PGE fractionation in seafloor hydrothermal systems: examples from mafic- and ultramafic-hosted hydrothermal fields at the slow-spreading Mid-Atlantic Ridge

The distribution of platinum group elements (PGEs) in massive sulfides and hematite–magnetite±pyrite assemblages from the recently discovered basalt-hosted Turtle Pits hydrothermal field and in massive sulfides from the ultramafic-hosted Logatchev vent field both on the Mid-Atlantic Ridge was studied and compared to that from selected ancient volcanic-hosted massive sulfide (VHMS) deposits. Cu-rich samples from black smoker chimneys of both vent fields are enriched in Pd and Rh (Pd up to 227 ppb and Rh up to 149 ppb) when compared to hematite–magnetite-rich samples from Turtle Pits (Pd up to 10 ppb, Rh up to 1.9 ppb). A significant positive correlation was established between Cu and Rh in sulfide samples from Turtle Pits. PGE chondrite-normalized patterns (with a positive Rh anomaly and Pd and Au enrichment), Pd/Pt and Pd/Au ratios close to global MORB, and high values of Pd/Ir and Pt/Ir ratios indicate mafic source rock and seawater involvement in the hydrothermal system at Turtle Pits. Similarly shaped PGE chondrite-normalized patterns and high values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides at Logatchev likely reflect a similar mechanism of PGE enrichment but with involvement of ultramafic source rocks.     

Composition and origin of hydrothermal petroleum and associated lipids in the sulfide deposits of the Rainbow field (Mid-Atlantic Ridge at 36°N)

The lipid components in hydrothermal sulfide deposits from the Rainbow vent field (Mid-Atlantic Ridge at 36°N) were studied by gas chromatography/mass spectrometry. The Rainbow vent field is one of two known active hydrothermal systems related to abyssal circulation, where high-temperature fluids are formed during serpentinization of ultrabasic crustal rocks. The major amount of the extractable organic matter from the sulfides consists of normal and branched alkanes, UCM, PAHs, terpenoids, and fatty acids. The branched alkanes are comprised of unique gem-diethylalkane series, possibly from sulfide oxidizing bacteria, and biphytanes from archaea. The characteristic lipid and biomarker compounds found in the hydrothermal samples support a predominantly biological origin of the bitumens from the thermal transformation of the biomass of microorganisms (bacteria and archea) and minor macrofauna of this vent field. A search for molecular evidence for abiogenic thermocatalytic synthesis of organic compounds was negative. However, methane in the hydrothermal fluids and possibly a minor amount of the alkanes in the sulfides may be of an abiogenic origin in the Rainbow vent field.     

Mineralogy and trace element geochemistry of sulfide minerals from the Wocan Hydrothermal Field on the slow-spreading Carlsberg Ridge,Indian Ocean

The basalt-hosted Wocan Hydrothermal Field (WHF), located on the NW slope of an axial volcanic ridge at a depth of ∼3000 m at 6°22′N on the slow-spreading Carlsberg Ridge, northwest Indian Ocean, was discovered in 2013 during Chinese DY28th cruise. Preliminary investigations show that the field consists of two hydrothermal sites: Wocan-1, which shows indications for recent high-temperature hydrothermal activity, is located near the peak of the axial volcanic ridge at a water depth of 2970–2990 m, and Wocan-2 site, located at a water depth of 3100 m, ∼1.7 km to the northwest of Wocan-1. The recovered hydrothermal precipitates can be classified into four groups: (i) Cu-rich chimneys; (ii) Cu-rich massive sulfides; (iii) Fe-rich massive sulfides; and (iv) silicified massive sulfides. We conducted mineral texture and assemblage observation and Laser-ablation ICP-MS analyses of the hydrothermal precipitates to study the mineralization processes. Our results show that there are distinct systematic trace element distributions throughout the different minerals in the four sample groups. In general, chalcopyrite from the group (i) is enriched in Pb, As, Mo, Ga, Ge, V, and Sb, metals that are commonly referred to as medium- to low-temperature elements. In contrast these elements are present in low contents in the chalcopyrite grains from other sample groups. Selenium, a typical high-temperature metal, is enriched in chalcopyrite from groups (ii) and (iv), whereas Ag and Sn are enriched only in some silicified massive sulfides. As with chalcopyrite, pyrite also shows distinct trace element associations in grains with different habitus. The low-temperature association of elements (Pb, Mo, Mn, U, Mg, Ag, and Tl) is typically present in colloform/framboidal pyrite, whereas the high-temperature association (Se, Co, and Bi) is enriched in euhedral pyrite. Sphalerite in the groups (i) and (iii) at Wocan-1 is characterized by high concentrations of Ga, Ge, Pb, Cd, As, and Sb, indicating that sphalerite in these sample groups likely precipitated at intermediate temperatures. Early bornite, which mainly occurs in the central part of the Cu-rich chimney, is typically enriched in Sn and In compared to the other minerals. In contrast, late bornite that likely formed during increasing interaction of hydrothermal fluids with cold, oxygenated seawater has low Sn and In, but significantly higher concentrations of Ag, Au, Mo and U. Digenite, also forming in the exterior parts of the samples during the late stages of hydrothermal fluid venting, is poor in most trace elements, except Ag and U. The notable Ag enrichment in the late-stage mineral assemblages at both Wocan-1 and Wocan-2 may therefore be related to lower temperatures and elevated pH. Our results indicate that Wocan-1 has experienced a cycle of heating with Cu-rich chimney growth and subsequent cooling, followed by late seafloor weathering, while Wocan-2 has seen intermediate- to high-temperature mineralization followed by intense silicification of sulfides. Seafloor weathering processes or mixing of hydrothermal fluids with seawater during the waning stages of hydrothermal fluid flow result in significant redistributions of trace elements in sulfide minerals.     

