Metal binding to dissolved organic matter and adsorption to ferrihydrite in shallow peat groundwaters: Application to diamond exploration in the James Bay Lowlands,Canada

The speciation and solubility of kimberlite pathfinder metals (Ni, Nd, Ba and K) in shallow peat groundwaters is investigated over the Yankee, Zulu and Golf kimberlites in the Attawapiskat region, James Bay Lowlands, Canada. The purpose of this study is to examine the relationship between dissolved organic matter (DOM) complexation with kimberlite pathfinder metals and determine the spatial distribution of those metals in shallow peat groundwaters along sampling transects over subcropping kimberlites. Nickel, Nd, Ba and K complexation with DOM and the adsorption of these metals onto ferrihydrite were calculated using Visual MINTEQ 3.0 and the NICA-Donnan database. Calculations predict almost 100% of soluble Nd, Ni and Ba form complexes with DOM at sampling sites with little to no contribution from upwelling groundwater (i.e., dissolved organic C (DOC) concentrations = 40–132 mg/L, pH = 3.9–5.5, and log ionic strength ??3). In only the most ombrotrophic peat groundwater conditions does a majority fraction of K bind to DOM. By contrast, under conditions with large contributions from upwelling groundwaters (i.e., DOC concentrations ?40 mg/L, pH = 5.5–6.5, and log ionic strength = ?3 to ?2), as little as 10% of Nd and Ni, and 0% K and Ba are predicted to complex with DOM. The modeling calculations suggest the dominant control on metal–DOM complexation, particularly with respect to Ni and Nd, is competitive effects for DOM binding sites due to elevated ionic strength where there is evidence of strong groundwater upwelling. Visual MINTEQ modeling of metal adsorption on ferrihydrite surfaces predicts that under strong upwelling conditions, Ni and Nd are scavenged from solution due to increased ferrihydrite precipitation and decreased fractions of metals complexed with DOM. Analytical geochemical data are consistent with model predictions of metal adsorption on ferrihydrite. Total dissolved Ni and Nd concentrations at sites of strong upwelling are up to five times lower than waters with little to no upwelling and log ferrihydrite saturation indices (logSI_ferr) indicate precipitation (values up to 5) at sites of strong groundwater upwelling. Where the majority of Ni and Nd complex with DOM and ferrihydrite is highly under saturated (logSI_ferr = ?18 to ?5), the concentrations of total Ni and Nd are elevated compared to other sites along sampling transects. Metal complexation with DOM effectively inhibits metal scavenging from solution via adsorption and/or from forming secondary mineral precipitates. Also, because alkaline earth metals do not compete strongly with Ni and Nd for adsorption sites on ferrihydrite surfaces, but do compete strongly for insoluble organic sites, Ni and Nd are more likely to adsorb onto ferrihydrite.     

Arsenate and chromate incorporation in schwertmannite

High concentrations of Cr (up to 812 ppm) and As (up to 6740 ppm) were detected in precipitates of the mineral schwertmannite in areas influenced by acid mine drainage. Schwertmannite may act as well as a natural filter for these elements in water as well as their source by releasing the previously bound elements during its dissolution or mineral-transformation. The mechanisms of uptake and potential release for the species arsenate and chromate were investigated by performing synthesis and stability experiments with schwertmannite.Schwertmannite, synthesized in solutions containing arsenate in addition to sulphate, was enriched by up to 10.3 wt% arsenate without detectable structural changes as demonstrated by powder X-ray diffraction (XRD). In contrast to arsenate, a total substitution of sulphate by chromate was possible in sulphate-free solutions. Thereby, the chromate content in schwertmannite could reach 15.3 wt%.To determine the release of oxyanions from schwertmannite over time, synthetic schwertmannite samples containing varying amounts of sulphate, chromate and arsenate were kept at a stable pH of either 2 or 4 over 1 year in suspension. At several time intervals Fe and the oxyanions were measured in solution and alterations of the solid part were observed by XRD and Fourier-Transform infrared (FT-IR) spectroscopy. At pH 2 schwertmannite partly dissolved and the total release of arsenate (24%) was low in contrast to chromate (35.4–57.5%) and sulphate (67–76%). Accordingly, the ionic activity product (log IAP) of arsenated schwertmannite was lowest (13.5), followed by the log IAP for chromated schwertmannite (16.2–18.5) and the log IAP for regular (=non-substituted) schwertmannite (18). At pH 4 schwertmannite transformed to goethite, an effect which occurred at the fastest rate for regular schwertmannite (=arsenate- and chromate-free), followed by chromate and arsenate containing schwertmannite. Both chromate and more evidently arsenate have a stabilizing effect on the schwertmannite structure, because they retarded the dissolution and transformation reactions.These kinetic investigations as well as crystallographic considerations demonstrated that the strength of the Fe(III) complexes with the anions controls the formation process and the stability of schwertmannite: with increasing affinity of the oxyanions to form complexes with Fe(III), the strength of the resulting binding and thus the stability and substitution preference increases.     

