Authigenic molybdenum formation in marine sediments: a link to pore water sulfide in the Santa Barbara Basin

Abstract

Pore water and sediment Mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the Santa Barbara Basin to examine the connection between authigenic Mo formation and pore water sulfide concentration. Only at the deepest site (580 m), where pore water sulfide concentrations rise to >0.1 μM right below the sediment water interface, was there active authigenic Mo formation. At shallower sites (550, 430, and 340 m), where pore water sulfide concentrations were consistently <0.05 μM, Mo precipitation was not occurring at the time of sampling. A sulfide concentration of ∼0.1 μM appears to be a threshold for the onset of Mo-Fe-S co-precipitation. A second threshold sulfide concentration of ∼100 μM is required for Mo precipitation without Fe, possibly as Mo-S or as particle-bound Mo. Mass budgets for Mo were constructed by combining pore water and sediment results for Mo with analyses of sediment trap material from Santa Barbara Basin as well as sediment accumulation rates derived from 210Pb. The calculations show that most of the authigenic Mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters. There is, however, a non-lithogenic particulate Mo associated with sinking particles that contributes ≤15% to the total authigenic Mo accumulation. Analysis of sediment trap samples and supernant brine solutions indicates the presence of non-lithogenic particulate Mo, a large fraction of which is easily remobilized and, perhaps, associated with Mn-oxides. Our observations show that even with the very high flux of organic carbon reaching the sediment of Santa Barbara Basin, active formation of sedimentary authigenic Mo requires a bottom water oxygen concentration below 3 μM. However, small but measurable rates of authigenic Mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 μM, indicating that the formation of authigenic Mo occurred in the recent past, but not at the time of sampling.