现代海底热液过程及成矿

原始的海水成分、基岩的组分及结构、热源性质等因素决定着现代海底热液喷口系统的流体成分, 同时, 各种地质构造背景下的岩浆脱气作用也在不同程度上影响热液流体的组成.热液流体一旦喷出海底, 就能形成不同类型的热液沉积体, 包括高温流体形成的金属硫化物或硫酸盐烟囱体、热液丘以及由低温弥散流及非浮力羽流形成的含金属沉积物堆积体.高温烟囱体的形成受控于海水和热液的混合比例, 常常表现为典型的两阶段模式, 即先形成环状硬石膏表层, 然后在其内部发生富Cu硫化物的沉淀.这一模式在更大尺度上也可以观察到, 如TAG热液丘.含金属沉积物遍布海底, 除热液羽流外, 金属硫化物烟囱体在氧化环境中氧化蚀变的产物也是其重要来源.生物的活动贯穿于现代热液过程的始终, 并在烟囱体的形成、分解以及羽流的扩散沉淀过程中起到了重要作用.当前, 热液生物矿化机理、Lost City型热液场以及超慢速扩张洋脊的有关研究是海底这一系统研究的热点, 前两者研究能使人们更好地理解地球早期的演化和生命的起源, 而后者的考察和研究能进一步丰富海底热液成矿理论, 并有助于寻找更大规模的热液矿体.      

Relative contribution of magmatic and post-magmatic processes in the genesis of the Thompson Mine Ni-Co sulfide ores,Manitoba, Canada

The Ni-Co-(PGE) sulfide deposits of the Thompson Nickel Belt (TNB) in Northern Manitoba, Canada are part of the fifth largest nickel camp in the world based on contained nickel; past production from the TNB deposits is 2500 kt Ni. The Thompson Deposit is located on the eastern and southern flanks of the Thompson Dome structure, which is a re-folded nappe structure formed during collision of the Trans-Hudson Orogen with the Canadian Shield at 1.9–1.7 Ga. The Thompson Deposit is almost entirely hosted by P2 member sulfidic metasedimentary rocks of the Paleoproterozoic Ospwagan Group. Variably serpentinised and altered dunites, peridotites and pyroxenites contain disseminated sulfides and have a spatial association with sediment-hosted Ni sulfides which comprise the bulk of the ore types. These rocks formed from rift-related komatiitic magmas that were emplaced at 1.88 Ga, and subsequently deformed by boudinage, thinning, folding, and stacking.Disseminated sulfide mineralization in the large serpentinised peridotite and dunite intrusions that host the Birchtree and Pipe Ni-Co sulfide deposits typically has 4–6 wt% Ni in 100% sulfide. The disseminated sulfides in the less abundant and much smaller boudinaged serpentinised peridotite and dunite bodies associated with the Thompson Deposit have 7–10 wt% Ni in 100% sulfide. The majority of Thompson Mine sulfides are hosted in the P2 member of the Pipe Formation which is a sulfidic schist developed from a shale prololith; the mineralization in the schist includes both low Ni tenor (<1 wt% Ni in sulfide) and barren sulfide (<200 ppm Ni) and a Ni-enriched sulfide with 1–18 wt% Ni in 100% sulfide. The semi-massive and massive sulfide ores show a similar range in Ni tenor to the metasediment-hosted mineralization, but there are discrete populations with maximum Ni tenors of ∼8, 11 and 13 wt% Ni in 100% sulfide. The variations in Ni tenor are related to the Ni/Co ratio (high Ni/Co correlates with high Ni tenor sulfide) and this relationship is produced by the different Ni/Co ratios in sulfides with a range in proportions of pyrrhotite and pentlandite. Geological models of the ore deposit, host rocks, and sulfide geochemical data in three dimensions reveal that the Thompson Deposit forms an anastomosing domain on the south and east flanks of a first order D3 structure which is the Thompson Dome. In detail, a series of second order doubly-plunging folds on the eastern and southern flank control the geometry of the mineral zones. The position of these folds on the flank of the Thompson Dome is a response to the anisotropy of the host rocks during deformation; ultramafic boudins and layers of massive quartzite in ductile metasedimentary rocks control the geometry of the doubly-plunging F3 structures. The envelope of mineralization is almost entirely contained within the P2 member of the Pipe formation, so the deposit is clearly folded by the first order and second order D3 structures. The sulfides with highest Ni tenor (typically >13 wt% Ni in sulfide) define a systematic trend that mirrors the configuration of the second order doubly-plunging F3 structures on the flanks of the Dome. Although moderate to high Ni tenor mineralization is sometimes localized in fold hinges, more typically the highest Ni tenor mineralization is located on the flanks of the fold structures.There is no indication of the mineralogical and geochemical signatures of sedimentary exhalative or hydrothermal processes in the genesis of the Thompson ores. The primary origin of the mineralization is undoubtedly magmatic and this was a critical stage in the development of economic mineralization. Variations in metal tenor in disseminated sulfides contained in ultramafic rock indicate a higher magma/sulfide ratio in the Thompson parental magma relative to Birchtree and Pipe. The variation in Ni tenor of the semi-massive and massive sulfide broadly supports this conclusion, but the variations in metal tenor in the Thompson ores was likely created partly during deformation. The sequence of rocks was modified by burial and loading of the crust (D2 events) to a peak temperature of 750 °C and pressure of 7.5 kbar. The third major phase of deformation (D3) was a sinistral transpression (D3 event) which generated the dome and basin configuration of the TNB. These conditions allowed for progressive deformation and reformation of pyrrhotite and pentlandite into monosulfide solid solution as pressure and temperature increased; this process is termed sulfide kinesis. Separation of the ductile monosulfide solid solution from granular pentlandite would result in an effective separation of Ni during metamorphism, and the monosulfide solid solution would likely be spread out in the stratigraphy to form a broad halo around the main deposit to produce the low Ni tenor sulfide. Reformation of pentlandite and pyrrhotite after the peak D2 event would explain the broad footprint of the mineral system. The effect of the D3 event at lower pressure and temperature would have been to locally redistribute, deform, and repeat the lenses of sulfide.The understanding of the relationships between petrology, stratigraphy, structure, and geochemistry has assisted in formulating a predictive exploration model that has triggered new discoveries to the north and south of the mine, and provides a framework for understanding ore genesis in deformed terrains and the future exploration of the Thompson Nickel Belt.     

