Barium stable isotopes in the global ocean: Tracer of Ba inputs and utilization

Barium has been used as a biogeochemical tracer for alkalinity, productivity, and riverine inputs in the ocean, but its oceanic cycle remains poorly constrained. Barium stable isotope measurements may improve the use of Ba as a tracer and better constrain the cycling of Ba, but data are only available in limited regions of the oceans. In this study, we present dissolved seawater Ba isotopic compositions in a sample collection spanning the North Atlantic, South Atlantic, North Pacific and Southern Oceans. Compiled global upper-ocean [Ba] data show a relatively constant [Ba] (35 ~ 45 nM) in the near-surface waters throughout the global ocean, with the exception of areas near river inputs or strong upwelling. The relatively uniform distribution of [Ba] in the upper ocean seawater indicates that Ba removal is slow relative to supply and mixing, and implies that near-surface Ba isotope values are controlled by basin-scale balances rather than by regional or short-term processes. Seawater Ba isotopic compositions show a large variation of d138/134Ba values ranging from 0.24 to 0.65‰, and a tight relationship with [Ba]. This global relationship can be simply modeled assuming a primary deep Southern Ocean source for Ba to yield a maximum isotope fractionation of a = 1.00058 ± 0.00010 (a = 138/134Baseawater/138/134Baparticle). This suggested isotope fractionation during Ba removal from seawater is larger than implied by laboratory measurement during barite formation, suggesting additional fractionating phases or a two-stage fractionation process. Riverine input from the Rio de la Plata to the South Atlantic has a signature of d138/134Ba = -0.06 ~ 0.11 ‰, which is too light to explain the heavy values (> 0.58 ‰) observed in the surface open ocean. Globally, the Ba isotope composition of the upper ocean waters is correlated with the fraction of Ba utilization at the basin scale (which varies from 15-70% at sites studied here). In the deep Atlantic Ocean, distinct d138/134Ba signals in the northern-sourced (≈0.45 ‰) 50 and the southern-sourced water (≈0.25 ‰) trace mixing and allow identification of non-conservative behavior of Ba, reflecting additional inputs or sinks of Ba during transport (most likely addition from sediment or hydrothermal). Ba isotopes may be useful to trace such inputs in the present and past ocean