquent qu’une augmentation de la longueur d’onde des SWIR correspond a une augmenta-tion respective du contenu en Mg–Fe et Fe dans la séricite et la chlorite. Prises ensemble, ces données ont été utilisées pourdévelopper un modèle tridimensionnel d’altération du gisement Boundray. [Traduit par la Rédaction]

IntroductionVolcanogenic massive sulphide (VMS) deposits are important

global resources of base and precious metals and represent oneof the best understood mineral deposit types (e.g., Barrie andHannington 1999; Franklin et al. 2005; Galley et al. 2007). They arewell represented in the ancient record and our understanding ofthese deposits has been greatly enhanced through observationson the modern seafloor (e.g., Hannington et al. 2005; de Rondeet al. 2005, 2014; Baker et al. 2012; Monecke et al. 2014; Petersen

et al. 2014). Modern seafloor deposits are associated with ventingof hydrothermal fluids in black (and white) smokers, and miner-alization typically occurs as a result of seafloor emplacementthrough mound building (Hekinian et al. 1980; Lydon 1988; Herzigand Hannington 1995; German and Von Damm 2003; Berkenboschet al. 2012; de Ronde et al. 2014; Petersen et al. 2014). In the ancientrecord, seafloor emplacement deposits are extremely common,but some deposits are interpreted to have formed via replacementof host strata at or slightly below the seafloor (Doyle and Huston1999; Doyle and Allen 2003). Replacement-style VMS deposits are

Received 14 December 2015. Accepted 1 February 2016.

Paper handled by Editor Ali Polat.

M.J. Buschette and S.J. Piercey. Department of Earth Sciences, Memorial University of Newfoundland, 300 Prince Phillip Drive, St. John’s, NL A1B 3X5,Canada.Corresponding author: Michael J. Buschette (email: [email protected]).

Pagination not final (cite DOI) / Pagination provisoire (citer le DOI)

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Can. J. Earth Sci. 53: 1–22 (2016) dx.doi.org/10.1139/cjes-2015-0237 Published at www.nrcresearchpress.com/cjes on xx xxx xxxx.

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http://dx.doi.org/10.1139/cjes-2015-0237

also recognized as some of the largest and highest grade VMSdeposits globally (e.g., Rosebery, Kid Creek; Galley 1993; Galleyet al. 1995; Doyle and Huston 1999; Hannington et al. 1999; Doyleand Allen 2003; Bradshaw et al. 2008). Despite their significanceand importance, the controls and characteristics of the ore-bearing fluid pathways are incompletely understood. This de-tailed study of the alteration mineralogy, lithogeochemistry, andthe associated 2D–3D distribution of these variables at the Bound-ary deposit will contribute to our understanding of replacementdeposits.

The Boundary VMS deposit (�0.5 Mt at 3.5% Cu, 4% Zn, and1% Pb, 34.0 g/t Ag) in the Canadian Appalachians is an outstandingexample of a replacement-style VMS deposit (Piercey et al. 2014).The deposit, while small, is flat lying, contains excellent texturaland alteration preservation, and has a low-grade greenschist met-amorphic overprint; therefore making it an ideal location to studyalteration, lithogeochemistry, and mineralogy in replacement-style VMS deposits. The goal of this paper is to build upon theprevious work undertaken on the Boundary deposit by Moore(2003), Squires and Moore (2004), Piercey and Hinchey (2012), andPiercey et al. (2014). Unlike these previous studies, however, we

have undertaken a detailed study of the alteration distribution,alteration assemblage mineralogy, and lithogeochemistry. The re-search includes utilization of immobile elements to understandthe tectonic setting of deposit formation and the genesis of thehost volcanic facies present at the Boundary deposit. Further-more, the mobile element geochemistry, mass balance calcula-tions, short-wave infrared (SWIR) spectroscopy, and electronmicroprobe data of key alteration minerals are utilized to con-struct an alteration model and provide insight into the key con-trols and processes involved with alteration and the genesis of theBoundary deposit. These results provide both descriptive and ge-netic insight into subseafloor replacement alteration processes.

Geologic settingThe Newfoundland Appalachians are divided into four tectono-

stratigraphic zones (Fig. 1): the Humber, Dunnage, Gander, andAvalon zones (Williams 1979; Williams et al. 1988). The Dunnagezone hosts the Boundary deposit and is comprised of arc, back-arc,and ophiolitic rocks that formed along the margins of Laurentia(Notre Dame subzone) and Gondwana (Exploits subzone) from the

Fig. 1. Geologic setting of the Victoria Lake supergroup and the Tally Pond group, displaying the Boundary deposit and the neighboring DuckPond and Lemarchant deposits. Modified from McNicoll et al. (2010) and Piercey et al. (2014). Tectonostratigraphic divisions modified fromvan Staal (2007) and van Staal and Barr (2012). [Colour online.]


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Cambrian to Ordovician (Swinden et al. 1989; Swinden 1991; Keanet al. 1995; van Staal and Colman-Sadd 1997; Evans and Kean 2002;Rogers and van Staal 2002; Rogers et al. 2006, 2007; van Staal2007). The closure of the Iapetus Ocean resulted in the accretion ofthe Notre Dame subzone onto the Laurentian margin during theTaconic orogeny (500–450 Ma), whereas the Exploits subzone wasaccreted to the Gondwanan margin during the Penobscot orogeny(486–478 Ma) (van Staal 2007; Zagorevski et al. 2007, 2010). Thetwo subzones were juxtaposed against each other during the finalstages of the Taconic orogeny, creating a suture between the twosubzones: the Red Indian Line (Fig. 1; van Staal 2007; Zagorevskiet al. 2007, 2010; van Staal and Barr 2012).

Within the Exploits subzone, the Boundary deposit is hosted bythe Tally Pond group (�513–509 Ma; Dunning et al. 1991; McNicollet al. 2010), one of six fault bounded packages that make up theVictoria Lake supergroup (Fig. 1; Evans and Kean 2002; Zagorevskiet al. 2007, 2010; McNicoll et al. 2010; Piercey et al. 2014). In addi-tion to the Boundary deposit, the Tally Pond group hosts the DuckPond and Lemarchant VMS deposits, as well as several other pros-pects (Squires et al. 1991, 2001; Evans and Kean 2002; Squires andMoore 2004; Piercey et al. 2014). The Tally Pond group is furtherdivided into two informal formations: the Lake Ambrose forma-tion and the Bindons Pond formation (Rogers and van Staal 2002;Rogers et al. 2006; Piercey et al. 2014). The Lake Ambrose forma-tion (�513 Ma; Dunning et al. 1991) is predominantly basalt, con-sisting of massive and pillow flows, volcaniclastic rocks, andlesser felsic and sedimentary rocks (Kean and Evans 1986; Evansand Kean 2002; Rogers and van Staal 2002; Rogers et al. 2006).Overlying the older Lake Ambrose formation, the felsic-dominatedBindons Pond formation (509 Ma; McNicoll et al. 2010) consists offelsic flows, volcaniclastic rocks, and carbonaceous clastic sedi-mentary rocks. The Bindons Pond formation hosts the DuckPond, Lemarchant, and Boundary deposits (Kean and Evans 1986;Squires et al. 1991; Evans and Kean 2002; Rogers and van Staal2002; Squires and Moore 2004; Rogers et al. 2006).

Deposit geologyThe Boundary deposit is located approximately 4 km northeast

of the Duck Pond deposit. It occurs in two fault-separated lenses,the North zone and the South zone (Fig. 2) (Wagner 1993; Pierceyet al. 2014). A third lens, the Southeast zone, occurs as an exten-sion of the South zone but was not the focus of this study. Strati-graphically, aphyric rhyolite flows (massive to flow-banded) andbreccias make up the base of the Boundary deposit footwall (clas-sification based on White and Houghton 2006). Overlying theaphyric flows and breccias, the aphyric lapilli tuff hosts the ma-jority of the deposit. This unit is matrix supported in the lowerfew metres but is typically clast-supported with 1–3 cm clasts.Bedded tuffs and aphyric rhyolite breccias are interlayeredthroughout the lapilli tuff. The top of the footwall is comprised ofa thin (<10 cm) tuff that has mostly been replaced by sulphides(G. Squires, pers. comm.). The hanging wall is found at or near thesurface below a few metres of till and consists of a quartz-phyricassemblage of massive and flow-banded rhyolite flows and brec-cias (Figs. 3A–3B). It is partially preserved in the North zone,whereas in the South zone, it has been mostly eroded exposingmassive sulphides at surface. Intrusions at the Boundary depositare relatively rare; only one quartz-porphyry intrusion has beenrecognized just east of the South zone where it crosscuts all units.The lithofacies and stratigraphic successions are shown in crosssection in Figs. 4A–4B.

The Boundary deposit is largely structurally intact with twoexceptions that involve post-mineralization faulting. The first isthe north–south-trending Wagner fault, which offsets the Northzone from the South zone (Fig. 2; Wagner 1993; G. Squires, pers.comm.). This fault is easily recognized in drill core as intense,friable zones of sericite. The second involves thrust faulting in the

western portion of the North zone. Shallow, metre-scale thrustfaults have resulted in apparent stacked massive sulphide lenseswithin the hanging wall; however, detailed core logging revealsthat the faulting took place at the hanging wall–ore contact andimbricated the ore horizon (Fig. 4A).

Mineralization and alteration

MineralizationIn both zones, ore occurs as a series of semi-conformable, dis-

continuous lenses, predominantly located below the contact be-tween the quartz-phyric rhyolite flows and breccias and theaphyric rhyolite lapilli tuff (Figs. 3A–3C, 4A–4B; Squires and Moore2004; Piercey et al. 2014). At the contact, the lenses consist primar-ily of massive Cu–Zn sulphide cores surrounded by massive pyrite.The basal portion of these lenses commonly contains lapilli tufffragmentswithinasulphidematrix (Fig.5C).Smaller, semi-conformableclast-rich lenses of chalcopyrite and pyrite occur less than 10 mbelow the hanging wall–footwall contact within the footwall lap-illi tuff. The clast-rich sulphides are indicative of replacementstyle mineralization at the Boundary deposit (Piercey et al. 2014)and account for the majority of the sulphide mineralization.Deeper in the footwall, pyrite stringers occur within the inter-fragment space of the flows and breccias. Bedded sulphides arepresent along the southern edges of both zones and consist ofmillimetre- to centimetre-scale bands of pyrite and sphaleritewith crosscutting millimetre-scale quartz-chalcopyrite veins. Thesebedded sulphides and corresponding massive sulphides at thehanging wall–footwall contact are interpreted to have formedthrough mound building and exhalative processes. The hangingwall in the South zone has mostly been eroded, leaving massivesulphides exposed near surface where they have undergone vari-able degrees of supergene enrichment that has resulted in surfacestaining and veinlets of chalcocite, bornite, and covellite.

AlterationThree major alteration styles are present in the Boundary deposit:

quartz-sericite, chlorite-sericite, and intense chlorite (Figs. 5A–5F).The quartz-sericite alteration occurs as varying shades of grey,with local white, purple, or black alteration observed. Locally,black quartz-sericite alteration often occurs near massive-semimassive sulphide. Clasts and flows are typically dominated by quartzalteration, whereas the matrix contains variable sericite, quartz, andminor epidote (Fig. 5B). Chlorite is rare within the quartz-sericitealteration, but in the more intensely quartz-sericite altered partsof the stratigraphy, it does become a minor matrix constituent(�5%). Disseminated pyrite is the dominant sulphide phase withlesser sphalerite and galena. Chalcopyrite is present as chalcopy-rite disease (Barton 1978) or as crosscutting veins.

The chlorite-sericite alteration forms an envelope around theintense chlorite alteration (see below), usually within a few me-tres of massive sulphides (Figs. 5C–5D). Texturally, the alterationmanifests itself with zoned lapilli tuff clasts that have quartz-altered rims and slightly sericite-altered cores (Fig. 5C), whereasthe matrix is dominated by fine-grained chlorite and sericite(Fig. 5D). The sulphide mineralogy consists of pyrite, chalcopyrite(± Bi-Te-sulphides), sphalerite, and trace galena.

The intense chlorite alteration occurs in close association withmassive and clast-rich sulphides, commonly as semi-conformablezones that form thin halos (<2 m) around the sulphides (Figs. 5E–5F). Within the intense chlorite zones, most, if not all, of theoriginal host rock has been replaced by chlorite and sulphidemineralization (Fig. 5E). The intense chlorite assemblage consistspredominantly of chlorite, quartz, and occasional chaotic carbon-ate (dolomite; �5%), a feature more common in the neighboringDuck Pond mine (Squires et al. 2001; Squires and Moore 2004;Piercey et al. 2014). The sulphide mineralogy in this assemblage


Buschette and Piercey 3


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includes pyrite, chalcopyrite (± Bi-Te-sulphides), and minor sphaler-ite and Co-rich arsenopyrite.

