The sedimentary flux of dissolved rare earth elements to the ocean

We determined pore fluid rare earth element (REE) concentrations in near-surface sediments retrieved from the continental margin off Oregon and California (USA). These sites represent shelf-to-slope settings, which lie above, within, and below the oxygen minimum zone of the Northeast Pacific. The sediments are characterized by varying degrees of net iron reduction, with pore fluids from the shelf sites being generally ferruginous, and the slope sediments having less-pronounced iron reduction zones that originate deeper in the sediment package. REE concentrations show maxima in shallow (upper 2-10 cm) subsurface pore fluids across all sites with concentrations that rise more than two orders of magnitude higher than seawater. These pore fluid enrichments highlight the importance of a sedimentary source of REEs to the ocean's water column. Here we use our measurements to estimate the diffusive flux of Nd out of ocean sediments resulting in a global flux between 18 and 110 x 10(6) mol Nd yr(-1). While we do assume that our pore fluid profiles as well as the very limited data previously published are representative of a wide array of ocean environments, this calculated flux can account for the modeled missing Nd source flux (76 x 10(6) mol Nd yr(-1)) in global budgets (Arsouze et al., 2009). Pore fluid normalized REE patterns show distinct variation in the middle REE and heavy REE enrichments with sediment depth and amongst sites. These patterns show that the heavy REE enrichment of pore fluids at our deep slope site (3000 m water depth) is closest to the heavy REE enrichment of seawater. This observation supports the view that REE cycling within the upper ten centimeters of deep-sea marine sediments, as opposed to shallower continental shelf and slope sediments, plays a significant role in controlling the integrated global REE flux from the pore fluids and consequently the broad-scale REE pattern in seawater. (C) 2015 Elsevier Ltd. All rights reserved.