Cu–(Ni–Co–Au)-bearing massive sulfide deposits associated with mafic–ultramafic rocks of the Main Urals Fault,South Urals: Geological structures,ore textural and mineralogical features,comparison with modern analogs

Cu-rich massive sulfide deposits associated with mafic–ultramafic rocks in the southern portion of the Main Urals Fault (MUF) are characterized by variable enrichments in Ni (up to 0.45 wt.%), Co (up to 10 wt.%) and Au (up to 16 ppm in individual hand-specimens). The Cu (Ni–Co)-rich composition of MUF deposits, as opposed to the Cu (Zn)-rich composition of more eastward massive sulfide deposits of broadly similar age along the western flank of the Magnitogorsk arc, reflects the abundance of seafloor-exposed, Ni–Co-rich ultramafic rocks in the most external portion of the Early-Devonian Magnitogorsk forearc. Morphological, textural, and compositional differences between individual deposits are interpreted to be the result of the sulfide deposition style and, in part, of the original subseafloor lithology. One deposit produced by dominantly on-seafloor hydrothermal processes is characterized by pyrite–marcasite ≫ pyrrhotite, not so low Zn grades (occasionally up to 2 wt.%), abundant clastic facies and periodical superficial oxidation. Deposits produced by dominantly subseafloor hydrothermal processes are characterized by pyrrhotite > pyrite, very low Zn (generally < to ≪ 0.1 wt.%), volumetrically minor clastic facies, and multi-layer deposit morphology. Very low Ni/Co ratios in the on-seafloor deposit may indicate a dominant metal contribution from a mafic rather than ultramafic source. The sulfide mineralization was associated with extensive hydrothermal alteration of the host ultramafic and mafic rocks, leading to formation of abundant talc, talc–carbonate and chlorite rocks. Occurrence of large volumes of such altered lithotypes in ophiolitic belts may be considered as a potential searching criteria for MUF-type (Cu, Co, Ni)-deposits. In spite of the contrasting geodynamic environment, geological, geochemical, textural and mineralogical peculiarities of the MUF deposits in many respects are similar to those of ultramafic-hosted massive sulfide deposits along the Mid-Atlantic Ridge. In geological time, supra subduction-zone settings appear to have been more effective than mid-ocean ridge settings for preservation of ultramafic-hosted massive sulfide deposits.     

