Highlights• First full seawater depth profile of co-located [Ba]-δ 138/134 Ba NIST• Origin of Ba-isotopic variations are best explained by barite cycling• Regional circulation strongly influences depth structure of δ 138/134 Ba NIST• Data establish a baseline of Ba-isotopic variability in the marine realm Keywords: barium; isotopic fractionation; barite; seawater; biogeochemistry
AbstractThe marine biogeochemical cycle of Ba is thought to be controlled by particulate BaSO 4 (barite) precipitation associated with the microbial oxidation of organic carbon and its subsequent dissolution in the BaSO 4 -undersaturated water column. Despite many of these processes being largely unique to Ba cycling, concentrations of Ba and Si in seawater exhibit a strong linear correlation. The reasons for this correlation are ambiguous, as are the depth ranges corresponding to the most active BaSO 4 cycling and the intermediate sources of Ba to particulate BaSO 4 . Stable isotopic analyses of dissolved Ba in seawater should help address these issues, as Ba-isotopic compositions are predicted to be sensitive to the physical and biogeochemical process that cycle Ba. We report a new methodology for the determination of dissolved Ba-isotopic compositions in seawater and results from a 4, 500 m depth profile in the South Atlantic at 39.99 • S, 0.92 • E that exhibit oceanographically-consistent variation with depth. These data reveal that water masses obtain their [Ba] and Ba-isotopic signatures when at or near the surface, which relates to the cycling of marine BaSO 4 . The shallow origin of these signatures requires that the substantial Ba-isotopic variations in the bathypelagic zone were inherited from when those deep waters were last ventilated. Indeed, the water column below 600 m is well explained by conservative mixing of water masses with distinct [Ba] and Ba-isotopic compositions. This leads us to conclude that large scale oceanic circulation is important for sustaining the similar oceanographic distributions of Ba and Si in the South Atlantic, and possibly elsewhere. These data demonstrate that the processes of organic carbon oxidation, BaSO 4 cycling, and Ba-isotopic fractionation in seawater are closely coupled, such that Ba-isotopic analyses harbor great potential as a tracer of the carbon cycle in the modern and paleo-oceans.