Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Effects of fO2, fS2, temperature, and melt composition on Fe-Ni exchange between olivine and sulfide liquid: implications for natural olivine-sulfide assemblages

The apparent equilibrium constant for the exchange of Fe and Ni between coexisting olivine and sulfide liquid (K_D = (X_NiS/X_FeS)_liquid/(X_NiSi12O2/X_FeSi12O2)_olivine; X_i = mole fraction) has been measured at controlled oxygen and sulfur fugacities (fO₂ = 10^−8.1 to 10⁻¹⁰ and fS₂ = 10^−0.9 to 10^−1.7) over the temperature range 1200 to 1385°C, with 5 to 37 wt% Ni and 7 to 18 wt% Cu in the sulfide liquid. At log fO₂ of −8.7 ± 0.1, and log fS₂ of −0.9 to −1.7, K_D is relatively insensitive to sulfur fugacity, but comparison with previous results shows that K_D increases at very low sulfur fugacities. K_D values show an increase with the nickel content of the sulfide liquid, but this effect is more complex than found previously, and is greatest at log fO₂ of −8.1, lessens with decreasing fO₂, and K_D becomes independent of melt Ni content at log fO₂ ≤ −9.5. The origin of this variation in K_D with fO₂ and fS₂ is most likely the result of nonideal mixing of Fe and Ni species in the sulfide liquid. Such behavior causes activity coefficients to change with either melt oxygen content or metal/sulfur ratio, effects that are well documented for metal-rich sulfide melts.Application of these experimental results to natural samples shows that the relatively large dispersion that exists in K_D values from different olivine + sulfide-saturated rock suites can be interpreted as arising from variations in fO₂, fS₂, and the nickel content of the sulfide liquid. Estimates of fO₂ based on K_D and sulfide melt composition in natural samples yields a range from fayalite-magnetite-quartz (FMQ)-1 to FMQ-2 or lower, which is in good agreement with previous values determined for oceanic basalts that use glass ferric/ferrous ratios. Anomalously high K_D values recorded in some suites, such as Disko Island, probably reflect low fS₂ during sulfide saturation, which is consistent with indications of low fO₂ for those samples. It is concluded that the variation in K_D values from natural samples reflects olivine-sulfide melt equilibrium at conditions within the T-fO₂-fS₂ range of terrestrial mafic magmas.     

Fractionation of sulfur isotopes by the yeast Saccharomyces cerevisiae

Growing and resting cell suspensions of Baker's yeast (Saccharomyces cerevisiae) were permitted to metabolize sulfite and sulfate under a variety of environmental conditions. Enrichment of S³² in the H₂S released during reduction of sulfate under growing conditions was consistently lower (δS³⁴ < ?25%.) than enrichment during reduction of sulfite under similar conditions (δS³⁴ ~ ?30 to ?50%.). Yeast cells harvested from a sulfite medium released small quantities of H₂S when suspended in glucose-sulfate solution; cells from a sulfate growth medium did not. The enrichment of H₂S in S³² by sulfite-grown resting cells suspended in either SO^2?₄ or SO^2?₃ solutions was about 10%.in less than the maximum obtained during growth on sulfite. Isotopic fractionation was always significantly less in assimilated, than in dissimilated sulfur.     

A paired sulfate-pyrite δS approach to understanding the evolution of the Ediacaran-Cambrian sulfur cycle

An anomalous enrichment in marine sulfate δ³⁴S_SO4 is preserved in globally-distributed latest Ediacaran-early Cambrian strata. The proximity of this anomaly to the Ediacaran-Cambrian boundary and the associated evolutionary radiation has invited speculation that the two are causally related. Here we present a high-resolution record of paired sulfate (δ³⁴S_SO4) and pyrite (δ³⁴S_pyr) from sediments spanning ca. 547-540 million years ago (Ma) from the Ara Group of the Huqf Supergroup, Sultanate of Oman. We observe an increase in δ³⁴S_SO4 from ∼20‰ to ∼42‰, beginning at ca. 550 Ma and continuing at least through ca. 540 Ma. There is a concomitant increase in δ³⁴S_pyr over this interval from ∼ −15‰ to 10‰. This globally correlative enrichment, here termed the Ara anomaly, constitutes a major perturbation to the sulfur cycle. The absolute values of δ³⁴S_pyr reported here and in equivalent sections around the world, require the isotopic composition of material entering the ocean (δ³⁴S_in) to be significantly more enriched than modern (∼3‰) values, likely in excess of 12‰ during the late Ediacaran-early Cambrian. Against this background of elevated δ³⁴S_in, the Ara anomaly is explained not by increased fractionation between sulfate and pyrite (Δδ³⁴S), but by an increase in pyrite burial (f_pyr), most likely driven by enhanced primary production and sequestration of organic carbon, consistent with earlier reports of elevated organic carbon burial and widespread phosphorite deposition.     

Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Redox evolution of differentiating hydrous basaltic magmas recorded by zircon and apatites in mafic cumulates: The case of the Malayer Plutonic Complex,Western Iran

Mafic-ultramafic cumulates can provide records of basaltic magma chambers' conditions and processes, which are often difficult to determine in areas dominated by crustal-derived felsic intrusions, such as the Malayer Plutonic Complex (MPC), Western Iran. New U-Pb zircon ages for mafic cumulates in the MPC confirm the presence of isolated magma chambers of contrasting compositions during Middle Jurassic. Mafic cumulates found in seven separate zones across the MPC vary from olivine gabbro to anorthosite. While the mineralogical, textural, and geochemical lines of evidence recorded in mafic cumulates indicate pH₂O controls on the liquidus phases, the estimated oxygen fugacity (logfO₂) using zircon and apatite chemistry suggests a smoothly rising redox state during the fractionation process, consistent with the trend expected for late-stages differentiation of hydrous arc magmas. This trend is further confirmed by sulfur speciation in apatites determined from microbeam sulfur K-edge X-ray absorption near edge structure (μ-XANES) spectra (S⁶⁺/∑S = 0.93–0.98 ~ FMQ + 2 to 0.99 ~ FMQ + 3, where ∑S = S⁶⁺+S⁴⁺+S²⁻). The low S content and increasing redox state of the fractionating basaltic melts most likely resulted from preferential removal of sulfur en-route to the magma chambers along with effective assimilation of oxidizing crustal components. The reduced condition in the early basaltic melt is also evidenced by the presence of pyrite and magnetite inclusions in olivines in mafic cumulates. The shift in the prevailing fO₂ from sulfide-saturated to sulfate-bearing recorded by MPC mafic cumulates, similar to that in other magmatic arcs, is accompanied by changes in the differentiation path from transitional tholeiitic to calc-alkaline.     

Sulfur in peridotites and gabbros at Lost City (30°N, MAR): Implications for hydrothermal alteration and microbial activity during serpentinization

Variations in sulfur mineralogy and chemistry of serpentinized peridotites and gabbros beneath the Lost City Hydrothermal Field at the southern face of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) were examined to better understand serpentinization and alteration processes and to study fluid fluxes, redox conditions, and the influence of microbial activity in this active, peridotite-hosted hydrothermal system. The serpentinized peridotites are characterized by low total sulfur contents and high bulk δ³⁴S values close to seawater composition. Low concentrations of ³⁴S-enriched sulfide phases and the predominance of sulfate with seawater-like δ³⁴S values indicate oxidation, loss of sulfide minerals and incorporation of seawater sulfate into the serpentinites. The predominance of pyrite in both serpentinites and gabbros indicates relatively high fO₂ conditions during progressive serpentinization and alteration, which likely result from high fluid fluxes during hydrothermal circulation and evolution of the Lost City system from temperatures of ∼250 to 150 °C. Sulfate and sulfide minerals in samples from near the base of hydrothermal carbonate towers at Lost City show δ³⁴S values that reflect the influence of microbial activity. Our study highlights the variations in sulfur chemistry of serpentinized peridotites in different marine environments and the influence of long-lived, moderate temperature peridotite-hosted hydrothermal system and high seawater fluxes on the global sulfur cycle.     