Accessory minerals such as anatase, apatite, and monazite arefound in all three alteration styles, whereas xenotime is presentonly in the quartz-sericite. Also common throughout the Bound-ary deposit are millimetre-scale Fe–Mg–(±Mn) carbonate spots(e.g., Figs. 5A, 5D, 5E). This type of alteration occurs throughoutthe Tally Pond group and is interpreted to be the result of regional

metamorphism during the late Silurian (van Staal 2007; Pierceyet al. 2014).

The hanging wall is much less altered relative to the footwall.The hanging wall exhibits weak to moderate quartz-sericite alter-ation with increasing alteration proximal to the Zn ore lenses.Minor chlorite-sericite alteration is found locally above the Cu-rich zones. The footwall contains all three alteration types withthe most intense alteration focused in the lapilli tuff that directly

Fig. 2. Boundary deposit surface geology plan map with distribution of sulphide mineralization and locations of sections in Figs. 5A–5B.Modified from D. Hennessey (unpublished). [Colour online.]




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underlies the deposit. In addition to being associated with thesulphide ore zones, the intense chlorite alteration also occurs asdiscordant pipes that cross cut the footwall stratigraphy. Less in-tense chlorite-sericite alteration is also common within the lapillituff unit in close association with the intense chlorite alteration.Varying degrees of quartz-sericite alteration are present in thefootwall. Weak quartz-sericite alteration is present throughoutthe footwall flows, breccia, and lapilli tuff distal to mineraliza-tion. Moderate to strong quartz-sericite alteration occurs withinthe lapilli tuff proximal to the Zn-rich ore lenses. The difference inalteration styles and intensity are further demonstrated by thelithogeochemsitry.

LithogeochemistryA total of 237 samples from the Boundary deposit were selected

from 51 diamond drill holes. Samples were selected every �5 m orwherever there was a significant change in alteration assemblage.Samples included the hanging wall flows and breccias as well asfootwall tuff, lapilli tuff, breccias, and flows from both the Northand South zones. Samples that exhibited evidence for faultingsuch as fractured core or extensive quartz veining were avoided.

All samples were analyzed for major element oxides (SiO2,Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, TiO2, P2O5) and selecttrace elements (Ba, Sr, Y, Sc, Zr, Be, V, Hg) at Activation Laboratories

Fig. 3. Lithologies of the Boundary deposit. (A) Hanging wall flow-banded rhyolite. (B) Hanging wall hyaloclastite breccia. (C) Footwall lapillituff. (D) Footwall tuff. (E) Footwall jig-saw breccia. (F) Footwall flow-banded rhyolite. (G) Quartz-porphyry intrusion. [Colour online.]




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Fig. 4. (A) Alteration cross section through the North zone of the Boundary deposit. Location of section shown in Fig. 2. (B) Alteration crosssections through the South zone of the Boundary deposit. Location of sections shown in Fig. 2. [Colour online.]




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Ltd. in Ancaster, ON, Canada. Samples were crushed and pulverizedusing mild steel before undergoing lithium metaborate/tetraboratefusion followed by HF-HNO3 dissolution and subsequent analysisby inductively coupled emission-mass spectroscopy (ICP-ES). Sep-arate Hg concentrations were determined via cold vapor flowinjection mercury system (Hg-FIMS). Additional trace elements,including trace metals, low field-strength elements (LFSE), rareearth elements (REE), and high field-strength elements (HFSE),were analyzed at the Department of Earth Sciences at MemorialUniversity. Base metals (Cu, Zn, Pb), transition metals (Sc, Ti, V, Cr,Mn, Co, Ni), volatile elements (As, Cd, Sn, Sb), and the LFSE (Sr,Ba, Th) were determined by multi-acid dissolution and analyzedby inductively coupled plasma-mass spectrometry (ICP-MS). Thewhole-rock dissolution process was a modified version of thatdescribed by Jenner et al. (1990) and Longerich et al. (1990) andis described in detail by Lode et al. (2015). The REE and HFSE weredetermined by means of sodium peroxide (Na2O2) sinter and ana-lyzed using the same ICP-MS at Memorial University using thefollowing procedure: sintering of a 0.2 g sample aliquot withNa2O2, dissolution of the sinter cake by addition of deionizedwater and subsequent REE precipitate formation, separation bycentrifuge, and acid dissolution of precipitate prior to ICP-MSanalysis. The complete method can be found in Longerich et al.(1990). Precision and accuracy of the various methods have beenpreviously reported in Piercey and Colpron (2009) for Actlabs,

Jenner et al. (1990) and Lode et al. (2015) for multi-acid dissolution,and Longerich et al. (1990) for Na2O2 sinter. Representative valuesare displayed in Table 1.

ResultsAll samples from the Boundary deposit exhibit some degree of

hydrothermal alteration, resulting in the mobility of most majorelements (except Al2O3 and TiO2), base metals, volatile metals,and LFSE (Spitz and Darling 1978; Saeki and Date 1980; Barrett andMacLean 1994; Jenner 1996; Large et al. 2001). The HFSE and theREE (except Eu) are often regarded as being immobile, but theymay become mobile (especially the light rare earth elements(LREE)) during intense hydrothermal alteration (e.g., MacLean1988). In extremely altered samples, Y and LREE mobility can becharacterized by “fan-shaped” REE patterns (e.g., MacLean 1988)and anomalous Y/Zr and La/Zr ratios relative to the more robustNb/Zr and Yb/Zr ratios (Barrett et al. 2008).

Affinity monitorsIn a Zr/Ti versus Nb/Y discrimination plot (Fig. 6A), most sam-

ples fall within the rhyolite/dacite field with the exception of twosignificantly altered lapilli tuff samples. Most samples exhibit Zr/Yratios between 2.8 and 4.5, indicating the rocks have transitionalaffinities (Fig. 6B). Samples that do not fall within this Zr/Y rangehave intense chlorite and (or) sericite alteration. The Zr/Y ratios

Fig. 5. Photographs and photomicrographs of the alteration assemblages present at the Boundary deposit. (A) Grey, quartz-sericite alteredlapilli tuff with tan carbonate spots. (B) Photomicrograph of quartz sericite alteration assemblage (cross-polarized light). Note the quartz-altered clasts within sericite replaced matrix. (C) Zoned lapilli clasts in chlorite–sericite–chalcopyrite matrix. (D) Photomicrograph of chlorite-sericite alteration assemblage (cross-polarized light). Matrix consists of fine-grained chlorite-sericite along with carbonate and sulphides(opaque). (E) Intense chlorite alteration with carbonate spots. (F) Photomicrograph of the intense chlorite alteration assemblage (cross-polarized light). Clasts have been completely altered to chlorite, whereas the matrix contains chaotic carbonate and fine-grained quartz-chlorite alteration. Abbreviations: Ser, sericite; Qtz, quartz; Chl, chlorite; Carb, carbonate. [Colour online.]




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and the low Nb/Y ratios (Fig. 6C) of most samples support theirformation in an arc environment or from re-melted arc crust(Lentz 1998; Piercey et al. 2014). Low Zr contents (Zr < 200 ppm;Fig. 6D) and upper crust-normalized La/Sm ratios (<1; Fig. 6E) areconsistent with the formation of felsic rocks from sources less

evolved than upper continental crust (e.g., post-Archean, juvenilecrust; Piercey 2009, 2011). Nearly all samples fall within the FIIIafield (Fig. 6F), indicating that partial melting likely took place atrelatively shallow levels in the crust (<10 km) (Lesher et al. 1986;Hart et al. 2004).

Table 1. Representative whole-rock analyses data for the Boundary deposit samples.

Sample ID: H501278 H500680 H501213 H501317 H501222 H501217 H500663Hole ID: BD10-11 BD10-87 BD10-40 BD10-6 BD10-50 BD10-98 BD10-102Depth (m): 4 17.9 9.5 7.3 9 13.7 25.1Deposit location: Hanging wall Footwall Hanging wall Footwall Hanging wall Footwall FootwallLithology: Flow Lapilli tuff Breccia Lapilli tuff Flow Lapilli tuff Lapilli tuffAlteration type: Least altered Quartz-sericite Quartz-sericite Chlorite-sericite Chlorite-sericite Chlorite Chlorite

SiO2 (wt %) 73.94 70.79 65.39 65.02 54.83 21.26 52.08Al2O3 11.79 11.14 12.23 11.35 13.10 18.10 6.05Fe2O3 (T) 2.34 8.06 7.94 8.49 13.69 24.73 21.35MnO 0.10 0.05 0.19 0.16 0.07 0.23 0.07MgO 2.46 3.00 2.41 3.11 4.75 16.23 5.47CaO 0.16 0.05 0.07 0.04 0.05 0.09 0.06Na2O 1.97 0.20 0.28 0.08 0.22 0.61 0.03K2O 2.29 2.06 3.01 2.56 2.41 0.71 0.12TiO2 0.14 0.17 0.16 0.14 0.16 0.24 0.10P2O5 0.01 <0.01 0.02 0.01 0.01 0.01 0.01LOI 2.93 5.42 6.85 6.14 9.44 17.88 11.66Total 98.15 100.90 98.54 97.10 98.73 100.10 97.00Ba 1408 811 1367 1776 1441 391 46Sr 22 11 12 5 12 34 4Y 39 43 45 36 46 70 23Sc 10 10 11 11 13 17 7Zr 145 126 153 120 158 250 86Be 1 <1 1 1 <1 <1 <1V <5 8 7 22 <5 11 6Hg 12 11 9 1580 333 68 100Cr <8.90 <8.90 32.25 12.73 <8.90 <8.90 14.01Co 1.11 15.34 3.11 18.74 6.04 16.42 133.23Ni <10 <10 <10 <10 <10 <10 <10Cu 83.36 <19.00 55.96 2252.77 108.98 198.95 16898.55Zn 150.64 58.08 287.07 5509.07 151.30 1109.40 167.78As 2.12 1.96 9.96 183.87 17.89 79.21 31.47Se <26.70 <26.70 <26.70 <26.70 <26.70 <26.70 61.22Br 176.10 247.70 257.37 267.29 142.76 240.93 162.60Mo <1.00 18.77 8.96 18.90 7.57 3.10 27.15Ag <1.00 <1.00 <1.00 9.78 <1.00 <1.00 2.13Cd <0.90 <0.90 <0.90 15.47 <0.90 3.14 <0.90Sn 5.61 4.11 3.92 13.47 4.47 3.46 4.25Sb 0.82 0.64 1.39 25.57 7.16 1.29 2.33Te <4.30 <4.30 <4.30 <4.30 <4.30 <4.30 45.98I <37 <37 <37 <37 <37 <37 <37W 1.32 6.89 3.41 3.32 1.71 6.01 15.59Pb <25.30 <25.30 <25.30 1331.20 <25.30 <25.30 <25.30Bi 0.30 2.09 1.34 9.38 5.33 4.02 44.03Nb 6.07 6.03 7.58 5.04 8.10 15.55 3.00La 20.65 33.51 21.14 16.75 19.53 27.67 9.32Ce 43.88 71.84 43.82 34.47 40.85 55.42 19.28Pr 5.49 9.16 5.50 4.35 5.35 6.86 2.41Nd 23.07 40.38 23.26 18.36 22.78 29.77 10.36Sm 5.55 9.22 5.97 4.48 5.62 7.36 2.36Eu 1.19 1.10 1.15 1.41 1.12 1.19 0.25Tb 1.04 1.29 1.22 0.87 1.20 1.73 0.55Dy 6.72 8.20 8.12 5.80 8.00 11.70 3.75Ho 1.48 1.69 1.69 1.25 1.61 2.45 0.83Er 4.53 4.87 5.20 3.92 5.05 7.50 2.53Tm 0.68 0.70 0.75 0.58 0.74 1.13 0.38Yb 4.80 4.49 5.29 4.04 4.91 7.87 2.65Lu 0.74 0.65 0.80 0.62 0.79 1.20 0.40Hf 4.70 3.04 5.15 3.77 6.26 7.09 2.03Ta 0.25 0.22 0.32 0.21 0.31 0.58 0.13Th 5.59 4.62 5.87 4.18 6.37 12.23 2.68




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Fig. 6. Immobile element plots for rhyolitic rocks from the Boundary VMS deposit. (A) Modified Winchester and Floyd (1977) Zr/TiO2–Nb/Ydiscrimination diagram for rock classification (from Pearce 1996). (B) Zr–Y diagram for discriminating magma affinity (from Ross and Bedard2009). (C) Zr–Nb diagram useful for discriminating juvenile environments from evolved environments (modified from Piercey 2009). (D) Nb–Ytectonic discrimination diagram (from Pearce et al. 1984). (E) Upper-crust normalized (UCN) La–Sm diagram (upper-crust values from Taylorand McLennan 1985; from Piercey and Colpron 2009). (F) La/Ybcn–Ybcn FI–FIV rhyolite discrimination diagram (chondrite-normalized (CN) tothe values of McDonough and Sun (1995); diagrams from Lesher et al. 1986; Hart et al. 2004). [Colour online.]