粤北大宝山铜多金属矿区黄铁矿与磁黄铁矿EPMA和LA-ICP-MS原位微区组分特征及其对矿床成因机制约束

粤北大宝山铜多金属矿床一直存在燕山期岩浆热液成因和海西期火山喷流成因之争,争议的焦点在于块状、似层状硫化物矿体的成因。本文在全面开展矿区地质调查和钻探查证的基础上,对块状、似层状和脉状硫化物矿石中的黄铁矿和磁黄铁矿开展EPMA和LA-ICP-MS原位分析。测试结果表明,不同产状黄铁矿的平均分子式相似,分别为FeS_(1.98)、FeS_(1.99)和FeS_(1.98),似层状和脉状硫化物中磁黄铁矿的平均化学式为Fe_(0.886)S和Fe_(0.874)S,属形成温度相对较低单斜磁黄铁矿。与花岗岩岩浆热液标型黄铁矿相比,不同产状的黄铁矿和磁黄铁矿中Co、Ni、Mn、Se和Ge等元素以类质同象形式赋存,它们含量较低但稳定,Cu、Pb、Zn、Ag、Bi和Tl及Ga主要以微细矿物子晶形式存在,其含量丰富,但变化明显。从块状、似层状到脉状硫化物矿体,黄铁矿和磁黄铁矿中Co、Zn和Se的含量及Co/Ni值降低,而Cu、Pb、Ag、Bi等元素的含量明显升高。结合矿区次英安斑岩的产状和含矿性特征表明,大宝山矿床块状、似层状和脉状硫化物矿体都是次英安斑岩深部岩浆房产出的含矿流体在不同赋矿环境中的产物。     

Geochemistry of high H2 and CH4 vent fluids issuing from ultramafic rocks at the Rainbow hydrothermal field (36°14′N, MAR)

The Flores diving cruise was part of the MAST III-AMORES (1995-1998) program funded by the European Union. One of the major achievements of the Flores cruise was the discovery of the Rainbow hydrothermal field hosted in ultramafic rocks south of the Amar segment on the Mid-Atlantic ridge (MAR). The Rainbow hydrothermal fluids exhibit temperatures of 365 °C, pH of 2.8, high chlorinity (750 mmol/kg), and low silica (6.9 mmol/kg). The uniformity in endmember major, minor, trace element concentrations and gas contents suggests that all Rainbow fluids originate from the same deep source. Although H₂S content is relatively low (1.20 mmol/kg), all vent fluids show extraordinary high H₂ (16 mmol/kg), CH₄ (2.5 mmol/kg) and CO (5 μmol/kg) endmember concentrations compared to fluids collected from other vent sites along the MAR. Hydrogen represents more than 40% of the total gas volume extracted from the fluids. At Rainbow, H₂ production is likely associated with alteration of olivine and orthopyroxene minerals during serpentinization. Given that exposures of ultramafic rock may be common, particularly along slow-spreading ridges, the production of H₂ may have important implications for microbial activity at and beneath the seafloor.     

Particle geochemistry in the Rainbow hydrothermal plume, Mid-Atlantic Ridge

We report the analysis of 18 large volume (500-1500 L) in situ filtered samples of particulate material from the largest hydrothermal plume on the Mid-Atlantic Ridge, overlying the ultramafic-hosted Rainbow hydrothermal field at 36° 14′N. Measured particulate iron concentrations reach 614 nM. High concentrations of particulate Fe oxyhydroxides result from the extremely high Fe concentration (∼24 mM) and Fe/H₂S ratio (∼24) of the vent fluids, and persist to at least 10 km away from the vent site due to the advection of plume material with the ambient along-axis flow. Two of the nine pairs of pump deployments appear to have intercepted the buoyant or otherwise very young portion of the hydrothermal plume. These samples are characterized by anomalously (compared to neutrally buoyant plume samples) high concentrations of Mg, U, and chalcophile elements, and low concentrations of Mn, Ca, V, Y, and the rare earth elements (REE). Within the neutrally buoyant plume, elemental distributions are largely consistent with previously observed behaviors: preferential removal of chalcophile elements, conservative behavior of oxyanions (P, V, and U), and continuous scavenging of Y and the REE. This consistency is particularly significant in light of the underlying differences in fluid chemistry between Rainbow and other studied sites. Chalcophile elements are preferentially removed from the plume in the order Cd>Zn>Co>Cu. Phosphorus/iron and vanadium/iron ratios for the neutrally buoyant plume are consistent with global trends with respect to the concentration of dissolved phosphate in ambient seawater. Comparison of buoyant and neutrally buoyant plume ratios with data from hydrothermal sediments underlying the Rainbow plume (Cave et al., 2002) indicates, however, that while P/Fe ratios are indeed constant V/Fe ratios increase progressively from early stage plume particles to sediments. REE distributions in the buoyant and neutrally buoyant plume appear most consistent with a continuous scavenging process during dispersion through the water column.     

