Stable isotopes, PCBs and pesticide concentrations in zooplankton, seawater and POM from Kongsfjorden and Liefdefjorden, Svalbard

Differences in bioaccumulation of persistent organic pollutants (POPs) between fjords characterized by different water masses were investigated by comparing POP concentrations, patterns and bioaccumulation factors (BAFs) in seven species of zooplankton from Liefdefjorden (Arctic water mass) and Kongsfjorden (Atlantic water mass), Svalbard, Norway. No difference in concentrations and patterns of POPs was observed in seawater and POM; however higher concentrations and BAFs for certain POPs were found in species of zooplankton from Kongsfjorden. The same species were sampled in both fjords and the differences in concentrations of POPs and BAFs were most likely due to fjord specific characteristics, such as ice cover and timing of snow/glacier melt. These confounding factors make it difficult to conclude on water mass (Arctic vs. Atlantic) specific differences and further to extrapolate these results to possible climate change effects on accumulation of POPs in zooplankton. The present study suggests that zooplankton do biomagnify POPs, which is important for understanding contaminant uptake and flux in zooplankton, though consciousness regarding the method of evaluation is important.

Chemical composition of manganese micronodules from expedition VA-05/1 in the Pacific Ocean

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel "Valdivia" during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn K alpha X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source. The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise. Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.

Foraminifera Mg/Ca, test weight and XDX for sediment core WIND28K

A record of deep-sea calcite saturation (D[CO3**-2]), derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (~15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ~4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ~4°C colder in MIS 3 compared to the Holocene (8 ka B.P.).

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.

High-resolution pore-water and solid-phase analyses of sediment cores GeoB6520-3 (Hydrate Hole) and GeoB6521-2 (Worm Hole) of the northern Congo Fan

The geochemical cycling of barium was investigated in sediments of pockmarks of the northern Congo Fan, characterized by surface and subsurface gas hydrates, chemosynthetic fauna, and authigenic carbonates. Two gravity cores retrieved from the so-called Hydrate Hole and Worm Hole pockmarks were examined using high-resolution pore-water and solid-phase analyses. The results indicate that, although gas hydrates in the study area are stable with respect to pressure and temperature, they are and have been subject to dissolution due to methane-undersaturated pore waters. The process significantly driving dissolution is the anaerobic oxidation of methane (AOM) above the shallowest hydrate-bearing sediment layer. It is suggested that episodic seep events temporarily increase the upward flux of methane, and induce hydrate formation close to the sediment surface. AOM establishes at a sediment depth where the upward flux of methane from the uppermost hydrate layer counterbalances the downward flux of seawater sulfate. After seepage ceases, AOM continues to consume methane at the sulfate/methane transition (SMT) above the hydrates, thereby driving the progressive dissolution of the hydrates "from above". As a result the SMT migrates downward, leaving behind enrichments of authigenic barite and carbonates that typically precipitate at this biogeochemical reaction front. Calculation of the time needed to produce the observed solid-phase barium enrichments above the present-day depths of the SMT served to track the net downward migration of the SMT and to estimate the total time of hydrate dissolution in the recovered sediments. Methane fluxes were higher, and the SMT was located closer to the sediment surface in the past at both sites. Active seepage and hydrate formation are inferred to have occurred only a few thousands of years ago at the Hydrate Hole site. By contrast, AOM-driven hydrate dissolution as a consequence of an overall net decrease in upward methane flux seems to have persisted for a considerably longer time at the Worm Hole site, amounting to a few tens of thousands of years.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

(Table 1) Major element composition of core 5022-2CP, Laguna Potrok Aike, southern Patagonia