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REE plotsREE patterns for both the hanging wall and footwall samples

are shown in Figs. 7A–7B, and have been normalized to the chon-drite values of McDonough and Sun (1995). The hanging wall andfootwall samples display slight LREE-enrichment with flat heavyrare earth elements (HREE) patterns; however, the hanging wallsamples have much tighter patterns with less scatter. The varia-tion displayed by the footwall rocks (Fig. 7B) is due to either mass/volume changes and (or) the actual mobility of the LREE duringhydrothermal alteration. The addition of Si and Fe results in a netmass gain, which can dilute the overall immobile REE concentra-tion; conversely, a net mass loss (e.g., chlorite or sericite altera-tion) can result in apparent inflating of REE concentrations(Fig. 7C) (Barrett et al. 2008). The effects of mass changes shouldresult in a uniform shift; however, the LREE contents in highlyaltered samples have likely been mobile resulting in shifts in LREEwithout concurrent shifts in HREE (Fig. 7D). The mobility of REEare further investigated below.

Mobile element lithogeochemistryRegardless of lithology, all samples from the Boundary deposit

have pronounced depletions in Na2O (often Na2O < 0.6%) and highSpitz-Darling index values (Al2O3/Na2O > 40; Fig. 8A). HighIshikawa index values, AI = 100(MgO + K2O)/(MgO + K2O + CaO +Na2O), (Ishikawa et al. 1976) and chlorite-carbonate-pyrite index(CCPI) values, CCPI = 100(MgO + Fe2O3)/(MgO + Fe2O3 + CaO +Na2O), (Large et al. 2001) are also characteristic of these samples,with the intense chlorite-altered samples plotting near thechlorite-pyrite node and the less altered quartz-sericite alteredsamples plotting near the sericite node (Fig. 8B). The three altera-tion styles are most easily differentiated using MgO/Al2O3 andK2O/Al2O3 ratios (Figs. 8C–8D).

Select trace elements also increase towards mineralization, in-cluding Hg/Na2O and Ba/Sr, which are elevated in all alterationassemblages, with the exception of those that display very intensechlorite and chaotic carbonate alteration (Ba/Sr < 10 and Hg/Na2O > 10) (Fig. 8E; Collins 1989). Increasing Hg/Na2O ratios alsocorrelate with increasing Zn contents (Fig. 8F) but not Cu contents,

Fig. 7. Rare earth element (REE) plots of the Boundary deposit (chondrite-normalized (CN) to the values of McDonough and Sun 1995).(A) Hanging wall. (B) Footwall. (C) Mass change effects on REE signature. (D) REE mobility effects on signature. [Colour online.]




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Fig. 8. Mobile element plots for rhyolitic rocks from the Boundary VMS deposit. (A) Spitz–Darling (Spitz and Darling 1978) index versus Na2O(diagram after Ruks et al. 2006). (B) Alteration box plot with the Hashimoto alteration index (AI; Ishikawa et al. 1976) plotted against thechlorite–carbonate–pyrite index (CCPI) (CCPI and diagram from Large et al. 2001). (C) Diagram of MgO plotted against Al2O3. (D) Diagram ofK2O plotted against Al2O3. (E) Hg/Na2O–Ba/Sr plot of the “Duck Pond index” (modified from Collins 1989). (F) Hg/Na2O plotted against Zn.[Colour online.]




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and thus likely mirrors the edge of high temperature mineraliza-tion/alteration.

Mass change calculationsAlthough raw lithogeochemical data can illustrate useful alter-

ation trends, the absolute gains and losses of mobile elementsyield true alteration dimensions and take into account massand volume changes during alteration, in addition to elementalchanges (e.g., Gresens 1967; Grant 1986; MacLean 1990). By plot-ting a series of immobile elements against one another, samplesfrom an originally homogeneous protolith will plot along a singleline that passes through the origin, whereas those from multiplesources will form additional trend lines (MacLean and Kranidiotis1987; Barrett and MacLean 1991; MacLean and Barrett 1993). Sam-ples from the Boundary deposit all plot along a single trend line(Fig. 9A), indicating that mass changes can be determined by usingthe single-precursor method; this paper employs the single pre-cursor method of MacLean (1990). The least altered precursor was

selected based on the sample(s) that had low loss on ignition (LOI)and base metal values, minimal Na2O depletions, and relativelyminor alteration mineral content.

Major oxidesAmong the major oxides, SiO2, K2O, and MgO are the most

sensitive to alteration mineralogy (Figs. 9B–9D). The quartz-sericitealteration generally displays gains in SiO2 (10%–50%), K2O (�1%),and MgO (±3%; gains if minor chlorite is present). The chlorite-sericite alteration displays losses in SiO2 (20%), variable K2O de-pending on the dominant observed matrix mineral (sericite = + 1%;chlorite = −1%–2%), and gains in MgO (1%–5%), particularly withinthe hanging wall breccias and footwall lapilli tuff and breccias.The intense chlorite alteration exhibits significant losses in bothSiO2 (up to 50%) and K2O (1%–2%) and gains in MgO (5%–20%).Because Fe2O3 is not only a major constituent of chlorite but alsoof the sulphide phases present, Fe2O3 gains range from 5% to 50%,with the highest gains present in the footwall lapilli tuff (Fig. 9D).

Fig. 9. Mass change plots showing gains and losses of key alteration elements. (A) Linear immobile trend line for the Boundary deposit. Massloss and gain of mobile elements have shifted the relative amounts of Al2O3 and Zr in the shown directions. (B) Mass change plot of K2Oversus SiO2 showing the formation of quartz and sericite. (C) Mass change plot of Fe2O3 + MgO versus SiO2 showing the formation of quartz,chlorite, and pyrite. (D) Mass change plot of MgO versus Fe2O3 differentiating between the formation of pyrite, chlorite, and carbonate.Abbreviations: Chl, chlorite; Py, pyrite; Qtz, quartz; Carb, carbonate. [Colour online.]




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Sodium is depleted throughout the deposit, whereas CaO gainsare present within the chlorite-sericite (3%) and intense chlorite(up to 9%) alteration in samples that have undergone carbonatealteration (i.e., chaotic carbonate, extensive carbonate spot over-printing). Manganese gains (up to 0.8%) are present only in theintense chlorite alteration that underlies the Cu-rich mineraliza-tion. Titanium is essentially immobile.

Trace elementsAll of the transition elements show some degree of enrichment;

however, only Co shows significant gains (500 ppm) within theintense chlorite-altered samples from below Cu-rich mineraliza-tion. Other elements such as V, Cr, and Ni show slight enrichmentthroughout the footwall. The base metals show gains within thechlorite-sericite and intense chlorite assemblages in the footwalllapilli tuff, whereas Zn and Pb are enriched in the upper footwalllapilli tuff and hanging wall flows and breccias. The LFSE all be-have different from one another. Strontium losses are commonthroughout the deposit (�10 ppm), with the exception of the foot-wall units below the South ore zones that display slight gains(3–10 ppm). Barium displays significant gains in the quartz-sericitealteration (up to 1000 ppm), moderate losses in the chlorite-sericite alteration (�200 ppm), and significant depletions in theintense chlorite-altered samples (�1000 ppm). Gains in As (75–100 ppm), Cd (�20 ppm), and Hg (>1 ppm) are common in samplesproximal to Zn-rich ore lenses, specifically within the chlorite-sericite samples in the lapilli tuff (As and Cd) and upper lapilli tuffand hanging wall units (Hg). Ytterbium displays minor gains(�10 ppm) proximal to Cu-rich ore zones. Elements that exhibitno mass changes include Sc, Th, Nb, Hf, Ta, and most of the REE.A subset of 12 samples display significant mass changes in regardsto the LREE. These samples are all found within tuff or matrix-supported lapilli tuff samples but are not tied to one specificalteration style.

SWIR spectroscopy and EMPASWIR spectrometry subjects a sample to a light source and mea-

sures the wavelengths of light that are absorbed by certain bondswithin minerals (AusSpec International 2008). Most absorptionfeatures are generated by OH, H2O, CO3, NH4, AlOH, FeOH, andMgOH bonds and are represented as minima in the reflectancespectrum over a specified range (AusSpec International 2008).

Two of the most commonly used features in mineral deposit ex-ploration are the AlOH absorption feature between 2190 and2225 nm and the FeOH absorption feature between 2245 and2260 nm which correspond to sericite and chlorite compositionsat the Boundary deposit, respectively (Fig. 10; AusSpec International2008). The depths of these absorption features relate to the relativemineral abundance (AusSpec International 2008).

The diagnostic absorption feature for sericite (fine-grainedwhite mica) [(K, Na)2(Al, Fe, Mg)4(Si,Al)8O20(OH)2] is a deep absorp-tion feature between 2180 and 2228 nm (Fig. 10). The exact wave-length at which the absorption feature occurs is directly related tothe compositional variation caused by one of two main substitu-tions: (i) Tschermak substitution: AlVI + AlIV↔(Fe, Mg, Mn)VI + SiIV;and (ii) the interlayer cation substitution between K and Na (e.g.,Velde 1978; Besson and Drits 1997a, 1997b; Guidotti and Sassi 1998;Herrmann et al. 2001; Yang et al. 2011). Shorter wavelengths (2180–2195 nm) are characteristic of sodic mica (paragonite), whereaslonger wavelengths (2210–2228 nm) are typically diagnostic ofFe–Mg mica (phengite) (Herrmann et al. 2001; Yang et al. 2011).Typical potassic mica (muscovite) produces absorption featuresbetween 2200 and 2204 nm. Intermediate wavelengths are theresult of intermediate compositions or mixed white mica phases(Herrmann et al. 2001).

Chlorite spectra contain two diagnostic absorption features:FeOH (2235–2260 nm) and MgOH (2320–2360 nm) (Fig. 10; Herrmannet al. 2001). Increases in absorption feature wavelengths (bothFeOH and MgOH) reflect increasing Fe content (McLeod andStanton 1984; Pontual et al. 1997). The compositional variation inchlorite is due to the following substitutions: (i) Tschermak sub-stitution: AlVI + AlIV↔(Fe, Mg, Mn)VI + SiIV; and (ii) octahedralsubstitution: Fe+2↔Mg+2(±Mn+2). The MgOH absorption featureoccurs over the same range of wavelengths as CO3. Because of thevarying degree of carbonate spot overprinting and potential over-lap of the MgOH wavelengths with those from CO3, the measuredMgOH wavelengths were not used in this study.

Hyperspectral analyses were carried out on the same samplesthat were used for lithogeochemistry, with analyses conducted atMemorial University using a TerraspecTM mineral spectrometerwith Hi-Brite Muglight. Minimal sample preparation was neededas SWIR absorption spectra were collected from fresh, clean drillcore. Optimization and white references were collected every

Fig. 10. Characteristic short wave infrared (SWIR) absorption features of white mica and chlorite highlighted in blue (other key hydroxylgroups highlighted in gray). Figure modified from Jones et al. (2005) and Herrmann et al. (2001). [Colour online.]




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�20 samples or 40 min to avoid instrument drifts. Analyses wereonly performed in a naturally sunlit room to avoid any interfer-ence from artificial lighting. Reference sample measurementswere made after each optimization and white reference, whichrevealed that the TerraspecTM was consistently within 1 nm ofthe accepted values. Reflectance spectra were collected using theRS3 Spectral Acquisition software. The resultant spectra were pro-cessed using The Spectral Geologist Hotcore v. 7.1.55 software inwhich the hull correction was applied. Hyperspectral scalars werecalculated using a fourth order polynomial fitting curve appliedover the ranges 2120–2245 nm (focused at 2180–2230 nm) for theAlOH wavelengths and 2230–2270 nm (focused at 2240–2260 nm)for FeOH. Spectral depth filters were applied to remove back-ground noise: 0.015% for AlOH and 0.01% for FeOH. Due to thevariable clast-matrix mineralogy, a minimum of three analysesper sample were made to ensure representative measurementswere collected.

