Stable oxygen isotope ratios of marine barite from Cenozoic sediments

We report new data on oxygen isotopes in marine sulfate (delta18O[SO4]), measured in marine barite (BaSO4), over the Cenozoic. The delta18O[SO4] varies by 6x over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The delta18O[SO4] does not co-vary with the delta18O[SO4], emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the delta18O[SO4] over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The delta18O[SO4] also does not co-vary with the d18O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the delta18O[SO4] to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the delta18O[SO4]. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.

Sulphate concentrations and sulphur isotopic composition in pore fluids from ODP Leg 168 sites

A numerical model of sulfate reduction and isotopic fractionation has been applied to pore fluid SO4**2- and d34S data from four sites drilled during Ocean Drilling Program (ODP) Leg 168 in the Cascadia Basin at 48°N, where basement temperatures reach up to 62°C. There is a source of sulfate both at the top and the bottom of the sediment column due to the presence of basement fluid flow, which promotes bacterial sulfate reduction below the sulfate minimum zone at elevated temperatures. Pore fluid d34S data show the highest values (135 per mil) yet found in the marine environment. The bacterial sulfur isotopic fractionation factor, a, is severely underestimated if the pore fluids of anoxic marine sediments are assumed to be closed systems and Rayleigh fractionation plots yield erroneous values for a by as much as 15 per mil in diffusive and advective pore fluid regimes. Model results are consistent with a = 1.077+/-0.007 with no temperature effect over the range 1.8 to 62°C and no effect of sulfate reduction rate over the range 2 to 10 pmol/ccm/day. The reason for this large isotopic fractionation is unknown, but one difference with previous studies is the very low sulfate reduction rates recorded, about two orders of magnitude lower than literature values that are in the range of µmol/ccm/day to tens of nmol/ccm/day. In general, the greatest 34S depletions are associated with the lowest sulfate reduction rates and vice versa, and it is possible that such extreme fractionation is a characteristic of open systems with low sulfate reduction rates.

Simultaneous determination of delta(33) SV-CDT and delta S-34(V-CDT) using masses 48, 49 and 50 on a continuous flow isotope ratio mass spectrometer

A new, fast, continuous flow technique is described for the simultaneous determination of 633 S and delta(34)S using SO masses 48, 49 and 50. Analysis time is similar to5min/sample with measurement precision and accuracy better than +/-0.3parts per thousand. This technique, which has been set up using IAEA Ag2S standards S-1, S-2 and S-3, allows for the fast determination of mass-dependent or mass-independent fractionation (MIF) effects in sulfide, organic sulfur samples and possibly sulfate. Small sample sizes can be analysed directly, without chemical pre-treatment. Robustness of the technique for natural versus artificial standards was demonstrated by analysis of a Canon Diablo troilite, which gave a delta(33)S of 0.04parts per thousand and a delta(34)S of -0.06parts per thousand compared to the values obtained for S-1 of 0.07parts per thousand and -0.20parts per thousand, respectively. Two pyrite samples from a banded-iron formation from the 3710 Ma Isua Greenstone Belt were analysed using this technique and yielded MIF (Delta(33)S of 2.45 and 3.31parts per thousand) comparable to pyrite previously analysed by secondary ion probe. Copyright (C) 2004 John Wiley Sons, Ltd.

Paragenesis, geochemistry and metallogeny of the Dublin Gulch intrusion-related Au deposit, Yukon Territory, Canada

This study concerns the Dublin Gulch intrusion-related gold system, Yukon Territory, Canada. Located 85 km, north northwest of the town of Mayo, YT, the property hosts a 3.3 M oz Au deposit associated with a mid-Cretaceous pluton. A detailed, 8 stage, hydrothermal paragenesis has been constructed for the deposit. At least two discrete fluids are responsible for sulfide mineralization at Dublin Gulch. The latter of the two hydrothermal fluids is responsible for the majority of Au endowment on the property. Geochemical signatures of mineralization support this finding, displaying distinct populations of arsenopyrite compositions and sulfur isotopes for each fluid. Lead isotopes from sulfosalts associated with the second fluid suggest hydrothermal scavenging from country rocks. Geochronology and petrogenetic studies show that a short lived intrusive event c. 93-94 Ma took place at Dublin Gulch and that the main Au mineralising fluid may be linked to a yet unseen intrusion at depth.

Sulfur and carbon isotopes in scapolite-bearing granulites of the São José do Rio Pardo area, Brazil

Sulfur and carbon isotope compositions of ten scapolites from granulite-facies rocks of the São José do Rio Pardo area, Guaxupé Complex, Brazil, were measured. Scapolite is the primary and major rock-forming mineral in these rocks (up to 40 volume %). The isotopic composition of the sulfate and carbonate group in the scapolite structure has δ34S values of +1.0‰ to +6.7‰, and δ13C values of -14.3‰ to -6.3‰, respectively. The sulfur isotope data may be related to an upper mantle (external) or lower crustal (internal) source for the sulfur, whereas the carbon appears to have been derived from an internal source. Thus, the carbon and sulfur isotope data can be explained without invoking an external (mantle) source. © 1993.