Total organic carbon, total inorganic carbon, biogenic silica content and total organic carbon/total nitrogen ratios of the Laguna Potrok Aike lacustrine sediment record are used to reconstruct the environmental history of south-east Patagonia during the past 51 ka in high resolution. High lake level conditions are assumed to have prevailed during the Last Glacial, as sediments are carbonate-free. Increased runoff linked to permafrost and reduced evaporation due to colder temperatures and reduced influence of Southern Hemispheric Westerlies (SHW) may have caused these high lake levels with lake productivity being low and organic matter mainly of algal or cyanobacterial origin. Aquatic moss growth and diatom blooms occurred synchronously with southern hemispheric glacial warming events such as the Antarctic A-events, the postglacial warming following the LGM and the Younger Dryas chronozone. During these times, a combination of warmer climatic conditions with related thawing permafrost could have increased the allochthonous input of nutrients and in combination with warmer surface waters increased aquatic moss growth and diatom production. The SHW were not observed to affect southern Patagonia during the Last Glacial. The Holocene presents a completely different lacustrine system because (a) permafrost no longer inhibits infiltration nor emits meltwater pulses and (b) the positioning of the SHW over the investigated area gives rise to strong and dry winds. Under these conditions total organic carbon, total organic carbon/total nitrogen ratios and biogenic silica cease to be first order productivity indicators. On the one hand, the biogenic silica is influenced by dissolution of diatoms due to higher salinity and pH of the lake water under evaporative stress characterizing low lake levels. On the other hand, total organic carbon and total organic carbon/total nitrogen profiles are influenced by reworked macrophytes from freshly exposed lake level terraces during lowstands. Total inorganic carbon remains the most reliable proxy for climatic variations during the Holocene as high precipitation of carbonates can be linked to low lake levels and high autochthonous production. The onset of inorganic carbon precipitation has been associated with the southward shift of the SHW over the latitudes of Laguna Potrok Aike. The refined age-depth model of this record suggests that this shift occurred around 9.4 cal. ka BP.

The benthic foraminiferal community in a naturally CO2-rich coastal habitat of the southwestern Baltic Sea

It is expected that the calcification of foraminifera will be negatively affected by the ongoing acidification of the oceans. Compared to the open oceans, these organisms are subjected to much more adverse carbonate system conditions in coastal and estuarine environments such as the southwestern Baltic Sea, where benthic foraminifera are abundant. This study documents the seasonal changes of carbonate chemistry and the ensuing response of the foraminiferal community with bi-monthly resolution in Flensburg Fjord. In comparison to the surface pCO2, which is close to equilibrium with the atmosphere, we observed large seasonal fluctuations of pCO2 in the bottom and sediment pore waters. The sediment pore water pCO2 was constantly high during the entire year ranging from 1244 to 3324 µatm. Nevertheless, in contrast to the bottom water, sediment pore water was slightly supersaturated with respect to calcite as a consequence of higher alkalinity (AT) for most of the year. Foraminiferal assemblages were dominated by two calcareous species, Ammonia aomoriensis and Elphidium incertum, and the agglutinated Ammotium cassis. The one-year cycle was characterised by seasonal community shifts. Our results revealed that there is no dynamic response of foraminiferal population density and diversity to elevated sediment pore water pCO2. Surprisingly, the fluctuations of sediment pore water undersaturation (Omega calc) co-vary with the population densities of living Ammonia aomoriensis. Further, we observed that most of the tests of living calcifying foraminifera were intact. Only Ammonia aomorienis showed dissolution and recalcification structures on the tests, especially at undersaturated conditions. Therefore, the benthic community is subjected to high pCO2 and tolerates elevated levels as long as sediment pore water remains supersaturated. Model calculations inferred that increasing atmospheric CO2 concentrations will finally lead to a perennial undersaturation in sediment pore waters. Whereas benthic foraminifera indeed may cope with a high sediment pore water pCO2, the steady undersaturation of sediment pore waters would likely cause a significant higher mortality of the dominating Ammonia aomoriensis. This shift may eventually lead to changes in the benthic foraminiferal communities in Flensburg Fjord, as well as in other regions experiencing naturally undersaturated Omega calc levels.

