Mineralogy of sulfides

Metal sulphides are the most important group of ore minerals. As shown in this brief introduction, much is known about their compositions, crystal structures, phase relations and paragenesis. Much less is known about their surface chemistry and, in particular, about their biogeochemistry, and about the formation and behaviour of ‘nanoparticle’ sulphides, whether formed abiotically or biogenically. These are large and complex topics which can only be touched upon in this article which also serves to direct readers to more comprehensive accounts

Sea-floor tectonics and submarine hydrothermal systems

The discovery of metal-depositing hot springs on the sea floor, and especially their link to chemosynthetic life, was among the most compelling and significant scientific advances of the twentieth century. More than 300 sites of hydrothermal activity and sea-floor mineralization are known on the ocean floor. About 100 of these are sites of high-temperature venting and polymetallic sulfide deposits. They occur at mid-ocean ridges (65%), in back-arc basins (22%), and on submarine volcanic arcs (12%). Although high-temperature, 350°C, black smoker vents are the most recognizable features of sea-floor hydrothermal activity, a wide range of different styles of mineralization has been found. Different volcanic substrates, including mid-ocean ridge basalt, ultramafic intrusive rocks, and more evolved volcanic suites in both oceanic and continental crust, as well as temperature-dependent solubility controls, account for the main geochemical associations found in the deposits. Although end-member hydrothermal fluids mainly originate in the deep volcanic basement, the presence of sediments and other substrates can have a large effect on the compositions of the vent fluids. In arc and backarc settings, vent fluid compositions are broadly similar to those at mid-ocean ridges, but the arc magmas also supply a number of components to the hydrothermal fluids. The majority of known black smoker vents occur on fast-spreading mid-ocean ridges, but the largest massive sulfide deposits are located at intermediate- and slow-spreading centers, at ridge-axis volcanoes, in deep backarc basins, and in sedimented rifts adjacent to continental margins. The range of deposit sizes in these settings is similar to that of ancient volcanic-associated massive sulfide (VMS) deposits. Detailed mapping, and in some cases drilling, indicates that a number of deposits contain 1 to 5 million tons (Mt) of massive sulfide (e.g., TAG hydrothermal field on the Mid-Atlantic Ridge, deposits of the Galapagos Rift, and at 13°N on the East Pacific Rise). Two sediment-hosted deposits, at Middle Valley on the Juan de Fuca Ridge and in the Atlantis II Deep of the Red Sea, are much larger (up to 15 and 90 Mt, respectively). In the western Pacific, high-temperature hydrothermal systems occur mainly at intraoceanic back-arc spreading centers (e.g., Lau basin, North Fiji basin, Mariana trough) and in arc-related rifts at continental margins (e.g., Okinawa trough). In contrast to the mid-ocean ridges, convergent margin settings are characterized by a range of different crustal thicknesses and compositions, variable heat flow regimes, and diverse magma types. These variations result in major differences in the compositions and isotopic systematics of the hydrothermal fluids and the mineralogy and bulk compositions of the associated mineral deposits. Intraoceanic back-arc basin spreading centers host black smoker vents that, for the most part, are very similar to those on the mid-ocean ridges. However, isotopic data from both the volcanic rocks and the sulfide deposits highlight the importance of subduction recycling in the origin of the magmas and hydrothermal fluids. Back-arc rifts in continental margin settings are typically sediment-filled basins, which derive their sediment load from the adjacent continental shelf. This has an insulating effect that enhances the high heat flow associated with rifting of the continental crust and also helps to preserve the contained sulfide deposits. Large hydrothermal systems have developed where initial rifting of continental crust or locally thickened arc crust has formed large calderalike sea-floor depressions, similar to those that contained major VMS-forming systems in the geologic record. Hydrothermal vents also occur in the summit calderas of submarine volcanoes at the volcanic fronts of arcs. However, this contrasts with the interpreted settings of most ancient VMS deposits, which are considered to have formed mainly during arc rifting. Hydrothermal vents associated with arc volcanoes show clear evidence of the direct input of magmatic volatiles, similar to magmatic-hydrothermal systems in subaerial volcanic arcs. Several compelling examples of submarine epithermal-style mineralization, including gold-base metal veins, have been found on submarine arc volcanoes,and this type of mineralization may be more common than is presently recognized. Mapping and sampling of the sea floor has dramatically improved geodynamic models of different submarine volcanic and tectonic settings and has helped to establish a framework for the characterization of many similar ancient terranes. Deposits forming at convergent margins are considered to be the closest analogs of ancient VMS. However, black smokers on the mid-ocean ridges continue to provide critically important information about metal transport and deposition in sea-floor hydrothermal systems of all types. Ongoing sea-floor exploration in other settings is providing clues to the diversity of mineral deposit types that occur in different environments and the conditions that are favorable for their formation

