(Table 1) Sample locations, Hf and Nd isotopic compositions and concentrations of Atlantic seawater samples with hydrographic details

The first full water column hafnium isotopic compositions of Atlantic seawater have been obtained at seven locations from the Labrador Sea to the Drake Passage. Despite subpicomolar concentrations in seawater, a precision of the Hf isotopic measurements of <0.7 epsilon-Hf units was achieved. An overall epsilon-Hf range between -3.1 in the Labrador Sea and +4.4 in Antarctic bottom water was determined, the distribution of which broadly reflects continental weathering inputs. Within particular water column profiles, significant differences of up to 4 epsilon-Hf units occur. Combined with Nd isotope data of the same samples, it is evident that the Hf isotopic composition of seawater is too radiogenic for a given Nd isotopic composition and that the largest difference between expected and measured Hf isotopic compositions in seawater occurs near the oldest continental crust in the Labrador Sea. This corroborates the previous proposition, which was mainly based on ferromanganese crust data, that the Hf isotopic composition of seawater is controlled by incongruent weathering of continental crust and possibly, to some extent, by hydrothermal contributions. Hafnium concentrations in the ocean do not increase along the deep ocean conveyer indicating an oceanic residence time of only a few hundred years, which is significantly shorter than previously assumed. The Hf isotopic composition of past seawater can therefore serve as a proxy for short distance, basin scale mixing processes and the regime and intensity of nearby continental weathering processes.

Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

Carbonate and Thorium concentrations of South Atlantic sediments

Rates of sedimentation of pelagic sediments in the South Atlantic have been determined using the ionium/thorium methodology. Values of the order of several millimeters per thousand years for sediments were found in the deposits in the valleys of the mid-Atlantic ridge. The equatorial deposits showed higher rates of accumulation than the corresponding deposits at higher latitudes, probably reflecting the added influx of materials to the sea floor from tropical rivers through the equatorial current systems. The deposits in the ridge valleys showed marked changes in sedimentation rates at about 115,000 years ago, at which time the present rates changed from higher to lower values. The ridge sediments were composed primarily of continentally derived materials, and there were no indications of solid phases being derived from the weathering of the ridge itself or from volcanic activity. The equatorial samples have mineral assemblages which are distinctly different from those in deposits at higher latitudes and which probably are indicative of contributions of materials from tropical weathering processes.

Strontium isotope analysis of seawater and at a mixture of planktic foraminifera during the Paleocene and Early Eocene from different holes of ODP Leg 2008

We refined the strontium isotope seawater curve for the Paleocene and early Eocene by analysis of samples recovered from the Walvis Ridge during Ocean Drilling Project (ODP) Leg 208. The highest 87Sr/86Sr values occurred in the earliest Paleocene at 65 Ma and generally decreased throughout the Paleocene, reaching minimum values between 53 and 51 Ma in the early Eocene before beginning to increase again at 50 Ma. A plausible explanation for the 87Sr/86Sr decrease between 65 and 51 Ma is increased rates of hydrothermal activity and/or the eruption and weathering of large igneous provinces (e.g., Deccan Traps and North Atlantic). Strontium isotope variations closely parallel sea level and benthic d18O changes during the late Paleocene and early Eocene, supporting previous studies linking tectonic reorganization and increased volcanism to high sea level, high CO2, and warm global temperatures.

Concentrations of brominated and chlorinated contaminants in adipose tissue of polar bears (Ursus maritimus) between 1991-2007

Adipose tissue was sampled from the western Hudson Bay (WHB) subpopulation of polar bears at intervals from 1991 to 2007 to examine temporal trends of PCB and OCP levels both on an individual and sum-contaminant basis. We also determined levels and temporal trends of emerging polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), polybrominated biphenyls (PBBs) and other current-use brominated flame retardants. Over the 17-year period, sum DDT (and p,p'-DDE, p,p'-DDD, p,p'-DDT) decreased (-8.4%/year); alpha-hexachlorocyclohexane (alpha-HCH) decreased (-11%/year); beta-HCH increased ( + 8.3%/year); and sum PCB and sum chlordane (CHL), both contaminants at highest concentrations in all years (>1 ppm), showed no distinct trends even when compared to previous data for this subpopulation dating back to 1968. Some of the less persistent PCB congeners decreased significantly (-1.6%/year to -6.3%/year), whereas CB153 levels tended to increase (+ 3.3%/year). Parent CHLs (c-nonachlor, t-nonachlor) declined, whereas non-monotonic trends were detected for metabolites (heptachlor epoxide, oxychlordane). sum chlorobenzene, octachlorostyrene, sum mirex, sum MeSO2-PCB and dieldrin did not significantly change. Increasing sum PBDE levels (+13%/year) matched increases in the four consistently detected congeners, BDE47, BDE99, BDE100 and BDE153. Although no trend was observed, total-(alpha)-HBCD was only detected post-2000. Levels of the highest concentration brominated contaminant, BB153, showed no temporal change. As long-term ecosystem changes affecting contaminant levels may also affect contaminant patterns, we examined the influence of year (i.e., aging or "weathering" of the contaminant pattern), dietary tracers (carbon stable isotope ratios, fatty acid patterns) and biological (age/sex) group on congener/metabolite profiles. Patterns of PCBs, CHLs and PBDEs were correlated with dietary tracers and biological group, but only PCB and CHL patterns were correlated with year. DDT patterns were not associated with any explanatory variables, possibly related to local DDT sources. Contaminant pattern trends may be useful in distinguishing the possible role of ecological/diet changes on contaminant burdens from expected dynamics due to atmospheric sources and weathering.