PGE distribution in massive sulfides from the P<Emphasis Type="SmallCaps">ACMANUS</Emphasis> hydrothermal field,eastern Manus basin,Papua New Guinea: implications for PGE enrichment in some ancient volcanogenic massive sulfide deposits

The distribution of platinum group elements (PGE) in Cu- and Zn-rich samples from the Roman Ruins and Satanic Mills vent sites in the PACMANUS hydrothermal field (Papua New Guinea) was studied and compared to that from selected ancient volcanogenic massive sulfide (VMS) deposits. Samples from the Satanic Mills site are enriched in Pd and Rh when compared to samples from Roman Ruins and reach highest values in active and inactive Cu-rich black smoker chimneys and chalcopyrite-cemented dacite breccias (up to 356 ppb Pd and up to 145 ppb Rh). A significant positive correlation was established between Cu and Pd and Rh in samples from both vent sites. Comparisons of chondrite normalized patterns and values of Pd/Pt and Pd/Ir ratios in Cu-rich sulfides and probable source rocks (felsic volcanic rocks/MORB) along with the evidence for a magmatic component in the PACMANUS hydrothermal system indicate that leaching of back-arc volcanic rocks together with addition of magmatic volatiles to the convecting hydrothermal system was the most important factor for PGE enrichment at PACMANUS and likely at some PGE-enriched ancient VMS deposits.An erratum to this article can be found at Editorial handling: B. Lehmann     

Serpentinization and heat generation: constraints from Lost City and Rainbow hydrothermal systems

The discovery of ultramafic hosted hydrothermal systems at Rainbow (36°N MAR) and Lost City, a vent site approximately 15 km west of the MAR at 30°N, provides unique perspectives on chemical and heat-generating processes associated with serpentinization at a range of chemical and physical conditions. Heat balance calculations together with constraints imposed by geochemical modeling indicate that significant changes in temperature are not likely to occur at either vent system as a result of the exothermic nature of olivine hydrolysis. At Rainbow, the relatively high temperatures in subseafloor reaction zones (in excess of 400°C), which must be linked to magmatic processes, inhibit olivine hydrolysis, effectively precluding mineralization-induced heating effects. Geochemical modeling of the Lost City vent fluids indicates temperatures in excess of those measured (40-75°C). The relatively high subseafloor temperatures (∼ 200 ± 50°C) requires conductive cooling of the fluids on ascent to the seafloor—a scenario in keeping with the mineralization of chimney structures actually observed. Although the intermediate temperatures predicted for subseafloor reaction zones at Lost City could be expected to enhance olivine to serpentine conversion, dissolved Cl, K/Cl and Na/Cl ratios of the Lost City vent fluids are virtually unchanged from seawater values and indicate little hydration of olivine, which is a necessary condition for exothermic heat generation by serpentinization. Apparently the fluid/rock mass ratio is too high or fluid residence times too low for this to occur to any significant extent. Thus, in spite of the off-axis location of the Lost City vents and apparent lack of a localized heat source, mineralization reactions likely play an insignificant role in accounting for hydrothermal circulation. It is more likely that tectonic processes associated with the slow spreading MAR, permit access of seawater to relatively deep and still hot lithospheric units and/or near axis magmatic heat sources, before venting. Additional chemical and physical (temperature, flow rate) data for Lost City and similar hydrothermal systems are needed to test key elements of the proposed model.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

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?CNE 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?C3?m in height, with some reaching 6?C7?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?C3?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 ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (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.     

The roles of magmatic and hydrothermal processes in PGE mineralization,Ferguson Lake deposit,Nunavut, Canada

The Ferguson Lake Ni–Cu–Co–platinum-group element (PGE) deposit in Nunavut, Canada, occurs near the structural hanging wall of a metamorphosed gabbroic sill that is concordant with the enclosing country rock gneisses and amphibolites. Massive to semi-massive sulfide occurs toward the structural hanging wall of the metagabbro, and a low-sulfide, high-PGE style of mineralization (sulfide veins and disseminations) locally occurs ~30–50 m below the main massive sulfide. Water–rock interaction in the Ferguson Lake Ni–Cu–Co–PGE deposit is manifested mostly as widespread, post-metamorphic, epidote–chlorite–calcite veins, and replacement assemblages that contain variable amounts of sulfides and platinum-group minerals (PGM). PGM occur as inclusions in magmatic pyrrhotite and chalcopyrite in both the massive sulfide and high-PGE zones, at the contact between sulfides and hornblende or magnetite inclusions in the massive sulfide, in undeformed sulfide veins and adjacent chlorite and/or epidote halos, in hornblende adjacent to hydrothermal veins, and in plagioclase–chlorite aggregates replacing garnet cemented by sulfide. The PGM are mostly represented by the kotulskite (PdTe)–sobolevskite (PdBi) solid solution but also include michenerite (PdBiTe), froodite (PdBi₂), merenskyite (PdTe₂), mertieite II (Pd₈[Sb,As]₃), and sperrylite (PtAs₂) and occur in variety of textural settings. Those that occur in massive and interstitial sulfides, interpreted to be of magmatic origin and formed through exsolution from base metal sulfides at temperatures <600°C, are dominantly Bi rich (i.e., Te-bearing sobolevskite), whereas those that occur in late-stage hydrothermal sulfide/silicate veins and their epidote–chlorite alteration halos tend to be more Te rich (i.e., Bi-bearing kotulskite). The chemistry and textural setting of the various PGM supports a genetic model that links the magmatic and hydrothermal end-members of the sulfide–PGM mineralization. The association of PGM with magmatic sulfides in the massive sulfide and high-PGE zones has been interpreted to indicate that PGE mineralization was initially formed through exsolution from base metal sulfides which formed by magmatic sulfide liquid segregation and crystallization. However, the occurrence of PGM in undeformed sulfide-bearing veins and in their chlorite–epidote halos and differences in PGM chemistry indicate that hydrothermal fluids were responsible for post-metamorphic redistribution and dispersion of PGE.     

