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.

AMS C-14 ages of coretops collected on RRS Charles Darwin cruise CD159, July 2004, N. Atlantic, for the NERC RAPID programme

Material and data were collected at 41 sites in the subpolar North Atlantic Ocean between Scotland and Newfoundland, during the RRS CharlesDarwin CD159 cruise in July 2004 (McCave, 2005). Sites were selected to reflect the major inputs of water that becomes the North Atlantic Deep Water (NADW); the Iceland-Scotland Overflow Water (ISOW), the Denmark Strait Overflow Water (DSOW) and the Labrador Sea Water (LSW). Areas cored were the south Iceland Rise, SE Greenland slope/rise and Eirik Drift, and the Labrador margin. A total of 29 box cores, 19 piston cores, 6 kasten cores, 9 short gravity cores and 20 CTD casts as well as 28 surface water samples were collected during the cruise. Here we present sediment core-top sample ages. The cores were sampled at 1 or 0.5 cm intervals and we used the top 1 or 2 cm, depending on availability of foraminifera in the samples. Sediment samples were disaggregated on an end-over-end wheel, wet sieved at >63 um, and dry sieved to 63-150 and >150 um. Accelerator Mass Spectrometer (AMS) radiocarbon dating was done for each core top based on between 900-1600 monospecific planktonic foraminifera (Globigerina bulloides or Neogloboquadrina pachyderma (sinistral)). All dates were of modern or late Holocene age except site RAPID-08-5B (9806 ± 38 uncorrected 14C years BP) and site RAPID-14-10B (11543 ± 40 uncorrected 14C years BP). The >150 um fraction was split until approximately 300 foraminifera remained and counted for number of lithic grains, benthic foraminifera, planktonic foraminifera and foraminifera fragments. In all but the shallowest sample (Greenland rise, 761m water depth) benthic foraminifera constituted less than 2% of the total >150 um fraction of the sample.