Selenium as paleo-oceanographic proxy: a first assessmen

Abstract

Selenium (Se) is an essential trace element, which, with multiple oxidation states and six stable isotopes, has the potential to be a powerful paleo-environmental proxy. In this study, Se concentrations and isotopic compositions were analyzed in a suite of about 120 samples of fine-grained marine sedimentary rocks and sediments spanning the entire Phanerozoic. While the selenium concentrations vary greatly (0.22 to 72 ppm), the δ82/76Se values fall in a fairly narrow range from -1 to +1 , with the exception of laminated black shales from the New Albany Shale formation (Devonian), which have δ82/76Se values of up to +2.20 . Black Sea sediments (Holocene) and sedimentary rocks from the Alum Shale formation (Late Cambrian) have Se/TOC ratios and δ82/76Se values close to those found in modern marine plankton (1.72x10-6±1.55x10-7 mol/mol and 0.42±0.22 ). (Note: TOC = total organic carbon.) For the other sedimentary sequences, the Se/TOC ratios indicate enrichment in selenium relative to marine plankton. Additional input of isotopically light terrigenous Se (δ82/76Se ≈ -0.42 ) may explain the Se data measured in recent Arabian Sea sediments (Pleistocene). The very high Se concentrations in sedimentary sequences that include the Cenomanian-Turonian Ocean Anoxic Event (OAE) 2 possibly reflect a significantly enhanced input of volcanogenic Se to the oceans. As the latter has an isotopic composition (δ82/76Se ≈ 0 ) not greatly different from marine plankton, the volcanogenic source does not impart a distinct signature to the sedimentary Se isotope record. The lowest δ82/76Se values are observed in the OAE2 samples from Demerara Rise and Cape Verde Basin cores (δ82/76Se = -0.95 to 1.16 ) and are likely due to fractionation associated with microbial or chemical reduction of Se oxyanions in the euxinic water column. In contrast, a limiting availability of seawater Se during periods of increased organic matter burial is thought to be responsible for the elevated δ82/76Se values and low Se/TOC ratios in the black shales of the New Albany Shale formation. Overall, our results suggest that Se data may provide useful information on paleodepositional conditions, when included in a multi-proxy approach.