The Avebury Ni deposit,Tasmania: A case study of an unconventional nickel deposit

The Avebury Ni deposit, which has a resource of 260,000 tons of Ni at a grade of 0.9%, is a unique example of a significant Ni sulfide deposit associated with an ophiolite sequence; the deposit is unique because it was formed by hydrothermal processes and also because ophiolites are generally considered unprospective for magmatic Ni sulfide mineralization. The deposit is hosted by Middle Cambrian cumulate peridotite and dunite rocks that were most probably formed from S-poor boninitic magmas. The mineralization, which consists principally of pentlandite, occurs in both serpentinites and skarns in the ultramafic cumulates. The ultramafic rocks are variably metasomatised as the result of the intrusion of the Late Devonian Heemskirk granite. Sulfide-rich and sulfide-poor portions of the ultramafic rocks are variably enriched in W, Bi, U, Pb, Mo, Sn and Sb relative to the primitive mantle. Modest to strong correlations between Cu, Au, Pd, REE, Sn, Mo, W and Ni provide strong evidence that the mineralization is hydrothermal in origin. In situ metasomatism of a magmatic Ni sulfide deposit is ruled out on the basis of poor or negative correlations between Ir, Ru, Rh and Pt when compared to Ni. Although the sulfide-free ultramafic rocks have high Ni contents, this Ni would have been unavailable to the ore-forming fluids as it was hosted in inaccessible sites, such as oxides and silicates. The strong correlations between Au, Pd and Ni suggest that the source of the Ni was magmatic sulfides somewhere at depth that not only have high Ni but also elevated Pd and Au contents.     

Controls on the emplacement and genesis of the MKD5 and Sarah’s Find Ni–Cu–PGE deposits,Mount Keith,Agnew–Wiluna Greenstone Belt,Western Australia

The Mount Keith (MKD5) nickel sulfide deposit is one of the largest komatiite-hosted nickel sulfide deposits in the world; it is hosted by a distinctive spinifex-free, cumulate-rich, ultramafic horizon/unit termed the Mount Keith Ultramafic (MKU). The Mount Keith Ultramafic shows significant variation along its lateral extent. The internal architecture is made up of adcumulate-textured pods and lenses, which are flanked by thinner meso- and orthocumulate-textured units, overlain by pyroxenitic and gabbroic horizons. The lateral and vertical changes in the geometry and internal architecture reflect variations in the lithological association and emplacement conditions along the strike extent of the belt. The chilled margins of the Mount Keith Ultramafic unit contain ∼1,200 ppm Ni. Olivine cumulates average ∼2,500–3,500 ppm Ni, with few exceptions (Ni > 4,500 ppm) reflecting occurrence of minor nickel sulfides, whereas pyroxenites and gabbros generally contain, respectively, ∼1,500–2,000 and ∼100–1,000 ppm Ni. Olivine cumulates generally contain low Cr concentrations (<2,500 ppm Cr), with the rare presence of chromite-rich intervals containing anomalously high values (>5,000 ppm Cr). The internal stratigraphy of the Mount Keith Ultramafic unit may be subdivided into two groups based on rare earth element distribution. The chilled margins and the internal units of the Main Adcumulate domain display LREE-enriched patterns [(La/Sm) _n  > 1–3] and negative Eu, Hf, Zr, Nb, and Ti anomalies. The internal units in the Western Mineralized Zone generally display flat chondrite-normalized REE patterns and only minor negative Nb anomalies. The pattern of platinum-group element (PGE) distribution varies greatly along the strike extent of the Mount Keith Ultramafic unit. The chilled margins display relatively low absolute concentrations [PGE (excl. Os) ∼16 ppb] and relatively fractionated patterns, with subchondritic Pt/Pd ratios (∼1.5), and superchondritic Pd/Ir ratios (∼3). The PGE trends in the thick adcumulate-textured pods containing widespread nickel sulfide mineralization display positive correlation with sulfide abundance, whereas fractionated pyroxenites and gabbros in the thinner domains display highly depleted PGE concentrations and generally show compatible PGE trends. The nickel sulfide ore typology and style vary greatly along the strike extension of the Mount Keith Ultramafic unit. Basal massive nickel sulfide mineralization (e.g., Sarah’s Find) occurs in the thinner meso- and orthocumulate-textured units, whereas stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit) is hosted in the adcumulate-textured pods. We hypothesize that the very low PGE content of the initial liquid of the Mount Keith Ultramafic unit indicates that the initial magma pulse that penetrated through the dacite host-rock had already equilibrated with sulfides at depth and/or carried entrained immiscible sulfide blebs. We argue that upon emplacement, the intruding magma experienced a significant thermal shock at the contact with water-saturated volcaniclastic breccias. The sudden chilling would have increased the viscosity of the magma, possibly to the point where it was no longer able to sustain the suspension of the immiscible sulfide liquid. As a result, the sulfide blebs coalesced and formed the basal massive sulfide nickel sulfide mineralization at the base of the sill (i.e., Sarah’s Find). Prolonged focused high volume magma flow within the sill resulted in the emplacement of a thick, lens-shaped accumulation of olivine adcumulate. Local variations in intensive parameters other than crustal assimilation (e.g., T, fO₂, fS₂) may be principally responsible for sulfide supersaturation and controlled the local distribution of stratabound disseminated nickel sulfide mineralization (e.g., MKD5 Ni Deposit), generally localized within the core of the thicker dunite lenses.     