Sedimentology and geochemistry of surface sediments from the Pagassitikos Gulf

Volos city and its port are situated in the northern part of Pagassitikos Gulf, a shallow, semi-enclosed marine area in central Greece. A wastewater treatment plant (WWTP) and pipeline operate in the same area. Muddy sediments with low carbonate contents cover most of the seabed, except for the Volos embayment and the western part of the gulf where sandy carbonates prevail. Bulk organic carbon contents and the organic carbon contents of the clay fractions are high in the vicinity of Volos embayment. High element (Pb, Cu, and Zn) contents and Igeo (geoaccumulation index) values were found for the clay fractions in the northern part of Pagassitikos Gulf. This enrichment is attributed to the discharge of raw domestic and industrial effluents of Volos city and port before the WWTP was installed. The dispersal of pollutants is essentially controlled by diffusion from point sources (city, port and WWTP) and is limited to Volos Bay. Relatively high Mn levels are ascribed to diagenetic formation of manganese carbonates (authigenic phase), whereas Cr and Ni are elevated due to weathering of ultrabasic formations on land.

Clay mineralogy of South Atlantic surface sediments

Surface samples, mostly from abyssal sediments of the South Atlantic, from parts of the equatorial Atlantic, and of the Antarctic Ocean, were investigated for clay content and clay mineral composition. Maps of relative clay mineral content were compiled, which improve previous maps by showing more details, especially at high latitudes. Large-scale relations regarding the origin and transport paths of detrital clay are revealed. High smectite concentrations are observed in abyssal regions, primarily derived from southernmost South America and from minor sources in Southwest Africa. Near submarine volcanoes of the Antarctic Ocean (South Sandwich, Bouvet Island) smectite contents exhibit distinct maxima, which is ascribed to the weathering of altered basalts and volcanic glasses. The illite distribution can be subdivided into five major zones including two maxima revealing both South African and Antarctic sources. A particularly high amount of Mg- and Fe-rich illites are observed close to East Antarctica. They are derived from biotite-bearing crystalline rocks and transported to the west by the East Antarctic Coastal Current. Chiorite and well-crystallized dioctaedral illite are typical minerals enriched within the Subantarctic and Polarfrontal-Zone but of minor importance off East Antarctica. Kaolinite dominates the clay mineral assemblage at low latitudes, where the continental source rocks (West Africa, Brazil) are mainly affected by intensive chemical weathering. Surprisingly, a slight increase of kaolinite is observed in the Enderby Basin and near the Filchner-Ronne Ice shelf. The investigated area can be subdivided into ten, large-scale clay facies zones with characteristic possible source regions and transport paths. Clay mineral assemblages of the largest part of the South Atlantic, especially of the western basins are dominated by chlorite and illite derived from the Antarctic Peninsula and southernmost South America and supported by advection within the Circumantarctic Deep Water flow. In contrast, the East Antarctic provinces are relatively small. Assemblages of the eastern basins north of 30°S are strongly influenced by African sources, controlled by weathering regimes on land and by a complex interaction of wind, river and deep ocean transport. The strong gradient in clay mineral composition at the Brazilian slope indicate a relatively low contribution of tropically derived assemblages to the western basins.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.

(Table 1) Water chemistry of groundwater and snow samples from three sites in Ontario, Canada