Insights into the extreme PGE enrichment of the W Horizon,Marathon Cu-Pd deposit,Coldwell Alkaline Complex,Canada: Platinum-group mineralogy,compositions and genetic implications

The W Horizon, Marathon Cu-Pd deposit in the Mesoproterozoic Midcontinent rift is one of the highest grade PGE repositories in magmatic ore deposits world-wide. The textural relationships and compositions of diverse platinum-group mineral (PGM) and sulfide assemblages in the extremely enriched ores (>100 ppm Pd-Pt-Au over 2 m) of the W Horizon have been investigated in mineral concentrates with ∼10,000 PGM grains and in situ using scanning electron microprobe and microprobe analyses.Here we show, from ore samples with concentrations up to 23.1 Pd ppm, 8.9 Pt ppm, 1.4 Au ppm and 0.73 Rh ppm, the diversity of minerals (n = 52) including several significant unknown minerals and three new mineral species marathonite (Pd₂₅Ge₉; McDonald et al., 2016), palladogermanide (Pd₂Ge; IMA 2016-086, McDonald et al., 2017), kravtsovite (PdAg₂S, IMA No 2016-092, Vymazalová et al., 2017). The PGM are distributed as PG-, sulfides (52 vol%), -arsenides (34 vol%), -intermetallics of Au-Ag-Pd-Cu and Pd-Ge(10 vol%) and -bismuthides and tellurides (4 vol%). The discovery of abundant (>330 grains) large unknown sulfide minerals with Rh allows us to present analyses three significant potentially new minerals (WUK-1, WUK-2, WUK-3) that are all clearly enriched in Rh (averaging 4.2, 8.5 and 28.21 wt% Rh respectively). Several examples of paragenetic sequences and mineral chemical changes for enrichment of Cu, Pd and Rh with time are revealed in the PGM and base-metal sulfides. We suggest this enhanced metal enrichment formed in response to increasing fO₂ causing the oxidation of Fe²⁺ to Fe³⁺ and to a lesser extent, S.Phase relations in the Ag-Pd-S, Rh-Ni-Fe-S, Pd-Ge, Au-Pd-Cu-Ag, Pd-Ag-Te systems help constrain the crystallization temperatures of the majority of ore minerals in the W Horizon at ∼500 °C or moderate to high subsolidus temperatures (400–600 °C). Local transport by aqueous fluids becomes evident as minerals recrystallize down to <300 °C. The PGE-enriched W Horizon ores exhibit a complex post-magmatic history dominated by the effects of oxidation during cooling of a Cu-PGE enriched magma source from a deep reservoir.     

Base metal mineral segregation and Fe-Mg exchange inducing extreme compositions of olivine and chromite from the Xiadong Alaskan-type complex in the southern part of the Central Asian Orogenic Belt

The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe³⁺/(Fe³⁺ + Cr + Al) (>70), high 100 × Fe²⁺/(Fe²⁺ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO₂ contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe²⁺/(Mg + Fe²⁺) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions.     

Biogeochemical indicators of buried mineralization under cover,Talbot VMS Cu–Zn prospect,Manitoba

Results are presented of a surficial geomicrobiological investigation of glacial cover overlying buried mineralization at the Talbot prospect, Manitoba, Canada, where previous surficial geochemistry surveys indicated anomalous concentrations of elements above the buried mineralization. The Cu–Zn volcanogenic massive sulfide (VMS) occurrence is overlain by 100 m of Paleozoic dolomites and Quaternary glacial cover. The geomicrobiological investigation demonstrates that there is a distinct microbial ecology at the anomalous sampling locations, especially directly overlying buried mineralization. The combined geochemical and geomicrobiological analyses reveal the presence of an anomaly directly over mineralization due to oxidation of the buried ore. Specifically, geomicrobiological analyses yield an inverse correlation between Zn in the clay-size (<2 μm) fraction and total microbial biomass and a direct correlation between Cu in the clay-size (<2 μm) fraction and abundance of methanotrophic bacteria. These results demonstrate that microbiological analyses can be a useful addition to geochemical exploration by revealing metal transport and sequestration processes and enhancing surficial anomalies.     

