Collaborative Research: Pedogenic fractionation of Fe and Mo isotopes: The role of soil redox status, organic matter and Fe-(oxyhydr)oxide composition

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This project investigates the behavior of the natural isotopes of iron (Fe) and molybdenum (Mo) in soils. Differences in the mass of individual isotopes of Fe and Mo confer small variations in their behavior. Laboratory experiments suggest the direction and magnitude of these variations in isotope behavior in soils are tied to specific biogeochemical processes associated with the presence of soil organic matter, the composition of Fe minerals in the soil, and the soil oxygen status. However, field measurements of these isotopes are extremely limited in soils and this knowledge gap is a key barrier for developing them as diagnostic indicators of soil biogeochemical processes in ways similar to how carbon, oxygen, and nitrogen isotopes are commonly used. For instance, Fe and Mo isotopes hold great promise for determining past responses of soils to changes in climate, vegetation type, and water content. Our field measurements will be made across well-constrained gradients in soil age and climate that naturally exist across the Hawaiian Islands (Hawaiian Climate-Age Matrix). The Hawaiian Islands are an ideal natural laboratory for soil research because of their extreme isolation and a similar basaltic soil parent material across all the islands. In this research project we will: (1) establish the range of Fe and Mo isotopic variation across the Hawaiian Climate-Age Matrix; (2) characterize the composition of Fe minerals using advanced molecular-scale techniques; and (3) establish the relative influence of organic matter, Fe minerals and soil redox status (water and oxygen content) on Fe and Mo isotopic variation. In addition to developing a new isotopic probe of key soil processes, our work will provide detailed knowledge of the Fe solid-phase composition of the Hawaiian Climate-Age Matrix sites, which will benefit ongoing ecological and earth science research at those sites. It will also provide constraints on the baseline isotopic composition of Fe and Mo efflux from terrestrial weathering to rivers and oceanic sediments, which is critical for the use of these isotopes to interpret the past redox status of ancient marine sediments. Lastly, this work will train two graduate students and two undergraduate students over the three-year grant period as well as provide summer research experiences for three students each year from disadvantaged high schools.