Mass-dependent cadmium isotopic variations in nature with emphasis on the marine environment

We report a survey of natural mass-dependent cadmium isotope fractionation measured by thermal ionization mass spectrometry using a double-spike technique (DS-TIMS). Over sixty samples of natural terrestrial Cd from diverse environments, including MORB, OIB, continental loess, hydrogenic and hydrothermal ferromanganese deposits, and sphalerites (both oceanic and from major continental ore deposits) were analysed. Our results are expressed in terms of epsilon Cd-112/110, which are deviations in Cd-112/Cd-110 from our in-house JMC Cd standard in parts per 10(4). The total epsilon Cd-112/110 variation is relatively small, with a range of only 5 epsilon-units, and is one-to-two orders of magnitude smaller than that previously found in meteorites. The MORB, OIB and loess epsilon Cd-112/110 values are similar and provide a good estimate for the bulk silicate Earth (BSE) value which is -0.95 +/- 0.12 relative to our Cd standard (epsilon Cd-112/110=+0.16 relative to Munster JMC Cd). Taken together, these data suggest little Cd isotope fractionation takes place during crust-mantle segregation. Cd isotopic compositions of continental sphalerite (ZnS) deposits worldwide and high-temperature oceanic hydrothermal sulphides show remarkably similar epsilon Cd-112/110 values, consistent with our estimate for the BSE. In contrast, mid-temperature oceanic sulphides from a single extinct hydrothermal chimney display over 4 epsilon-units variation - along with the most negative values. These variations are most probably caused by precipitation/redissolution of sulphide phases en route within the hydrothermal system. The epsilon Cd-112/110 variability found in worldwide marine Fe-Mn deposits reflects the seawater Cd isotope signal upon precipitation from ambient seawater. A decrease in epsilon Cd-112/110 is observed in passing from shallow-water Fe-Mn deposits to those from deeper waters (>2000 m depth). This shift is explained by biological fractionation related to the uptake of dissolved seawater Cd by phytoplankton in the upper water column. The relatively uniform epsilon Cd-112/110 values close to zero at great depths are consistent with regeneration and remineralization of Cd at depth. Our data suggest that Cd isotopes - much like the Cd/Ca ratio in foraminifera - could potentially serve as a proxy for past changes in biological productivity. The temporal Cd isotope record in a Fe-Mn crust archive at 2000 m depth from the NE Atlantic suggests no gross long-term changes in Cd cycling took place over the past 8 Ma. (C) 2008 Elsevier B.V. All rights reserved.