The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea.

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

A first analysis of metallome biosignatures of hyperthermophilic Archaea.

To date, no experimental data has been reported for the metallome of hyperthermophilic microorganisms although their metal requirements for growth are known to be unique. Here, experiments were conducted to determine (i) cellular trace metal concentrations of the hyperthermophilic Archaea Methanococcus jannaschii and Pyrococcus furiosus, and (ii) a first estimate of the metallome for these hyperthermophilic species via ICP-MS. The metal contents of these cells were compared to parallel experiments using the mesophilic bacterium Escherichia coli grown under aerobic and anaerobic conditions. Fe and Zn were typically the most abundant metals in cells. Metal concentrations for E. coli grown aerobically decreased in the order Fe > Zn > Cu > Mo > Ni > W > Co. In contrast, M. jannaschii and P. furiosus show almost the reverse pattern with elevated Ni, Co, and W concentrations. Of the three organisms, a biosignature is potentially demonstrated for the methanogen M. jannaschii that may, in part, be related to the metallome requirements of methanogenesis. The bioavailability of trace metals more than likely has varied through time. If hyperthermophiles are very ancient, then the trace metal patterns observed here may begin to provide some insights regarding Earth's earliest cells and in turn, early Earth chemistry.

A biomarker based on the stable isotopes of nickel.

The new stable isotope systems of transition metals are increasingly used to understand and quantify the impact of primitive microbial metabolisms on the modern and ancient Earth. To date, little effort has been expended on nickel (Ni) isotopes but there are good reasons to believe that this system may be more straightforward, and useful in this respect, than some others. Here, we present Ni stable isotope data for abiotic terrestrial samples and pure cultures of methanogens. The dataset for rocks reveals little isotopic variability and provides a lithologic baseline for terrestrial Ni isotope studies. In contrast, methanogens assimilate the light isotopes, yielding residual media with a complementary heavy isotopic enrichment. Methanogenesis may have evolved during or before the Archean, when methane could have been key to Earth's early systems. Our data suggest significant potential in Ni stable isotopes for identifying and quantifying methanogenesis on the early planet. Additionally, Ni stable isotope fractionation may well prove to be the fundamental unambiguous trace metal biomarker for methanogens.