Mineralogic and sulfur isotopic effects accompanying oxidation of pyrite in millimolar solutions of hydrogen peroxide at temperatures from 4 to 150 °C

Oxidation of pyrite by hydrogen peroxide (H₂O₂) at millimolar levels has been studied from 4 to 150 °C in order to evaluate isotopic effects potentially associated with radiolytic oxidation of pyrite. Gaseous, aqueous, and solid phases were collected and measured following sealed-tube experiments that lasted from 1 to 14 days. The dominant gaseous product was molecular oxygen. No volatile sulfur species were recovered from any experiment. Sulfate was the only aqueous sulfur species detected in solution, with sulfite and thiosulfate below the detection limits. X-ray diffraction patterns and images from scanning electron microscopy reveal solid residues composed primarily of hydrated ferric iron sulfates and sporadic ferric-ferrous iron sulfates. Hematite was detected only in solid residue produced during high temperature experiments. Elemental sulfur and/or polysulfides are inferred to be form on reacting pyrite surface based on extraction with organic solvents. Pyrite oxidation by H₂O₂ increases in rate with increasing H₂O₂concentration, pyrite surface area, and temperature. Rates measured in sealed-tube experiments at 25°C, for H₂O₂ concentration of 2 × 10⁻³ M are 8.8 × 10⁻⁹ M/m²/sec, which are higher than previous estimates. A combination of reactive oxygen species from H₂O₂ decomposition products and reactive iron species from pyrite dissolution is inferred to aggressively oxidize the receding pyrite surface. Competing oxidants with temperature-dependent oxidation efficiencies results in multiple reaction mechanisms for different temperatures and surface conditions. Sulfur isotope values of remaining pyrite were unchanged during the experiments, but showed distinct enrichment of ³⁴S in produced sulfate and depletion in elemental sulfur. The Δ_{sulfate-pyrite} and Δ_{elemental sulfur-pyrite} was +0.5 to +1.5‰ and was −0.2 to −1‰, respectively. Isotope data from high-temperature experiments indicate an additional ³⁴S-depleted sulfur fraction, with up to 4‰ depletion of ³⁴S, in the hematite. Sulfur isotope trends were not influenced by H₂O₂ concentration, temperature, or reaction time. Results of this study indicate that radiolytically produced oxidants, such as hydrogen peroxide and hydroxyl radicals, could efficiently oxidize pyrite in an otherwise oxygen-limited environment. Although H₂O₂ is generally regarded as being of minor geochemical significance on Earth, the H₂O₂ molecule plays a pivotal role in Martian atmospheric and soil chemistry. Additional experimental and field studies are needed to characterize sulfur and oxygen isotope systematics during radiolytical oxidation of metallic sulfides and elemental sulfur.     

Reconstruction of Physicochemical Environment of Hydrothermal Mineralization at Malanjkhand Copper Deposit,Central India: Constraints from Sulfur Isotope Ratios in Pyrite,Molybdenite and Chalcopyrite

δ³⁴S values of pyrite, molybdenite and chalcopyrite were determined from the Malanjkhand copper deposit. These minerals constitute the primary sulfide phases that were deposited after the initial magnetite deposition in the main orebody and host granitoid. Pyrite exhibits a depleted range of values (?2.63 to ?0.56‰), chalcopyrite, a very narrow range of values around zero (?0.039 to 0.201‰) and molybdenite furnishes a range of enriched values (0.68 to 1.98‰). On back calculation of the δ³⁴S values of H₂S in the fluid from which the minerals were likely to have precipitated, using standard expressions for equilibrium fractionation at the temperature range obtained from fluid inclusion and mineral fluid equilibria, it is observed that H₂S in the fluid at pyrite deposition was depleted and gradually became enriched towards molybdenite and chalcopyrite deposition. This trend is best explained as being due to inorganic reduction of SO₄^2? in the fluid and is very much in agreement with the paragenetic sequence indicating increasing activity of H₂S in the fluid. The very restricted range in the δ³⁴S values of sulfide minerals in the fluid does indicate a single, possibly magmatic, source of sulfur that also agrees well with the earlier deduced model of genesis of the deposit as an ancient geothermal system associated with granitic magmatism.     

