Constraining the major pathways of vanadium incorporation into sediments underlying natural sulfidic waters

Vanadium (V) is a redox-sensitive trace metal. Interconversion between different vanadium species (e.g., VIII, VIV, VV) occurs rapidly in association with changes in redox conditions in natural environments. Different vanadium species exhibit variable geochemical behavior that impacts if and how they are sequestered into sediments, which makes vanadium a useful proxy for ancient ocean redox conditions. However, we still lack constraints on how different dissolved vanadium sink pathways impact distributions of vanadium in water column, pore waters, and sediments, especially in natural sulfidic settings. In the present study, we combined field and experimental data to constrain the major scavenging processes that influence the partitioning of vanadium between aqueous and solid phases to provide an improved picture of vanadium geochemical cycling under anoxic-sulfidic conditions. We find that in the sulfidic bottom waters and sediment pore waters of the Chesapeake Bay, vanadium concentrations are correlated with manganese (Mn) concentrations in both aqueous and solid phases. Our experimental results support our interpretation that elevated concentrations of vanadium in anoxic-sulfidic waters result from the release of vanadium due to desorption from and/or dissolution of Mn oxides in anoxic/sulfidic waters. While sorption of vanadium results in strongly adsorbed complexes on both Mn oxides and pyrite surfaces, vanadium preferentially sorbs to Mn oxides rather than to pyrite. Thus, the impact of Mn oxides on vanadium geochemistry is greater than that imposed by scavenging via sorption on pyrite, although both processes should be considered. Mn oxides also have a greater impact on vanadium geochemistry than reductive formation of solid V(OH)3 by H2S. Sorption of vanadium is sensitive to pH conditions (especially in anoxic waters), moderately sensitive to ionic strength, and weakly sensitive to phosphate concentrations. In addition, our results show that as waters become more sulfidic, dissolved V/Mn molar ratios increase, whereas solid phase V/Mn molar ratios decrease, indicating that the V/Mn molar ratio can be used to trace redox changes. Finally, we investigate the V/Mn record of black shales that span the Proterozoic and Phanerozoic to show a framework of utilizing this proxy with applicability to identify changes in redox conditions associated with both oxygenation and anoxic events in ancient oceans.