Dissolution of a spatially variable DNAPL (dense non aqueous phase liquid) source

Dissolution of non-aqueous phase liquids (NAPLs) or gases into groundwater is a key process, both for contamination problems originating from organic liquid sources, and for dissolution trapping in geological storage of CO2. Dissolution in natural systems typically will involve both high and low NAPL saturations and a wide range of pore water flow velocities within the same source zone for dissolution to groundwater. To correctly predict dissolution in such complex systems and as the NAPL saturations change over time, models must be capable of predicting dissolution under a range of saturations and flow conditions. To provide data to test and validate such models, an experiment was conducted in a two-dimensional sand tank, where the dissolution of a spatially variable, 5x5 cm**2 DNAPL tetrachloroethene source was carefully measured using x-ray attenuation techniques at a resolution of 0.2x0.2 cm**2. By continuously measuring the NAPL saturations, the temporal evolution of DNAPL mass loss by dissolution to groundwater could be measured at each pixel. Next, a general dissolution and solute transport code was written and several published rate-limited (RL) dissolution models and a local equilibrium (LE) approach were tested against the experimental data. It was found that none of the models could adequately predict the observed dissolution pattern, particularly in the zones of higher NAPL saturation. Combining these models with a model for NAPL pool dissolution produced qualitatively better agreement with experimental data, but the total matching error was not significantly improved. A sensitivity study of commonly used fitting parameters further showed that several combinations of these parameters could produce equally good fits to the experimental observations. The results indicate that common empirical model formulations for RL dissolution may be inadequate in complex, variable saturation NAPL source zones, and that further model developments and testing is desirable.

Annotated record of the detailed examination of Mn deposits from Drift Station Alpha in the Arctic Ocean

The cores described were taken by the personnel of the Lamont-Doherty Earth Observatory (LDEO) on the Drift Station Alpha in the Arctic Ocean from August 1957 until June 1958. A total of 16 cores were recovered and are available at Lamont-Doherty Earth Observatory for sampling and study.

Seawater carbonate chemistry and biological processes of zooplankton Amphiascoides atopus and Schizopera knabeni during experiments, 2010

Increased atmospheric CO2 concentrations are causing greater dissolution of CO2 into seawater, and are ultimately responsible for today's ongoing ocean acidification. We manipulated seawater acidity by addition of HCl and by increasing CO2 concentration and observed that two coastal harpacticoid copepods, Amphiascoides atopus and Schizopera knabeni were both more sensitive to increased acidity when generated by CO2. The present study indicates that copepods living in environments more prone to hypercapnia, such as mudflats where S. knabeni lives, may be less sensitive to future acidification. Ocean acidification is also expected to alter the toxicity of waterborne metals by influencing their speciation in seawater. CO2 enrichment did not affect the free-ion concentration of Cd but did increase the free-ion concentration of Cu. Antagonistic toxicities were observed between CO2 with Cd, Cu and Cu free-ion in A. atopus. This interaction could be due to a competition for H+ and metals for binding sites.

Activity concentrations of radionuclides in 5 short cores taken in 2007-2008 measured by ICP-MS and HPGe gamma spectrometry

Natural radionuclides and man-made 137Cs were analyzed in five short sediment cores taken in northern part of the Gulf of Eilat (Gulf of Aqaba) in order to provide information on sedimentation and mixing rates and sediment sources. The maximum estimates of sedimentation rates based on excess 210Pb were found to vary between 0.105 ± 0.020 and 0.35 ± 0.23 cm · year**-1. Even the lowest estimates are significantly higher than those expected from dust deposition, suggesting other sources and processes being responsible for most of the allochthonous material accumulation, including periodical floods following heavy rain events, internal erosion or triggers, like earthquakes. In 137Cs depth profiles no 1963 related nuclear weapon test maxima were found; instead, the activities decrease monotonically, suggesting that a major process leading to radionuclides' depth distribution might be mixing. The mixing rates calculated from 137Cs, excess 210Pb and excess 228Th reach values up to 2.18 ± 0.69 cm**2 · year**-1.