Genesis of the Khaluta alkaline-basic Ba-Sr carbonatite complex (West Transbaikala, Russia)

The Khaluta carbonatite complex comprizes fenites, alkaline syenites and shonkinites, and calcite and dolomite carbonatites. Textural and compositional criteria, melt inclusions, geochemical and isotopic data, and comparisons with relevant experimental systems show that the complex formed by liquid immiscibility of a carbonate-saturated parental silicate melt. Mineral and stable isotope geothermometers and melt inclusion measurements for the silicate rocks and carbonatite all give temperatures of crystallization of 915–1,000°C and 890–470°C, respectively. Melt inclusions containing sulphate minerals, and sulphate-rich minerals, most notably apatite and monazite, occur in all of the lithologies in the Khaluta complex. All lithologies, from fenites through shonkinites and syenites to calcite and dolomite carbonatites, and to hydrothermal mineralisation are further characterized by high Ba and Sr activity, as well as that of SO3 with formation of the sulphate minerals baryte, celestine and baryte-celestine. Thus, the characteristic features of the Khaluta parental melt were elevated concentrations of SO₃, Ba and Sr. In addition to the presence of SO₃, calculated fO₂ for magnetites indicate a high oxygen fugacity and that Fe⁺³>Fe⁺² in the Khaluta parental melt. Our findings suggest that the mantle source for Khaluta carbonatite and associated rocks, as well as for other carbonatites of the West Transbaikalia carbonatite province, were SO₃-rich and characterized by high oxygen fugacity.     

Gold Mineralization in Banded Iron Formation in the Amalia Greenstone Belt,South Africa: A Mineralogical and Sulfur Isotope Study

The Blue Dot gold deposit, located in the Archean Amalia greenstone belt of South Africa, is hosted in an oxide (± carbonate) facies banded iron formation (BIF). It consists of three stratabound orebodies; Goudplaats, Abelskop, and Bothmasrust. The orebodies are flanked by quartz‐chlorite‐ferroan dolomite‐albite schist in the hanging wall and mafic (volcanic) schists in the footwall. Alteration minerals associated with the main hydrothermal stage in the BIF are dominated by quartz, ankerite‐dolomite series, siderite, chlorite, muscovite, sericite, hematite, pyrite, and minor amounts of chalcopyrite and arsenopyrite. This study investigates the characteristics of gold mineralization in the Amalia BIF based on ore textures, mineral‐chemical data and sulfur isotope analysis. Gold mineralization of the Blue Dot deposit is associated with quartz‐carbonate veins that crosscut the BIF layering. In contrast to previous works, petrographic evidence suggests that the gold mineralization is not solely attributed to replacement reactions between ore fluid and the magnetite or hematite in the host BIF because coarse hydrothermal pyrite grains do not show mutual replacement textures of the oxide minerals. Rather, the parallel‐bedded and generally chert‐hosted pyrites are in sharp contact with re‐crystallized euhedral to subhedral magnetite ± hematite grains, and the nature of their coexistence suggests that pyrite (and gold) precipitation was contemporaneous with magnetite–hematite re‐crystallization. The Fe/(Fe+Mg) ratio of the dolomite–ankerite series and chlorite decreased from veins through mineralized BIF and non‐mineralized BIF, in contrast to most Archean BIF‐hosted gold deposits. This is interpreted to be due to the effect of a high sulfur activity and increase in fO₂ in a H₂S‐dominant fluid during progressive fluid‐rock interaction. High sulfur activity of the hydrothermal fluid fixed pyrite in the BIF by consuming Fe²⁺ released into the chert layers and leaving the co‐precipitating carbonates and chlorites with less available ferrous iron content. Alternatively, the occurrence of hematite in the alteration assemblage of the host BIF caused a structural limitation in the assignment of Fe³⁺ in chlorite which favored the incorporation of magnesium (rather than ferric iron) in chlorite under increasing fO₂ conditions, and is consistent with deposits hosted in hematite‐bearing rocks. The combined effects of reduction in sulfur contents due to sulfide precipitation and increasing fO₂ during progressive fluid‐rock interactions are likely to be the principal factors to have caused gold deposition. Arsenopyrite–pyrite geothermometry indicated a temperature range of 300–350°C for the associated gold mineralization. The estimated δ³⁴S_ΣS (= +1.8 to +2.5‰) and low base metal contents of the sulfide ore mineralogy are consistent with sulfides that have been sourced from magma or derived by the dissolution of magmatic sulfides from volcanic rocks during fluid migration.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