Volcanic-hosted massive sulfide deposits in the Murchison greenstone belt, South Africa

The Archean Murchison greenstone belt, Limpopo Province, South Africa, represents a rifted epicontinental arc sequence containing the largest volcanic-hosted massive sulfide (VMS) district in Southern Africa. The so-called Cu–Zn line is host to 12 deposits of massive sulfide mineralization including: Maranda J, LCZ, Romotshidi, Mon Desir, Solomons, and Mashawa with a total tonnage of three million metric tons of very high grade Zn, subordinate Cu, and variable Pb and Au ore. The deposits developed during initial phases of highly evolved felsic volcanism between 2,974.8 ± 3.6 and 2,963.2 ± 6.4 Ma and are closely associated with quartz porphyritic rhyolite domes. Elevated heat supply ensured regional hydrothermal convection along the entire rift. Recurrent volcanism resulted in frequent disruption of hydrothermal discharge and relative short-lived episodes of hydrothermal activity, probably responsible for the small size of the deposits. Stable thermal conditions led to the development of mature hydrothermal vent fields from focused fluid discharge and sulfide precipitation within thin layers of felsic volcaniclastic rocks. Two main ore suites occur in the massive sulfide deposits of the “Cu–Zn line”: (1) a low-temperature venting, polymetallic assemblage of Zn, Pb, Sb, As, Cd, Te, Bi, Sn, ±In, ±Au, ±Mo occurring in the pyrite- and sphalerite-dominated ore types and (2) a higher temperature suite of Cu, Ag, Au, Se, In, Co, Ni is associated with chalcopyrite-bearing ores. Sphalerite ore, mineralogy, and geochemical composition attest to hydrothermal activity at relatively low temperatures of ≤250 °C for the entire rift, with short-lived pulses of higher temperature upflow, reflected by proportions of Zn-rich versus Cu-rich deposits. Major- and trace-metal composition of the deposits and Pb isotope signatures reflect the highly evolved felsic source rock composition. Geological setting, host rock composition, and metallogenesis share many similarities not only with Archean VMS districts in Canada and Australia but also with recent arc–back-arc systems on the modern seafloor where fragments of continental crust and areas of elevated heat flow are involved in petrogenetic and associated metallogenic processes.     

Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back-Arc Basin

The Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg^?1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO₂ droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.     

Hydrothermal precipitates associated with bimodal volcanism in the Central Bransfield Strait,Antarctica

Polymetallic sulfide-sulfate mineralization enriched in Pb-Ag-As-Sb-Hg occurs in the Bransfield Strait, a late Tertiary-Quaternary marginal basin close to the Antarctic Peninsula. The mineralization is associated with bimodal volcanism and pelagic and volcaniclastic sediment in rifted continental crust. Hydrothermal precipitates have been recovered from two shallow (1,050–1,000 m water depth) submarine volcanoes (Hook Ridge and Three Sisters) in the Central Bransfield Strait. Mineralization at Hook Ridge consists of polymetallic sulfides, massive barite, and pyrite and marcasite crusts in semilithified pelagic and volcaniclastic sediment. Native sulfur commonly infills void space and cements the volcaniclastic sediment. The polymetallic sulfides are dominated by sphalerite with minor galena, enargite, tetrahedrite-tennantite, pyrite, chalcopyrite, and traces of orpiment cemented by barite and opal-A. The presence of enargite at Hook Ridge, the abundance of native sulfur, and the low Fe content of sphalerite indicate a high sulfur activity of the hydrothermal fluids responsible for mineralization. The sulfur isotopic composition of Hook Ridge precipitates documents the complexity of the sulfur sources in this hydrothermal system with variable influence of biological activity and possibly magmatic contributions. Homogenization temperatures and salinities of fluid inclusions in barite and opal-A suggest that boiling may have affected the hydrothermal fluids during their ascent. The discovery of massive barite-silica precipitates at another shallow marine volcano (Three Sisters volcano) attests to the potential for hydrothermal mineralization at other volcanic edifices in the area. The characteristics of the mineralization in the Bransfield Strait with rifting of continental crust, the presence of bimodal volcanism, including highly evolved felsic volcanic rocks, the association with sediments, and the Pb-Ag-As-Sb-Hg enrichment are similar to the setting of massive sulfide deposits in the Okinawa Trough, and distinct from those of sediment-dominated hydrothermal systems such as Escanaba Trough, Middle Valley, and Guaymas Basin. The geological setting of the Bransfield Strait is also broadly similar to that of some of the largest volcanogenic massive sulfide deposits in the ancient record, such as the Iberian Pyrite Belt.Editorial handling: B. Lehmann     

