Mineralium Deposita (v.46, #5-6)

The northeast (NE) Honshu arc was formed by three major volcano-tectonic events resulting from Late Cenozoic orogenic movement: continental margin volcanism (before 21 Ma), seafloor basaltic lava flows and subsequent bimodal volcanism accompanied by back-arc rifting (21 to 14 Ma), and felsic volcanism related to island arc uplift (12 to 2 Ma). Eight petrotectonic domains, parallel to the NE Honshu arc, were formed as a result of the eastward migration of volcanic activity with time. Major Kuroko volcanogenic massive sulfide (VMS) deposits are located within the eastern marginal rift zone (Kuroko rift) that formed in the final period of back-arc rifting (16 to 14 Ma). Volcanic activity in the NE Honshu arc is divided into six volcanic stages. The eruption volumes of volcanic rocks have gradually decreased from 4,600 km3 (per 1 my for a 200-km-long section along the arc) of basaltic lava flows in the back-arc spreading stage to 1,000–2,000 km3 of bimodal hyaloclastites in the back-arc rift stage, and about 200 km3 of felsic pumice eruptions in the island arc stage. The Kuroko VMS deposits were formed at the time of abrupt decrease in the eruption volume and change in the mode of occurrence of the volcanic rocks during the final period of back-arc rifting. In the area of the Kuroko rift, felsic volcanism changed from aphyric or weakly plagioclase phyric (before 14 Ma), to quartz and plagioclase phyric with minor clinopyroxene (12 to 8 Ma), to hornblende phyric (after 8 Ma), and hornblende and biotite phyric (after 4 Ma). The Kuroko VMS deposits are closely related to the aphyric rhyolitic activity before 14 Ma. The rhyolite was generated at a relatively high temperature from a highly differentiated part of felsic magma seated at a relatively great depth and contains higher Nb, Ce, and Y contents than the post-Kuroko felsic volcanism. The Kuroko VMS deposits were formed within a specific tectonic setting, at a specific period, and associated with a particular volcanism of the arc evolution process. Therefore, detailed study of the evolutional process from rift opening to island arc tectonics is very important for the exploration of Kuroko-type VMS deposits.
Keywords: Kuroko; Volcanogenic massive sulfide; VMS; Felsic volcanism; Island arc; Back-arc rifting; Japan

Throughout Earth’s history, all volcanogenic massive sulfide (VMS)-hosting environments are associated with specific assemblages of mafic and felsic rocks with distinct petrochemistry (petrochemical assemblages) indicative of formation at anomalously high temperatures within extensional geodynamic environments. In mafic-dominated (juvenile/ophiolitic) VMS environments, there is a preferential association with mafic rocks with boninite and low-Ti tholeiite, mid-ocean ridge basalt (MORB), and/or back-arc basin basalt affinities representing forearc rifting or back-arc initiation, mid-ocean ridges or back-arc basin spreading, or back-arc basins, respectively. Felsic rocks in juvenile oceanic arc environments in Archean terrains are high field strength element (HFSE) and rare earth element (REE) enriched. In post-Archean juvenile oceanic arc terrains, felsic rocks are commonly HFSE and REE depleted and have boninite like to tholeiitic signatures. In VMS environments that are associated with continental crust (i.e., continental arc and back-arc) and dominated by felsic volcanic and/or sedimentary rocks (evolved environments), felsic rocks are the dominant hosts to mineralization and are generally HFSE and REE enriched with calc-alkalic, A-type, and/or peralkalic affinities, representing continental arc rifts, continental back-arcs, and continental back-arcs to continental rifts, respectively. Coeval mafic rocks in evolved environments have alkalic (within-plate/ocean island basalt like) and MORB signatures that represent arc to back-arc rift versus back-arc spreading, respectively. The high-temperature magmatic activity in VMS environments is directly related to the upwelling of mafic magma beneath rifts in extensional geodynamic environments (e.g., mid-ocean ridges, back-arc basins, and intra-arc rifts). Underplated basaltic magma provides the heat required to drive hydrothermal circulation. Extensional geodynamic activity also provides accommodation space at the base of the lithosphere that allows for the underplated basalt to drive hydrothermal circulation and induce crustal melting, the latter leading to the formation of VMS-associated rhyolites in felsic-dominated and bimodal VMS environments. Rifts also provide extensional faults and the permeability and porosity required for recharge and discharge of VMS-related hydrothermal fluids. Rifts are also critical in creating environments conducive to preservation of VMS mineralization, either through shielding massive sulfides from seafloor weathering and mass wasting or by creating environments conducive to the precipitation of subseafloor replacement-style mineralization in sedimented rifts. Subvolcanic intrusions are also products of the elevated heat flow regime common to VMS-forming environments. Shallow-level