Sulphur contents and partition of iron in ODP Leg 112 sediments

Porewaters in site 680 Peru Margin sediments contain dissolved sulfide over a depth of approximately 70 m which, at a sedimentation rate of 0.005 cm/yr, gives a sediment exposure time to dissolved sulfide of about 1.4 Myr. Reactions with dissolved sulfide cause the site 680 sediments to show a progressive decrease in a poorly-reactive silicate iron fraction, defined as the difference between iron extracted by dithionite (FeD) at room temperature and that extracted by boiling concentrated HCl (FeH), normalised to the total iron content (FeT). Straight line plots are obtained for ln[(FeH - FeD)/FeT] against time of burial, from which a first order rate constant of 0.29 1/Myr (equivalent to a half-life of 2.4 Myr) can be derived for the sulfidation of this silicate iron. Comparable half-lives are also found for the same poorly-reactive iron fraction in the nearby site 681 and 684 sediments. This silicate Fe fraction comprises 0.8-1.0% Fe, only 30-60% of which reacts even with 1.5-3 million years exposure to dissolved sulfide. Diagenetic models based on porewater concentrations of sulfate and sulfide, and solid phase iron contents, at site 680 are consistent in indicating that this poorly-reactive iron fraction is only sulfidized on a million year time scale. Silicate iron not extracted by HCl can be regarded as unreactive towards dissolved sulfide on the time scales encountered in marine sediments.

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.

Grain properties of rock fragments from shelf bottom sediments of the Sea of Okhotsk

Grain size, shape and roundness of rock fragments, texture, composition of bottom sediments from the Sea of Okhotsk are under study. These data are compared with parameters of modern lithodynamic conditions of the sea and genetic types of deposits are identified. These criteria are used for partition of Holocene and Upper Pleistocene sediment series and for identifying conditions of their formation. Dependence of structure of different genetic types of deposits on intensity of hydrodynamic processes, of terrigenous contribution, and on direction consedimentational tectonic movements is under consideration.

Pigments at time series station DYNAPROC

Phytoplankton taxonomic pigments and primary production were measured at the JGOFS-France time-series station DYFAMED in the northwestern Mediterranean Sea during May 1995 to investigate changes in phytoplankton composition and the biogeochemical implications (DYNAPROC experiment). The study period covered the transitional situation from late spring bloom to pre-oligotrophic. The late spring bloom situation, occurring at the beginning of the study, revealed high chlorophyll a concentrations (maximum 3 mg/m**3 at 30 m) and high primary production (maximum 497 mg C/m**2/ 14 h). At the end of the experiment, the trophic regime shifted towards pre-oligotrophic and was characterized by lower chlorophyll a concentrations (<1 mg/m**3), although primary production still remained high (659 mg C/m**2/ 14 h). At termination of the spring bloom, the phytoplankton community was composed of chromophyte nanoflagellates (38±4%), diatoms (29±2%), cryptophytes (12±1%) and cyanobacteria (8±1%). During the transition to the pre-oligotrophic period, the contribution of small cells increased (e.g. cyanobacteria 18±2%, green flagellates 5±1%). Vertical profiles of pigments revealed a partition of the phytoplankton groups: cyanobacteria were most abundant in the surface layer, nanoflagellates containing 19'-HF+19'BF at the depth of chlorophyll maximum, whereas diatoms were located below the chlorophyll maximum. At termination of the spring bloom, a wind event induced vertical transport of nutrients into the euphotic layer. Phytoplankton groups responded differently to the event: initially, diatom concentrations increased (for 24 h) then rapidly decreased. In contrast, all others groups decreased just after the event. The long-term effect was a decrease of biomass of dominant groups (diatoms and chromophyte nanoflagellates), which accelerated the community succession and hence contributed to the oligotrophic transition.

Plant Functional Type (PFT) map over Siberia derived from GlobCover 2005 dataset, link to dataset in NetCDF format

High-latitude ecosystems play an important role in the global carbon cycle and in regulating the climate system and are presently undergoing rapid environmental change. Accurate land cover data sets are required to both document these changes as well as to provide land-surface information for benchmarking and initializing Earth system models. Earth system models also require specific land cover classification systems based on plant functional types (PFTs), rather than species or ecosystems, and so post-processing of existing land cover data is often required. This study compares over Siberia, multiple land cover data sets against one another and with auxiliary data to identify key uncertainties that contribute to variability in PFT classifications that would introduce errors in Earth system modeling. Land cover classification systems from GLC 2000, GlobCover 2005 and 2009, and MODIS collections 5 and 5.1 are first aggregated to a common legend, and then compared to high-resolution land cover classification systems, vegetation continuous fields (MODIS VCFs) and satellite-derived tree heights (to discriminate against sparse, shrub, and forest vegetation). The GlobCover data set, with a lower threshold for tree cover and taller tree heights and a better spatial resolution, tends to have better distributions of tree cover compared to high-resolution data. It has therefore been chosen to build new PFT maps for the ORCHIDEE land surface model at 1 km scale. Compared to the original PFT data set, the new PFT maps based on GlobCover 2005 and an updated cross-walking approach mainly differ in the characterization of forests and degree of tree cover. The partition of grasslands and bare soils now appears more realistic compared with ground truth data. This new vegetation map provides a framework for further development of new PFTs in the ORCHIDEE model like shrubs, lichens and mosses, to represent the water and carbon cycles in northern latitudes better. Updated land cover data sets are critical for improving and maintaining the relevance of Earth system models for assessing climate and human impacts on biogeochemistry and biophysics.