Gold and platinum group minerals in placers of the South Urals: Composition,microinclusions of ore minerals and primary sources

Gold and platinum group minerals from the gold placers of the South Urals are studied in order to identify the metal sources. In placers from the Main Uralian fault zone (MUF), the primary gold contains Ag (up to 29 wt.%), Cu (up to 2 wt.%) and Hg (up to 4 wt.%) and its fineness ranges from 538 to 997‰. Tetra-auricupride and cupriferous gold (up to 20 wt.% Cu) are common for the Nizhny Karabash placer of the MUF zone. In the eastern part of the South Urals, the placer gold is mainly characterized by high fineness of 900–1000‰ and low Cu contents (max 1.38 wt.%). Most of the placer gold grains consist of the primary domains, which are rimmed by secondary high-fineness gold with diffuse and clear boundaries. The secondary gold also develops along the shear dislocations of primary gold. Gold contains microinclusions of geerite, balkanite, chalcopyrite, Se-bearing galena, sphalerite, pyrite, pyrrhotite, arsenopyrite and hematite.Twenty four (including five unnamed) platinum group minerals (PGMs) were found in 28 placers; those from the Kialim and Maly Iremel placers of the Miass placer zone were studied in details. In the Kialim placer, ruthenium is most abundant PGM, which hosts microinclusions of isoferroplatinum, ferroan platinum, laurite, cupriferous gold, a mineral similar in composition to tolovkite, heazlewoodite and unnamed RhSbS phase. The osmium contains microinclusions of erlichmanite and laurite. The iridium grains hosts various sulfides and arsenides of platinum group elements (PGEs). The inclusion-free PGMs form Ru compositional trend in contrast to Os–Ru trend of the Ir-depleted inclusion-hosted PGMs. The isoferroplatinum from the Maly Iremel placer hosts laurite, rhodarsenite, bowieite, a mineral similar in composition to miassite and unnamed sulfide of Pt (Pt_1.11S_2.00) and antimonide of Pd ((Pd_2.41Rh_0.43Fe_0.17)_3.01(Sb_0.91Te_0.09)_1.00). Ruthenium is a host to isoferroplatinum, PGE sulfides and arsenides, and heazlewoodite. Osmium contains microinclusions of ferroan platinum; iridium is a host to a mineral similar in composition to hongshiite. Three types of PGM intergrowths were identified in the Maly Iremel samples: (1) the intergrowths of platy grains of ruthenium with isoferroplatinum and a mineral similar in composition to tulameenite; (2) the open-latticework intergrowths of platy crystals of ruthenium with interstitial aggregates made up of gold, isoferroplatinum and a mineral similar in composition to xingzhongite and (3) the intergrowths of osmium and irarsite and iridarsenite, which are developed along cleavage of the osmium grains. Nickel sulfides associated with some PGMs contain Ru (11.32 wt.%) and Rh (2.21 wt.%) in millerite and Ir (31.00 wt.%), Ru (5.81 wt.%) and Rh (2.87 wt.%) in vaesite.The primary metal sources were determined on the basis of the mineral assemblages and composition of minerals, taking into account the nearby mineral deposits and directions of rivers. The rodingite-associated gold, gold-bearing massive sulfide and chromite deposits are major sources of gold and PGMs in placers of the Miass placer zone confined to the MUF structure of the South Urals. In the southern part of this structure, gold was mainly originated from orogenic gold–sulfide deposits associated with volcanic/volcaniclastic rocks and listvenite-associated gold deposits. The placer PGMs were derived from the adjacent ultramafic massifs of ophiolitic origin. The distance between the placers and primary deposits varies from 2 to 5 km (up to 20 km in the extended valley of the Miass River). Usage of ore microinclusions and associated PGMs in study of placer gold is far more advanced than an ordinary consideration of gold composition alone. This approach allowed us to identify the concrete sources for individual placers and to predict some mineralogical findings in already known primary occurrences.     

