Speciation of metals in bottom sediments from the south Kara Sea and Ob and Yenisei estuarine zones

Speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V "Dmitry Mendeleev" to the estuaries of the Ob and Yenisei rivers and to the southwest Kara Sea. Immediately after sampling the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. Atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. Distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by predominance of lithogenic or geochemically inert modes (70-95% of bulk contents), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of total Mn amount and 15-30% of Zn and Cu are contained in geochemically mobile modes. Spatiotemporal variations in proportions of the metal species in the surface layer of sediments along sub-meridional sections and through vertical sections of bottom sediment cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.

Concentrations of heavy and precious metals in animals from hydrothermal vents of the Axial Seamount (Juan de Fuca Ridge) and Guaymas Basin (Gulf of California)

A series of samples of inhabitants of hydrothermal vents were collected during the 12-th cruise of R/V Akademik Mstislav Keldysh in Guaymas Basin (the Gulf of California) and the Axial Seamount area (Juan de Fuca Ridge). Concentrations of trace and heavy metals in the tissues of Ridgeia piscesae, Riftia pachyptila, and Paralvinella palmiformis were analyzed. Neutron-activation analysis revealed significantly higher concentrations of uranium in tissues of Paralvinella palmiformis as compared to ambient seawater. Possible reasons for such phenomenon are discussed. The data obtained by neutron-activation method are compared with those obtained by atomic-absorption method for the same tissues analyzed.

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.

Trace metals in shells of mussels and clams from deep-sea hydrothermal vent fields of the Mid-Atlantic Ridge and East Pacific Rise

Bioaccumulation of trace metals in carbonate shells of mussels and clams was investigated at seven hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, Rainbow, and Broken Spur) and the Eastern Pacific (9°N and 21°N at the East Pacific Rise and the southern trough of Guaymas Basin, Gulf of California). Mineralogical analysis showed that carbonate skeletons of mytilid mussel Bathymodiolus sp. and vesicomyid clam Calyptogena m. are composed mainly of calcite and aragonite, respectively. The first data were obtained for contents of a variety of chemical elements in bivalve carbonate shells from various hydrothermal vent sites. Analyses of chemical compositions (including Fe, Mn, Zn, Cu, Cd, Pb, Ag, Ni, Cr, Co, As, Se, Sb, and Hg) of 35 shell samples and 14 water samples from mollusk biotopes revealed influences of environmental conditions and some biological parameters on bioaccumulation of metals. Bivalve shells from hydrothermal fields with black smokers are enriched in Fe and Mn by factor of 20-30 relative to the same species from the Menez Gwen low-temperature vent site. It was shown that essential elements (Fe, Mn, Ni, and Cu) more actively accumulated during early ontogeny of the shells. High enrichment factors of most metals (n x 100 - n x 10000) indicate efficient accumulation function of bivalve carbonate shells. Passive metal accumulation owing to adsorption on shell surfaces was estimated to be no higher than 50% of total amount and varied from 14% for Fe to 46% for Mn.

Concentrations of dissolved and particulate heavy metals in waters above the northwestern slope of the Paramushir Island (Sea of Okhotsk)

Distributions of Mn, Fe, Cu, Cd, Cr, Co and Ni in sea water are investigated (42 samples, dissolved and particulate forms) in the vicinity of the underwater gas vent field on the northwestern slope of the Paramushir Island. While regular background distributions of the elements occur in the shore zone, there is a column of elevated concentrations of particulate matter, particulate Mn, and dissolved Mn, Fe, Cu, Cd, Cr, Co and Ni that coincides with location of the gas plume. This column can be traced as high as 780 m above the bottom. High metal concentrations in water of the plume are attributable to physico-chemical concentration at the phase interface; the source of elevated mineral concentrations is obviously flux of dissolved minerals from interstitial waters, which extends to considerable distances in vertical direction.

Graphs of experimental results given in concentration of trace metals versus time in days

The impact of CO2 leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), "dissolved" (<0.2 µm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO2 seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO2 chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (MeDGT) of all metals increased substantially during the first phase of CO2 seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO2 chamber than that of in the control chamber. AlDGT, CrDGT, NiDGT, and PbDGT continued to increase during the second phase of the experiment. There was no change in CdDGT during the second phase, while CuDGT and ZnDGT decreased by 30% and 25%, respectively in the CO2 chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO2 chamber. Our results show that CO2 leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO2 acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity of the metals to biota.