Based on hyperspectral signatures and sericite-chlorite content,a subset of 12 samples were selected for electron probe microanal-ysis (EPMA) to determine the composition of the sericite and chlo-rite. Eight samples contained both sericite and chlorite, twocontained only sericite, and two contained only chlorite. On aver-age, 3–5 grains of each mineral were analyzed via a JEOL EPMA atMemorial University under the following operating conditions:15 kv, 1 �m spot size, and 20–45 s count times per element ana-lyzed. Mineral formulas were calculated based on 11 and 14 total Ofor sericite and chlorite, respectively. All Fe was assumed to beFe2+. Average representative analyses (including Terraspec data)are displayed in Table 2.

SWIRThe AlOH wavelength of sericite within the Boundary deposit

ranges from 2190 to 2213 nm with a majority of samples falling in

the range of 2200–2205 nm (Fig. 11A). The FeOH wavelength rangesfrom 2248 to 2257 nm (Mg- to Mg–Fe- to Fe-rich chlorite) anddisplays a normal distribution centered at 2252 nm (Mg–Fe chlo-rite; Fig. 11B). For ease of description, samples that exhibit AlOHwavelengths ≤ 2204 nm are designated as muscovite mica, whereasthose with wavelengths ≥ 2210 nm are termed phengitic mica. AlOHwavelengths tend to increase in samples from the upper 30 m of thedeposit, specifically those with high Zn–Pb contents (Fig. 11C). TheAlOH/FeOH depth ratio, which approximates the ratio of mica tochlorite (e.g., Huston et al. 1997; Herrmann et al. 2001), decreases insamples that exhibit high CCPI values (Fig. 11D).

EMPA

SericiteThe sericite (white mica) compositions have been recalculated

on an atomic basis of 11 oxygens, and Fe was assumed to be Fe2+.The compositional range for the sericite is (K0.40–0.66 Na0.01–0.08)(Al1.80–2.06 Fe0.02–0.18 Mg0.09–0.38)(Si2.96–3.48 Al0.52–1.04)O10(OH). Aver-age representative analyses are displayed in Table 2. High resolu-tion scanning electron microprobe (SEM) imaging reveals phengiticmica (Mg-rich) occurs as altered muscovite (Figs. 12A–12B). Theformation of phengite is the result of the Tschermak substitution:AlVI + AlIV↔(Fe, Mg, Mn)VI + SiIV, as illustrated in Fig. 13B. The lowNa (<0.08 apfu) contents indicate that paragonite was not a prom-inent mineral phase in the samples analyzed.

ChloriteThe chlorite compositions have been recalculated on an atomic

basis of 14 oxygens, and again all Fe was assumed to be Fe2+. Mostchlorite compositions fall within the ripidolite and sheridanitefields (Fig. 13B). Four analyses from a sample from the quartzporphyry intrusion exhibit significantly higher Fe contents than

Table 2. Representative electron probe microanalysis (EPMA) results with short-wave infrared (SWIR) data.

Sample ID: H500700 H501206 H501307 H501319 H501349 H500662Alteration type: Chlorite-sericite Chlorite-sericite Chlorite-sericite Quartz-sericite Quartz-sericite ChloriteMineral: Sericite Chlorite Sericite Chlorite Sericite Chlorite Sericite Chlorite Sericite Chlorite Chlorite SericiteAnalyses: n=7 n=3 n=4 n=4 n=6 n=3 n=6 n=3 n=7 n=4 n=7 n=0

Si (IV) apfu 3.09 2.58 3.05 2.57 3.12 2.62 3.20 2.56 3.13 2.52 2.61 —Al (IV) 0.91 1.42 0.95 1.43 0.88 1.38 0.80 1.44 0.87 1.48 1.39 —Al (VI) 1.99 1.50 1.97 1.54 1.94 1.41 1.92 1.54 1.95 1.60 1.53 —Al total 2.90 2.92 2.92 2.97 2.82 2.79 2.72 2.98 2.82 3.08 2.92 —Fe 0.04 1.68 0.07 1.61 0.03 0.62 0.05 1.59 0.08 2.36 1.22 —Mg 0.13 2.74 0.14 2.77 0.23 3.88 0.18 2.77 0.14 1.96 3.13 —Mn — 0.01 — 0.01 — 0.02 — 0.04 — 0.01 0.01 —Ca — — — — — — — — — — — —Na 0.05 — 0.05 — 0.03 — 0.02 — 0.04 — — —K 0.50 — 0.52 — 0.44 — 0.52 0.02 0.50 0.01 — —Ti — — — — — — 0.01 — — — — —F 0.02 0.02 0.03 0.03 0.04 0.08 0.01 — 0.03 — 0.05 —Cl 0.01 — — — 0.01 — — — — — — —Total apfu 6.75 12.89 6.79 12.93 6.73 12.82 6.71 12.95 6.75 13.20 12.88 —Ba (ppm) 3300 — 6308 85 3418 — 4389 104 4262 358 107.48 —V 40 — 119 75 35 — 37 — 9 25 105.85 —Cr 139 — 335 — 43 — 103 98 — — 58.65 —Ni 146 39 35 — 119 128 35 31 24 41 70.73 —Cu 83 35 36 — 113 64 63 — 52 — 171.19 —Zn 283 327 — 530 154 — 159 292 — 434 272.01 —Pb 1285 — 724 337 2018 783 1335 1640 516 1007 424.37 —Sn 9 110 14 91 39 — 26 — 34 114 34.88 —Absorption feature

2200 nm2197 2204 2208 2213 2202 —

Absorption (%) 2.74 1.91 14.13 21.15 21.80 —Absorption feature

2250 nm2253 2255 2250 — 2256 2251

Absorption (%) 6.41 1.37 6.83 — 3.56 22.8

Note: apfu, atoms per formula unit; IV, tetrahedral site; VI, octahedral site.




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the other samples throughout the deposit but still fall within theripidolite field. The compositional range for chlorite is (Al1.10–1.85

Fe0.61–2.54 Mg1.80–4.13)(Si2.48–2.81 Al1.19–1.52)O10(OH)8. Tetrahedral oc-cupancy ranges from (Si2.48Al1.52) to (Si2.8Al1.19) and the octahedralsite sum ranges from 5.66 to 5.99 apfu.

Comparison of Terraspec and EMPABoth the 2200 and 2250 nm absorption features display direct

correlations with the Fe–Mg contents in sericite and chlorite asillustrated using the averaged sample analyses shown in Figs. 13C–13D. In sericite, the AlOH wavelengths correlate with increasingphengite content via the Tschermak substitution (Fig. 13C). TheFeOH wavelengths negatively correlate with the octahedral sub-stitution Fe+2↔Mg+2(±Mn+2) rather than the Tschermak substitu-tion (Fig. 13D). Additionally, the intrusion sample represents theFe end-member of the sample set and has the longest FeOH wave-length (2256 nm).

Discussion

Rhyolite formation and tectonic implicationsRhyolites from the Boundary deposit have FIIIa chemical signa-

tures (Fig. 6F). Rocks with FIIIa signatures are interpreted to haveformed via partial melting of either continental or oceanic crustdue to basaltic underplating during rifting (Lesher et al. 1986;Barrie et al. 1993; Barrett and MacLean 1999; Hart et al. 2004;Piercey 2011). Hart et al. (2004) further argued that FIIIa rhyolitesform at shallow depths (<10 km), due to low pressure (<0.5 Gpa)and high temperature (900–1000 °C) melting. Melts generated un-der such conditions typically have negative Ti–Nb anomalies andweakly depleted HREE, Y, and Eu: features present in the rhyoliticrocks of the Boundary deposit (this study, Zagorevski et al. 2010;Piercey et al. 2014), implying formation at shallow levels and athigh temperatures.

Previous studies have argued that the Tally Pond group formedas the result of continental arc magmatism based on U–Pb geo-

Fig. 11. Short wave infrared (SWIR) results. (A) Histogram of the AlOH wavelengths present at the Boundary deposit. (B) Histogram of FeOHwavelengths. (C) Plot of sample depth versus AlOH wavelength of samples from the chlorite-sericite and quartz-sericite zones. (D) Plot of theAlOH absorption depth/FeOH absorption depth versus chlorite–carbonate–pyrite index (CCPI). [Colour online.]




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chronology and evolved Nd and Pb isotopic signatures (e.g.,Swinden and Thorpe 1984; Dunning et al. 1991; Pollock 2004;Rogers et al. 2006; McNicoll et al. 2010). However, rhyolites fromthe Boundary deposit display geochemical signatures that aremore akin to those that have formed in post-Archean, juvenileenvironments (e.g., Fig. 6; Hart et al. 2004; Piercey 2011; Pierceyet al. 2014). These data therefore suggest that the rocks could nothave formed from solely continental crustal sources but musthave had input from sources more juvenile than typical, evolvedupper continental crust. Additionally, the Tally Pond group ispredominantly bimodal, a characteristic commonly observed incontinental rift environments in which felsic rocks are producedby partial melting of overlying crust by basaltic underplating(Barrie et al. 1993; Barrie 1995; Wright et al. 1996; Smith et al. 2003)as opposed to the full volcanic spectrum (basalt-andesite-dacite-rhyolite) produced by continuous fractionation in continental arcenvironments (Arculus 1994; Lentz 1998; Hart et al. 2004).

Zagorevski et al. (2010) and Piercey et al. (2014) provided tectonicmodels that incorporate both the juvenile rift and continental arcsignatures present within the Tally Pond group: a rifted continen-

tal arc on the Iapetus-side of Ganderia. A rift environment wouldresult in crustal thinning and asthenospheric mantle upwellingleading to basaltic underplating of the overlying arc crust (Hartet al. 2004; Zagorevski et al. 2010; Piercey et al. 2014). Shallow(<10 km) partial melting of this crust would result in the produc-tion of bimodal volcanic rocks, as observed at the Boundary de-posit (Hart et al. 2004; Zagorevski et al. 2010; Piercey et al. 2014).Furthermore, the partial melting of arc crust would have resultedin rhyolitic melts with hybrid geochemical signatures containinga juvenile component from the basaltic underplating and acrustal signature from the arc crust.

The rifted arc model also explains the VMS endowment in theTally Pond group, as arc rifting creates a geodynamic environ-ment favorable to VMS formation. In particular, as rifting occursthe thinning of the overlying crust and upwelling of astheno-spheric mantle allow for shallow emplacement of heat sources(magma chambers, intrusions, etc.) needed to drive the convec-tion of hydrothermal fluids (e.g., Lesher et al. 1986; Lentz 1998;Hart et al. 2004; Piercey 2009, 2011). In addition, rifting increasesthe fracture permeability and porosity, which creates hydrothermalfluid pathways necessary for constant discharge and recharge ofhydrothermal fluids (e.g., Franklin et al. 1981, 2005; Lydon 1984,1988; Large 1992; Lentz 1998; Barrie and Hannington 1999; Galleyet al. 2007; Piercey 2009, 2011).

Characteristics and controls on hydrothermal alterationBecause the Boundary deposit has not undergone significant

metamorphism and has remained mostly structurally intact,most, if not all, of the hydrothermal alteration features are ex-tremely well preserved and close to their original distribution.Whereas most VMS deposits only exhibit classic discordant, pipe-like alteration (e.g., Riverin and Hodgson 1980; Gemmell andLarge 1992; Franklin et al. 2005), the Boundary deposit exhibitsboth discordant alteration and laterally extensive alteration, es-pecially near the ore body. The laterally extensive alteration isinterpreted to be a product of upflow, in contrast to the semi-conformable alteration that is associated with hydrothermal re-charge (e.g., Galley 1993; Franklin et al. 2005). Its stratigraphic,semi-conformable geometry is a function of unfocused dischargeinto relatively unconsolidated and porous volcaniclastic rocksthat make up the footwall that were overlain by an impermeable(to semi-permeable), flow-dominated hanging wall (e.g., Doyle andAllen 2003; Gibson 2005). This stratigraphic and hydrothermalarchitecture was also responsible for the development of thereplacement-type mineralization and alteration preserved in theBoundary deposit (Piercey et al. 2014).

The intense depletion of Na2O throughout both the hangingwall and footwall (Fig. 8A) is due to the destruction of feldsparduring hydrothermal alteration (e.g., Riverin and Hodgson 1980;Knuckey et al. 1982; Date et al. 1983; Barrett and MacLean 1994).The addition of most elements can be explained through the mod-ification of seawater and leaching of felsic rock (e.g., Franklinet al. 2005; Hannington et al. 2005); however, the addition of mostof the transition elements (i.e., Cr, Co, Ni, V) remains somewhatenigmatic. The presence of Bi–Te sulphides suggests some mag-matic input, though the underlying basaltic Lake Ambrose forma-tion is also a potential source for the metals to have been leachedfrom.