Paragenesis of cobalt and nickel in the Black Butte shale-hosted copper deposit,Belt Basin,Montana, USA

The Black Butte copper deposits (formerly known as Sheep Creek) are a group of sediment hosted, laterally extensive Cu–(Co–Ag) deposits hosted in dolomitic shale of the mid-Proterozoic Newland Formation. Copper–cobalt mineralization occurs in zones of massive, laminated pyrite that were locally reworked and infiltrated by Cu-rich fluids during early diagenesis. Cobalt, along with substantial nickel and arsenic, mainly occurs as impurities within early, porous pyrite, or as minute grains of sulpharsenides (i.e., cobaltite, glaucodot, and/or alloclasite). Later thermal events remobilized the Co, Ni, and As to form intergrowths of siegenite (Co,Ni)₃S₄ and tennantite. The temperature of this later event is constrained by the mineralogical assemblage to have been relatively low, between 125 and 225 °C. Although many of the characteristics of SEDEX-type deposits are present at Black Butte (e.g., laterally extensive massive pyrite horizons, interbedded black shales, abundant barite and local phosphate horizons, and rifted continental margin setting), the lack of economic Pb and Zn mineralization in the main deposits, and the abundance of Cu with high Co, is more typical of sediment-hosted stratiform copper deposits. The Neihart Formation, a hematitic quartz sandstone resting below the base of the Belt Supergroup, may have been an important source bed for Cu–Co–Ni–Ag fluids. It is speculated that these fluids, ideal for forming Cu deposits, were expelled along growth faults near the margin of the Belt Basin and deposited metals on or just below the sea floor in a setting that is typical of SEDEX deposits. This unique mineral deposit model may have applications to other districts where Cu–Co-rich sulfides are deposited in an exhalative setting.     

Siderophile and chalcophile elemental constraints on the origin of the Jinchuan Ni-Cu-(PGE) sulfide deposit, NW China

The Jinchuan deposit, NW China, is one of the world’s most important Ni-Cu-(PGE) sulfide deposits related to a magma conduit system and is hosted in an ultramafic intrusion. The intrusion is composed of lherzolite and dunite with the two largest sulfide ore bodies (named as ore body 1 and 2) in its middle portion. The sulfide ores may be disseminated, net-textured, or massive. The disseminated and net-textured sulfide ores are characterized by variable but generally low PGE concentrations: 10-3200 ppb Pt, 240-9800 ppb Pd, 17-800 ppb Ir, 25-1500 ppb Ru, and 15-400 ppb Rh in 100% sulfides. The massive sulfide ores are extremely low in Pt (<30 ppb) on a 100% sulfides and have very high Cu/Pd ratios, ranging from 10⁴ to 4.5 × 10⁵. The low PGE contents suggest that the sulfide ores formed from the silicate magmas that had already experienced prior-sulfide separation.Our calculations indicate that if the first stage basaltic magmas had contained 6.3 ppb Pt, 6.2 ppb Pd, and 0.1 ppb Ir, 0.008% sulfide removal would result in PGE-depletion in the residual magma with 0.57 ppb Pt, 0.25 ppb Pd, and 0.009 ppb Ir. The Jinchuan sulfides were formed by a second stage of sulfide segregation from a PGE-depleted magma under silicate/sulfide liquid ratios (R-factor) ranging from 10³ to 10⁴ in a deep-seated staging chamber. The massive sulfide ores and some of the net-textured sulfide ores exhibit strong negative Pt-anomalies that cannot be explained by sulfide segregation under variable R-factors. Instead, the sulfide melts that formed the massive ores were segregated from magmas experienced prior fractionation of Pt-Fe alloy. Alternatively, the Pt may have been selectively leached by hydrothermal fluids during remobilization of the sulfide melts that produced the massive sulfides, which occur in cross-cutting veins. We propose that the Jinchuan intrusion and ore bodies were formed by injections of sulfide-free and sulfide-bearing olivine mushes from a deep-seated staging chamber.