The globally-observed relationship between oceanic barium and the macronutrient silicic acid results from the shared influence of large-scale ocean circulation and mixing on the two elements, and the inherent link between barium and organic matter formation and dissolution. A detailed examination of deviations from barium-silicon correlations can reveal variations in non-conservative processes within the marine barium cycle. Here, we present a high-resolution dataset of dissolved barium and macronutrients from the Drake Passage and the Scotia and Weddell Seas. Our new results highlight the influence of Southern Ocean frontal zones on barium cycling and the deviations of barium and macronutrient distributions as a result of spatial variations in phytoplankton assemblages and in barite formation processes. These new data also reinforce findings that water mass mixing and ocean circulation, in particular the location of oxygen minima, play a key role in barium distribution. Our findings have implications for the use of sedimentary barium as a proxy for export production, which may be complicated by physical water circulation changes or shifts in plankton community structure.