Particulate Trace Metal Sources, Cycling, and Distributions on the Southwest African Shelf

We present labile (L-pTM) and refractory (R-pTM) particulate trace metal distributions of Fe, Mn, Al, Ti, Co, Zn, Cd, Ni, Pb, Cu, and P for a transect along the southwest African shelf and an off-shore section at 3 degrees S of the GEOTRACES GA08 section cruise. Particle sources and biogeochemical cycling processes are inferred using particle-type proxies and elemental ratios. Enhanced concentrations of bio-essential L-pTMs (Zn, Cu, Ni, Cd, Co, and P) were observed in the Benguela upwelling region, attributed to enhanced primary production. Bio-essential pTM stoichiometric ratios (normalized to pP) were consistent with phytoplankton biomass across the transect, except for Fe and Mn, which included adsorbed and labile oxide phases. Low pP lability (similar to 41%) suggests a potential refractory biogenic source on the Benguela shelf. Variable labilities observed between stations along the transect indicated potentially different biogenic pP labilities among different plankton groups. Benthic resuspension was prevalent in (near-)bottom waters along the transect and formed an important source of Fe and Mn oxides. Lithogenic particles along the entire shelf were Mn deficient and particles on the Benguela shelf were enriched in Fe, consistent with regional sediment compositions. Enhanced available-Fe (dissolved + labile particulate Fe) concentrations (up to 39.6 nM) were observed in oxygen-deficient (near-)bottom waters of the Benguela shelf coinciding with low L-pMn. This was attributed to the faster oxidation kinetics of Fe, allowing Fe-oxide precipitation and retention on the shelf, while Mn oxidation was slower. Enhanced L-pFe in the Congo River plume, which comprised as much as 93% of the available-Fe pool, was attributed to increased scavenging and formation of Fe oxides. Increased scavenging of other particle-reactive trace metals (TMs) (Mn, Al, and Pb) was also apparent in Congo-influenced waters. However, particles did not play a significant role in transporting TMs off-shelf within Congo plume waters.