intrusive complexes (i.e., within 1–3 km of the seafloor) may not be the main drivers of VMS-related hydrothermal circulation, but are likely the manifestation of deeper-seated mantle-derived heat (i.e., ~3–10 km depth) that drives hydrothermal circulation. These shallower intrusive complexes are commonly long-lived (i.e., millions of years), and reflect a sustained thermally anomalous geodynamic environment. Such a thermally anomalous environment has the potential to drive significant hydrothermal circulation, and, therefore multi-phase, long-lived subvolcanic intrusive complexes are excellent indicators of a potentially fertile VMS environment. The absence of intrusive complexes, however, does not indicate an area of low potential, as they may have been moved or removed due to post-VMS tectonic activity. In some cases, shallow-level intrusive systems contribute metals to the VMS-hydrothermal system.
Keywords: Volcanogenic massive sulfide (VMS); Lithogeochemistry; Rifting; Heat flow; Bimodal magmatism; Hydrothermal circulation

The role of granites in volcanic-hosted massive sulphide ore-forming systems: an assessment of magmatic–hydrothermal contributions by David L. Huston; Jorge M. R. S. Relvas; J. Bruce Gemmell; Susan Drieberg (473-507).
Assessment of geological, geochemical and isotopic data indicates that a significant subgroup of volcanic-hosted massive sulphide (VHMS) deposits has a major or dominant magmatic–hydrothermal source of ore fluids and metals. This group, which is typically characterised by high Cu and Au grades, includes deposits such as those in the Neoarchean Doyon-Bousquet-LaRonde and Cambrian Mount Lyell districts. These deposits are distinguished by aluminous advanced argillic alteration assemblages or metamorphosed equivalents intimately associated with ore zones. In many of these deposits, δ34Ssulphide is low, with a major population below −3‰; δ34Ssulphate differs from coexisting seawater and Δ34Ssulphate–sulphide ∼ 20–30‰. These characteristics are interpreted as the consequence of disproportionation of magmatic SO2 as magmatic–hydrothermal fluids ascended and cooled and as a definitive evidence for a significant magmatic–hydrothermal contribution. Other characteristics that we consider diagnostic of significant magmatic–hydrothermal input into VHMS ore fluids include uniformly high (>3 times modern seawater values) salinities or very 18O-enriched (δ18O > 5‰) ore fluids. We do not consider other criteria [e.g. variable salinity, moderately high δ18Ofluid (2–5‰), δ34Ssulphide near 0‰, metal assemblages or a spatial association with porphyry Cu or other clearly magmatic-hydrothermal deposits] that have been used previously to advocate significant magmatic–hydrothermal contributions to be diagnostic as they can be produced by non-magmatic processes known to occur in VHMS mineral systems. However, in general, a small magmatic–hydrothermal contribution cannot be excluded in most VHMS systems considered. Conclusive data that imply minimal magmatic–hydrothermal contributions are only available in the Paleoarchean Panorama district where coeval seawater-dominated and magmatic–hydrothermal systems appear to have been physically separated. This district, which is characterised by chloritic and sericitic alteration assemblages and lacks aluminous advanced argillic alteration assemblages, is typical of many VHMS deposits around the world, suggesting that for “garden variety” VHMS deposits, a significant magmatic–hydrothermal contribution is not required. Other than deposits associated with advanced argillic alteration assemblages, the only deposit for which we ascribe a major magmatic–hydrothermal contribution is the Devonian Neves Corvo deposit. This deposit differs from other deposits in the Iberian Pyrite Belt and around the world in being extremely Sn-rich, with the Sn closely associated with Cu and in having formed from high 18O-rich fluids (δ18Ofluid ∼8.5‰). We consider these characteristics, particularly the last, as diagnostic of a significant magmatic hydrothermal contribution. Our analysis indicates that two subgroups of VHMS deposits have a major magmatic–hydrothermal contribution: Cu/Au-rich deposits with aluminous alteration assemblages and reduced, very Sn-rich deposits in which Sn was introduced in a high-temperature ore assemblage. Comparison with “normal” VHMS deposits suggests that these subgroups of VHMS deposits may form in specialised tectonic environments. The Cu/Au-rich deposits appear to form adjacent to magmatic arcs, an environment conducive to the generation of hydrous, oxidised melts by melting metasomatised mantle in the wedge above the subducting slab. This contrasts with the back-arc setting of “normal” VHMS deposits in which relatively dry granites (In this contribution, we use the term granite sensu latto) formed by decompression melting drive seawater-dominated hydrothermal circulation. The tectonic setting of highly Sn-rich VHMS deposits such as Neves Corvo is less clear; however, thick continental crust below the ore-hosting basin may be critical, as it is in other Sn deposits.