Trace metal retention through the schwertmannite to goethite transformation as observed in a field setting,Alta Mine,MT

Solutions draining the Alta Mine, Jefferson County, MT, were contaminated by acid sulfate waters (ASW) generated from anthropogenic exposure of meteoric waters to sulfidic underground mine workings and a waste-rock pile. In 1999, a remediation effort was initiated in an attempt to improve the quality of water draining the site through removal of the waste-rock pile with which these solutions come in contact. ASW were sampled in the mineshaft prior to entering the waste-rock pile and upon discharge from the waste-rock pile aquifer near the pile toe. ASW composition changed as solutions flowed through the waste-rock pile due to sulfide and silicate weathering and schwertmannite precipitation.Schwertmannite and goethite were both sampled in the waste-rock pile where a distinct field relation was observed between the two minerals. Schwertmannite was always in contact with actively flowing ASW, while goethite was never in direct contact with ASW and was generally above the waste-rock water table. Goethite is hypothesized to be re-dissolved/re-precipitated schwertmannite that was deposited under higher flow conditions and subsequently transformed to goethite through exposure to wet/dry cycling associated with seasonal fluctuations in the amount of water moving through the hydrogeologic system. Trace metal concentrations in ammonium oxalate extracts of these minerals provides the first published data on the behavior of multiple trace metals through this phase transformation, which has important ramifications for considering schwertmannite as a long term metal sink due to its known metastability with respect to goethite. A relative retention scale through this phase transformation of Pb > Zn, Mn > As, Al, Cu is potentially applicable to other ASW systems.     

Silicon isotopes in allophane as a proxy for mineral formation in volcanic soils

Weathering of basaltic ash in volcanic areas produces andosols, rich in allophane and ferrihydrite. Since the rate of mineral formation is very useful in climate and geochemical modelling, this study investigates Si isotope compositions of allophane as a proxy for mineral formation. Allophane formed in contrasting conditions in five Icelandic soil profiles displays silicon isotope signatures lighter than the basalt in less weathered soils (?0.64 ± 0.15‰), and heavier in more weathered organic-rich soils (+0.23 ± 0.10‰). The fate of the dissolved Si in those volcanic soils strongly depends on Al availability. In organic-rich soils, most of Al is humus-complexed, and the results support that Si precipitates as opaline silica by super-saturation, leaving an isotopically heavier dissolved Si pool to form allophane with uncomplexed Al. This study highlights that Si isotopes can be useful to record successive soil processes involved in mineral formation, which is potentially useful in environmental paleo-reconstruction.     

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite–water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7–9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8–9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)–Fe bond distances of ∼2.92–2.94 and 3.41–3.44 Å, respectively. The As–Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As–Fe bonding mechanisms.     

Reduction of buried oxidized oceanic crust during subduction

The relationship among subducted oxidized oceanic crust and oxidation state of the subarc mantle, and arc magmas is one of the important aspects to evaluate convergent margin tectonics. However details of the oxidized mass transferred from buried oceanic crust to the overlying subarc mantle wedge remain obscure. Here we investigate the Songduo eclogites from south Tibet formed by the subduction of the paleo-Tethyan oceanic crust, and identify an abrupt decrease in pyrope and increase in almandine contents from the mantle to rim of garnet grains. This is coupled with a decrease in the Fe^3 + content of epidote and Fe^3 +/(Fe^2 ++ Fe^3 +) ratios from garnet core to rim domains, as well as speciation of calcite, a new mineral phase, in the rock matrix. Minor sulfates occur only as inclusions in garnet core domains, whereas sulfides are confined to the matrix as an accessory mineral phase. Aegirine augite occurs as relics or inclusions in garnet and omphacite. These features clearly suggest that oxidized components, Fe^3 + and S^6 +, were reduced as Fe^2 + and S^2 −, respectively, at the subduction zone. Thermodynamic modeling in the P–T-log₁₀f_O2 space using updated Perplex_X programs further revealed that the Songduo eclogites experienced oxygen fugacity variation of up to 8 log₁₀ units, with decreasing pressure. Petrological observations further suggest that the strong redox processes took place, after breaking of garnet, during the initial exhumation of the eclogites. CO₂ and minor sulfur are subsequently transferred from the cold oceanic subduction zone to the overlying mantle wedge, partially released by arc volcanoes to atmosphere. Our study presents a case of C and S recycling between the Earth's exterior and interior.     

