Alkenone composition, UK'37 index, and carbon, sulphur, nitrogen and element oxides of ODP Site 186-1151

Ocean Drilling Program (ODP) Site 1151 (Sacks, Suyehiro, Acton, et al., 2000, doi:10.2973/odp.proc.ir.186.2000) is located in an area where the surface water mass is influenced by both the Kuroshio and Oyashio Currents. The site also receives a relatively high flux of detrital materials from riverine input from Honsyu Island and eolian input from Central and East Asia. We analyzed alkenones and alkenoates in the sediments to reconstruct alkenone unsaturation index (Uk'37)-based sea-surface temperature (SST), total organic carbon, and total nitrogen to estimate the terrigenous contribution by the C/N ratio during the last glacial-interglacial cycle. The major elements were also analyzed to examine the variation in terrigenous composition.

Contents, partition, and isotopic composition of sulphur in sediments from ODP Sites 680 and 686

We have determined (1) the abundance and isotopic composition of pyrite, monosulphide, elemental sulphur, organically bound sulphur, and dissolved sulphide; (2) the partition of ferric and ferrous iron; (3) the organic carbon contents of sediments recovered at two sites drilled on the Peru Margin during Leg 112 of the Ocean Drilling Program. Sediments at both sites are characterised by high levels of organically bound sulphur (OBS). OBS comprises up to 50% of total sedimentary sulphur and up to 1% of bulk sediment. The weight ratio of S to C in organic matter varies from 0.03 to 0.15 (mean = 0.10). Such ratios are like those measured in lithologically similar, but more deeply buried petroleum source rocks of the Monterey and Sisquoc formations in California. The sulphur content of organic matter is not limited by the availability of porewater sulphide. Isotopic data suggest that sulphur is incorporated into organic matter within a metre of the sediment surface, at least partly by reaction with polysulphides. Most inorganic Sulphur occurs as pyrite. Pyrite formation occurred within surface sediments and was limited by the availability of reactive iron. But despite highly reducing sulphidic conditions, only 35-65% of the total iron was converted to sulphide; 10-30% of the total iron still occurs as Fe(III). In surface sediments, the isotopic composition of pyrite is similar to that of both iron monosulphide and dissolved sulphide. Either pyrite, like monosulphide, formed by direct reaction between dissolved sulphide and detrital iron, and/or the sulphur species responsible for converting FeS to FeS2 is isotopically similar to dissolved sulphide. Likely stoichiometries for the reaction between ferric iron and excess sulphide imply a maximum resulting FeS2:FeS ratio of 1:1. Where pyrite dominates the pool of iron sulphides, at least some pyrite must have formed by reaction between monosulphide and elemental sulphur and/or polysulphide. Elemental sulphur (S°) is most abundant in surface sediments and probably formed by oxidation of sulphide diffusing across the sediment-water interface. In surface sediments, S° is isotopically heavier than dissolved sulphide, FeS and FeS2 and is unlikely to have been involved in the conversion of FeS to FeS2. Polysulphides are thus implicated as the link between FeS and FeS2.

Sulphur isotope analyses in the southern ocean and the central Dronning Maud Land, East Antarctica

Sulphur isotope analyses are an important tool for the study of the natural sulphur cycle. On the northern hemisphere such studies of the atmospheric part of the cycle are practically impossible due to the high emission rate of anthropogenic sulphur. Merely in remote areas of the world such as the Antarctic 34S analyses can be used to identify the various sulphur sources (sea spray, biogenic und volcanic sources). We report here results of 34S measurements on sulphates from recent atmospheric precipitations (snow), lake waters, and salt efflorescences sampled in the Schirmacher Oasis and the Gruber Mountains, central Dronning Maud Land, East Antarctica. By plotting the delta 34S of precipitation versus % sea-spray sulphate the isotopic composition of the excess sulphate (which is probably of marine-biogenic origin) is extrapolated to be +4 per mil. Lake water sulphate and atmospheric precipitations have a comparable sulphur isotope composition (about +5 per mil). The analyzed secondary sulphates from the salt efflorescences, mainly gypsum and a few water-soluble sulphatcs (hexahydrite, epsomite, burkeite. and pickeringite), vary in their isotopic composition between about -12 and +8 per mil. This wide scatter is probably due to chemical weathering of primary sulphides having different delta 34S values in the substratum.

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.