The loss of Na (and Ca) and gains in K and Si (and Mg), asillustrated by mass balance calculations, correlate with abundantquartz-sericite alteration (Fig. 9B). This alteration does not showsignificant Mg gains; however, samples with elevated Mg do con-tain chlorite within relict feldspar grains or along sulphide grainedges. The formation of chlorite in the chlorite-sericite and in-tense chlorite alteration is due to the destruction of primary feld-spar or previously formed mica, as illustrated by the resultant netgain of Mg and Fe and the loss of K (±Si) (e.g., Riverin and Hodgson1980; Knuckey et al. 1982) (Table 2; Figs. 9C–9D). Samples within the

Fig. 12. High resolution SEM-BSE images of the mica phases presentat the Boundary deposit. Dark mica lathes are muscovitic incomposition (K-rich, Mg-poor), whereas the lighter lathes are morephengitic (Mg-rich). (A) Phengite occurs as thinly altered muscovitesheets. (B) Phengite occurs both as partially altered muscovite andlarger patches. Abbreviations: Ph, phengite; Ms, muscovite.




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chlorite-sericite assemblage show varying degrees of K2O lossesdepending on the abundance of sericite relative to chlorite in therocks. Losses of SiO2 are greatest in the intense chlorite samples,which also exhibit losses of K2O (Fig. 9B). Increasing chlorite con-tent alone, however, does not account for gains of both MgO andFe2O3 as the gains in these elements are also attributed to chaoticcarbonate alteration (MgO and Fe2O3) and pyrite stringers com-monly found within the quartz-sericite assemblage (Fig. 9D).

A series of 3D models representing the Boundary deposit withthe main lithologic contacts, ore zones, Wagner fault, and keyalteration features are shown in Fig. 13. The mineralized horizonis comprised of the upper �30 m of lapilli tuff and tuff, where theupper contact marks the first significant (>2 m) aphyric flow orflow breccia; massive pyrite zones are those with >15% Fe and arecorrelated with observations from drill logs and cross sections(Fig. 14A). Longer AlOH wavelengths (phengitic mica) have beendocumented in zones proximal to high Zn-rich zones (e.g., Joneset al. 2005; Yang et al. 2011), and are consistent with results in thisstudy as well, where the highest AlOH values are proximal to

zones with greatest Zn grades (Fig. 14B). In contrast, the shortestAlOH wavelengths are found in samples that directly underlie theCu ore zones. Figure 13C represents a complete 3D alterationmodel with the distribution of mass change results using MgO,K2O, and SiO2. The interpreted hydrothermal upflow zones ex-hibit >3% MgO gains near the center of the upflow zones (i.e.,intense chlorite alteration) and �2% MgO and >0.5% K2O gainsforming an envelope around the upflow zone (chlorite-sericiteand quartz-sericite alteration); each upflow zone broadly coin-cides with Cu-enrichment above it and coincident losses in SiO2(Fig. 14C).

The alteration patterns and the chemical attributes outlinedabove are controlled by two factors: (i) the host volcanic lithology;and (ii) the fluid conditions (i.e., temperature, composition, pH).The hanging wall and footwall flows and breccias are more crys-talline and resistant to hydrothermal alteration, whereas the foot-wall lapilli tuff and tuff unit are typically glassy and moresusceptible to alteration (e.g., McPhie et al. 1993; Large et al. 2001).Furthermore, the porosity and permeability of these units differ.

Fig. 13. Electron probe microanalyses (EPMA) results. (A) Sericite samples show increasing proportions of phengite via the Tschermaksubstitution. (B) Chlorite discrimination diagram. Most samples fall within the Ripidolite–Sheridanite fields. Note the chlorites from theintrusion sample plot considerably further from the bulk of the samples. (C) Comparison of average sericite composition and short waveinfrared (SWIR) wavelengths. Samples increase in phengisity as the SWIR wavelengths increase. (D) Comparison of average chloritecompositions and SWIR wavelengths. [Colour online.]




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Alteration and hydrothermal fluid migration in the flows andbreccias would have been dependent on fracture-controlled po-rosity and permeability, which includes quench fractures or cool-ing joints (Large et al. 2001). In both footwall and hanging wallbreccias (and flow-banded flows), the inter-fragment regions showalteration, whereas the coherent fragments and massive flowsdisplay little to no alteration (Figs. 3A–3B, 3E–3F), implying fracturecontrolled fluid flow and alteration. Conversely, the permeabilityand porosity of volcaniclastic rocks (i.e., lapilli tuff or tuffs) iscontrolled by inter-clast and inter-particle pore space (McPhieet al. 1993; Large et al. 2001). The lapilli tuff at the Boundarydeposit are generally clast-supported (Fig. 3C), which would haveleft an extremely porous matrix consisting of loosely packed ashor void space. As such, hydrothermal fluids would have been ableto move along numerous paths rather than just through a singlesynvolcanic structure; thus, resulting in much more widespreadand intense fluid-rock interaction and alteration. This is observedat the Boundary deposit (e.g., Figs. 4A–4B, 13C), and is also recordedas much greater mass changes in the lapilli tuff (e.g., Si, K, Fe, Mg,Cu, Zn) relative to the more coherent flows and breccias, espe-cially those within the hanging wall (Figs. 7A–7B, 9). Of the limited

hanging wall rocks, the hanging wall flows are significantly lessaltered than the footwall rocks and predominantly exhibit minorquartz-sericite alteration and localized chlorite-sericite alteration.

The physiochemical conditions of fluid rock interaction mayhave also played a role in the alteration zoning and chemistry offootwall alteration (e.g., Riverin and Hodgson 1980; Lydon 1984,1988; Gemmell and Large 1992; Large et al. 2001; Schardt et al.2001; Franklin et al. 2005; Galley et al. 2007). The well-developedzoning from distal quartz-sericite, to chlorite-sericite, to intensechlorite reflects changing fluid-rock interaction, fluid tempera-tures, and pH. Schardt et al. (2001) demonstrated in Cu–Zn sys-tems, the inner, intense chlorite alteration generally forms athigh temperatures (250–350 °C) and at moderate pH levels (4.5–5.5). As Mg is fixed from circulating modified seawater within themain upflow zones forming chlorite, the fluids on the peripheryof the vent are not only cooler but become more acidic, leading tothe formation of the chlorite-sericite and quartz-sericite altera-tion assemblages. Increased fluid–rock interactions counter someof the pH-lowering effects of Mg fixation and allow chlorite toform in some areas of the quartz-sericite alteration assemblage.Additionally, this explains the absence of chlorite alteration

Fig. 14. Three-dimensional model of the Boundary deposit. (A) Model showing key lithology contacts, major sulphide zones, and drill holesused to determine alteration extents. Ore zones are defined by assays from additional drill holes not shown. (B) Model showing AlOHwavelengths. Note that wavelengths are significantly longer in the South zone. Long wavelengths in the North zone only occur on the westernend of the deposit. (C) Alteration model of the Boundary deposit based on mass balance changes. Ore zones are typically surrounded bysignificant losses of SiO2. Samples that exhibit MgO gains >3% represent the intense chlorite samples (and interpreted upflow pathways). Theperiphery of the deposit is enveloped by gains (>0.5%) in K2O, which represents the quartz-sericite alteration that surrounds the deposit.[Colour online.]




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above the vent structures within the hanging wall. By the time thefluids reached the hanging wall, nearly all the Mg had been fixedwithin the chloritic pipe leaving only acidic (and cooler) fluids,which created the intense quartz-sericite alteration within thehanging wall.

Relationships between SWIR spectroscopy, alterationmineralogy, and alteration mineral genesis

The relative proportions of sericite and chlorite are often diffi-cult to determine macroscopically and can be time consuming todetermine petrographically. The absorption depth feature forboth FeOH and AlOH do appear to correspond to the petrograph-ically observed abundances of sericite and chlorite. Huston et al.(1997) and Herrmann et al. (2001) also demonstrated that sericite/chlorite ratios can be estimated semi-quantitatively using theratio of AlOH to FeOH absorption depths in SWIR spectra (i.e., AlOH/FeOH). The AlOH/FeOH depth ratios in the Boundary depositsamples show a distinct correlation with deceasing AlOH/FeOHdepths as CCPI increases (Fig. 11D). The high CCPI values are char-acteristic of intensely chlorite-altered samples (MgO gains >3%) thatmake up the upflow zones that underlie the Cu-rich ore zones,thereby implying that the AlOH/FeOH depth ratio could be used toidentify prospective chlorite- and Cu-rich alteration zones. In con-trast, the best indicator for Zn-rich zones are AlOH wavelengths,particularly values greater than 2208 nm (Figs. 11C, 14B). The dis-tribution and variation of the AlOH and FeOH absorption featuresat the Boundary deposit provide an effective method in tracingfluid pathways and potential vectors to mineralization (Fig. 15).

Though the study by Schardt et al. (2001) was performed onandesites, the chlorite-sericite distribution is consistent withmany VMS deposits including the Boundary deposit. The FeOH-

AlOH absorption depth features (as well as petrographic studies)indicate that the intense chlorite alteration assemblage, whichrepresents the major upflow zone, contains the most chlorite andtransitions to dominantly quartz-sericite alteration style furtherfrom the center of the upflow zone. Furthermore, chlorite in theupflow zone is closer to sheridanite (Fe–Mg chlorite) in composi-tion, whereas chlorite from the other zones is more ripidolite(Fe-rich) in composition. This is expected as the central upflowzone was likely the hottest, most reduced part of the hydrothermalsystem. These conditions favored the formation of chlorite oversericite, and because of the significant amount of Mg (frommodified/unmodified seawater), the chlorite was Fe–Mg rich. Pe-ripheral to the edges of the upflow zone and into the lapilli tuff,temperatures would have been cooler (and more acidic as Mg wasfixed into chlorite) thus prompting sericite formation. With thedecreasing amount of Mg available (and possibly due to decreas-ing temperature and increasing pH) chlorite compositions shiftedtowards a more Fe-rich composition. The documented AlOH SWIRwavelengths and the increasing phengite mica proximal to Zn-rich ore zones likely represent smaller offshoots of the main up-flow zones. These offshoots would have been hotter and morereduced near the upflow zone, but as they migrated towards theseafloor, increasing amounts of unmodified seawater would havebeen incorporated into the pathway. This would have lowered thetemperature and added Mg, thus prompting the formation ofphengitic sericite in the upper few metres of the lapilli tuff.

Interestingly, a number of intense chlorite-altered samples haveAlOH absorption wavelengths of �2196 nm, indicative of sodicsericite; however, no sericite was identified in the two intenselychlorite-altered samples analyzed by EPMA (although these sam-

Fig. 15. Schematic diagram showing the short wave infrared (SWIR) data variation with geologic explanations. Although the alterationdistribution is primarily controlled by the host rock permeability and porosity, the SWIR variation is heavily dependent on the addition ofunmodified seawater, temperature, and pH. [Colour online.]




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ples lack AlOH wavelengths). Further investigation of the in-tensely chlorite-altered samples is warranted, as the sodic sericitesignature within the intense alteration pipe may result from late-stage overprinting during the waning stages of hydrothermal ac-tivity during which unmodified Na-rich seawater flushed throughthe hydrothermal system, forming sodic mica (e.g., Date et al.1983; Green et al. 1983).

ConclusionsThe following are the main conclusions of this manuscript:

1. The Boundary deposit formed on the leading edge of Ganderiain rhyolitic rocks within a rifted continental arc. This is sup-ported by immobile element geochemistry and is consistentwith previous studies within the Tally Pond group.

2. The Boundary deposit contains three alteration styles: quartz-sericite, chlorite-sericite, and intense chlorite, each which havedistinct geochemical and hyperspectral signatures. These altera-tion styles are predominantly controlled by the host rock perme-ability and porosity in addition to hydrothermal fluid conditions.

3. Alteration indices, such as CCPI, and element gains (e.g., Cu,MgO, MnO, Fe2O3) provide useful vectors for Cu-mineraliza-tion; whereas, Hg/Na2O and Hg, Zn, Pb, and Ba increase inproximity to Zn mineralization.

4. Mass changes among the major oxides (e.g., SiO2, MgO, Fe2O3,K2O), base metals, and LFSE (e.g., Ba, Sr) vary with each alter-ation style. Other elements, such as the HREE and HFSE, areimmobile throughout the deposit.