Geochemistry, Mineralogy and Microbiology of Molybdenum in Mining-Affected Environments

This is the final version of the article. Available from MDPI via the DOI in this record.Molybdenum is an essential element for life, with growing production due to a constantly expanding variety of industrial applications. The potentially harmful effects of Mo on the environment, and on human and ecosystem health, require knowledge of Mo behavior in mining-affected environments. Mo is usually present in trace amounts in ore deposits, but mining exploitation can lead to wastes with very high Mo concentrations (up to 4000 mg/kg Mo for tailings), as well as soil, sediments and water contamination in surrounding areas. In mine wastes, molybdenum is liberated from sulfide mineral oxidation and can be sorbed onto secondary Fe(III)-minerals surfaces (jarosite, schwertmannite, ferrihydrite) at moderately acidic waters, or taken up in secondary minerals such as powellite and wulfenite at neutral to alkaline pH. To date, no Mo-metabolising bacteria have been isolated from mine wastes. However, laboratory and in-situ experiments in other types of contaminated land have suggested that several Mo-reducing and -oxidising bacteria may be involved in the cycling of Mo in and from mine wastes, with good potential for bioremediation. Overall, a general lack of data is highlighted, emphasizing the need for further research on the contamination, geochemistry, bio-availability and microbial cycling of Mo in mining-affected environments to improve environmental management and remediation actions.Francesca Frascoli was supported by an Erasmus+ traineeship studentship EQF level 7

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River, SW France)

International audienceMining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM-EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water-sediment interface of (i) dissolved SO4 promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), not, vert, similar6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary

The role of the Kupferschiefer in the formation of hydrothermal base metal mineralization in the Spessart ore district, Germany: insight from detailed sulfur isotope studies

The Spessart district (SW Germany), located at the southwestern margin of the Permian Kupferschiefer basin in Central Europe, hosts abundant stratabound and structurally controlled base metal mineralization. The mineralization styles identified are (1) stratabound Cu-Pb-Zn-(Ag) ores in Zechstein sedimentary rocks, (2) structurally controlled Cu-As-(Ag) ores in Zechstein sedimentary rocks, (3) crosscutting Co-Ni-(Bi)-As and Cu-Fe-As veins, (4) stratabound metasomatic Fe-Mn carbonate ores in Zechstein dolomite, (5) barren barite veins, and (6) Fe-Mn-As veins in Permian rhyolites. Building on previous work that involved mineralogical, textural, and chemical characterization of the major mineralization types, we have performed a comprehensive sulfur isotope study that applied both conventional and novel laser-ablation multi-collector inductively coupled plasma mass spectrometry techniques. The δ34S values of sulfide minerals from the different ore types are consistently negative and highly variable, in the range between −44.5‰ and −3.9‰, whereas the δ34S values of barite are all positive in the range between 4.7‰ and 18.9‰. Remarkably, stratabound and structurally controlled mineralization in Zechstein sedimentary rocks has the least negative δ34S values, whereas vein-type deposits have consistently more negative δ34S values. The observed pattern of sulfide δ34S values can be best interpreted in terms of fluid mixing at the basement-cover interface. Hydrothermal fluids originating from the crystalline basement migrated upward along subvertical fault zones and were periodically injected into groundwaters that were flowing in the post-Variscan sedimentary cover. These groundwaters had interacted with the Zechstein sedimentary rocks, resulting in fluids characterized by elevated concentrations of reduced sulfur (with negative δ34S values) and alkaline pH. Repeated mixing between both chemically contrasting fluids caused rapid and efficient precipitation of sulfide ore minerals in hydrothermal veins with highly variable but distinctly negative δ34S value

Multidisciplinary Investigation of Hydrothermal Fluids in the Janggun Zn-Pb Mineralization (South Korea): Mineralogy, Trace Elements, Pb and S Isotopic Compositions

