Paleoproterozoic massive Cu-Zn±Pb±Au±Ag sulphide deposits metamorphosed to the middle-upper amphibolite facies in central-south Colorado formed in a volcanic arc setting on the edge of the Yavapai crustal province. Previously published U-Pb ages on spatially related granitoids range from ∼1.9 to ∼1.1 Ga, while Pb isotope studies on galena from massive sulphides suggest mineralization formed at around 1.8–1.7 Ga. Some deposits in the Dawson-Green Mountain trend (DGMT) and the Gunnison belt are composed of Cu-Zn-Au-(Pb-Ag) mineralization that were overprinted by later Au-(Ag-Cu-Bi-Se-Te) mineralization. Sulphide mineralization is spatially related to amphibolite and bimodal, mafic-felsic volcanic rocks (gabbro, amphibolite, rhyolite and dacite) and granitoids, but it occurs mostly in biotite-garnet-quartz±sillimanite±cordierite schists and gneisses, spatially related to nodular sillimanite rocks, and in some locations, exhalative rocks (iron formations, gahnite-rich rocks and quartz-garnetite). The major metallic minerals of the massive sulphides include chalcopyrite, sphalerite, pyrite, pyrrhotite, and magnetite, with minor galena and gahnite. Altered rocks intimately associated with mineralization primarily consist of various amphiboles (gedrite, tremolite and hornblende), gahnite, biotite, garnet, cordierite, carbonate and rare högbomite. The Zn/Cd ratios of sphalerite (44 to 307) in deposits in the DGMT fall within the range of global volcanogenic massive sulphide (VMS) deposits but overlap with sphalerite from sedimentary exhalative (Sedex) deposits. Sulphur isotope values of sulphides (δ34S = −3.3 to +6.5) suggest sulphur was largely derived from magmatic sources, and that variations in isotopic values resulting from thermochemical sulphate reduction are due to small differences in physicochemical conditions. The preferred genetic model is for the deposits to be bimodal-mafic (Gunnison) to mafic-siliciclastic VMS deposits (Cotopaxi, Cinderella-Bon Ton, DGMT).

The carbonate-hosted Pb–Zn deposits in the Sichuan–Yunnan–Guizhou (SYG) triangle region are important Indosinian deposits in South China. The Tianbaoshan deposit is a typical large Pb–Zn deposit in the SYG area and occurs as pipe-like type, hosted by Sinian dolostone. It contains ∼26 Mt Zn–Pb ore (7.76–10.09 % Zn, 1.28–1.50 % Pb and 93.6 g t−1 Ag) and >0.1 Mt Cu ore (2.55 % Cu). In this study, the detailed mineral textures, mineral chemical and sulphur isotopic compositions of the various sulphides have been analysed to constrain the abnormal enrichment mechanism and mineralization relationship. Four mineralization stages have been recognized: Stage 1, minor early pyrite (Py1) with relics and infill of intergranular dolomite or quartz grains; Stage 2, Cu mineralization with coarse-grained, elliptical crystal chalcopyrite (Cp1); (3) Stage 3, Zn mineralization with dark fine-grained sphalerite (Sph1) and light coarse-grained sphalerite (Sph2); and (4) Stage 4, as represented by a quartz–calcite assemblage with galena, minor pyrite (Py2) and chalcopyrite (Cp2). The petrography of the sulphide minerals (Py1, Cp1, Sph1 and Sph2) demonstrates a mutual inclusion relationship. The nature of this relationship from core to rim and their similar sulphur isotope values (5.5–8.3 ‰) indicates a single sulphur source, suggesting that the different mineralization types are the result of different stages of a continuous hydrothermal system. Sphalerite geothermometer study suggests that sphalerite in the Tianbaoshan deposit formed in a low-temperature (<200 °C) hydrothermal system. The low concentrations of Mn and In, low In/Ge ratios and high Fe/Cd ratios in the sphalerite are consistent with those of Mississippi Valley-type (MVT) deposits, but different from those of magmatism-related deposits (e.g. epithermal, skarn and VMS deposits). The positive δ34S values for Py1 (5.1–7.9 ‰), Cp1 (5.1–7.2 ‰), Sph1 (4.7–7.4 ‰), Sph2 (3.9–8.7 ‰), Py2 (4.4–9.3 ‰) and Cp2 (5.0–6.8 ‰) indicate a sulphur source from thermochemical reduction of coeval seawater sulphate. Widely developed dissolved textures (caverns and breccias) with massive sulphide infillings and deformed host rock remnants suggest that replacement of host dolostones by ore fluids was volumetrically significant and the ore formed nearly simultaneously with the cavities. The Tianbaoshan deposit is a typical MVT deposit, which resulted from mixing of a H2S-rich fluid and a metal-rich fluid, with thermochemical sulphate reduction occurring before ore precipitation rather than during ore precipitation.