The sulfur isotope composition of basaltic rocks

The sulfur isotope composition of tholeiitic basalts, olivine alkali basalts and alkalirich undersaturated basalts were investigated. A method of preparation was devised

1. for the extraction of the small amounts of sulfur contained in the rock samples (about 100 ppm S),
2. for the separation of sulfide- and sulfate-sulfur.

Tholeiitic and olivine alkali basalts show a predominance of sulfide-sulfur. Alkali-rich undersaturated basalts show sulfide- and sulfate-sulfur. The oxidation potential of the magma is reflected in the proportions of sulfide- and sulfate-sulfur. Differences in the conditions of oxidation are also the cause of the sulfur isotope fractionation observed. The mean in the isotope composition of the sulfur in the olivine alkali basalts (with the exception of two samples which show extreme deviation) is δ ³⁴S= +1.3 per mil. The values for the olivine alkali basalts are concentrated around this mean in a remarkable way, showing only small deviation for the individual samples. When the tholeiitic basalts deviate from this mean, it is only with a relative enrichment in the ³²S isotope. With a pronounced variation of the individual values, the mean for the sulfide-sulfur is δ ³⁴S=?0.3 per mil. The few sulfate values of both types of basalt are without significance for the discussion of their origin. However, this does not apply to the alkali-rich undersaturated basalts. Due to the higher water content, this basaltic magma had a higher oxygen partial pressure which favoured the formation of SO₂ and SO ₄ ^2? besides H₂S while pressure was released during the ascent of the magma. The sulfur isotope fractionation connected with this oxidation led to a total enrichment of ³⁴S in the rock, (δ ³⁴S for total sulfur: +3.1 per mil) with particular favouring the sulfate (δ ³⁴S=+4.2 per mil). It is accepted that the sulfur of all three types of basalts derives directly from the mantle. The olivine alkali basalts show the least deviation from the mantle value, which, in the place of origin of the basalts from the region investigated, would probably have been δ ³⁴S=+1.3(±0.5) per mil. From this it may be concluded that the olivine alkali basalts — the most frequent type of basalt in this region — had their origin in the partial melting of the mantle without further differentiation. From the sulfur isotope data we concluded that the primary isotope composition of the continental tholeiitic basalts probably corresponds to that of the olivine-alkali basalts, and to that of the mantle. However, due to degasing in the layers near to the surface, some samples lost ³⁴S, which may be related to the formation of SO₂ during the release of pressure. There is no positive indication of a differentiation in shallow depths (<15 km — in the sense of Green and Ringwood, 1967). The reason for the obvious isotopic fractionation of the alkali-rich undersaturated basalts may be seen in their higher primary water content. This is a pronounced indication of the origin of this type of magma. Bultitude and Green (1968) proved by experiment, that the formation of alkali-rich undersaturated basaltic magma is possible in the mantle in the presence of water. Only a small amount of water is available for the formation of magma in the mantle. With a water content higher than normal for basalts, only small amounts of magma can be formed, but at lower temperatures this would allow the melting of a larger fraction of mantle material. By reaction with the wall rock, these magmas could be enriched in those components of mantle minerals which have the lowest melting point. This may help to explain their geochemical characteristics.     

