Polyaromatic hydrocarbons in sediments from the Barents and White Seas

Polycyclic aromatic hydrocarbons (PAHs) are common environmental contaminants which can be derived from anthropogenic sources, such as combustion and discharges from extraction and transport, and natural processes, including leakage and erosion of fossil carbon. Natural PAH sources contribute, along with biological activities and terrestrial run-off, to the organic carbon content in sediments.The Barents Sea region is far from many anthropogenic sources of PAH, but production and trans-shipment of hydrocarbons is increasing. We present data for polycyclic aromatic hydrocarbon (PAH) concentrations in bottom sediments from 510 stations in the Barents and White Seas, and along the northern coast of Norway.

Ge/Si ratios in marine siliceous microfossils

A procedure is presented to separate diatoms and radiolaria from marine sediments and from each other, to purify them of elements associated with other phases, and to dissolve them to determine their elemental composition. The cleaning procedure eliminates artifacts due to the presence of detrital clays and the high sorption capacity of hydrated silica. The concentration of trace elements (Al, Fe, Mg, and Ba) that we find in alkaline dissolutions of clean diatoms are at least an order of magnitude lower than previously reported. The overall long-term precision in the determination of Ge/Si in a sub-standard of clean diatoms is ±0.024 * 10**-6 (1 sigma). Ge/Si measured in diatoms and radiolaria from core tops indicates that high-latitude Holocene diatoms accurately record the present-day oceanic Ge/Si, while radiolarian ratios are systematically lower and display more scatter. Evaluation of Ge/Si in diatoms and radiolaria from Hole DSDP 265 (Plio-Pleistocene) suggests that post-depositional alteration of the ratio does not occur at this site, but the average ratio carried by diatoms over this time interval was lower than that in the present ocean.

Composition of organic matter in bottom sediments from the Antarctic sector of the Atlantic Ocean

We identify geochemical features of sedimentary organic matter in various morphostructural zones of the Antarctic sector of the Atlantic. We present background geochemical organic parameters for shelf and deep-sea sediments from the Weddell and Scotia Seas and the Bransfield Strait. Geochemical organic parameters are good indicators of environmental and facial variations in sediments and could be used for environmental monitoring of the World Ocean.

(Table 2) Composition of polycyclic aromatics in bottom sediments from the Weddell Sea

Distribution, composition and genesis of organic matter in recent bottom sediments of the Weddell Sea (Western Antarctic) are discussed. Geochemical background levels of bitumen, organic matter, and polycyclic aromatics in the sediments are respectively 0.01-0.1%, 0.003-0.005%, and 0.0001-0.0002%. Deviations from the background level, probably caused by secondary processes, are found. Organic matter has characteristic properties resulting from distinctive character of aquatic biota organic matter, from which it has been formed.

Hydrocarbons in water, suspended matter, and bottom sediments of the White Sea

Data are presented on concentration and composition of aliphatic and polycyclic aromatic hydrocarbons (HC) in water, suspended matter (collected with a Juday net and by a separator), and in bottom sediments of the White Sea. It was found that during the last years the level of aliphatic HC concentrations in waters of the White Sea (aver. 18 µg/l) practically did not change and was comparable with average concentrations in shelf areas of the World Ocean. In water and bottom sediments distribution of HC is determined by discharge of river marginal filters. Here sedimentation of the bulk of anthropogenic HC occurs. That is why a grain-size controlling factor is not active in the zone of the river depocenter (in particular, of the North Dvina River). The same reasons most probably may explain differences in degree of geochemical relationships between contents of TOC and HC in suspended matter and bottom sediments. After passing through marginal filters natural HC are dominant in all migration forms.

Contents of metal cations exchange capacity of ore minerals in ferromanganese micronodules from the Atlantic, Indian and Pacific Oceans

Results of experimental studies of ion exchange properties of manganese and iron minerals in micronodules from diverse bioproductive zones of the World Ocean were considered. It was found that sorption behavior of these minerals was similar to that of ore minerals from ferromanganese nodules and low-temperature hydrothermal crusts. The exchange complex of minerals in the micronodules includes the major (Na**+, K**+, Ca**2+, Mg**2+, and Mn**2+) and subordinate (Ni**2+, Cu**2+, Co**2+, Pb**2+, and others) cations. Reactivity of theses cations increases from Pb**2+ and Co**2+ to Na**+ and Ca**2+. Exchange capacity of micronodule minerals increases from alkali to heavy metal cations. Capacity of iron and manganese minerals in oceanic micronodules increases in the following series: goethite < goethite + birnessite < todorokite + asbolane-buserite + birnessite < asbolane-buserite + birnessite < birnessite + asbolane-buserite < birnessite + vernadite ~= Fe-vernadite + Mn-feroxyhyte. Obtained data supplement available information on ion exchange properties of oceanic ferromanganese sediments and refine the role of sorption processes in redistribution of metal cations at the bottom water - sediment interface during micronodule formation and growth.