The Biga Peninsula of NW Turkey is host to six major halloysite deposits in the Go¨nen, Yenice and Balya districts. Mineralization took place in areas of Permian limestone blocks where the Triassic Karakaya Complex is in contact with early Miocene calc-alkaline volcanic rocks. Hypogene halloysite mineralization was controlled by the intersection of minor faults in the vicinity of clay deposits. During the Pleistocene, activity of the North Anatolian Fault (NAF) brought ascending geothermal solutions through the fault zones to the surface, which led to hydrothermal alteration and halloysite formation. N-MORB normalized element values for each halloysite deposit and the volcanic rocks suggest genetic links. Alunite and halloysite were formed in the Turplu area where upwelling hydrothermal waters contained major H2S and SO2 acids. Only halloysite mineralization occurred in outflow areas of the same fossil geothermal field.

Pyrite and alunite samples from the Turplu deposits have δ34S values of 0.6–1.8% and 4.8–7.9%, respectively, with values for gypsum of 3.1–3.5%. The δ34S values of pyrite suggest that local meteoric waters had partially mixed with the dominant fluid during the closure stage of fossil hydrothermal activities. The range of δD values of halloysite samples from Turplu is –58.4 to –68.6%. The δ18O values for halloysite are in the range 16.7–18.1%. All halloysite deposits in the study areas are either overlying or adjacent to limestone blocks, and these provide excellent drainage for the discharging geothermal waters. Subsurface drainage systems in the karstic environment and the SO2-bearing thermal waters indicate the importance of acidic waters and the continuous leaching of elements in forming relatively pure hydrated halloysite. A steam-heated dissolution-precipitation model is proposed for the occurrence of all halloysite and alunite deposits. Sulphur gases (H2S-SO2) of hypogene origin rose from deep in the fault zone to the surface where they encountered oxygenated groundwater at the water table. The occurrence of H2SO4 in this hydrothermal system enhanced the acidity of geothermal waters provoking advanced argillic alteration. Hypogene alunite deposits also have large P2O5 contents, suggesting a parent material with a magmatic origin deeper than the alkaline tuffs. Halloysite is a fast-forming metastable precursor to kaolinite.

Pyritic slates from the late Precambrian, Middle Dalradian Argyll Group Easdale Slate Formation, contain mainly quartz, muscovite and chlorite with variable amounts of dolomite, albite and paragonite. Slates from Easdale Island and Cuan Ferry contain pyrite porphyroblasts with δ34S = + 12 to + 16‰. The pyrite grew during a post-tectonic retrogressive event at the expense ofpyrrhotine which formed during the main regional metamorphism of the Grampian orogeny by reduction of diagenetic pyrite. Slate from Oban contains abundant diagenetic framboidal pyrite and small syn-tectonic pyrite porphyroblasts with δ34S = +22‰. This pyrite was not all reduced to pyrrhotine on metamorphism so there was little retrogressive growth of pyrite. Metamorphism appears to have homogenized local (cm scale at least) isotopic inhomogeneities and preserved an average seawater-sulphate-sulphide isotopic fractionation value. Middle Dalradian seawater-sulphate had a δ34S value of about + 35‰, so the small fractionations are appropriate for bacteriogenic reduction in bituminous sediments, the heavier sulphide in the case of the Oban slate indicating more rapid reduction of sulphate. Lower Dalradian Appin Group, Ballachulish slate contains pyrite with δ34S = +15±2‰ and is best interpreted as forming in the same manner as the Easdale slates of Easdale Island and Cuan Ferry; the sharp increase in late Precambrian ocean-sulphate sulphur isotope signature from +15 to > +30‰ therefore occurred by Lower Dalradian Appin Group times.

Gypsum evaporites are forming under desiccating conditions in relict cave passages in Mynydd Llangattwg, south Wales. Sulphur isotope compositions of these sulphates indicate that oxidation of diagenetic pyrite in the overlying Millstone Grit is the source of sulphate solutions, rather than dissolution of evaporitic sulphate in the limestones.

