Element enrichment and provenance of the detrital component in Holocene sediments from the western Black Sea

Place: Sopot Publisher: Polish Acad Sciences Inst Oceanology WOS:000528728600003International audienceConcentrations of a large set of major and trace elements, and Sr, Nd and Pb isotope ratios were measured in Holocene sediments cored in the western deep Black Sea in order to unravel: (1) the controls of element enrichment, and (2) sources of the detrital component. The transition of the basin from oxic to euxinic resulted in enrichment or depletion in a number of elements in the deep-sea sediments. Authigenic Fe enrichment appears to depend on the amount of Fe mobilized from the sediment through the benthic redox shuttle mechanism and free H2S in the water column (degree of “euxinization”). Manganese enrichment is controlled by diagenetic reactions within the sediment: the dissolution of Mn minerals, Mn2+ diffusion upward and reprecipitation. Barium enrichment is also controlled by diagenetic reactions, sulfate reduction and methanogenesis, that take place above and below the sulfate-methane transition, respectively. The major part of V, Co, Ni, Cu, Zn, Cr, Mo, Cd and Sb is inferred to have co-precipitated with Fe in the euxinic deep waters and to have been incorporated into authigenic Fe-sulfides. Basin reservoir effect additionally influences the Mo enrichment. The U enrichment is interpreted to have a different origin in the two organic-rich stratigraphic units (II and I). It is inferred to be: (i) at the expense of the U inventory of the deepwater pool and a result of inorganic reduction of U at euxinic conditions in the lower Unit II; and (ii) at the expense of the U inventory of the surface water pool and a result of biogenic uptake and transfer to the sediment by the plankton in the upper Unit I. The high field strength elements are closely linked to the detrital component and their depletion in the organic-rich sediments reflects a dilution of the detrital component by the biogenic one. The enrichments of REE, Sn and Th are likely controlled by adsorption on clay minerals. Sr-Nd-Pb isotope compositions of the alumino-silicate component of the studied sediments are relatively uniform. They are most likely controlled by riverine suspended matter supplied mainly in the NW Black Sea (Danube Delta) and transported southward by marine currents, and to a lesser degree by suspended matter from the small rivers draining SE Bulgaria and NW Turkey. Wind-blown dust from the Sahara Desert appears to have a minor contribution to the alumino-silicate component of the sediments. The slight shift in the Pb isotopes in Unit I upper layers is possibly caused by the addition of anthropogenic Pb

Interlaboratory study for coral Sr/Ca and other element/Ca ratio measurements

The Sr/Ca ratio of coral aragonite is used to reconstruct past sea surface temperature (SST). Twenty-one laboratories took part in an interlaboratory study of coral Sr/Ca measurements. Results show interlaboratory bias can be significant, and in the extreme case could result in a range in SST estimates of 7°C. However, most of the data fall within a narrower range and the Porites coral reference material JCp-1 is now characterized well enough to have a certified Sr/Ca value of 8.838 mmol/mol with an expanded uncertainty of 0.089 mmol/mol following International Association of Geoanalysts (IAG) guidelines. This uncertainty, at the 95% confidence level, equates to 1.5°C for SST estimates using Porites, so is approaching fitness for purpose. The comparable median within laboratory error is \u3c0.5°C. This difference in uncertainties illustrates the interlaboratory bias component that should be reduced through the use of reference materials like the JCp-1. There are many potential sources contributing to biases in comparative methods but traces of Sr in Ca standards and uncertainties in reference solution composition can account for half of the combined uncertainty. Consensus values that fulfil the requirements to be certified values were also obtained for Mg/Ca in JCp-1 and for Sr/Ca and Mg/Ca ratios in the JCt-1 giant clam reference material. Reference values with variable fitness for purpose have also been obtained for Li/Ca, B/Ca, Ba/Ca, and U/Ca in both reference materials. In future, studies reporting coral element/Ca data should also report the average value obtained for a reference material such as the JCp-1