5. Hyperspectral and EPMA data reveal distinct trends that cor-relate with alteration styes and geochemistry: (i) AlOH wave-lengths increase with phengite content proximal to Zn-richmineralization; (ii) the FeOH wavelengths correlate with chlo-rite compositions and indicate a high abundance of Mg-richchlorite in the most intense chlorite alteration; and (iii) theabsorption hull depths for both AlOH and FeOH are useful indifferentiating between styles of alteration and the ratio of thetwo (AlOH depth and FeOH depth) correlates strongly with theCCPI.

AcknowledgementsFinancial and logistical support for this project was provided by

Teck Resources Ltd., a Natural Sciences and Engineering ResearchCouncil of Canada (NSERC) Discovery grant to S.J.P., and SEG Grad-uate Fellowship and Research Grant to M.J.B. S.J.P. is also fundedby the NSERC-Altius Industrial Research Chair at Memorial Uni-versity, which is supported by NSERC, Altius Resources Inc., andthe Research and Development Corporation of Newfoundlandand Labrador. Numerous discussions with the staff of the DuckPond mine, particularly Gerry Squires and Darren Hennessey, aregratefully acknowledged. Additionally, numerous discussions andsupport from Jonathan Cloutier, Stefanie Lode, and Jean-LucPilote have significantly aided in improving this manuscript. Lab-oratory assistance provided by Pam King and Lakmali Hewa ofCREAIT at Memorial University is appreciatively acknowledged.We acknowledge reviews by Mark Hannington and ThomasMonecke on an earlier version of this manuscript, and thankCanadian Journal of Earth Sciences reviewers John Hinchey and DavidLentz for their comments. The comments from all reviewers greatlyimproved the final manuscript.

ReferencesArculus, R.J. 1994. Aspects of magma genesis in arcs. Lithos, 33: 189–208. doi:10.

1016/0024-4937(94)90060-4.AusSpec International. 2008. Spectral Interpretation Field Manual. GMEX Edi-

tion 3, Vols. 1–10.Baker, E.T., Walker, S.L., Embley, R.W., and de Ronde, C.E.J. 2012. High-

resolution hydrothermal mapping of Brothers Caldera, Kermadec Arc. Eco-nomic Geology, 107: 1583–1593. doi:10.2113/econgeo.107.8.1583.

Barrett, T.J., and MacLean, W.H. 1991. Chemical, mass, and oxygen isotope

changes during extreme hydrothermal alteration of an Archean rhyolite,Noranda, Quebec. Economic Geology, 86: 406–414. doi:10.2113/gsecongeo.86.2.406.

Barrett, T.J., and MacLean, W.H. 1994. Chemostratigraphy and hydrothermalalteration in exploration for VHMS deposits in greenstones and youngerrocks. In Alteration and Alteration Processes Associated with Ore-FormingSystems, Short Course Notes Volume 11. Edited by D.R. Lentz. Geological As-sociation of Canada, pp. 433–467.

Barrett, T.J., and MacLean, W.H. 1999. Volcanic sequences, lithogeochemistry,and hydrothermal alteration in some bimodal volcanic-associated massivesulfide systems. Reviews in Economic Geology, 8: 101–131.

Barrett, T.J., Dawson, G.L., and MacLean, W.H. 2008. Volcanic stratigraphy, al-teration, and sea-floor setting of the Paleozoic Feitais massive sulfide deposit,Aljustrel, Portugal. Economic Geology, 103: 215–239. doi:10.2113/gsecongeo.103.1.215.

Barrie, C.T. 1995. Zircon thermometry of high-temperature rhyolites nearvolcanic-associated massive sulfide deposits, Abitibi subprovince, Canada.Geology, 23: 169–172. doi:10.1130/0091-7613(1995)023<0169:ZTOHTR>2.3.CO;2.

Barrie, C.T., and Hannington, M.D. 1999. Introduction: classification of VMSdeposits based on host rock composition, in volcanic-associated massive sul-fide deposits: processes and examples in modern and ancient environments.In Society of Economic Geologists, Reviews in Economic Geology. Edited byC.T. Barrie and M.D. Hannington. 8: 2–10.

Barrie, C.T., Ludden, J.N., and Green, T.H. 1993. Geochemistry of volcanic rocksassociated with Cu–Zn and Ni–Cu deposits in the Abitibi Subprovince. Eco-nomic Geology, 88: 1341–1358. doi:10.2113/gsecongeo.88.6.1341.

Barton, P.B. 1978. Some ore textures involving sphalerite from the Furutobemine, Akita prefecture, Japan. Mining Geology, 28: 293–300. doi:10.11456/shigenchishitsu1951.28.293.

Berkenbosch, H.A., de Ronde, C.E.J., Gemmell, J.B., McNeill, A.W., andGoeman, K. 2012. Mineralogy and formation of black smoker chimneys fromBrothers submarine volcano, Kermadec arc. Economic Geology, 107: 1613–1633. doi:10.2113/econgeo.107.8.1613.

Besson, G., and Drits, V.A. 1997a. Refined relationships between chemical com-position of dioctahedral fine-grained micaceous minerals and their infraredspectra within the OH stretching region. Part 1: Identification of the OHstretching band. Clays and Clay Minerals, 45: 158–169.

Besson, G., and Drits, V.A. 1997b. Refined relationships between chemical com-position of dioctahedral fine-grained micaceous minerals and their infraredspectra within the OH stretching region. Part II: The main factors affectingOH vibrations and quantitative analysis. Clays and Clay Minerals, 45: 170–183.

Bradshaw, G.D., Rowins, S.M., Peter, J.M., and Taylor, B.E. 2008. Genesis of theWolverine volcanic sediment-hosted massive sulfide deposit, Finlayson Lakedistrict, Yukon, Canada: mineralogical, mineral chemical, fluid inclusion,and sulfur isotope evidence. Economic Geology, 103: 35–60. doi:10.2113/gsecongeo.103.1.35.

Collins, C.J. 1989. Report on lithogeochemical study of the Tally Pond volcanicsand associated alteration and mineralization. Unpublished Report forNoranda Exploration Company Limited (Assessment File 012A/1033 New-foundland Department of Mines and Energy, Mineral Lands Division).St. John’s, Newfoundland, 87 pp.

Date, J., Watanabe, Y., and Saeki, Y. 1983. Zonal alteration around the FukazawaKuroko deposits, Akita Prefecture, northern Japan. Economic Geology Mono-graph, 5: 365–386.

de Ronde, C.E.J., Hannington, M.D., Stoffers, P., Wright, I.C., Ditchburn, R.G.,Reyes, A.G., et al. 2005. Evolution of a submarine magmatic-hydrothermalsystem: Brothers volcano, southern Kermadec arc, New Zealand. EconomicGeology, 100: 1097–1133. doi:10.2113/gsecongeo.100.6.1097.

de Ronde, C.E.J., Walker, S.L., Ditchburn, R.G., Tontini, F.C., Hannington, M.D.,Merle, S.G., et al. 2014. The anatomy of a buried submarine hydrothermalsystem, Clark volcano, Kermadec arc, New Zealand. Economic Geology, 109:2261–2292. doi:10.2113/econgeo.109.8.2261.

Doyle, M.G., and Allen, R.L. 2003. Subsea-floor replacement in volcanic-hostedmassive sulfide deposits. Ore Geology Reviews, 23: 183–222. doi:10.1016/S0169-1368(03)00035-0.

Doyle, M.G., and Huston, D.L. 1999. The subsea-floor replacement origin of theOrdovician Highway-Reward Volcanic-associated Massive Sulfide deposit,Mount Windsor Subprovince, northern Queensland. Economic Geology, 94:825–843. doi:10.2113/gsecongeo.94.6.825.

Dunning, G.R., Swinden, H.S., Kean, B.F., Evans, D.T.W., and Jenner, G.A. 1991. ACambrian island arc in Iapetus: geochronology and geochemistry of the LakeAmbrose volcanic belt, Newfoundland Appalachians. Geological Magazine,128: 1–17. doi:10.1017/S0016756800018008.

Evans, D.T.W., and Kean, B.F. 2002. The Victoria Lake Supergroup, centralNewfoundland: its definition, setting and volcanogenic massive sulfide min-eralization. Newfoundland and Labrador Department of Mines and Energy,Geological Survey, Open File NFLD/2790, 68 p.

Franklin, J.M., Lydon, J.W., and Sangster, D.F. 1981. Volcanic-associated massivesulfide deposits. Economic Geology, 75th Anniversary Volume, pp. 485–627.

Franklin, J.M., Gibson, H.L., Galley, A.G., and Jonasson, I.R. 2005. Volcanogenicmassive sulfide deposits. Economic Geology, 100th Anniversary Volume,pp. 523–560.




Can

. J. E

arth

Sci

. Dow

nloa

ded

from

ww

w.n

rcre

sear

chpr

ess.

com

by

Mem

oria

l Uni

vers

ity-B

F on

04/

01/1

6Fo

r pe

rson

al u

se o

nly.

http://dx.doi.org/10.1016/0024-4937(94)90060-4

http://dx.doi.org/10.1016/0024-4937(94)90060-4

http://dx.doi.org/10.2113/econgeo.107.8.1583

http://dx.doi.org/10.2113/gsecongeo.86.2.406




http://dx.doi.org/10.1130/0091-7613(1995)023%3C0169%3AZTOHTR%3E2.3.CO;2


http://dx.doi.org/10.11456/shigenchishitsu1951.28.293

http://dx.doi.org/10.11456/shigenchishitsu1951.28.293






http://dx.doi.org/10.1016/S0169-1368(03)00035-0

http://dx.doi.org/10.1016/S0169-1368(03)00035-0


http://dx.doi.org/10.1017/S0016756800018008

http://www.nrcresearchpress.com/action/showLinks?crossref=10.2113%2Fgsecongeo.103.1.35

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1346%2FCCMN.1997.0450204


http://www.nrcresearchpress.com/action/showLinks?crossref=10.1017%2FS0016756800018008&isi=A1991EY87700001


http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2FS0169-1368%2803%2900035-0&isi=000186690500006

http://www.nrcresearchpress.com/action/showLinks?crossref=10.2113%2Fecongeo.107.8.1583

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http://www.nrcresearchpress.com/action/showLinks?crossref=10.1130%2F0091-7613%281995%29023%3C0169%3AZTOHTR%3E2.3.CO%3B2&isi=A1995QF59900019






Galley, A.G. 1993. Characteristics of semi-conformable alteration zones associ-ated with volcanogenic massive sulphide districts. Journal of GeochemicalExploration, 48: 175–200. doi:10.1016/0375-6742(93)90004-6.

Galley, A.G., Watkinson, D.H., Jonasson, I.R., and Riverin, G. 1995. The subsea-floor formation of volcanic-hosted massive sulfide: evidence from the Ansildeposit, Rouyn-Noranda, Canada. Economic Geology, 90: 2006–2017. doi:10.2113/gsecongeo.90.7.2006.

Galley, A.G., Hannington, M.D., and Jonasson, I.R. 2007. Volcanogenic massivesulphide deposits. In mineral deposits of Canada: a synthesis of major deposittypes, district metallogeny, the evolution of geological provinces, and explo-ration methods. Geolocial Association of Canada, Mineral Deposits Division,Special Publication No. 5.

Gemmell, J.B., and Large, R.R. 1992. Stringer system and alteration zones under-lying the Hellyer volcanogenic-hosted massive sulfide deposit, Tasmania,Australia. Economic Geology, 87: 620–649. doi:10.2113/gsecongeo.87.3.620.

German, C.R., and Von Damm, K.L. 2003. Hydrothermal systems. In Treatise onGeochemistry - The Oceans. Edited by H. Elderfield. Vol. 6, pp. 181–222.

Gibson, H.L. 2005. Volcanic-hosted ore deposits. In Volcanoes in the environ-ment. Edited by J. Marti and G.G.J. Ernst. New York, Cambridge UniversityPress, pp. 332–386.

Grant, J.A. 1986. The isocon diagram: a simple solution to Gresens’ equationfor metasomatic alteration. Economic Geology, 81: 1976–1982. doi:10.2113/gsecongeo.81.8.1976.

Green, G.R., Ohmoto, H., Date, J., and Takahashi, T. 1983. Whole-rock oxygenisotope distribution in the Fukazawa-Kosaka area, Hokuroku District, Japan,and its potential application to mineral exploration. Economic GeologyMonolith, 5: 395–411.

Gresens, R.L. 1967. Composition-volume relationships of metasomatism. Chem-ical Geology, 2: 47–65. doi:10.1016/0009-2541(67)90004-6.

Guidotti, C.V., and Sassi, F.P. 1998. Petrogenetic significance of Na–K white micamineralogy: recent advances for metamorphic rocks. European Journal ofMineralogy, 10: 815–854. doi:10.1127/ejm/10/5/0815.