The gold content of volcanogenic massive sulfide deposits by Patrick Mercier-Langevin; Mark D. Hannington; Benoît Dubé; Valérie Bécu (509-539).
Volcanogenic massive sulfide deposits contain variable amounts of gold, both in terms of average grade and total gold content, with some VMS deposits hosting world-class gold mines with more than 100 t Au. Previous studies have identified gold-rich VMS as having an average gold grade, expressed in g/t, exceeding the total abundance of base metals, expressed in wt.%. However, statistically meaningful criteria for the identification of truly anomalous deposits have not been established. This paper presents a more extensive analysis of gold grades and tonnages of 513 VMS deposits worldwide, revealing a number of important features in the distribution of the data. A large proportion of deposits are characterized by a relatively low gold grade (<2 g/t), with a gradual decrease in frequency towards maximum gold grades, defining a log-normal distribution. In the analysis presented in this paper, the geometric mean and geometric standard deviation appear to be the simplest metric for identifying subclasses of VMS deposits based on gold grade, especially when comparing deposits within individual belts and districts. The geometric mean gold grade of 513 VMS deposits worldwide is 0.76 g/t; the geometric standard deviation is +2.70 g/t Au. In this analysis, deposits with more than 3.46 g/t Au (geometric mean plus one geometric standard deviation) are considered auriferous. The geometric mean gold content is 4.7 t Au, with a geometric standard deviation of +26.3 t Au. Deposits containing 31 t Au or more (geometric mean plus one geometric standard deviation) are also considered to be anomalous in terms of gold content, irrespective of the gold grade. Deposits with more than 3.46 g/t Au and 31 t Au are considered gold-rich VMS. A large proportion of the total gold hosted in VMS worldwide is found in a relatively small number of such deposits. The identification of these truly anomalous systems helps shed light on the geological parameters that control unusual enrichment of gold in VMS. At the district scale, the gold-rich deposits occupy a stratigraphic position and volcanic setting that commonly differs from other deposits of the district possibly due to a step change in the geodynamic and magmatic evolution of local volcanic complexes. The gold-rich VMS are commonly associated with transitional to calc-alkaline intermediate to felsic volcanic rocks, which may reflect a particularly fertile geodynamic setting and/or timing (e.g., early arc rifting or rifting front). At the deposit scale, uncommon alteration assemblages (e.g., advanced argillic, aluminous, strongly siliceous, or potassium feldspar alteration) and trace element signatures may be recognized (e.g., Au–Ag–As–Sb ± Bi–Hg–Te), suggesting a direct magmatic input in some systems.
Keywords: Gold; Volcanogenic massive sulfides; Gold-rich VMS; World-class; Base metals

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand by Cornel E. J. de Ronde; Gary J. Massoth; David A. Butterfield; Bruce W. Christenson; Junichiro Ishibashi; Robert G. Ditchburn; Mark D. Hannington; Robert L. Brathwaite; John E. Lupton; Vadim S. Kamenetsky; Ian J. Graham; Georg F. Zellmer; Robert P. Dziak; Robert W. Embley; Vesselin M. Dekov; Frank Munnik; Janine Lahr; Leigh J. Evans; Ken Takai (541-584).
Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ∼600 m in a SW–NE direction with chimneys occurring over a ∼145-m depth interval, between ∼1,690 and 1,545 m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2–3 m in height, with some reaching 6–7 m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35 years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2–3 m thick. Two main types of chimney predominate: Cu-rich (up to 28.5 wt.% Cu) and, more commonly, Zn-rich (up to 43.8 wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91 ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (≤0.5 m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (≤300°C), acidic (pH ≥ 2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (≤122°C), more acidic (pH 1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO4 and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3 years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO2 (e.g., 206 mM/kg at the Cone site); high CO2/3He; negative δD and δ18OH2O for vent fluids; negative δ34S for sulfides (to −4.6‰), sulfur (to −10.2‰), and δ15N2 (to −3.5‰); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu + Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in 3He/4He values for both Cone and NW Caldera sites, and overprinting of “magmatic” mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (∼2.5 km long), narrow (∼300-m diameter) “pipes,” consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.

Black shales and massive sulfide deposits: causal or casual relationships? Insights from Rammelsberg, Tharsis, and Draa Sfar by Reinaldo Sáez; Carmen Moreno; Felipe González; Gabriel R. Almodóvar (585-614).
Black shales and massive sulfides represent reduced lithofacies that require isolation from oxic environments to be preserved. This, together with the sedimentary affinity of both lithofacies, can explain their common concurrence in the geologic record. The present study is based on the comparison of Rammelsberg in Germany, Tharsis in Spain, and Draa Sfar in Morocco, three massive sulfide deposits closely associated with black shales that are distributed along the European and North African Variscan orogen. The study entails geochemical, biostratigraphic, and stratigraphic analyses of the black shale sequences hosting the three deposits and mineralogical and textural analyses of the sulfides. All three deposits were formed in immature, tectonically unstable basins within an active continental margin or continental magmatic arc. Their stratigraphic records consist of a sequence of black shales enclosing massive sulfides and variable proportions of bimodal volcanic and subvolcanic rocks. The major differences among the three deposits concern the size, composition, and mineralogy. Regarding age, they are diachronous and younger southward: Rammelsberg is middle Eifelian, Tharsis latest Famennian, and Draa Sfar late Viséan. The study of redox conditions of the paleoenvironment using organic and inorganic proxies highlights similarities and significant differences among the three ore-hosting basins during massive sulfide and black shale deposition. The black shales generally display low Corg and high Stot contents. At Rammelsberg, the Stot/Ctot ratios provide values typical for normal Middle Devonian marine environments, which suggests that the original reactive organic C is now fixed in carbonates. At Tharsis, most of the samples have Corg >1 and Stot/Corg values equivalent to those of Devonian–Carboniferous normal marine sediments. However, some pyritic hanging-wall samples have Corg <1 and Stot up to 5 wt.%, suggesting the epigenetic addition of HS. The Stot/Corg ratio for the Draa Sfar samples resembles that of Middle Carboniferous normal marine environments. Geochemical inorganic proxies used to define the environmental conditions include the enrichment factors of U (UEF) and Mo (MoEF) together with V/Cr and V/(V + Ni) ratios. Footwall shales at Filón Norte (Tharsis) show positive and eventually elevated UEF and MoEF values, which suggests anoxic conditions, whereas at Rammelsberg and Draa Sfar oxic bottom water is indicated. The relations V/Cr and V/(V + Ni) in all three cases point to a redox boundary near the sediment–water interface, although at Tharsis some samples indicate anoxic/euxinic conditions (i.e., V/(V + Ni) >0.9). Regarding the environmental conditions of the source areas, feldspar illitization and selective depletion in Na and Ca occurred at the three studies sites. Available sulfur isotopic data from the Rammelsberg and Tharsis sulfide ore indicate that biogenic reduction of marine sulfate was a major sulfur source during massive sulfide generation. Nevertheless, a hydrothermal sulfur source has also been detected. At Rammelsberg, this is indicated from the polymetallic sulfides that replace sedimentary and diagenetic pyrite. At Tharsis, the bacteriogenic sulfur signature is also restricted to sulfide with less evolved textures, whereas a hydrothermal source is more evident in sulfides showing evidence of recrystallization. Both geochemical and isotopic data suggest that the bacteriogenic reduction process was inhibited by rapid burial. The sedimentation rates calculated for Rammelsberg, Tharsis, and Draa Sfar were in the range 7–13, 8–14, and 19–27 cm/ka, respectively. Continuous sedimentation of black shale favored the isolation of the massive sulfides and organic material from bottom waters and hence favored their preservation. Accordingly, the relationships between black shales and massive sulfides are considered to be casual. Nevertheless, the tectono-sedimentary evolution of each basin controlled the deposition of both black shales and massive sulfides and the parameters that favored their coeval deposition.
