Description: The correlation between concentrations of dissolved barium (dBa) and silicon (dSi) in the modern ocean supports the use of Ba as a paleoceanographic proxy. However, the mechanisms behind their linkage and the exact processes controlling oceanic Ba cycling remain enigmatic. To discern the extent to which this association arises from biogeochemical processes versus physical mixing, we examine the behavior of Ba and Si at the Congo River-dominated Southeast Atlantic margin where active biological processes and large boundary inputs override the large-scale ocean circulation. Here we present the first combined measurements of dissolved stable Ba (δ138Ba) and Si (δ30Si) isotopes as well as Ba and Si fluxes estimated based on 228Ra from the Congo River mouth to the northern Angola Basin. In the surface waters, river-borne particle desorption or dissolution and shelf inputs lead to non-conservative additions of both dBa and dSi to the Congo-shelf-zone, with the Ba flux increasing more strongly than that of Si across the shelf. In the epipelagic and mesopelagic layers, Ba and Si are decoupled likely due to different depths of in situ barite precipitation and biogenic silica production. In the deep waters of the northern Angola Basin, we observe large enrichment of dBa, likely originating from high benthic inputs from the Congo deep-sea fan sediments. Our results reveal different mechanisms controlling the biogeochemical cycling of Ba and Si and highlight a strong margin influence on marine Ba cycling. Their close association across the global ocean must therefore mainly be a consequence of the large-scale ocean circulation. Key Points Stronger enrichment of dissolved barium (dBa) than silicon (dSi) observed in the shelf-zone of the Congo plume Diatom silica production has negligible effect on dissolved Ba isotopic compositions in large river plumes Strong dBa enrichment (up to 24 nM) in the deep water of the northern Angola Basin likely originates from high benthic inputs