Isotopic signatures and mercury content of arctic char and their prey, and water chemistry of 18 arctic Canadian lakes

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to d13C and d15N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The d13C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 ± 1.1 to 64.3 ± 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.

Geochemistry of Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian-Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, d13Corg values lie mostly between -30 per mil and -27 per mil, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low d13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian-Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.

Geochemical composition of surface sediments in the Trondheimsfjord, central Norway

High sedimentation rates in fjords provide excellent possibilities for high resolution sedimentary and geochemical records over the Holocene. As a baseline for an improved interpretation of geochemical data from fjord sediment cores, this study aims to investigate the inorganic/organic geochemistry of surface sediments and to identify geochemical proxies for terrestrial input and river discharge in the Trondheimsfjord, central Norway. Sixty evenly distributed surface sediment samples were analysed for their elemental composition, total organic carbon (Corg), nitrogen (Norg) and organic carbon stable isotopes (d13Corg), bulk mineral composition and grain size distribution. Our results indicate carbonate marine productivity to be the main CaCO3 source. Also, a strong decreasing gradient of marine-derived organic matter from the entrance towards the fjord inner part is consistent with modern primary production data. We show that the origin of the organic matter as well as the distribution of CaCO3 in Trondheimsfjord sediments can be used as a proxy for the variable inflow of Atlantic water and changes in river runoff. Furthermore, the comparison of grain size independent Al-based trace element ratios with geochemical analysis from terrigenous sediments and bedrocks provides evidence that the distribution of K/Al, Ni/Al and K/Ni in the fjord sediments reflect regional sources of K and Ni in the northern and southern drainage basin of the Trondheimsfjord. Applying these findings to temporally well-constrained sediment records will provide important insights into both the palaeoenvironmental changes of the hinterland and the palaeoceanographic modifications in the Norwegian Sea as response to rapid climate changes and associated feedback mechanisms.

TOC, carbonate, opal composition and trace element concentration from ODP Holes 175-1082A and 175-1084A

Distinctive light-dark color cycles in sediment beneath the Benguela Current Upwelling System indicate repetitive alternations in sediment delivery and deposition. Geochemical proxies for paleoproductivity and for depositional conditions were employed to investigate the paleoceanographic processes involved in creating these cycles in three mid-Pleistocene intervals from ODP Sites 1082 and 1084. Concentrations of total organic carbon (TOC) vary between 3.5 and 17.1%. Concentrations of CaCO3 vary inversely to TOC and Al, which suggests that both carbonate dissolution and terrigenous dilution contribute to the light-dark cycles. Opal concentrations are independent of both TOC and CaCO3, therefore eliminating diatom production and lateral transport of shelf material as causes of the light-dark cycles. d13Corg and d15Ntot values do not vary across light-dark sediment intervals, implying that the extent of relative nutrient utilization did not change. The stable d15Ntot values represent a balanced change in nitrate supply and export production and therefore indicate that productivity was elevated during deposition of the TOC-rich layers. Parallel changes in concentrations of indicator trace elements and TOC imply that changes in organic matter delivery influenced geochemical processes on the seafloor by controlling consumption of pore water oxygen. Cu, Ni, and Zn are enriched in the darker sediment as a consequence of greater organic matter delivery. Redox-sensitive metals vary due to loss (Mn and Ba) or enrichment (Mo) under reducing conditions created by TOC oxidation. Organic matter delivery impacts subsequent geochemical changes such as carbonate dissolution, sulfate reduction and the concentration of metals. Thus, export production is considered ultimately responsible for the generation of the color cycles.

Organic geochemistry of Lower Cretaceous sediments from the northwetsern Pacific guyits

Organic geochemical data of Lower Cretaceous shallow water sediments from two sites (865 and 866) drilled during ODP leg 143 are presented. The organic matter is mainly terrestrial at the bottom of the sedimentary column at site 865, whereas algal and/or bacterial organic matter is dominant at site 866. This is the first evidence of shallow water deposition of organic matter during the Early Cretaceous in the Northwestern Pacific. The lower Aptian organic carbon-rich layers from the shallow water sediments of site 866 are geochemically similar to coeval mid-water sediments of site 463.

Strontium and oxygen isotope data for DSDP Hole 44-390A and ODP Leg 171 holes

Differences in regional responses to climate fluctuations are well documented on short time scales (e.g., El Niño-Southern Oscillation), but with the exception of latitudinal temperature gradients, regional patterns are seldom considered in discussions of ancient greenhouse climates. Contrary to the expectation of global warming or global cooling implicit in most treatments of climate evolution over millions of years, this paper shows that the North Atlantic warmed by as much as 6°C (1.5% decrease in d18O values of planktic foraminifera) during the Maastrichtian global cooling interval. We suggest that warming was the result of the importation of heat from the South Atlantic. Decreasing North Atlantic d18O values are also associated with increasing gradients in planktic d13C values, suggesting increasing surface-water stratification and a correlated strengthening of the North Atlantic Polar Front. If correct, this conclusion predicts arctic cooling during the late Maastrichtian. Beyond implications for the Maastrichtian, these data demonstrate that climate does not behave as if there is a simple global thermostat, even on geologic time scales.

