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.

Sulfur geochemistry at ODP Site 112-680 and 112-686

We have measured the concentrations of (1) pore-water sulfide and (2) solid-phase pyrite, iron monosulfide (=acid volatile sulfide), elemental sulfur, and extractable and nonextractable organic ("kerogen") sulfur in sediments from Ocean Drilling Program (ODP) Sites 680 and 686. Pore-water sulfide defines classic "bell-shaped" profiles. Maximum concentrations of 6 to 12 mM occur where sulfate is exhausted, or is most depleted, at depths between 15 and 50 mbsf. Sulfide resulting from bacterial sulfate reduction reacts in three ways: (1) some is reoxidized to elemental sulfur in surface sediments; (2) some reacts with detrital iron minerals to form iron monosulfide and pyrite, primarily in the top meter or two of the sediment; and (3) some reacts with, and is incorporated into, kerogen. Incorporation of reduced sulfur into kerogen occurs over the top 15 m of the sediment at both Sites 680 and 686, after the main phase of pyrite formation. Up to 45% of the total sedimentary sulfur is organically bound, and concentrations of 12 wt% sulfur are reached in the kerogen. These values are like those measured in lithologically similar, but more deeply buried, sediments from the Monterey Formation.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.