Hannington, M.D., Barrie, C.T., and Bleeker, W. 1999. The giant Kidd Creekvolcanogenic massive sulfide deposit, western Abitibi Subprovince, Canada:preface and introduction. Economic Geology Monograph, 10: 1–30. doi:10.5382/Mono.10.01.

Hannington, M.D., de Ronde, C.E.J., and Petersen, S. 2005. Sea floor tectonics andsubmarine hydrothermal systems. Economic Geology, 100th AnniversaryVolume, pp. 111–142.

Hart, T.R., Gibson, H.L., and Lesher, C.M. 2004. Trace element geochemistry andpetrogenesis of felsic volcanic rocks associated with volcanogenic massiveCu–Zn–Pb sulphide deposits. Economic Geology, 99: 1003–1013. doi:10.2113/gsecongeo.99.5.1003.

Hekinian, R., Fevrier, M., Bischoff, J.L., Picot, P., and Shanks, W.C. 1980. Sulfidedeposits from the East Pacific Rise near 2°N. Science, 207: 1433–1444. doi:10.1126/science.207.4438.1433. PMID:17779603.

Herrmann, W., Blake, M., Doyle, M., Huston, D., Kamprad, J., Merry, N., andPontual, S. 2001. Short wavelength infrared (SWIR) spectral analysis of hydro-thermal alteration zones associated with base metal sulfide deposits at Rose-bery and Western Tharsis, Tasmania, and Highway-Reward, Queensland.Economic Geology, 96: 939–955. doi:10.2113/gsecongeo.96.5.939.

Herzig, P.M., and Hannington, M.D. 1995. Polymetallic massive sulfides at themodern seafloor — a review. Ore Geology, 10: 95–115. doi:10.1016/0169-1368(95)00009-7.

Huston, D.L., Kamprad, J., and Brauhart, C. 1997. Preliminary results of PIMAanalysis of the alteration zone underlying the Sulphur Springs deposit, Pan-orama district, Pilbara block, Western Australia. Australian Geological Sur-vey Organization Record, 1997(14): 36.

Ishikawa, Y., Sawaguchi, T., Ywaya, S., and Horiuchi, M. 1976. Delineation ofprospecting targets for Kuroko deposits based on modes of volcanism ofunderlying dacite and alteration halos. Mining Geology, 26: 105–117.

Jenner, G.A. 1996. Trace element geochemistry of igneous rocks: geochemicalnomenclature and analytical geochemistry. In Trace element geochemistryof volcanic rocks: applications for massive sulfide exploration. Edited byD.A. Wyman. Geological Association of Canada, Short Course Notes, 12,pp. 51–77.

Jenner, G.A., Longerich, H.P., Jackson, S.E., and Fryer, B.J. 1990. ICP-MS — Apowerful tool for high-precision trace element analysis in Earth sciences:evidence from analysis of selected U.S.G.S. reference samples. Chemical Ge-ology, 83: 133–148. doi:10.1016/0009-2541(90)90145-W.

Jones, S., Herrmann, W., and Gemmell, J.B. 2005. Short wavelength infraredspectral characteristics of the HW horizon: implications for exploration inthe Myra Falls volcanic-hosted massive sulfide camp, Vancouver Island, BritishColumbia, Canada. Economic Geology, 100: 273–294. doi:10.2113/gsecongeo.100.2.273.

Kean, B.F., and Evans, D.T.W. 1986. Metallogeny of the Tulks Hill volcanics,Victoria Lake Group, central Newfoundland. Government of Newfoundlandand Labrador Report 86-1, Department of Mines and Energy, Mineral Devel-opment Division.

Kean, B.F., Evans, D.T.W., and Jenner, G.A. 1995. Geology and mineralization ofthe Lushs Bight Group: St. John’s, Newfoundland. Geological Survey of New-foundland and Labrador Report 95-05, Mineral Development Division.

Knuckey, M.J., Comba, C.D.A., and Riverin, G. 1982. Structure, metal zoning and

alteration at the Millenbach Deposit, Noranda, Quebec. Special Paper – Geo-logical Association of Canada, 25: 255–295.

Large, R.R. 1992. Australian volcanic-hosted massive sulfide deposits: features,styles, and genetic models. Economic Geology, 87: 471–510. doi:10.2113/gsecongeo.87.3.471.

Large, R.R., Gemmell, J.B., Paulick, H., and Huston, D.L. 2001. The alteration boxplot: a simple approach to understanding the relationships between altera-tion mineralogy and lithogeochemistry associated with VHMS deposits. Eco-nomic Geology, 96: 957–971. doi:10.2113/gsecongeo.96.5.957.

Lentz, D.R. 1998. Petrogenetic evolution of felsic volcanic sequences associatedwith Phanerozoic volcanic-hosted massive sulphide systems: the role of ex-tensional geodynamics. Ore Geology Reviews, 12: 289–327. doi:10.1016/S0169-1368(98)00005-5.

Lesher, C.M., Goodwin, A.M., Campbell, I.H., and Gorton, M.P. 1986. Trace-element geochemistry of ore-associated and barren, felsic metavolcanicrocks in the Superior Province, Canada. Canadian Journal of Earth Sciences,23: 222–237. doi:10.1139/e86-025.

Lode, S., Piercey, J.S., and Devine, C.A. 2015. Geology, mineralogy, and lithogeo-chemistry of metalliferous mudstones associated with the Lemarchant vol-canogenic massive sulfide deposit, Tally Pond belt, central Newfoundland.Economic Geology, 110: 1835–1859. doi:10.2113/econgeo.110.7.1835.

Longerich, H.P., Jenner, G.A., Fryer, B.J., and Jackson, S.E. 1990. Inductively cou-pled plasma–mass spectrometric analysis of geological samples: a criticalevaluation based on case studies. Chemical Geology, 83: 105–118. doi:10.1016/0009-2541(90)90143-U.

Lydon, J.W. 1984. Volcanogenic sulphide deposits. Part 1: A descriptive model.Geoscience Canada, 11: 195–202.

Lydon, J.W. 1988. Volcanogenic massive sulphide deposits. Part 2: Genetic mod-els. Geoscience Canada, 15: 43–65.

MacLean, W.H. 1988. Rare earth element mobility at constant inter-REE ratios inthe alteration zone at the Phelps Dodge massive sulphide deposit, Matagami,Quebec. Mineralium Deposita, 23: 231–238. doi:10.1007/BF00206399.

MacLean, W.H. 1990. Mass change calculations in altered rock series. Minera-lium Deposita, 25: 44–49. doi:10.1007/BF03326382.

MacLean, W.H., and Barrett, T.J. 1993. Lithogeochemical techniques using im-mobile elements. Journal of Geochemical Exploration, 48: 109–133. doi:10.1016/0375-6742(93)90002-4.

MacLean, W.H., and Kranidiotis, P. 1987. Immobile elements as monitors of masstransfer in hydrothermal alteration: Phelps Dodge massive sulfide deposit,Matagami, Quebec. Economic Geology, 82: 951–962. doi:10.2113/gsecongeo.82.4.951.

McDonough, W.F., and Sun, S. 1995. The composition of the earth. ChemicalGeology, 120: 223–253. doi:10.1016/0009-2541(94)00140-4.

McLeod, R.L., and Stanton, R.L. 1984. Phyllosilicates and associated minerals insome Paleozoic stratiform sulfide deposits of southeastern Australia. Eco-nomic Geology, 79: 1–22. doi:10.2113/gsecongeo.79.1.1.

McNicoll, V., Squires, G., Kerr, A., and Moore, P.J. 2010. The Duck Pond andBoundary Cu–Zn deposits, Newfoundland: new insights into the ages of hostrocks and the timing of VHMS mineralization. Canadian Journal of EarthSciences, 47: 1481–1506. doi:10.1139/E10-075.

McPhie, J., Doyle, M., and Allen, R.L. 1993. Volcanic textures: a guide to theinterpretation of textures in volcanic rocks. Centre for Ore Deposit and Ex-ploration Studies, University of Tasmania, Hobart, Australia.

Monecke, T., Petersen, S., and Hannington, M.D. 2014. Constraints on waterdepth of massive sulfide formation: evidence from modern seafloor hydro-thermal systems in arc-related settings. Economic Geology, 109: 2079–2101.doi:10.2113/econgeo.109.8.2079.

Moore, P.J. 2003. Stratigraphic implications for mineralization: preliminaryfindings of a metallogenic investigation of the Tally Pond volcanics, centralNewfoundland. Current Research Report 03-1: St. John’s, Newfoundland,Geological Survey Branch.

Pearce, J.A. 1996. A user’s guide to basalt discrimination diagrams. In Traceelement geochemistry of volcanic rocks: applications for massive sulfideexploration. Edited by D.A. Wyman. Geological Association of Canada, ShortCourse Notes, Vol. 12, pp. 79–113.

Pearce, J.A., Harris, N.B.W., and Tindle, A.G. 1984. Trace element discriminationdiagrams for the tectonic interpretation of granitic rocks. Journal of Petrol-ogy, 25: 956–983. doi:10.1093/petrology/25.4.956.

Petersen, S., Monecke, T., Westhues, A., Hannington, M.D., Gemmell, J.B.,Sharpe, R., et al. 2014. Drilling shallow-water massive sulfides at the Palinurovolcanic complex, Aeolian island arc, Italy. Economic Geology, 109: 2129–2158. doi:10.2113/econgeo.109.8.2129.

Piercey, S.J. 2009. Lithogeochemistry of volcanic rocks associated with volcano-genic massive sulfide deposits and applications to exploration. In Submarinevolcanism and mineralization: modern through ancient. Edited by B. Cousensand S.J. Piercey. Geological Association of Canada, Short Course 29–30 May2008, Quebec City, Canada.

Piercey, S. 2011. The setting, style, and role of magmatism in the formation ofvolcanogenic massive sulfide deposits. Mineralium Deposita, 46: 449–471.doi:10.1007/s00126-011-0341-z.

Piercey, S.J., and Colpron, M. 2009. Composition and provenance of the Snowcapassemblage, basement to the Yukon-Tanana terrane, northern Cordillera:




Can

. J. E

arth

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. Dow

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http://dx.doi.org/10.1016/0375-6742(93)90004-6






http://dx.doi.org/10.1016/0009-2541(67)90004-6

http://dx.doi.org/10.1127/ejm/10/5/0815

http://dx.doi.org/10.5382/Mono.10.01

http://dx.doi.org/10.5382/Mono.10.01



http://dx.doi.org/10.1126/science.207.4438.1433

http://dx.doi.org/10.1126/science.207.4438.1433

http://www.ncbi.nlm.nih.gov/pubmed/17779603


http://dx.doi.org/10.1016/0169-1368(95)00009-7

http://dx.doi.org/10.1016/0169-1368(95)00009-7

http://dx.doi.org/10.1016/0009-2541(90)90145-W






http://dx.doi.org/10.1016/S0169-1368(98)00005-5

http://dx.doi.org/10.1016/S0169-1368(98)00005-5

http://dx.doi.org/10.1139/e86-025


http://dx.doi.org/10.1016/0009-2541(90)90143-U

http://dx.doi.org/10.1016/0009-2541(90)90143-U

http://dx.doi.org/10.1007/BF00206399

http://dx.doi.org/10.1007/BF03326382

http://dx.doi.org/10.1016/0375-6742(93)90002-4

http://dx.doi.org/10.1016/0375-6742(93)90002-4



http://dx.doi.org/10.1016/0009-2541(94)00140-4


http://dx.doi.org/10.1139/E10-075


http://dx.doi.org/10.1093/petrology/25.4.956


http://dx.doi.org/10.1007/s00126-011-0341-z


http://www.nrcresearchpress.com/action/showLinks?pmid=17779603&crossref=10.1126%2Fscience.207.4438.1433


http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2FS0169-1368%2898%2900005-5&isi=000075448000001

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2F0375-6742%2893%2990004-6&isi=A1993LR13100004



http://www.nrcresearchpress.com/action/showLinks?crossref=10.1007%2FBF03326382

http://www.nrcresearchpress.com/action/showLinks?crossref=10.2113%2Fgsecongeo.82.4.951&isi=A1987J663800008

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1127%2Fejm%2F10%2F5%2F0815

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1007%2Fs00126-011-0341-z

http://www.nrcresearchpress.com/action/showLinks?isi=A1988N336600004


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http://www.nrcresearchpress.com/action/showLinks?system=10.1139%2Fe86-025&isi=A1986A655100009


http://www.nrcresearchpress.com/action/showLinks?system=10.1139%2FE10-075


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http://www.nrcresearchpress.com/action/showLinks?crossref=10.1130%2FGES00505.1&isi=000270351800003

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2F0375-6742%2893%2990002-4&isi=A1993LR13100002

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http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2F0009-2541%2890%2990145-W&isi=A1990DP42100012

http://www.nrcresearchpress.com/action/showLinks?isi=A1984ADZ6100002

http://www.nrcresearchpress.com/action/showLinks?crossref=10.2113%2Fgsecongeo.81.8.1976&isi=A1986F960300009

implications for Cordilleran crustal growth. Geosphere, 5: 439–464. doi:10.1130/GES00505.S3.