Seawater carbonate chemistry, calcification and dissolution of a coral reef in the northern Red Sea, 2007

In this study we investigated the relations between community calcification of an entire coral reef in the northern Red Sea and annual changes in temperature, aragonite saturation and nutrient loading over a two year period. Summer (April-October) and winter (November-March) average calcification rates varied between 60 ± 20 and 30 ± 20 mmol·m-2·d-1, respectively. In general, calcification increased with temperature and aragonite saturation state of reef water with an apparent effect of nutrients, which is in agreement with most laboratory studies and in situ measurements of single coral growth rates. The calcification rates we measured in the reef correlated remarkably well with precipitation rates of inorganic aragonite calculated for the same temperature and degree of saturation ranges using empirical equations from the literature. This is a very significant finding considering that only a minute portion of reef calcification is inorganic. Hence, these relations could be used to predict the response of coral reefs to ocean acidification and warming.

Seawater carbonate chemistry and community metabolism during an experiment with a coral reef, 2003

The effect of elevated pCO2 on the metabolism of a coral reef community dominated by macroalgae has been investigated utilizing the large 2650 m3 coral reef mesocosm at the Biosphere-2 facility near Tucson, Arizona. The carbonate chemistry of the water was manipulated to simulate present-day and a doubled CO2 future condition. Each experiment consisted of a 1-2 month preconditioning period followed by a 7-9 day observational period. The pCO2 was 404 ± 63 ?atm during the present-day pCO2 experiment and 658 ± 59 ?atm during the elevated pCO2 experiment. Nutrient levels were low and typical of natural reefs waters (NO3? 0.5-0.9 ?M, NH4+ 0.4 ?M, PO43? 0.07-0.09 ?M). The temperature and salinity of the water were held constant at 26.5 ± 0.2°C and 34.4 ± 0.2 ppt. Photosynthetically available irradiance was 10 ± 2 during the present-day experiment and 7.4 ± 0.5 mol photons m?2 d?1 during the elevated pCO2 experiment. The primary producer biomass in the mesocosm was dominated by four species of macroalgae; Haptilon cubense, Amphiroa fragillisima, Gelidiopsis intricata and Chondria dasyphylla. Algal biomass was 10.4 mol C m?2 during the present-day and 8.7 mol C m?2 and during the elevated pCO2 experiments. As previously observed, the increase in pCO2 resulted in a decrease in calcification from 0.041 ± 0.007 to 0.006 ± 0.003 mol CaCO3 m?2 d?1. Net community production (NCP) and dark respiration did not change in response to elevated pCO2. Light respiration measured by a new radiocarbon isotope dilution method exceeded dark respiration by a factor of 1.2 ± 0.3 to 2.1 ± 0.4 on a daily basis and by 2.2 ± 0.6 to 3.9 ± 0.8 on an hourly basis. The 1.8-fold increase with increasing pCO2 indicates that the enhanced respiration in the light was not due to photorespiration. Gross production (GPP) computed as the sum of NCP plus daily respiration (light + dark) increased significantly (0.24 ± 0.03 vs. 0.32 ± 0.04 mol C m?2 d?1). However, the conventional calculation of GPP based on the assumption that respiration in the light proceeds at the same rate as the dark underestimated the true rate of GPP by 41-100% and completely missed the increased rate of carbon cycling due to elevated pCO2. We conclude that under natural, undisturbed, nutrient-limited conditions elevated CO2 depresses calcification, stimulates the rate of turnover of organic carbon, particularly in the light, but has no effect on net organic production. The hypothesis that an increase pCO2 would produce an increase in net production that would counterbalance the effect of decreasing saturation state on calcification is not supported by these data.

Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera. New data for Cd/Ca support previous work in defining a contrast between waters shallower and deeper than ~2500 m. Measured element partition coefficients in foraminiferal calcium carbonate relative to sea water (D) have been described by means of a one-box model in which elements are extracted by Rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor (alpha), such that D = (1 - f**alpha)/(l - f), where f is the proportion of Ca remaining after precipitation. A modification to the model recognises differences in element speciation. The model is consistent with differences between D[Sr], D[Ba], and D[Cd] in benthic but not planktonic foraminifera. Depth variations in D for Sr and Ba are consistent with the model, as are differences in depth variation of D[Cd] in calcitic and aragonitic benthic foraminifera. The shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m. Observations of unusually lower DCd for some deep waters, not accompanied by similar [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.