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.

Hydrocarbon gases in Tertiary and Quaternary sediments offshore Peru

Hydrocarbon gases (methane, ethane, propane, isobutane, n-butane, ethene, and propene) are present in Tertiary and Quaternary shelf, upper-slope, and lower-slope deposits of the Peruvian continental margin. Methane dominates the composition of the hydrocarbon gas at all 10 sites examined during Ocean Drilling Program (ODP) Leg 112. Generation of methane is regulated by the amount of sulfate in pore water. Wherever sulfate concentrations approach or equal zero, methane concentrations increase rapidly, reaching values near 100,000 µL/L of wet sediment at eight of the 10 sites. Methane at all 10 sites results from methanogenesis, which is inhibited where sulfate is present and microbial reduction of sulfate occurs. Hydrocarbon gases heavier than methane also are present, but at much lower concentrations than methane. These hydrocarbons are thought to result from early thermal and microbial diagenesis, based on relative gas compositions and trends of concentrations with depth. With few exceptions, the results obtained in the shipboard and shore-based laboratories are comparable for methane and ethane in sediments of Leg 112. Reanalyses of canned sediments from ODP Leg 104 and from Deep Sea Drilling Project (DSDP) Legs 76 and 84 show that gas samples can be stored for as long as 8 yr, but the amounts of individual hydrocarbon gases retained vary. Nevertheless, the trends of the data sets with depth are similar for fresh and stored samples.

Characterization of sorbed volatile hydrocarbons from the Peru margin

Bacterial and thermogenic hydrocarbons are present in the sorbed-gas fraction of Peru margin sediments. At Ocean Drilling Program (ODP) Sites 681, 682, 684, and 686, bacterial gases are restricted to the early diagenetic zones, where dissolved sulfate has been exhausted and methanogenesis occurs. Methane migrating into the sulfate zone at Sites 681, 684, 686, and possibly 682, has been consumed anaerobically by methanotrophs, maintaining the low concentrations and causing an isotope shift in d13C(CH4) to more positive values. Significant amounts of C2+ hydrocarbons occur at the shelf Sites 680/681, 684, and 686/687, where these hydrocarbons may be associated with hypersaline fluids. There is evidence at Site 679 that sorbed C2+ hydrocarbons may also have been transported by hypersaline fluids. This characteristic C2+ hydrocarbon signature in the sorbed-gas fractions of sediments at Site 679 is not reflected in data obtained using the conventional "free-," "canned-," or "headspace-gas" procedures. The molecular and isotope compositions of the sorbed-gas fraction indicate that this gas may have a thermogenic source and may have spilled over with the hypersaline fluids from the Salaverry Basin into the Lima Basin. These traces of thermogenic hydrocarbon gases are over-mature (about 1.5% Ro) and are discordant with the less-mature sediments in which they are found. This observation supports the migration of these hydrocarbons, possibly from continental sources. Sorbed-gas analyses may provide important geochemical information, in addition to that of the free-gases. Sorbed-gases are less sensitive to activities in the interstitial fluids, such as methanogenesis and methanotrophy, and may faithfully record the migration of hydrocarbons associated with hypersaline fluids.

Quaternary through early Eocene benthic foraminifera off Peru

Stratigraphic assemblages of Quaternary through early Eocene benthic foraminifers were recovered among 10 Peru margin drill sites. Various hiatuses and intervals barren in foraminifers characterize the sections, but numerous samples contain abundant, well-preserved benthic foraminifers. Bathymetry of the extant species and California-based estimates of the paleobathymetry of the extinct species permit recognition of Quaternary sea-level fluctuations between shelf and upper bathyal depths that produced vertical migrations of oxygenated and low-oxygen habitats at the six shallow sites. Assemblages from lower-slope sites at about 9° and 11°S indicate a general subsidence of the continental margin from shelf or upper bathyal depths in Eocene time to the present lower bathyal depths. Data from 11°S suggest a major part of this subsidence occurred in late Oligocene to early Miocene time. Downslope-transported shelf specimens, particularly the small biserial species, Bolivina costata and B. vaughani, are major contributors to these lower bathyal assemblages from the middle Miocene through Quaternary time.

Volcanic ash from the Peru continental margin

During Leg 112 off Peru, volcanic material was recorded from middle Eocene to Holocene time. The petrographical and chemical composition of tephra is consistent with an origin from the Andean volcanic arc. The amount and thickness of ash layers provide valuable evidence for explosive volcanic episodicity. The first indication of volcanism was found in mid-Eocene sediments. Three volcanic pulses date from Miocene time. Two intense episodes took place in upper Pliocene and from Pleistocene to Holocene time. Pliocene-Pleistocene tephra are restricted to the southern upper-slope and shelf sites, indicating a removal of the volcanic arc and the extinction of the northern Peru volcanoes. The Cenozoic tectonic phases of the Andean margin may be correlated with the Leg 112 volcanic records. The explosive supply of evolved magmatic products succeeded the Incaic and Quechua tectonic phases. Acidic glasses are related to both andesitic and shoshonitic series. The calc-alkaline factor (CAF) of these glasses exhibited moderate magmatic variations during middle and late Miocene time. A dramatic change occurred during the Pliocene-Pleistocene, reflected in a strong CAF increase and the appearance of potassium-rich evolved shoshonitic glasses. This took place when the Nazca Ridge subduction began. This change in the magma genesis and/or differentiation conditions is probably related to thickening of the upper continental plate and to a new configuration of the Benioff Zone.

Temperature and d18O measurements from different ODP Sites at the shelf and upper slope of the Peru Margin

The first experimentally determined temperature dependent oxygen-18 fractionation factor between dolomite and water at low temperatures [Vasconcelos et al. 1995 doi:10.1130/G20992.1] allows now the precise calculation of temperatures during early diagenetic dolomite precipitation. We use d18O values of early diagenetic dolomite beds sampled during ODP Legs 112 and 201 on the Peru continental margin (Sites 1227, 1228 and 1229) [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x] to calculate paleo-porewater temperatures at the time of dolomite precipitation. We assumed unaltered seawater d18O values in the porewater, which is supported by d18O values of the modern porewater presented in this study. The dolomite layers in the Pleistocene part of the sedimentary columns showed oxygen isotope temperatures up to 5 °C lower than today. Since Sites 1228 and 1229 are located at 150 and 250 m below sealevel, respectively, their paleo-porewater temperatures would be influenced by considerably colder surface water during glacial sealevel lowstands. Thus, Pleistocene dolomite layers in the Peru Continental margin probably formed during glacial times. This finding is consistent with a model for dolomite precipitation in the Peru Margin recently discussed by Meister et al. [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x], where dolomite forms episodically at the sulphate methane interface. It was shown that the sulphate methane interface migrates upwards and downwards within the sedimentary column, but dolomite layers may only form when the sulphate-methane interface stays at a fixed depth for a sufficient amount of time. We hypothesize that the sulphate-methane interface persists within TOC-rich interglacial sediments, while this zone is buried by TOC-poor sedimentation during glacial times. Thus, the presented oxygen isotope data provide additional information on the timing of early diagenetic dolomite formation and a possible link between episodicity in dolomite formation and sealevel variations. A similar link between early diagenesis and oceanography may also explain spacing of dolomite layers in a Milankovitch type pattern observed in the geological record, such as in the Miocene Monterey Formation.

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.