Sulfur speciation and stable isotope trends of water-soluble sulfates in mine tailings profiles

Sulfur speciation and the sources of water-soluble sulfate in three oxidizing sulfidic mine tailings impoundments were investigated by selective dissolution and stable isotopes. The studied tailings impoundments-Piuquenes, Cauquenes, and Salvador No. 1-formed from the exploitation of the Rio Blanco/La Andina, El Teniente, and El Salvador Chilean porphyry copper deposits, which are located in Alpine, Mediterranean, and hyperarid climates, respectively. The water-soluble sulfate may originate from dissolution of primary ore sulfates (e.g., gypsum, anhydrite, jarosite) or from oxidation of sulfide minerals exposed to aerobic conditions during mining activity. With increasing aridity and decreasing pyrite content of the tailings, the sulfur speciation in the unsaturated oxidation zones showed a trend from dominantly Fe(Ill) oxyhydroxide fixed sulfate (e.g., jarosite and schwertmannite) in Piuquenes toward increasing presence of water-soluble sulfate at Cauquenes and Salvador No. 1. In the saturated primary zones, sulfate is predominantly present in water-soluble form (mainly as anhydrite and/or gypsum). In the unsaturated zone at Piuquenes and Cauquenes,the delta(34)S(S04) values ranged from +0.5 parts per thousand to +2.0 parts per thousand and from -0.4 parts per thousand to +1.4 parts per thousand Vienna Canyon Diablo Troilite (V-CDT), respectively, indicating a major sulfate source from pyrite oxidation (delta(34)S(pyrite) -1.1 parts per thousand and -0.9 parts per thousand). In the saturated zone at Piuquenes and Cauquenes, the values ranged from -0.8%. to +0.3 parts per thousand and from +2.2 parts per thousand to +3.9 parts per thousand, respectively. At Cauquenes the 34 S enrichment in the saturated zone toward depth indicates the increasing contribution of isotopically heavy dissolved sulfate from primary anhydrite (similar to+10.9%o). At El Salvador No. 1, the delta(34)S(SO4) average value is -0.9 parts per thousand, suggesting dissolution of supergene sulfate minerals (jarosite, alunite, gypsum) with a delta(34)S similar to -0.7 parts per thousand as the most probable sulfate source. The gradual decrease Of delta(18)O(S04) values from the surface to the oxidation front in the tailings impoundments at Piuquenes (from -4.5 parts per thousand to -8.6 parts per thousand Vienna Standard Mean Ocean Water, V-SMOW) and at Cauquenes (from -1.3 parts per thousand to -3.5 parts per thousand) indicates the increasing importance of ferric iron as the main electron acceptor in the oxidation of pyrite. The different delta(18)O(SO4) values between the tailings impoundments studied here reflect the local climates.

Isotope determination of sulfur by mass spectrometry in soil samples

Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Isotope determination of sulfur by mass spectrometry in soil samples

Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S) with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS) in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-)), which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2-) concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms) was carried out by isotope ratio mass spectrometry (IRMS). In this work, the labeled material (K2(34)SO4) was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

Sulfur isotope analysis of aerosol particles by NanoSIMS

A new method to measure the sulfur isotopic composition of individual aerosol particles by NanoSIMS has been developed and tested on several standards such as barite (BaSO4), anhydrite (CaSO4), gypsum (CaSO4·2H2O), mascagnite ((NH4)2SO4), epsomite (MgSO4·7H2O), magnesium sulfate (MgSO4·xH2O), thenardite (Na2SO4), boetite (K2SO4) and cysteine (an amino acid). This ion microprobe technique employs a Cs+ primary ion beam and measures negative secondary ions permitting the analysis of sulfur isotope ratios in individual aerosol particles down to 500 nm in size (0.001-0.5 ng of sample material). The grain-to-grain reproducibility of measurements is typically 5‰ (1σ) for micron-sized grains, <5‰ for submicron-sized grains, and <2‰ for polished thin sections and ultra microtome sections which were studied for comparison. The role of chemical omposition (matrix effect) and sample preparation techniques on the instrumental mass fractionation (IMF) of the 34S/32S ratio in the NanoSIMS has been investigated. The IMF varies by ~15‰ between the standards studied here. A good correlation between IMF and ionic radius of the cations in sulfates was observed. This permits to infer IMF corrections even for sulfates for which no isotope standards are available. The new technique allows to identify different types of primary and secondary sulfates based on their chemical composition and to measure their isotopic signature separately. It was applied to marine aerosol samples collected in Mace Head and urban aerosol samples collected in Mainz. It was shown that primary sulfate particles such as sulfate in NaCl or gypsum particles precipitated from ocean water retain the original isotopic signature of their source. The isotopic composition of secondary sulfate depends on the isotopic composition of precursor SO2 and the oxidation pathway. The 34S/32S fractionation with respect to the precursor SO2 is -9‰ for homogeneous oxidation and +16.5‰ for heterogeneous oxidation. This large difference between the isotopic fractionation of both pathways allows identifying the oxidation pathway from which the SO42- in a secondary sulfate particle is derived, by means of its sulfur isotope ratio, provided that the isotopic signature of the precursor SO2 is known. The isotopic composition of the precursor SO2 of secondary sulfates was calculated based on the isotopic composition of particles with known oxidation pathway such as fine mode ammonium sulfate.