Snow samples collected from hand-dug pits at two sites in Simcoe County, Ontario, Canada were analysed for major and trace elements using the clean lab methods established for polar ice. Potentially toxic, chalcophile elements are highly enriched in snow, relative to their natural abundance in crustal rocks, with enrichment factor (EF) values (calculated using Sc) in the range 107 to 1081 for Ag, As, Bi, Cd, Cu, Mo, Pb, Sb, Te, and Zn. Relative to M/Sc ratios in snow, water samples collected at two artesian flows in this area are significantly depleted in Ag, Al, Be, Bi, Cd, Cr, Cu, Ni, Pb, Sb, Tl, V, and Zn at both sites, and in Co, Th and Tl at one of the sites. The removal from the waters of these elements is presumably due to such processes as physical retention (filtration) of metal-bearing atmospheric aerosols by organic and mineral soil components as well as adsorption and surface complexation of ionic species onto organic, metal oxyhydroxide and clay mineral surfaces. In the case of Pb, the removal processes are so effective that apparently ''natural'' ratios of Pb to Sc are found in the groundwaters. Tritium measurements show that the groundwater at one of the sites is modern (ie not more than 30 years old) meaning that the inputs of Pb and other trace elements to the groundwaters may originally have been much higher than they are today; the M/Sc ratios measured in the groundwaters today, therefore, represent a conservative estimate of the extent of metal removal along the flow path. Lithogenic elements significantly enriched in the groundwaters at both sites include Ba, Ca, Li, Mg, Mn, Na, Rb, S, Si, Sr, and Ti. The abundance of these elements can largely be explained in terms of weathering of the dominant silicate (plagioclase, potassium feldspar, amphibole and biotite) and carbonate minerals (calcite, dolomite and ankerite) in the soils and sediments of the watershed. Arsenic, Mo, Te, and especially U are also highly enriched in the groundwaters, due to chemical weathering: these could easily be explained if there are small amounts of sulfides (As, Mo, Te) and apatite (U) in the soils of the source area. Elements neither significantly enriched nor depleted at both sites include Fe, Ga, Ge, and P.

Characteristics of light and dark alternations in Owen Ridge sediments (Appendix)

Clay mineral relative abundances in approximately 450 samples from cores recovered during ODP Leg 117 in the Arabian Sea have been used to examine the paleoclimatic, paleoenvironmental, and tectonic histories of the Indus Fan, Owen Ridge, Oman margin, and adjacent continental source regions. Geographic variations in the relative abundances of minerals and correlations with depositional processes support previous interpretations that smectite has been supplied from weathering of the Deccan Traps; illite and chlorite have been supplied either from the Himalayas via marine transport or from the Iran-Makran region by winds; and palygorskite has been supplied from the Arabian peninsula and Somalia by winds. Pleistocene sediments of the Indus Fan record two modes of deposition: turbidites supplied from the Indus drainage and dominated by illite and chlorite, and pelagic carbonates containing smectites and wind-transported palygorskite. Local and regional causes for shifts between these depositional processes cannot be demonstrated conclusively with the data available, but sea-level fluctuations probably exerted a significant control on the rate of turbidite influx. Lower Miocene sediments on the Owen Ridge are also turbidites supplied by the Indus drainage; in the middle Miocene, a shift to pelagic carbonates records the uplift of the Owen Ridge, and is accompanied by the increased relative importance of wind-transported palygorskite. Associations of palygorskite and biosiliceous components in middle to upper Miocene sediments are interpreted to record vigorous monsoonal circulation and accompanying upwelling-produced biological productivity. Mineralogic and geochemical data indicate that light/dark color alternations in upper Miocene sediments on the Owen Ridge record climatic fluctuations, but the climatic significance of similar alternations in Pliocene-Pleistocene sediments is unclear. Palygorskite is the dominant clay on the Oman margin, reflecting proximity to its source areas. On the Oman margin, clay mineral relative abundances are most variable at structurally complex sites, indicating that local depositional settings have been influenced by their tectonic histories since the Miocene.

Trace element concentrations and Li isotope composition in DSDP and ODP sediments from island arcs

We have studied the sedimentary and basaltic inputs of lithium to subduction zones. Various sediments from DSDP and ODP drill cores in front of the Mariana, South Sandwich, Banda, East Sunda and Lesser Antilles island arcs have been analysed and show highly variable Li contents and d7Li values. The sediment piles in front of the Mariana and South Sandwich arcs largely consist of pelagic sediments (clays and oozes). The pelagic clays have high Li contents (up to 57.3 ppm) and Li isotope compositions ranging from +1.3? to +4.1?. The oozes have lower Li contents (7.3-16 ppm) with d7Li values of the diatom oozes from the South Sandwich lower (+2.8? to +3.2?) than those of the radiolarian oozes from the Mariana arc (+8.1? to +14.5?). Mariana sediment also contains a significant portion of volcanogenic material, which is characterised by a moderate Li content (14 ppm) and a relatively heavy isotope composition (+6.4?). Sediments from the Banda and Lesser Antilles contain considerable amounts of continental detritus, and have high Li contents (up to 74.3 ppm) and low d7Li values (around 0?), caused by weathering of continental bedrock. East Sunda sediments largely consist of calcareous oozes. These carbonate sediments display intermediate to high Li contents (2.4-41.9 ppm) and highly variable d7Li values (-1.6? to +12.8?). Basaltic oceanic crust samples from worldwide DSDP and ODP drill cores are characterised by enrichment of Li compared to fresh MORB (6.6-33.1 vs. 3.6-7.5 ppm, respectively), and show a large range in Li isotope compositions (+1.7? to +11.8?). The elemental and isotopic enrichment of Li in altered basalts is due to the uptake of isotopically heavy seawater Li during weathering. However, old oceanic crust samples from Sites 417/418 exhibit lighter Li isotope compositions compared to young basaltic crust samples from Sites 332B and 504B. This lighter Li isotope signature in old crust is unexpected and further research is needed to explore this issue.