Lead and cadmium in the Weser Estuary and the German Bight: Correlations between bacteria populations, heavy metals and organic carbon

Organic carbon, lead and cadmium contents of 20 sediments were determined and compared with the colony counts of anaerobic heterotrophic, anaerobic nitrogen fixing, chitinoclastic and cellulolytic bacteria. Organic carbon content, which is dependent on the sediment type, was positively correlated with lead and cadmium as well as with colony counts of all 4 physiological groups of bacteria. Even the sediments with the highest concentrations of 251.7 ppm Pb and 3.1 ppm Cd showed no reduction in their colony counts. From 2 different sediment sampIes with lead contents of 140 ppm and 21 ppm lead tolerance of the aerobic heterotrophic bacteria was investigated. However, no significant difference in lead tolerance of the 2 heterotrophic populations was found. Water from 6 stations was analysed for dissolved and particulate organic carbon, lead and cadmium. Dissolved lead concentrations were in the range of 0.2-0.5 µg/l and the particulate lead contents were between 0.05 and 4.3 µg/l. The concentrations of total lead for the stations off-shore were only one order of magnitude from the concentrations of the near-shore stations. The same phenomenon was observed for dissolved cadmium (0.02 - 0.25 µg/l) and particulate cadmium (0.003 - 0.15 µg/I) concentrations. Correlations between dissolved (1.6 - 10.8 mg/I) and particulate organic carbon (0.25 - 1.53 mg/I) with dissolved and particulate lead or cadmium were not found.

Characterization of insoluble organic matter in sediments at DSDP Site 87-582

Lipids, humic acids, and kerogens were isolated from Site 582 sediment cores. The amount of each organic fraction in the samples taken from 5.6 to 694 m sub-bottom is almost unrelated to depth of the sample. A study of the oxidation of organic matter by the alkaline KMnO4 method reveals that distribution of polymethylene chain lengths of the kerogens and humic acids in the marine sediments differ from those in lacustrine sediments. The order of abundance of these chains in the sediments is: kerogens, 52-66% of total methylene chains; humic acids, 25-33%; and lipids, 8-16%. The results suggest that polyunsaturated fatty acids (>=4 double bonds) may be important in the formation of polymethylene chains of kerogens and humic acids in marine sediments.

Dissolved organic matter in the Lena Delta in 2009

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

Calcium isotope ratios of pore fluids and solid phase of organic rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (d44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of d44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, d44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the d44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.