Chemistry of organic matter of glacial and Cretaceous sediments from the Prydz Bay

Organic matter in Miocene glacial sediments in Hole 739C on the Antarctic Shelf represents erosional recycled continental material. Various indications of maturity in bulk organic matter, kerogens, and extracts imply that an exposed section of mature organic carbon-rich material was present during the Miocene. Based on biomarker, n-alkane, and kerogen analysis, a massive diamictite of early Eocene/Oligocene age at Hole 739C contains immature organic matter. Visual and pyrolysis analyses of the kerogens suggest a predominance of terrestrial organic matter in all samples from Hole 739C. A reversal of thermal maturities, i.e., more-mature overlying less-mature sections, may be related to redeposition generated from glacial erosion. Siliciclastic fluviatile sediments of Lower Cretaceous age from Hole 741A were analyzed. The organic matter from this hole contains immature aliphatic and aromatic biomarkers as well as a suite of odd carbon number-dominated nalkanes. Visual examination and pyrolysis analysis of the kerogen suggests that predominantly immature terrestrial organic matter is present at Hole 741A. The similarities between Hole 739C Unit V and Hole 741A suggest that the source of the organic matter in the glacial sediments in Unit V at Hole 739C could be Cretaceous in age and similar to sediments sampled at Hole 741A in Prydz Bay.

Stable isotope and Mg/Ca ratios of Paleogene benthic foraminifera in the western North Atlantic

Global cooling and the development of continental-scale Antarctic glaciation occurred in the late middle Eocene to early Oligocene (~38 to 28 million years ago), accompanied by deep-ocean reorganization attributed to gradual Antarctic Circumpolar Current (ACC) development. Our benthic foraminiferal stable isotope comparisons show that a large d13C offset developed between mid-depth (~600 meters) and deep (>1000 meters) western North Atlantic waters in the early Oligocene, indicating the development of intermediate-depth d13C and O2 minima closely linked in the modern ocean to northward incursion of Antarctic Intermediate Water. At the same time, the ocean's coldest waters became restricted to south of the ACC, probably forming a bottom-ocean layer, as in the modern ocean. We show that the modern four-layer ocean structure (surface, intermediate, deep, and bottom waters) developed during the early Oligocene as a consequence of the ACC.

Radiocarbon ages of sediment core PG1414-2 from Beall Lake, Windmill Islands

A mid-Holocene climate optimum is inferred from a palaeosalinity reconstruction of a closed saline lake (Beall Lake) from the Windmill Islands, East Antarctica using an expanded diatom salinity weighted averaging (WA) regression and calibration model. The addition of 14 lakes and ponds from the Windmill Islands, East Antarctica, to an existing weighted averaging regression and calibration palaeosalinity model of 33 lakes from the Vestfold Hills, East Antarctica expands the number of taxa and lakes and the range of salinity in the existing model and improves the model's predictive ability. This improved model was used to infer Holocene changes in lake water salinity in Beall Lake, Windmill Islands. Six changes in diatom-inferred salinity in Beall Lake are put into broad chronological context based on three radiocarbon dates: as the East Antarctic Ice Sheet (EAIS) retreated from the Windmill Islands during the early Holocene (~9000-8130 corr. yr BP), Beall Lake formed as a melt water-fed freshwater lake, which gradually became more saline as marine influence increased from ~8000 corr. yr BP. Between ~8000 and 4800 corr. yr BP, the diatom assemblage included planktonic marine taxa such as Chaetoceros spp. and cryophilic taxa such as Fragilariopsis cylindrus, which indicate favourable summer growth conditions. A mid-Holocene warm period produced a climate that was warmer and more humid with increased precipitation and snow accumulation. This is reflected in the Beall Lake core as a reduction in the salinity of the lake diatom assemblage from ~4800-4600 corr. yr BP. Holocene isostatic uplift rates in the Windmill Islands vary from 5-6 m/1000 yr. By applying this uplift rate, it is calculated that the bedrock would have risen above sea level by ~4000 yr BP. The Beall Lake core diatom assemblage from ~4600-2900 corr. yr BP includes both marine cryophilic and planktonic taxa together with freshwater benthic and planktonic lacustrine taxa. This mix of species indicates the emergence of the lake from the sea around ~4600 corr. yr BP. From ~2800 corr. yr BP, retreat of the ice margin led to increasing melt water inputs and associated freshening of the lake basin until ~1900 corr. yr BP. The lake basin had no oceanic influence by this time, allowing a terrestrial freshwater flora to establish and thrive for the next ~1000 yr. At ~1850 corr. yr BP, a sudden and rapid salinity change is evident in Beall Lake. A late Holocene warm period between 2000 and 1000 yr BP has been observed in ice core records from Law Dome (an ice cap abutting the Windmill Islands to the east and north). It is therefore inferred that, at ~1850 corr. yr BP, summer temperatures within the Beall Lake catchment area were much higher than present summer temperatures. The climate optimum identified in the Beall Lake core ~4800 yr BP confirms mid-Holocene warming of the Windmill Islands and suggests a synchronous mid-Holocene climate optimum occurred across coastal East Antarctica. In addition, the abrupt climate change inferred at ~1850 yr BP suggests that higher resolution sampling of sediment cores from coastal East Antarctic limnological oases will provide more evidence of rapid climate change events over coastal East Antarctica in future.

(Table 1) Mercury concentrations and carbon and nitrogen isotopic ratios in 14 marine species from West Greenland sampled between 2003-2004

Total mercury (THg), methylmercury (MeHg) and stable isotopes of nitrogen (d15N) and carbon (d13C) were measured in three invertebrate, five fish, three seabird and three marine mammal species of central West Greenland to investigate trophic transfer of mercury in this Arctic marine food web. The food web magnification factor (FWMF) estimated as the slope of the regression between the natural logarithm of THg or MeHg concentrations (mg/kg dw) and tissue d15N (per mil) was estimated to 0.183 (SE = 0.052) for THg and 0.339 (SE = 0.075) for MeHg. The FWMFs were not only comparable with those reported for other Arctic marine food webs but also with quite different food webs such as freshwater lakes in the sub-Arctic, East Africa and Papua New Guinea. This suggests similar mechanisms of mercury assimilation and isotopic (d15N) discrimination among a broad range of aquatic taxa and underlines the possibility of broad ecosystem comparisons using the combined contaminant and stable isotope approach.