Arsenate and antimonate adsorption competition on 6-line ferrihydrite monitored by infrared spectroscopy

Arsenate and antimonate are water-soluble toxic mining waste species which often occur together and can be sequestered with varying success by a hydrous ferric oxide known as ferrihydrite. The competitive adsorption of arsenate and antimonate to thin films of 6-line ferrihydrite has been investigated using primarily adsorption/desorption kinetics monitored by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy on flowed solutions containing 10⁻³ and 10⁻⁵ mol L⁻¹ of both species at pH 3, 5, and 7. ICP-MS analysis of arsenate and antimonate adsorbed to 6-line ferrihydrite from 10⁻³ mol L⁻¹ mixtures in batch adsorption experiments at pH 3 and 7 was carried out to calibrate the relative surface concentrations giving rise to the IR spectral absorptions. The kinetic data from 10⁻³ and 10⁻⁵ mol L⁻¹ mixtures showed that at pH 3 antimonate achieved a greater surface concentration than arsenate after 60 min adsorption on 6-line ferrihydrite. However, at pH 7, the adsorbed arsenate surface concentration remained relatively high while that of adsorbed antimonate was much reduced compared with pH 3 conditions. Both species desorbed slowly into pH 3 solution while at pH 7 most adsorbed arsenate showed little desorption and adsorbed antimonate concentration was too low to register its desorption behaviour. The nature of arsenate which is almost irreversibly adsorbed to 6-line ferrihydrite remains to be clarified.     

A magmatic source of hydrothermal sulfur for the Prominent Hill deposit and associated prospects in the Olympic iron oxide copper-gold (IOCG) province of South Australia

The Prominent Hill deposit is a world-class iron oxide copper–gold (IOCG) deposit in South Australia, characterized by a high Cu/S ratio of the dominant Cu-(Fe) sulfides hosted by hematite breccias. It contains a total resource of 278 Mt of ore at 0.98% Cu and 0.75 g/t Au. Prominent Hill is one of several IOCG deposits and numerous prospects in the Olympic IOCG province that are temporally associated with the 1603–1575 Ma Gawler Range Volcanics, a large igneous province including co-magmatic granitoid intrusions of the Hiltaba Suite. Globally, IOCG deposits share many similar features in terms of their geological environment and mineral association. However, it is not yet clear whether sulfur and copper originate from the same source rocks and which hydrothermal redox processes created the characteristic iron oxide enrichment. Highly variable sulfur isotope compositions of sulfides and sulfates in IOCG deposits have previously been interpreted in terms of diverse sulfur sources that may include contributions from magmatic, sedimentary, seawater or evaporitic sulfur. In order to test these alternatives, we performed a detailed sulfur isotope study of Cu-(Fe) sulfides from Prominent Hill and IOCG prospects nearby. The Prominent Hill deposit shows a wide range in δ³⁴S_V-CDT between − 33.5‰ and 29.9‰ for Cu-(Fe) sulfides, and a narrower range of 4.3‰ to 15.8‰ for barite. Iron sulfides (pyrite, pyrrhotite) show a narrow range in sulfur isotope composition, whereas Cu-bearing sulfides show a much wider range, and more negative δ³⁴S_V-CDT values on average. We propose a two-stage sulfide mineralization model for the IOCG system in the Prominent Hill area, in which all hydrothermal sulfur is ultimately derived from a magmatic source that had a composition of 4.4 ± 2‰. The diversity in sulfur isotope composition can be produced by different fluid evolution pathways along reducing or oxidizing trajectories. A reduced sulfur evolution pathway is responsible for stage I mineralization, when intrusion-derived magmatic-hydrothermal fluids produced early pyrite and minor chalcopyrite at Prominent Hill, and iron ± copper sulfides in regional magnetite skarns and in some pervasively altered volcanic rocks of the Gawler Range Volcanics. Shallow-venting magmatic-hydrothermal fluids and subaerial volcanic gases that became completely oxidized by reaction with atmospheric oxygen produced sulfate and sulfuric acid with a sulfur isotope composition equal to their magmatic source. This highly oxidized ore fluid probably consisted dominantly of water from the hydrosphere, but contained magmatic solute components, notably sulfate, acidity and Cu. Sulfate reduction produced hydrothermal Cu sulfides with a wide range in sulfur isotope compositions from very negative to moderately positive values. Partial reaction of the Cu-rich stage II fluid with earlier stage I sulfides resulted in mixing of sulfur derived from sulfate reduction and from sulfides deposited during stage I. Modeling of the sulfur isotope fractionation processes in response to reducing and oxidizing pathways demonstrates that the entire spectrum of sulfur isotope data from stage I and stage II mineralization can be explained with a single, ultimately magmatic sulfur source. Such a magmatic sulfur source is also adequate to explain the complete spectrum of sulfur isotope data of other IOCG prospects and deposits in the Olympic province, including Olympic Dam. The results of our study challenge the conventional model that suggests the requirement of multiple and compositionally diverse sulfur sources in hematite-breccia hosted IOCG style mineralization.     

