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.

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.