Keywords: Black shales; Massive sulfide deposits; Rammelsberg; Tharsis; Draa Sfar; Variscan orogen

Post-depositional tectonic modification of VMS deposits in Iberia and its economic significance by Ricardo Castroviejo; Cecilio Quesada; Miguel Soler (615-637).
The original stratigraphic relationships and structure of VMS deposits are commonly obscured by deformation. This can also affect their economic significance, as shown by several Iberian Pyrite Belt (IPB, SW Iberia) examples. The contrasting rheologic properties of the different lithologies present in an orebody (massive sulphide, feeder stockwork, alteration envelope, volcanic and sedimentary rocks) play a major role in determining its overall behaviour. Variscan thin-skinned tectonics led to stacking of the massive pyrite and stockwork bodies in duplex structures, resulting in local thickening and increased tonnage of minable mineralization. Furthermore, differential mechanical behaviour of the different sulphide minerals localised the detachments along relatively ductile sulphide-rich bands. The result was a geochemical and mineralogical reorganisation of most deposits, which now consist of barren, massive pyrite horses, bounded by base metal-rich ductile shear zones. Metal redistribution was enhanced by mobilisation of the base metal sulphides from the initially impoverished massive pyrite, through pressure-solution processes, to tensional fissures within the already ductile shear zones. In NW Iberia, VMS deposits were also strongly overprinted by the Variscan deformation during emplacement of the Cabo Ortegal and Órdenes allochthonous nappe complexes, but no stacking of the orebodies was produced. Original contacts were transposed, and the orebodies, their feeder zones and the country rock acquired pronounced laminar geometry. In lower-grade rocks (greenschist facies, Cabo Ortegal Complex), solution transfer mechanisms are common in pyrite, which remains in the brittle domain, while chalcopyrite shows ductile behaviour. In higher-grade rocks (amphibolite facies, Órdenes Complex), metamorphic recrystallisation overprints earlier deformation textures. The contrasting behaviour of the IPB and NW Iberian deposits is explained by key factors that affect their final geometry, composition and economics, such as pre-deformation structure, size and mineralogical composition of the orebody and associated lithologies, temperature, crustal level, deviatoric stress and availability of a fluid phase during deformation and the style and rate of deformation.
Keywords: VMS exploration; Sulphide deformation; Iberian Pyrite Belt; Masa Valverde deposit; NW Iberia

Episodic seafloor spreading, ridge topography, and fault movement at ridges find (more extreme) analogs in the arc and back-arc setting where the volcanogenic massive sulfide (VMS) deposits that we mine today were formed. The factors affecting sulfide accumulation efficiency and the extent to which sulfides are concentrated spatially are the same in both settings, however. The processes occurring at mid-ocean ridges therefore provide a useful insight into those producing VMS deposits in arcs and back-arcs. The critical observation investigated here is that all the heat introduced by seafloor spreading at mid-ocean ridges is carried out of the crust within a few hundred meters of the ridge axis by ∼350°C hydrothermal fluids. The high-temperature ridge hydrothermal systems are tied to the presence of magma at the ridge axis and greatly reduce the size and control the shape of axial magma intrusions. The amount of heat introduced to each square kilometer of ocean crust during its formation can be calculated, and its removal by high-temperature convection allows calculation of the total base metal endowment of the ocean basins. Using reasonable metal deposition efficiencies, we conclude that the ocean floor is a giant VMS district with metal resources >600 times the total known VMS reserves on land and a copper resource which would last >6,000 years at current production rates.