Actively forming Kuroko-type volcanic-hosted massive sulfide (VHMS) mineralization at Iheya North,Okinawa Trough,Japan

Modern seafloor hydrothermal systems provide important insights into the formation and discovery of ancient volcanic-hosted massive sulfide (VHMS) deposits. In 2010, Integrated Ocean Drilling Program (IODP) Expedition 331 drilled five sites in the Iheya North hydrothermal field in the middle Okinawa Trough back-arc basin, Japan. Hydrothermal alteration and sulfide mineralization is hosted in a geologically complex, mixed sequence of coarse pumiceous volcaniclastic and fine hemipelagic sediments, overlying a dacitic to rhyolitic volcanic substrate. At site C0016, located adjacent to the foot of the actively venting North Big Chimney massive sulfide mound, massive sphalerite-(pyrite-chalcopyrite ± galena)-rich sulfides were intersected (to 30.2% Zn, 12.3% Pb, 2.68% Cu, 33.1 ppm Ag and 0.07 ppm Au) that strongly resemble the black ore of the Miocene-age Kuroko deposits of Japan. Sulfide mineralization shows clear evidence of formation through a combination of surface detrital and subsurface chemical processes, with at least some sphalerite precipitating into void space in the rock. Volcanic rocks beneath massive sulfides exhibit quartz-muscovite/illite and quartz-Mg-chlorite alteration reminiscent of VHMS proximal footwall alteration associated with Kuroko-type deposits, characterized by increasing MgO, Fe/Zn and Cu/Zn with depth. Recovered felsic footwall rocks are of FII to FIII affinity with well-developed negative Eu anomalies, consistent with VHMS-hosting felsic rocks in Phanerozoic ensialic arc/back-arc settings worldwide.Site C0013, ∼100 m east of North Big Chimney, represents a likely location of recent high temperature discharge, preserved as surficial coarse-grained sulfidic sediments (43.2% Zn, 4.4% Pb, 5.4% Cu, 42 ppm Ag and 0.02 ppm Au) containing high concentrations of As, Cd, Mo, Sb, and W. Near surface hydrothermal alteration is dominated by kaolinite and muscovite with locally abundant native sulfur, indicative of acidic hydrothermal fluids. Alteration grades to Mg-chlorite dominated assemblages at depths of >5 mbsf (metres below sea floor). Late coarse-grained anhydrite veining overprints earlier alteration and is interpreted to have precipitated from down welling seawater as hydrothermal activity waned. At site C0014, ∼350 m farther east, hydrothermal assemblages are characterized by illite/montmorillonite, with Mg-chlorite present at depths below ∼30 mbsf. Recovered lithologies from distal, recharge site C0017 are unaltered, with low MgO, Fe₂O₃ and base metal concentrations.Mineralization and alteration assemblages are consistent with the Iheya North system representing a modern analogue for Kuroko-type VHMS mineralization. Fluid flow is focussed laterally along pumiceous volcaniclastic strata (compartmentalized between impermeable hemipelagic sediments), and vertically along faults. The abundance of Fe-poor sphalerite and Mg-rich chlorite (clinochlore/penninite) is consistent with the lower Fe budget, temperature and higher oxidation state of felsic volcanic-hosted hydrothermal systems worldwide compared to Mid Ocean Ridge black smoker systems.     

