Controls on redox-sensitive trace metals in the Mauritanian oxygen minimum zone

The availability of the micronutrient iron (Fe) in surface waters determines primary production, N-2 fixation, and microbial community structure in large parts of the world's ocean, and thus it plays an important role in ocean carbon and nitrogen cycles. Eastern boundary up-welling systems and the connected oxygen minimum zones (OMZs) are typically associated with elevated concentrations of redox-sensitive trace metals (e.g., Fe, manganese (Mn), and cobalt (Co)), with shelf sediments typically forming a key source. Over the last 5 decades, an expansion and intensification of OMZs has been observed and this trend is likely to proceed. However, it is unclear how trace-metal (TM) distributions and transport are influenced by decreasing oxygen (O-2) concentrations. Here we present dissolved (d; < 0.2 mu m) and leachable particulate (Lp; > 0.2 mu m) TM data collected at seven stations along a 50 km transect in the Mauritanian shelf region. We observed enhanced concentrations of Fe, Co, and Mn corresponding with low O-2 concentrations ( < 50 mu mol kg(-1)), which were decoupled from major nutrients and nutrient-like and scavenged TMs (cadmium (Cd), lead (Pb), nickel (Ni), and copper (Cu)). Additionally, data from repeated station occupations indicated a direct link between dissolved and leachable particulate Fe, Co, Mn, and O-2. An observed dFe (dissolved iron) decrease from 10 to 5 nmol L-1 coincided with an O-2 increase from 30 to 50 mu mol kg(-1) and with a concomitant decrease in turbidity. The changes in Fe (Co and Mn) were likely driven by variations in their release from sediment pore water, facilitated by lower O-2 concentrations and longer residence time of the water mass on the shelf. Variations in organic matter remineralization and lithogenic inputs (atmospheric deposition or sediment resuspension; assessed using Al as indicator for lithogenic inputs) only played a minor role in redox-sensitive TM variability. Vertical dFe fluxes from O-2-depleted subsurface-to-surface waters (0.08-13.5 mu mol m(-2) d(-1)) driven by turbulent mixing and vertical advection were an order of magnitude larger than atmospheric deposition fluxes (0.63-1.43 mu mol m(-2) d(-1); estimated using dAl inventories in the surface mixed layer) in the continental slope and shelf region. Benthic fluxes are therefore the dominant dFe supply to surface waters on the continental margins of the Mauritanian upwelling region. Overall, our results indicated that the projected future decrease in O-2 concentrations in OMZs may result in increases in Fe, Mn, and Co concentrations.