Piercey, S.J. and Hinchey, J. 2012. Volcanogenic massive sulphide (VMS) depositsof the Central Mineral Belt, Newfoundland. In Geological Association ofCanada–Mineralogical Association of Canada Joint Annual Meeting, FieldTrip Guidebook B4. Newfoundland and Labrador Department of Natural Re-sources, Geological Survey, Open File NFLD/3173.

Piercey, S.J., Squires, G.C., and Brace, T.D. 2014. Lithostratigraphic, hydrother-mal, and tectonic setting of the Boundary volcanogenic massive sulfide de-posit, Newfoundland Appalachians, Canada: formation by subseafloorreplacement in a Cambrian rifted arc. Economic Geology, 109: 661–687. doi:10.2113/econgeo.109.3.661.

Pollock, J. 2004. Geology and paletectonic history of the Tally Pond Group,Dunnage zone, Newfoundland Appalachians: an integrated geochemical,geochronological, metallogenic and isotopic study of a Cambrian island arcalong the Peri-Gondwanan margin of Iapetus. M.Sc. thesis, Department ofEarth Science, Memorial University, St. John’s, Newfoundland.

Pontual, S., Merry, N., and Gamson, P. 1997. G-Mex Vol. 1, Spectral interpretationfield manual. Ausspec International Pty. Ltd., Kew, Victoria 3101, Australia.

Riverin, G., and Hodgson, C.J. 1980. Wall-rock alteration at the MillenbachCu–Zn mine, Noranda, Quebec. Economic Geology, 75: 424–444. doi:10.2113/gsecongeo.75.3.424.

Rogers, N., and van Staal, C.R. 2002. Toward a Victoria Lake Supergroup: aprovisional stratigraphic revision of the Red Indian to Victoria Lakes area,central Newfoundland. Current Research – Report 02-1. Newfoundland, Geo-logical Survey Branch.

Rogers, N., van Staal, C.R., McNicoll, V., Pollock, J., Zagorevski, A., and Whalen, J.2006. Neoproterozoic and Cambrian arc magmatism along the eastern mar-gin of the Victoria Lake Supergroup: a remnant of Ganderian basement incentral Newfoundland? Precambrian Research, 147: 320–341. doi:10.1016/j.precamres.2006.01.025.

Rogers, N., van Staal, C., Zagorevski, A., Skulski, T., Piercey, S.J., and McNicoll, V.2007. Timing and tectonic setting of volcanogenic massive sulfide bearingterranes within the Central Mobile belt of the Canadian Appalachians. InProceedings of Exploration 07, Milkereit, Fifth Decennial International Con-ference on Mineral Exploration, Toronto. pp. 1199–1205.

Ross, P.-S., and Bédard, J.H. 2009. Magmatic affinity of modern and ancientsubalkaline volcanic rocks determined from trace-element discriminant di-agrams. Canadian Journal of Earth Sciences, 46: 823–839. doi:10.1139/E09-054.

Ruks, T.W., Piercey, S.J., Ryan, J.J., Villeneuve, M.E., and Creaser, R.A. 2006. Mid-to late Paleozoic K-feldspar augen granitoids of the Yukon-Tanana terrane,Yukon, Canada: implications for crustal growth and tectonic evolution of thenorthern Cordillera. Geological Society of America Bulletin, 118: 1212–1231.doi:10.1130/B25854.1.

Saeki, Y., and Date, J. 1980. Computer application to the alteration data of thefootwall dacite lava at the Ezuri Kuroko deposits, Akito Prefecture. MiningGeology, 30: 241–250.

Schardt, C., Cooke, D.R., Gemmell, J.B., and Large, R.R. 2001. Geochemical mod-eling of the zoned footwall alteration pipe, Hellyer volcanic-hosted massivesulfide deposit, Western Tasmania, Australia. Economic Geology, 96: 1037–1054. doi:10.2113/gsecongeo.96.5.1037.

Smith, I., Worthington, T.J., Stewart, R.B., Price, R.C., and Gamble, J.A. 2003.Felsic volcanism in the Kermadec Arc, SW Pacific: crustal recycling in anoceanic setting. Geological Society, London, Special Publications, 219: 99–118. doi:10.1144/GSL.SP.2003.219.01.05.

Spitz, G., and Darling, R. 1978. Major and minor element lithogeochemicalanomalies surrounding the Louvem copper deposit, Val d’Or, Quebec. Cana-dian Journal of Earth Sciences, 15: 1161–1169. doi:10.1139/e78-122.

Squires, G.C., and Moore, P.J. 2004. Volcanogenic massive sulfide environmentsof the Tally Pond Volcanics and adjacent area: geological, lithogeochemicaland geochronological results. In Current Research Report 04-1. Edited byD.G. Walsh and B.F. Kean. St. John’s, Newfoundland, Geological SurveyBranch, pp. 63–91.

Squires, G.C., MacKenzie, A.C., and MacInnis, D. 1991. Geology and genesis of theDuck Pond volcanogenic massive sulfide deposit. In Metallogenic frameworkof base and precious metal deposits, central and western Newfoundland.

Edited by H.S. Swinden, D.T.W Evans, and B.F. Kean. Geological Survey ofCanada Open File 2156, pp. 56–64.

Squires, G.C., Brace, T.D., and Hussey, A.M. 2001. Newfoundland’s polymetallicDuck Pond deposit: Earliest Iapetan VMS mineralization formed within asub-seafloor, carbonate-rich alteration system. In Geology and mineral depos-its of the northern Dunnage zone, Newfoundland Appalachians. Edited byD.T.W. Evans and A. Kerr. St. John’s, Newfoundland, Geological Associationof Canada-Mineralogical Association of Canada, Field Trip Guide A2,pp. 167–187.

Swinden, H.S. 1991. Paleotectonic settings of volcanogenic massive sulfide de-posits in the Dunnage zone, Newfoundland Appalachians. Canadian Insti-tute of Mining and Metallurgy Bulletin, 84: 59–89.

Swinden, H.S., and Thorpe, R.I. 1984. Variations in style of volcanism and mas-sive sulfide deposition in Early to Middle Ordovician island-arc sequences ofthe Newfoundland Central Mobile belt. Economic Geology, 79: 1596–1619.doi:10.2113/gsecongeo.79.7.1596.

Swinden, H.S., Jenner, G.A., Kean, B.F., and Evans, D.T.W. 1989. Volcanic rockgeochemistry as a guide for massive sulfide exploration in central Newfound-land. Current Research Report 89-1, Newfoundland Department of Mines.

Taylor, S.R., and McLennan, S.M. 1985. The continental crust: its compositionand evolution. Oxford, Blackwell Scientific Publication, pp. 312.

van Staal, C.R. 2007. Pre-Carboniferous tectonic evolution and metallogeny ofthe Canadian Appalachians. In Mineral deposits of Canada: a synthesis ofmajor deposit types, district metallogeny, the evolution of geological prov-inces, and exploration methods. Edited by W.D. Goodfellow. Geological Asso-ciation of Canada, Mineral Deposits Division Special Publication, 5: 793–818.

van Staal, C.R. and Barr, S.M. 2012. Lithospheric architecture and tectonic evo-lution of the Canadian Appalachians and associated Atlantic margin. In Tec-tonic styles in Canada: the LITHOPROBE perspective. Edited by J.A. Percival,F.A. Cook, and R.M. Clowes. Geological Association of Canada, Special Paper 49.

van Staal, C.R., and Colman-Sadd, S.P. 1997. The Central Mobile belt of thenorthern Appalachians. Oxford Monographs on Geology and Geophysics, 35:747–760.

Velde, B. 1978. Infrared spectra of synthetic micas in the series muscovite–MgAlceladonite. American Mineralogist, 63: 341–349.

Wagner, D.W. 1993. Volcanic stratigraphy and hydrothermal alteration associ-ated with the Duck Pond and Boundary volcanogenic massive sulphide de-posits, Central Newfoundland. MSc. thesis, Department of Earth Sciences,Carleton University, Ottawa, Ontario.

White, J.D.L., and Houghton, B.F. 2006. Primary volcaniclastic rocks. GeologicSociety of America, 34: 677–680. doi:10.1130/G22346.1.

Williams, H. 1979. Appalachian orogen in Canada. Canadian Journal of EarthSciences, 16: 792–807. doi:10.1139/e79-070.

Williams, H., Colman-Sadd, S.P., and Swinden, H.S. 1988. Tectonostratigraphicsubdivisions of central Newfoundland. Geological Survey of Canada, CurrentResearch, Part B, Paper 88-1B, pp. 91–98.

Winchester, J.A., and Floyd, P.A. 1977. Geochemical discrimination of differentmagma series and their differentiation products using immobile elements.Chemical Geology, 20: 325–343. doi:10.1016/0009-2541(77)90057-2.

Wright, I., Parson, L.M., and Gamble, J.A. 1996. Evolution and interaction ofmigrating cross-arc volcanism and backarc rifting: an example from theSouthern Havre Trough (35°20=–37°S). Journal of Geophysical Research: SolidEarth, 101: 22071–22086. doi:10.1029/96JB01761.

Yang, K., Huntington, J.F., Gemmell, J.B., and Scott, K.M. 2011. Variations incomposition and abundance of white mica in the hydrothermal alterationsystem at Hellyer, Tasmania, as revealed by infrared reflectance spectros-copy. Journal of Geochemical Exploration, 108: 143–156. doi:10.1016/j.gexplo.2011.01.001.

Zagorevski, A., van Staal, C.R., McNicoll, V.J., and Rogers, N. 2007. Upper Cam-brian to Upper Ordovician peri-Gondwanan island arc activity in the VictoriaLake Supergroup, central Newfoundland: tectonic development of the north-ern Ganderian margin. American Journal of Science, 307: 339–370. doi:10.2475/02.2007.02.

Zagorevski, A., van Staal, C.R., Rogers, N., McNicoll, V.J., and Pollock, J. 2010.Middle Cambrian to Ordovician arc-backarc development on the leadingedge of Ganderia, Newfoundland Appalachians. Geological Society of Amer-ica Memoir, 206: 367–396. doi:10.1130/2010.1206(16).




Can

. J. E

arth

Sci

. Dow

nloa

ded

from

ww

w.n

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com

by

Mem

oria

l Uni

vers

ity-B

F on

04/

01/1

6Fo

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al u

se o

nly.

http://dx.doi.org/10.1130/GES00505.S3

http://dx.doi.org/10.1130/GES00505.S3




http://dx.doi.org/10.1016/j.precamres.2006.01.025

http://dx.doi.org/10.1016/j.precamres.2006.01.025

http://dx.doi.org/10.1139/E09-054

http://dx.doi.org/10.1139/E09-054

http://dx.doi.org/10.1130/B25854.1


http://dx.doi.org/10.1144/GSL.SP.2003.219.01.05

http://dx.doi.org/10.1139/e78-122


http://dx.doi.org/10.1130/G22346.1

http://dx.doi.org/10.1139/e79-070

http://dx.doi.org/10.1016/0009-2541(77)90057-2

http://dx.doi.org/10.1029/96JB01761

http://dx.doi.org/10.1016/j.gexplo.2011.01.001

http://dx.doi.org/10.1016/j.gexplo.2011.01.001

http://dx.doi.org/10.2475/02.2007.02

http://dx.doi.org/10.2475/02.2007.02

http://dx.doi.org/10.1130/2010.1206(16)

http://www.nrcresearchpress.com/action/showLinks?system=10.1139%2Fe78-122&isi=A1978FK51300011

http://www.nrcresearchpress.com/action/showLinks?crossref=10.2475%2F02.2007.02&isi=000246863700002

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http://www.nrcresearchpress.com/action/showLinks?crossref=10.1144%2FGSL.SP.2003.219.01.05

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2Fj.gexplo.2011.01.001

http://www.nrcresearchpress.com/action/showLinks?crossref=10.1016%2F0009-2541%2877%2990057-2&isi=A1977DX99400005

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http://www.nrcresearchpress.com/action/showLinks?system=10.1139%2Fe79-070&isi=A1979GR65700009

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