The Janggun lead-zinc-(silver) deposit in South Korea was formed by hydrothermal-metasomatic processes. We collected 12 samples over a 100 m transect in one of the five orebodies recognized in the deposit and analyzed a total of 68 sulfide minerals. Detailed mineralogical observations show successive modifications and overprint of pristine sulfide by replacement reactions, suggesting several distinct petrogenetic events. We distinguished four different phase assemblages, which occur in contiguous zones of the transect. This suggests multiple alteration fronts. Major and minor element concentrations of sulfide phases were measured for the different sulfide generations. Milligram-sized sulfide mineral samples were micro-drilled for Pb and S isotope analyses with a resolution of 200 μm to 1 mm. Pb and S isotopic compositions (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb and δ34S) are variable, showing 206Pb/204Pb ranges from 18.334 to 18.879, 207Pb/204Pb; 15.667 to 15.692, and 208Pb/204Pb; 38.682 to 38.899, and δ34S ranges from + 4.4 to + 6.2‰. Although Pb isotopic compositions and δ34S data are similar to literature data from different areas of the Janggun deposit, the Pb isotopic variations between the different samples (at the 10 m scale), and within individual polished sections (at the cm scale) are well over 100 times larger than the analytical uncertainty. The scatter in sulfur isotopic compositions confirms the Pb isotopic heterogeneity at both the cm and 10 m scales. At least seven isotopically well distinct fluid circulation episodes are required in the study area to explain different projections of common-denominator Pb isotope diagrams. This suggests that fluid pulses of distinct chemical and isotopic compositions circulated in distinct spatial and temporal episodes. To investigate the role of country rocks as sources of the metals transported by the ore-forming fluids, we leached 13 samples of country rocks (Janggun limestone, Chunyang granite, granophyre, and dyke) with dilute acid and analyzed both leachates and residues. Correlations are observed between Pb isotopic compositions and trace ratios (e.g. Co/Ni, Cu/Ag, and Zn/Cd). The Pb isotopic compositions of country rocks and Precambrian basement suggest that leaching of country rocks by circulating fluids is able to produce the observed Pb isotope and trace elements variations in the sulfide minerals, whereby different end-members in the isotope correlation diagrams can be linked to different country rocks

New Insights into the mineralogy of the Atlantis II deep metalliferous sediments, Red Sea

The Atlantis II Deep of the Red Sea hosts the largest known hydrothermal ore deposit on the ocean floor and the only modern analog of brine pool-type metal deposition. The deposit consists mainly of chemical-clastic sediments with input from basin-scale hydrothermal and detrital sources. A characteristic feature is the millimeter-scale layering of the sediments, which bears a strong resemblance to banded iron formation (BIF). Quantitative assessment of the mineralogy based on relogging of archived cores, detailed petrography, and sequential leaching experiments shows that Fe-(oxy)hydroxides, hydrothermal carbonates, sulfides, and authigenic clays are the main “ore” minerals. Mn-oxides were mainly deposited when the brine pool was more oxidized than it is today, but detailed logging shows that Fe-deposition and Mn-deposition also alternated at the scale of individual laminae, reflecting short-term fluctuations in the Lower Brine. Previous studies underestimated the importance of nonsulfide metal-bearing components, which formed by metal adsorption onto poorly crystalline Si-Fe-OOH particles. During diagenesis, the crystallinity of all phases increased, and the fine layering of the sediment was enhanced. Within a few meters of burial (corresponding to a few thousand years of deposition), biogenic (Ca)-carbonate was dissolved, manganosiderite formed, and metals originally in poorly crystalline phases or in pore water were incorporated into diagenetic sulfides, clays, and Fe-oxides. Permeable layers with abundant radiolarian tests were the focus for late-stage hydrothermal alteration and replacement, including deposition of amorphous silica and enrichment in elements such as Ba and Au

Opportunities and threats of selenium supply from unconventional and low-grade ores: A critical review

Research on selenium has increased in recent years due to its extensive use in electronic applications, solar cells, glass industry, photocopying, cosmetic industry, and as a dietary supplement. New data and discoveries on the importance of this metalloid in the fields of medical biotechnology and human health have further increased its commercial value. This paper identifies challenges associated with selenium recovery from geogenic ores and topical unconventional ores such as marine geo-resources and anthropogenic stocks. Emphasis is given on opportunities and challenges of non-commercial processes for selenium resource extraction that may be developed at full-scale soon. Characteristics and global uses of selenium are also described to help predicting future scenarios of alternate supply. Considering the scarcity of increasingly wanted selenium metal and the recent advancements that have been made in mining from alternative and urban ores, it is possible that selenium can be effectively recovered from other sources to secure a stable and diversified supply