Impact of Preindustrial Biomass-Burning Emissions on the Oxidation Pathways of Tropospheric Sulfur and Nitrogen

Ice core measurements (H2O2 and CH4/HCHO) and modeling studies indicate a change in the oxidation capacity of the atmosphere since the onset of the Industrial Revolution due to increases in fossil fuel burning emissions [e. g., Lelieveld et al., 2002; Hauglustaine and Brasseur, 2001; Wang and Jacob, 1998; Staffelbach et al., 1991]. The mass-independent fractionation (MIF) in the oxygen isotopes of sulfate and nitrate from a Greenland ice core reveal that biomass-burning events in North America just prior to the Industrial Revolution significantly impacted the oxidation pathways of sulfur and nitrogen species deposited in Greenland ice. This finding highlights the importance of biomass-burning emissions for atmospheric chemistry in preindustrial North America and warrants the inclusion of this impact in modeling studies estimating changes in atmospheric oxidant chemistry since the Industrial Revolution, particularly when using paleo-oxidant data as a reference for model evaluation.

Geochemistry and isotopes at DSDP Site 68-503

Nodules occur in the siliceous calcareous ooze and siliceous marl at Site 503 in the eastern equatorial Pacific. They are present below a depth of about 11 meters throughout the green-colored reduced part of the section down to 228 meters, although they are most abundant between 30 and 85 meters. They are cylindrical or barrel-shaped, up to 70 mm long, and usually have an axial channel through them or are hollow. They appear to have formed around and/or within burrows. XRD studies and microprobe analyses show that they are homogeneous and consist of calcian rhododrosite and minor calcite; Mn is present to the extent of about 30%. Isotopic analyses of the carbonate give carbon values which range from -1.2 per mil to -3.8 per mil, and oxygen isotope compositions vary from +4.0 per mil to +6.0 per mil. These values are different from those for marine-derived carbonates as exemplified by the soft sediment filling of a burrow: d13C, -0.26 per mil; d18O, +1.05 per mil. The carbon isotope data indicate that carbonate derived (possibly indirectly) from seawater was mixed with some produced by organic diagenesis to form the nodules. The d18O values suggest that although they formed near the sediment surface, some modification or the introduction of additional diagenetic carbonate occurred during burial.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

Sulfur and carbon in mIcrobial processes in waters and sediments of the Kara Sea in September 2007

Results of microbiological, biogeochemical and isotope geochemical studies in the Kara Sea are described. Samples for these studies were obtained during Cruise 54 of R/V Akademik Mstislav Keldysh in September 2007. The studied area covered the northern, central, and southwestern parts of the Kara Sea and the Obskaya Guba (Ob River estuary). Quantitative characteristics of total bacterial population and activity of microbial processes in the water column and bottom sediments were obtained. Total abundance of bacterioplankton (BP) varied from 250000 cells/ml in the northern Kara Sea to 3000000 cells/ml in the Obskaya Guba. BP abundance depended on concentration of suspensded matter. Net BP production was minimal in the central Kara Sea (up to 0.15-0.2 µg C/l/day) and maximal (0.5-0.75 µg C/l/day) in the Obskaya Guba. Organic material at the majority of stations at the Ob transect predominantly contained light carbon isotopes (-28.0 to -30.18 per mil) of terrigenous origin. Methane concentration in the surface water layer varied from 0.18 to 2.0 µl CH4/l, and methane oxidation rate varied from 0.1 to 100 nl CH4/l/day. Methane concentration in the upper sediment layer varied from 30 to 300 µl CH4/dm**3; rate of methane formation was varied from 44 to 500 nl CH4/dm**3/day and rate of methane oxidation - from 30 to 2000 nl CH4/dm**3/day. Rate of sulfate reduction varied from 4 to 184 µg S/dm**3/day.

Geochemistry and isotopes at DSDP Hole 79-546

At Site 546, below the Mazagan Escarpment at a water depth of 4 km, 36 m of salt rock was cored from the top of one of a field of salt domes. The core was studied by thin section and a variety of geochemical procedures. The salt rock contains 0.1 to 3% carnallite and lesser amounts of sylvite and polyhalite, which with the corresponding high level of bromide place it within the potash evaporite facies. The bromide profile is of a dominantly marine evaporite deposited in moderately shallow brine which, however, was not repeatedly desiccated. A mineralogical argument suggests that the brine surface was not below sea level. An average of about 5% elastics, with dispersed anhydrite, darken the salt rock to deep shades of red, brown, and gray green. Most of the included materials are in highly deformed boudins or dispersions in the salt rock that has also undergone cataclasis in a subsequent, probably tectonic, deformation. The salt rock is slightly deficient in anhydrite, and the usual separate beds and laminae of anhydrite are virtually absent. Stable isotope ratios of sulfur and oxygen in the sulfate are clearly derived from sea water of Permian to Scythian age, in contrast to the late Triassic or Early Jurassic age of evaporites onshore in Morocco and Portugal and the corresponding evaporites offshore Maritime Canada. In contrast to those evaporites off the axis of Atlantic rifting, the salt at Site 546 may have been deposited in a very early central rift fed by marine waters from Tethys through the Gibraltar or South Atlas fracture zones.

Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.