Oxygen solubility and speciation in sulphide-rich mattes

Sulphide-rich liquids are common in magmatic environments forming over a wide range of temperature, pressure, fO₂ and fS₂. They are economically important because they sequester valuable metals such as Cu, Ni, Au and Pt from silicate melts. The presence of accessory amounts of primary oxides associated with sulphide mineralisations is often ignored or unexplained. Experimental work has shown that large amounts of oxygen can dissolve into mattes at fO₂ typical of terrestrial environments. At the quartz-fayalite-magnetite fO₂ buffer, the molar fraction of O in the matte exceeds that of S, placing the composition of the matte to the magnetite side of the mss (monosulphide solid solution)-magnetite join in the Fe-S-O system. However, sulphides crystallise before magnetite in most sulphide mineralisations and are much more abundant. Moreover, the speciation of O in a matte is not well known. Here we report the results of an experimental study of the solubility of O in mattes as a function of fS₂, fO₂, temperature, and composition. We confirm previous observations that Ni and Cu have a negative effect on the solubility of O in mattes. We show evidence for the existence of FeSO as a structural constituent of mattes in the Fe-S-O system. We present a simple parameterisation of the amount of O dissolved in mattes under relevant geological conditions, and use this parameterisation to discuss mechanisms for the crystallisation of primary spinels associated with sulphides in the Kambalda massive sulphide deposit (Western Australia) and the Sudbury Igneous Complex (Ontario, Canada).     

Stable isotope characterization of fluids from the Lake Chany complex,western Siberia,Russian Federation

The Lake Chany complex and nearby lakes in western Siberia (Russian Federation) were studied to constrain the S cycle in these terrestrial lake environments. Surface water chemistry was characterized by Na–SO₄–Cl composition, comparable to other inland basins in semi-arid climatic zones associated with marine evaporite-bearing formations at depth. Dissolved sulfates showed elevated δ³⁴S (up to +32.3‰). These values are quite distinct from those in similar saline lakes in northern Kazakhstan, the Aral Sea, Lake Barhashi, and a gypsum deposit in the Altai Mountains. The localized distribution of such a unique S isotopic signature in dissolved SO₄ negates both aeolian and catastrophic flooding hypotheses previously suggested for the genesis of the dissolved salts. The probable source of the dissolved SO₄ in Lake Chany basin is inherited from hidden saline groundwaters (whose location and origins remain unclear) from eastern Paleozoic ranges with Upper Devonian formations with heavy S isotope values. Post-depositional enrichment of heavy S in the dissolved SO₄ from saline sediments may be caused by local activity of SO₄-reducing bacteria under the ambient supply of electron donors (dissolved river load organic matter and decaying bacterial mats) in the lake complex. Such microbial processes can remove up to ca. 60% of SO₄ from the system. Extensive and intensive evaporation of lake fluids, ca. 40%, was indicated by the progressive enrichment of δ¹⁸O values in meteoric water samples collected along the river and lake system. This evaporation process compensates the microbial loss of SO₄ dissolved in the incoming river water.     

岩浆-热液系统中铁的富集机制探讨

与岩浆-热液系统有关的铁矿类型有岩浆型钒钛磁铁矿床、玢岩铁矿、矽卡岩型铁矿和海相火山岩型铁矿,与这些铁矿有关的岩浆岩从基性-超基性、中性到中酸性岩均有,其中岩浆型钒钛磁铁矿床与基性-超基性深成侵入岩有关,形成于岩浆阶段,主要与分离结晶作用有关,但是厚大的富铁矿石的形成则可归结于原始的富铁钛苦橄质岩浆、分离结晶作用、多期次的岩浆补充以及流动分异等联合过程。钒钛磁铁矿石产于岩体下部还是上部与母岩浆的氧逸度有关:高的氧逸度导致磁铁矿早期结晶而使得其堆积于岩体的下部,相反,低氧逸度则导致低品位的浸染状矿石产于岩体的上部。虽然野外一些证据表明,元古宙斜长岩中的磷铁矿石可能是不混溶作用形成的,但是目前尚无实验证据。某些玢岩铁矿的一些磷灰石-磁铁矿石可能与闪长质岩浆同化混染了地壳中的磷导致的不混溶作用有关。除此之外,其他各类与岩浆作用有关的铁矿床均与岩浆后期的岩浆-热液作用有关。这些不同类型铁矿床的蚀变和矿化过程具有相似性,反映了它们形成过程具有相似的物理化学条件。成矿实验以及流体包裹体研究表明,岩浆-流体转换过程中出溶流体的数量以及成分受多种因素控制,其中岩浆分离结晶作用以及碳酸盐地层和膏盐层的混染可导致出溶的流体中Cl浓度的升高。早期高氧逸度环境可以使得硫以SO42-形式存在,抑制硫与铁的结合形成黄铁矿,有利于铁在早期以Cl的络合物发生迁移。大型富铁矿的形成需要一个长期稳定的流体对流循环系统,而岩浆的多期侵位或岩浆房以及在相对封闭的环境中(需要一个不透水层)一个有利于流体循环的断裂/裂隙系统是形成一个长期稳定的流体对流循环系统的必要条件。但是由于不同地质环境,流体中铁的卸载方式和位置会有明显差别,由此导致不同的矿石结构构造和不同的矿体产状。     