Element contents, sulfur and oxygen isotopes, and molecular biomarkers of phosphatic crust samples from the Chimbote Platform of the shelf off Peru

Authigenic phosphatic laminites enclosed in phosphorite crusts from the shelf off Peru (10°01' S and 10°24' S) consist of carbonate fluorapatite layers, which contain abundant sulfide minerals including pyrite (FeS2) and sphalerite (ZnS). Low d34Spyrite values (average -28.8 per mill) agree with bacterial sulfate reduction and subsequent pyrite formation. Stable sulfur isotopic compositions of sulfate bound in carbonate fluorapatite are lower than that of sulfate from ambient sea water, suggesting bacterial reoxidation of sulfide by sulfide-oxidizing bacteria. The release of phosphorus and subsequent formation of the autochthonous phosphatic laminites are apparently caused by the activity of sulfate-reducing bacteria and associated sulfide-oxidizing bacteria. Following an extraction-phosphorite dissolution-extraction procedure, molecular fossils of sulfate-reducing bacteria (mono-O-alkyl glycerol ethers, di-O-alkyl glycerol ethers, as well as the short-chain branched fatty acids i/ai-C15:0, i/ai-C17:0 and 10MeC16:0) are found to be among the most abundant compounds. The fact that these molecular fossils of sulfate-reducing bacteria are distinctly more abundant after dissolution of the phosphatic laminite reveals that the lipids are tightly bound to the mineral lattice of carbonate fluorapatite. Moreover, compared with the autochthonous laminite, molecular fossils of sulfate-reducing bacteria are: (1) significantly less abundant and (2) not as tightly bound to the mineral lattice in the other, allochthonous facies of the Peruvian crusts consisting of phosphatic coated grains. These observations confirm the importance of sulfate-reducing bacteria in the formation of the phosphatic laminite. Model calculations highlight that organic matter degradation by sulfate-reducing bacteria has the potential to liberate sufficient phosphorus for phosphogenesis.

(Table 1) Sulfur and oxygen isotopes from two anhydrite samples recovered from DSDP Hole 70-504B

The first anhydrite reported from oceanic basalts occurs in altered basalts drilled during DSDP Leg 70 from Hole 504B. Anhydrite has been identified in several samples, two of which were studied in detail. Anhydrite in Sample 504B-40-3 (130-135 cm), which was acquired at 310 meters sub-basement, occurs in a dolerite at the center of a vug rimmed by saponite and calcite. Red iron-hydroxide-rich alteration halos occur from 0 to 310 meters sub-basement; primary sulfides in these halos are oxidized, and the rocks have lost large amounts of sulfur. The anhydrite in this sample has a d34S value of 18.5 per mil, and it is interpreted to have formed from a fluid containing a mixture of seawater sulfate (20.9 per mil) and basaltic sulfur (0 per mil) released during the oxidation of primary sulfides. Anhydrite in Sample 504B-48-3 (14-18 cm), which was found at 376 meters sub-basement, occurs intergrown with gyrolite at the center of a 1-cm-wide vein that is rimmed by saponite and quartz. At sub-basement depths below 310 meters to the bottom of the Leg 70 section (562 m sub-basement), the rocks exhibit the effects of anoxic alteration with common secondary pyrite. Anhydrite in Sample 504B-48-3 (14-18 cm) has a d34S value of 36.7 per mil, and it is interpreted to have formed from seawater-derived fluids enriched in 34S through sulfate reduction. Temperatures of alteration calculated from oxygen isotope data range from 60 to 100°C. Sulfate reduction may have occurred in situ, or elsewhere at higher temperature, possibly deeper in the crust. The secondary mineral paragenetic sequence indicates a progressive decrease in Mg and increase in Ca in the circulating fluids. This eventually led to anhydrite formation late in the alteration process.

Sulfur and strontium isotope composition of the Llobregat River (NE Spain): Tracers of natural and anthropogenic chemicals in stream waters

The use of sulfur and strontium isotopes as tracers for the source/s of water contaminants have been applied to the water of the Llobregat River system (NE Spain). Surface water samples from June 1997 were collected from the Llobregat River and its main tributaries and creeks. The chemistry of most stream waters are controlled mainly by the weathering of Tertiary chemical sediments within the drainage basin. The largest variation in delta(34)S values were found in the small creeks with values ranging from -9.9 to 15parts per thousand, whilst in the main river channels values ranged from 6.3 to 12.4parts per thousand. The Sr-87/Sr-86 ratio for dissolved strontium ranged from 0.70795 for a non-polluted site to 0.70882 for a polluted one. Most of the waters with high NO3 and low Ca/Na ratio converge to the same Sr-87/Sr-86 value, pointing to dominant pollutant end member contribution or a mixing of pollutants with an isotopic composition around 0.7083-0.7085. Although the concentration of the natural inputs in the river for sulfate and strontium are high, as a result of the sulfate outcrops within the geology of the basin, their isotopic characteristics suggest that they can be used as a discriminating device in water pollution problems. However to establish the detailed characteristics of the isotopes as geochemical tools, specific high-resolution case studies are necessary in small areas, where the inputs are well known.