Geomicrobiology, bulk sediment characteristics and pore water chemistry of sediment cores from Laguna Potrok Aike, southern Patagonia

Authigenic minerals can form in the water column and sediments of lakes, either abiotically or mediated by biological activity. Such minerals have been used as paleosalinity and paleoproductivity indicators and reflect trophic state and early diagenetic conditions. They are also considered potential indicators of past and perhaps ongoing microbial activity within sediments. Authigenic concretions, including vivianite, were described in late glacial sediments of Laguna Potrok Aike, a maar lake in southernmost Argentina. Occurrence of iron phosphate implies specific phosphorus sorption behavior and a reducing environment, with methane present. Because organic matter content in these sediments was generally low during glacial times, there must have been alternative sources of phosphorus and biogenic methane. Identifying these sources can help define past trophic state of the lake and diagenetic processes in the sediments. We used scanning electron microscopy, phosphorus speciation in bulk sediment, pore water analyses, in situ ATP measurements, microbial cell counts, and measurements of methane content and its carbon isotope composition (d13C CH4) to identify components of and processes in the sediment. The multiple approaches indicated that volcanic materials in the catchment are important suppliers of iron, sulfur and phosphorus. These elements influence primary productivity and play a role in microbial metabolism during early diagenesis. Authigenic processes led to the formation of pyrite framboids and revealed sulfate reduction. Anaerobic oxidation of methane and shifts in pore water ion concentration indicated microbial influence with depth. This study documents the presence of active microbes within the sediments and their relationship to changing environmental conditions. It also illustrates the substantial role played by microbes in the formation of Laguna Potrok Aike concretions. Thus, authigenic minerals can be used as biosignatures in these late Pleistocene maar sediments.

(Table) Content of organic compounds in the bottom sediments of the Volga River estuary

Materials from different spheres of the Earth are ultimately delivered to bottom sediments, which serve as a natural recorder of the functioning of other spheres and originate as a result of the accumulation of their substances. Sedimentary material and species of river-transported elements are subjected to dramatic reworking in marginal filters, where river and sea waters are mixed. These processes are most important for the Caspian Sea, where runoffs of rivers (especially the Volga River) and the intense development and transportation of hydrocarbon fuel by tankers and pipelines (related to the coastal petroleum industry in the Sumgait and Baku ports, Apsheron Peninsula) are potential sources of hydrocarbon pollution. Previously obtained data showed that the total content of hydrocarbon fraction (i.e., the sum of aliphatic hydrocarbons (AHC) and polycyclic aromatic hydrocarbons (PAH)) in bottom sediments varied within 29-1820 µg/g. The content of petroleum hydrocarbons in the northeastern Caspian region varied from 0.052 to 34.09 µg/g with the maximum content in the Tengiz field. The content of six polyarenes in the Volga delta sediments was no more than 40 ng/g. To determine the recent HC pollution of bottom sediments and trends in the functioning of the Volga marginal filter, in summer of 2003 and 2004 we analyzed bottom sediments (58 samples) in the river waterway; Kirovsk channel; Bakhtemir and Ikryanoe branches; tributaries of the Kizan, Chagan, and other rivers; and the Caspian seashore.

Contents of hydrocarbons in waters and bottom sediments of the southwestern Amur Bay (Sea of Japan) in April 2005

Abundances and compositions of aliphatic hydrocarbons (AHC) and polyaromatic hydrocarbons (PAH) were investigated in water and bottom sediments of the southwestern Amur Bay, Sea of Japan. Water contained 0-129 ?g/l AHC (average 42.2 ?g/l) and 5-85 ng/l PAH (average 18 ng/l). Bottom sediments contained 168-2098 ?g/g AHC and 7.2-1100 ng/g dry mass PAH. It was shown that input of anthropogenic hydrocarbons is better recorded by molecular markers than by distribution of AHC and PAH concentrations. Discovery of elevated hydrocarbon concentrations in the bottom water layer suggests that bottom sediments induced secondary contamination of the water body.

Results of Closed-Flow Column Experiments (zip-archive 2.3 MB)

The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to observations of the solute breakthrough in column outflow experiments. This parameters uncertainty can be approached by the application of multiple experimental designs such as column experiments in open-flow mode and the recently proposed closed-flow mode. Latter are characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow. Depending on the experimental conditions, the solute concentration in the solution supply vessel and the effluent follows a damped sinusoidal oscillation. As a result, the closed-flow experiment provides additional observables in the breakthrough curve. The evaluation of these emergent features allows intrinsic control over boundary conditions and impacts the uncertainty of parameters in inverse modeling. We present a comprehensive sensitivity analysis to illustrate the potential application of closed-flow experiments. We show that the sensitivity with respect to the apparent dispersion can be controlled by the experimenter leading to a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude for optimal settings. With these finding we are also able to reduce the equifinality found for situations, where rate-limited interactions impede a proper determination of the apparent dispersion and rate coefficients. Furthermore, we show the expected breakthrough curve for equilibrium and kinetic sorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. This renders the closed-flow mode a useful complementary approach to classical column experiments.