Origin of a barite-sulfide ore deposit in the Mykonos intrusion,cyclades: Trace element,isotopic, fluid inclusion and raman spectroscopy evidence

The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H₂S and SO₂.Calculated δ¹⁸O_H2O and δD_H2O, initial ⁸⁷Sr/⁸⁶Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ³⁴S_SO4^− 2 and δ³⁴S_H2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO₄^− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logf_S2 = − 13.8 to − 12.5, logf_O2 = − 31.9 to − 30.9, logf_H2S(g) = − 1.9 to − 1.7, logf_Te2 = − 7.9 and logα(SO₄^− 2_(aq)/H₂S_(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO₄^− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.     

Design,calibration and geological application of the first operational Australian laser ablation sulphur isotope microprobe

This contribution describes the setup and operating procedures of the first operational laser ablation microprobe for stable (sulphur) isotope analysis in Australia as well as some brief geological applications. A significant feature on this laser ablation microprobe is automated gas purification and analysis; operator control is only required to locate and ablate sample targets. As with other laboratories, samples were ablated in an oxygen atmosphere, producing a SO₂/O₂ gas mixture. SO₂ was separated from this mixture by either of two techniques. In the first technique, SO₂ was condensed into a liquid N₂ trap by cryogenic pumping, and O₂ was pumped away. This resulted in the collection of 60–70% of the produced SO₂. In the second technique, SO₂ was condensed into a liquid N₂ trap as the SO₂/O₂ mixture was slowly bled away. This technique collected 90–95% of the SO₂, with a small fractionation of 0.16%. Laser ablation and SO₂ collection via the second technique required a mineral dependent, additive correction of 2.85–5.75% to convert raw δ³⁴S values to δ³⁴S_CDT. These correction factors are mineral and laboratory dependent, and from our data, seem to be dependent on the quality of polish of the ablated sample. Precision (1σ) of laser ablation sulphur isotope analysis is 0.4–0.5%o for 150 μm ablation craters.

Preliminary results of studies on samples from the Broken Hill, Hellyer and active sea floor Pacmanus deposits indicate that laser ablation microprobe analysis can show subtle variations in δ³⁴S not apparent using either conventional or SHRIMP analysis. Laser ablation analysis indicates a larger range, but similar mean values, to conventional analysis on the same samples.     

Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai, Shandong Province

Multiple sulfur isotope ratios （^34S/^33S/^32S） of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; 633S = -0.7%o to 3.8‰,δ^34S = 0.1‰-8.8‰, △^33S = -2.3‰ to -0.7‰. The sulfur isotope compositions show obvious mass-independent fractionation （MIF） signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5 PAL （the present atmosphere level）. The sulfate produced by photolysis of SO2 with negative △^33S precipitated near the volcanic activity center; and the product of element S with positive △^33S precipitated far away from the volcanic activity center. The lower △^33S values of sulfide （-2.30‰ to --0.25‰） show that Shihezhuang was near the volcanic center, and sulfur was mostly from sulfate produced by photolysis. The higher △^33S values （-0.5‰ to -‰） indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL （mass dependent fractionation line） on the plot of δ^34S--δ^33S, showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.     

Sulfur isotope fractionation during the May 2003 eruption of Anatahan volcano, Mariana Islands: Implications for sulfur sources and plume processes

Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ³⁴S_V-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO₂ raised the δ³⁴S_V-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ³⁴S_V-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ³⁴S_V-CDT +21‰). Modeling also suggests that the δ³⁴S_V-CDT value of SO₂ gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ³⁴S_V-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO₂ in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ³⁴S values for ash erupted early in the eruption to higher δ³⁴S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO₂ released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO₂ gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.