Soil-geochemical factors controlling the distribution and oral bioaccessibility of nickel,vanadium and chromium in soil

Geogenic nickel (Ni), vanadium (V) and chromium (Cr) are present at elevated levels in soils in Northern Ireland. Whilst Ni, V and Cr total soil concentrations share common geological origins, their respective levels of oral bioaccessibility are influenced by different soil-geochemical factors. Oral bioaccessibility extractions were carried out on 145 soil samples overlying 9 different bedrock types to measure the bioaccessible portions of Ni, V and Cr. Principal component analysis identified two components (PC1 and PC2) accounting for 69% of variance across 13 variables from the Northern Ireland Tellus Survey geochemical data. PC1 was associated with underlying basalt bedrock, higher bioaccessible Cr concentrations and lower Ni bioaccessibility. PC2 was associated with regional variance in soil chemistry and hosted factors accounting for higher Ni and V bioaccessibility. Eight percent of total V was solubilised by gastric extraction on average across the study area. High median proportions of bioaccessible Ni were observed in soils overlying sedimentary rock types. Whilst Cr bioaccessible fractions were low (max = 5.4%), the highest measured bioaccessible Cr concentration reached 10.0 mg kg⁻¹, explained by factors linked to PC1 including high total Cr concentrations in soils overlying basalt bedrock.     

Nickel sulfide deposits in Australia: Characteristics,resources, and potential

Australia's nickel sulfide industry has had a fluctuating history since the discovery in 1966 of massive sulfides at Kambalda in the Eastern Goldfields of Western Australia. Periods of buoyant nickel prices and high demand, speculative exploration, and frenetic investment (the ‘nickel boom’ years) have been interspersed by protracted periods of relatively depressed metal prices, exploration inactivity, and low discovery rates. Despite this unpredictable evolution, the industry has had a significant impact on the world nickel scene with Australia having a global resource of nickel metal from sulfide ores of ∼ 12.9 Mt, five world-class deposits (> 1 Mt contained Ni), and a production status of number three after Russia and Canada. More than 90% of the nation's known global resources of nickel metal from sulfide sources were discovered during the relative short period of 1966 to 1973. Australia's nickel sulfide deposits are associated with ultramafic and/or mafic igneous rocks in three major geotectonic settings: (1) Archean komatiites emplaced in rift zones of granite–greenstone belts; (2) Precambrian tholeiitic mafic–ultramafic intrusions emplaced in rift zones of Archean cratons and Proterozoic orogens; and (3) hydrothermal-remobilized deposits of various ages and settings. The komatiitic association is economically by far the most important, accounting for more than 95% of the nation's identified nickel sulfide resources. The ages of Australian komatiitic- and tholeiitic-hosted deposits generally correlate with three major global-scale nickel-metallogenic events at ∼ 3000 Ma, ∼ 2700 Ma, and ∼ 1900 Ma. These events are interpreted to correspond to periods of juvenile crustal growth and the development of large volumes of primitive komatiitic and tholeiitic magmas caused by large-scale mantle overturn and mantle plume activities. There is considerable potential for the further discovery of komatiite-hosted deposits in Archean granite–greenstone terranes including both large, and smaller high-grade (5 to 9% Ni) deposits, that may be enriched in PGEs (2 to 5 g/t), especially where the host ultramafic sequences are poorly exposed.Analysis of the major komatiite provinces of the world reveals that fertile komatiitic sequences are generally of late Archean (∼ 2700 Ma) or Paleoproterozoic (∼ 1900 Ma) age, have dominantly Al-undepleted (Al₂O₃/TiO₂ = 15 to 25) chemical affinities, and often occur with sulfur-bearing country rocks in dynamic high-magma-flux environments, such as compound sheet flows with internal pathways facies (Kambalda-type) or dunitic compound sheet flow facies (Mt Keith-type). Most Precambrian provinces in Australia, particularly the Proterozoic orogenic belts, contain an abundance of sulfur-saturated tholeiitic mafic ± ultramafic intrusions that have not been fully investigated for their potential to host basal Ni–Cu sulfides (Voisey's Bay-type mineralization). The major exploration challenges for finding these deposits are to determine the pre-deformational geometries and younging directions of the intrusions, and to locate structural depressions in the basal contacts and feeder conduits under cover. Stratabound PGE–Ni–Cu ± Cr deposits hosted by large Archean–Proterozoic layered mafic–ultramafic intrusions (Munni Munni, Panton) of tholeiitic affinity have comparable global nickel resources to many komatiite deposits, but low-grades (< 0.2% Ni). There are also hydrothermal nickel sulfide deposits, including the unusual Avebury deposit in western Tasmania, and some potential for ‘Noril'sk-type’ Ni–Cu–PGE deposits associated with major flood basaltic provinces in western and northern Australia.     

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.     

