Iron Cycle in Oceans


Book Description

This book presents an up to date view of iron biogeochemistry in the ocean. It encompasses the description of iron speciation, the analytical methods used to measure the different iron forms in seawater and the different iron biogeochemical models.




QUATERNARY SULFUR CYCLE DYNAMICS.


Book Description

The past 3 million years of Earth history are characterized by dramatic changes, which greatly affected the biogeochemical cycling of elements like carbon, sulfur and phosphorous. Here I investigate the effect of these changes on sulfur fluxes and microbially mediated sulfur cycling in marine sediments. Climate driven sea level fluctuations and dynamic topography have greatly affected the areal extent of the continental shelf during the Quaternary. In turn this affects organic matter burial rates and the relative importance of different organic matter remineralization pathways. Since microbial sulfur cycling is the dominant organic matter re-mineralization pathway in marine sediments, this must have affected marine sulfur cycling. Furthermore, previous studies suggested that Quaternary sea level fluctuations caused a considerable increase in the erosion of shelf sediments, which is closely tied to the re-oxidation of pyrite. Here, I use the marine barite record of sulfur and oxygen isotope ratios (d34S and d18O) of seawater sulfate for the past 4Ma to evaluate the implications of Quaternary sea level changes on the sulfur cycling. Quantitative interpretation of d34S and d18O data suggests that erosion during sea level lowstands was only partly compensated by increased sedimentation during times of rising sea levels and sea level highstands. Furthermore, my findings indicate that shelf systems reached a new equilibrium state about 700 kyr ago, which considerably slowed or terminated erosion of shelf sediments. Modeling results also show that microbial sulfur cycling changes proportionally with shelf area, resulting in a 15% reduction of microbial sulfur cycling over the last 2 Ma. This results in a 1-1.5 / drop in the marine sulfate d18O isotope value. While further work is needed to understand how shelf area changes affect the cycling of carbon, phosphorous and other elements, results presented here highlight the dynamic role of continental shelves in the global biogeochemical cycles.







Geochemical Transformations of Sedimentary Sulfur


Book Description

Offers a comprehensive discussion of the geochemistry of sedimentary sulfur, including low temperature transformation in early diagenesis, thermal reactions occurring during later diagenesis and catagenesis. Provides a detailed examination of sulfur-organic matter interactions. Presents an interdisciplinary overview of recent research in the complex process of sedimentary sulfur transformations. Includes contributions from internationally recognized experts in the field.










Water Quality in Dynamic Redox Environments


Book Description

Rising population and changing climate threaten to amplify the risks posed by metal contaminants to our freshwater resources. Altered hydrologic cycles and increased demand for freshwater will shift biogeochemical conditions in soils and sediments, potentially transforming metal contaminants from stationary (solid) phases to mobile forms, which are subject to transport and human consumption. Often, redox processes control partitioning of metal contaminants, whether by changing the redox state of the metal itself, or by transforming the metal host(s). In soils and sediments, these redox processes are commonly driven by hydrologic conditions. My research seeks to understand how redox-associated biogeochemical processes arising from and coupled to hydrologic conditions impact metal contaminant partitioning and mobilization. I employ a combination of experimental, spectroscopic, field and modeling approaches to study the partitioning of U, Pb and Cd to solid and dissolved phases in dynamic redox environments. In my first chapter, I find that the calcium-uranyl-carbonato species kinetically limit U(VI) reduction by Fe(II)(aq), thereby impeding transformation of U from a soluble form to an insoluble form. In my second chapter, I show that the stability of Pb in a range of bonding environments limits dissolved Pb concentrations in contaminated floodplain sediments, despite redox-driven dissolution of Pb hosts. In my third chapter, I reveal that soil redox conditions influence the metal-binding properties of dissolved organic matter, leading to increased complexation of Cd by soft ligands in reduced environments. Finally, in my fourth chapter, I find that the impacts of beaver dams on hyporheic biogeochemical activity dwarfs that of seasonal hydrologic dynamics. Overall, my work both furthers our understanding of the biogeochemical cycles of U, Pb, and Cd and deepens our understanding of how changes in hydrology couple with biogeochemical redox processes to determine water quality.