Cr Isotope Oceanography of the Eastern Tropical North Pacific Ocean

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Surface seawater equilibrates with the atmosphere and has high oxygen levels, supporting the sea life within it. When this water is cooled in the winter, it becomes denser and sinks into the depths of the ocean, and begins to lose its oxygen as microbes respire while feeding on sinking organic matter falling from the upper ocean. In some regions, such as the eastern tropical North Pacific Ocean, this process leads to such low oxygen concentrations that oxygen-respiring organisms such as fish cannot survive. There is evidence that these regions are growing larger in recent decades raising concerns over the consequences should these trends continue. Geologists looking at ancient sediments have surmised that some periods in the past have had much larger oxygen-depleted portions of the ocean, so we know the possibility exists. We are working on a new tracer of these oxygen deficient zones, the chromium isotope ratio of seawater. Chromium (Cr) is a trace element found throughout the ocean; in oxygen depleted zones it is reduced from the highly soluble 6+ oxidation state (hexavalent Cr, a toxic pollutant at high concentrations) to the relatively insoluble 3+ state (trivalent Cr) which is removed from the ocean attached to sinking particles. This process favors lighter Cr isotopes hence Cr with 24 protons and 28 neutrons is preferentially transformed compared to Cr with 24 protons and 29 neutrons. This transformation can be used to study the extent and activity of oxygen deficient zones in the modern ocean and in geological ancient oceans. There is very little data for Cr isotopes in these environments, and this project will obtain some of the first data with fieldwork sample collection in the eastern tropical North Pacific Ocean and laboratory measurements using plasma mass spectrometry. This research can contribute to sedimentary geological and geochemical understanding. A female Ph.D. student at Massachusetts Institute of Oceanography will participate in the project that will comprise most of her thesis research. Chromium (Cr) in the aquatic environment exists in two redox states, Cr(III) and Cr(VI). Cr(VI) is thermodynamically stable and the dominant form observed in the oxic ocean, although a few percent of unstable Cr(III) is also observed. Cr(III) is particle-reactive and is scavenged onto sinking particulate matter, whereas Cr(VI) is relatively unreactive. Both species can be taken up by marine biota, although diatoms take up Cr(III) ~20 times faster. Cr(III) has biochemical functionality (e.g. lipid and protein metabolism), whereas Cr(VI) is a toxin that damages cellular biochemistry. When oxygen is less than about 2 uM, Cr(III) becomes the thermodynamically stable species, but slow reaction kinetics lets microbial activity or environmental reductants such as Fe(II) dominate the conversion. Theory and lab experiments indicate that this redox transformation should be accompanied by a stable isotope ratio shift when partial conversion occurs, with Cr(III) enriched in the lighter isotopes. Of the four Cr stable isotopes, this process is observed using the ratio of the most abundant natural isotopes 53Cr and 52Cr while using an enriched double spike of the scarce 50Cr and 54Cr isotopes to correct for laboratory and instrument mass fractionation. This sensitivity to environmental oxygen has inspired geologists to use Cr isotope ratios as an indicator of past oxygenation conditions on earth. But there is little data on the Cr isotope composition in marine aquatic systems with which to ground-truth the geological inferences. We will illuminate the Cr isotope geochemistry of the marine environment with measurements on the horizontal and vertical distribution of Cr concentrations and Cr isotope ratios for the Cr redox species and particulate matter for samples from the eastern tropical North Pacific oxygen deficient zone. Cr isotope ratios are sensitive to biological uptake and regeneration in the oxic ocean and redox processes in oxygen deficient zones (and the latter's consequent outmixing into adjacent oxic zones). This data will be examined in relationship to standard hydrographic properties and nutrients and to the oceanic redox systems of nitrogen, iron, and manganese.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.