Sulfur and lead isotopic compositions of massive sulfides from deep-sea hydrothermal systems: Implications for ore genesis and fluid circulation

Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ³⁴S 0.0 to 9.6‰, avg. δ³⁴S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ³⁴S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb 17.541 ± 0.004 to 19.268 ± 0.001, ²⁰⁷Pb/²⁰⁴Pb 15.451 ± 0.001 to 15.684 ± 0.001, ²⁰⁸Pb/²⁰⁴Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ³⁴S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.     

Ages of sediment-hosted Himalayan Pb–Zn–Cu–Ag polymetallic deposits in the Lanping basin,China: Re–Os geochronology of molybdenite and Sm–Nd dating of calcite

The Lanping basin is a significant Pb–Zn–Cu–Ag mineralization belt of the Sanjiang Tethyan metallogenic province in China. Over 100 thrust-controlled, sediment-hosted, Himalayan base metal deposits have been discovered in this basin, including the largest sandstone-hosted Pb–Zn deposit in the world (Jinding), and several Cu ± Ag ± Co deposits (Baiyangping, Baiyangchang and Jinman). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7000 t Ag, are mainly hosted in Meso-Cenozoic mottled clastic rocks, and strictly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the Lanping basin.To define the metallogenic history of the study area, we dated nine calcite samples associated with copper sulfides from the Jinman Cu deposit by the Sm–Nd method and five molybdenite samples from the Liancheng Cu–Mo deposit by the Re–Os method. The calcite Sm–Nd age for the Jinman deposit (58 ± 5 Ma) and the molybdenite Re–Os age for the Liancheng deposit (48 ± 2 Ma), together with previously published chronological data, demonstrate (1) the Cu–Ag mineralization in the western Lanping basin mainly occurred in three episodes (i.e., ∼56–54, 51–48, and 31–29 Ma), corresponding to the main- and late-collisional stages of the Indo–Asian orogeny; and (2) the Pb–Zn–Ag (±Cu) mineralization in the eastern Lanping basin lacked precise and direct dating, however, the apatite fission track ages of several representative deposits (21 ± 4 Ma to 32 ± 5 Ma) may offer some constraints on the mineralization age.     

Hydrothermal and metamorphic fluid-rock interaction associated with hypogene “hard” iron ore mineralisation in the Quadrilátero Ferrífero,Brazil: Implications from in-situ laser ablation ICP-MS iron oxide chemistry

In-situ laser ablation ICP-MS analyses on iron oxides in itabirite and iron ore from the Quadrilátero Ferrífero (Brazil) reveal a wide range in trace element abundances (e.g., average concentrations in hematite: Al = 40–2200 ppm, Mg = 1–930 ppm, Mn = 5–540 ppm, Ti = 3–500 ppm, V = 2–390 ppm, Cr = 1–98 ppm, As = 0.5–60 ppm). The chemistry of early hematite stages is mostly inherited from host rock and precursor magnetite, e.g., Mn concentrations correlate with bulk Mn content in itabirite. With progressive iron ore formation and modification, external fluids play a more prominent role. This is reflected by REE-Y switching from seawater-like Y/Ho ratios (> 44) in early-, to more chondrite-like Y/Ho ratios (< 34), in late-hematite stages, likely due to fluid–rock reactions with country rocks (e.g., phyllites) or exchange with magmatic hydrothermal fluids.The following ore formation stages and key processes, supported by mineral scale mass balance calculations, are constrained: (1) martitisation, cogenetic with gangue leaching, is driven by large volumes of oxidising, Si-undersaturated fluids resulting in an absolute depletion of Mg, Mn, Al, Ti, Ni and Zn, and enrichment of Pb, As, LREE and Y; (2) the formation of granoblastic hematite and locally microplaty hematite represents a largely isochemical recrystallisation of magnetite and/or martite accompanied by a depletion of Mg and Y and an elevated Ti mobility at the mineral scale; and (3) precipitation of schistose and vein-hosted specular hematite along shear and fracture zones is driven by an external Fe–Si-rich hydrothermal fluid likely under high fluid/rock ratios.     

Geochemical constraints on Cu–Fe and Fe skarn deposits in the Edong district,Middle–Lower Yangtze River metallogenic belt,China

Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad_29–100Gr_0–68) and diopside (Di_54–100Hd_0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)_N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)_N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (⁸⁷Sr/⁸⁶Sr)_i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ³⁴S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ³⁴S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.