Pyrite, the most widespread and abundant of sulphide minerals in the Earth's surficial rocks, commonly constitutes the primary opaque phase in ore deposits. Consequently, an understanding of the behaviour of pyrite and its relationships with coexisting phases during the metamorphism of pyritebearing rocks is vital to the interpretation of their genesis and post-depositional history. Metamorphism is commonly responsible for the obliteration of primary textures but recent studies have shown that the refractory nature of pyrite allows it to preserve some pre-metamorphic textures. Pyrrhotite in pyritic ores has often been attributed to the breakdown of pyrite during metamorphism. It is now clear that pyrrhotite can be primary and that the presence of pyrrhotite with the pyrite provides a buffer that constrains sulphur activity during metamorphism. Pyrite-pyrrhotite ratios change during metamorphism as prograde heating results in sulphur release from pyrite to form pyrrhotite and as retrograde cooling permits re-growth of pyrite as the pyrrhotite releases sulphur. Retrograde growth of pyrite may encapsulate textures developed during earlier stages as well as preserve evidence of retrograde events. Sulphur isotope exchange of pyrite with pyrrhotite tends to homogenise phases during prograde periods but leaves signatures of increasingly heavy sulphur in the pyrite during retrograde periods.

The investigation of Gale Crater has highlighted the occurrence of lake sediments in the geological record of Mars. Lacustrine basins include a diversity of potential habitats for life. An analogue terrestrial lacustrine basin of Devonian age in Scotland contains sulphide minerals in several settings where subsurface microbial colonization can be envisaged. Sulphur isotope compositions for the sulphides imply that they were precipitated by microbial sulphate reduction. The data suggest that the search for life in martian lacustrine basins should include investigation of potential subsurface habitats, and that any sulphides in martian lacustrine basins could be useful indicators in the search for life.

Evidence of microbial activity associated with mineralization of secondary Na-sulphate minerals (thenardite, mirabilite) in the basaltic subsurface of Craters of the Moon National Monument (COM), Idaho were examined by scanning electron microscopy, X-ray diffraction, laser desorption Fourier transform ion cyclotron resonance mass spectrometry (LD-FTICR-MS), Fourier transform infrared spectroscopy (FTIR) and isotope ratio mass spectrometry. Peaks suggestive of bio/organic compounds were observed in the secondary Na-sulphate deposits by LD-FTICR-MS. FTIR provided additional evidence for the presence of bio/organic compounds. Sulphur fractionation was explored to assist in determining if microbes may play a role in oxidizing sulphur. The presence of bio/organic compounds associated with Na-sulphate deposits, along with the necessity of oxidizing reduced sulphur to sulphate, suggests that biological activity may be involved in the formation of these secondary minerals. The secondary Na-sulphate minerals probably form from the overlying basalt through leached sodium ions and sulphate ions produced by bio-oxidation of Fe-sulphide minerals. Since the COM basalts are one of the most comparable terrestrial analogues for their Martian counterparts, the occurrence of biological activity in the formation of sulphate minerals at COM has direct implications for the search for life on Mars. In addition, the presence of caves on Mars suggests the importance of these environments as possible locations for growth and preservation of microbial activity. Therefore, understanding the physiochemical pathways of abiotic and biotic mineralization in the COM subsurface and similar basaltic settings has direct implications for the search for extinct or extant life on Mars.

Sulphur isotopic data are presented for the four horizons of stratabound mineralisation in the Argyll Group Dalradian (Vendian) of the Central Highlands of Scotland. The styles of mineralisation reflect the stratigraphic and tectonic evolution of the Dalradian basin. The SEDEX-type Ba + (Zn + Pb) Loch Lyon Horizon has δ34S values for pyrite of +17% and for baryte of +27%. The baryte sulphur source was Dalradian sea-water although the values were modified by isotopic exchange with an H2S-rich metamorphic fluid derived from the surrounding graphitic schists. The sulphur source for sulphide in the horizon was probably the underlying strata; sulphide values were only slightly affected by metamorphism. Sulphides in the Pyrite Horizon are isotopically indistinguishable from those in the remainder of the volcanogenic Ben Lawers Schist Formation (0 ± 4%); these values suggest that, at least in the Tyndrum area, sulphides in the Pyrite Horizon are of igneous origin. VMS-type Cu + Zn + Pb mineralisation in the Ben Challum Quartzite Formation has a narrow range of values around + ll%. The likely source of this sulphide sulphur is reduced sea-water sulphate, the isotopic values remaining consistent owing to the buffering effect of anhydrite in the underlying calcium-rich rocks.