Geochemistry of trace metals in shelf sediments affected by seasonal and permanent low oxygen conditions off central Chile, SE Pacific (∼36°S)

Trace metals (Cd, U, Co, Ni, Cu, Ba, Fe, Mn), total organic carbon (TOC) and C and N stable isotope signatures (δ13C and δ15N) were determined in short sediments cores from the inner and outer shelf off Concepción, Chile (∼36°S). The objectives were to establish the effect of environmental conditions on trace metal distributions at two shelf sites, one affected by seasonal oxygenation and the other by permanent low oxygen conditions due to the presence of the oxygen minimum zone (OMZ). We evaluate trace metals as proxies of past changes in primary productivity and the bottom water oxygen regime. Concentrations of pore water sulfides and NH4+NH4+ were also measured as indicators of the main diagenetic pathways at each site. Our results for the inner shelf (seasonal suboxia) suggest that the oxidative state of the sediments responds to seasonal pulses of organic matter and that seasonal oxygenation develops during high and low primary productivity in the water column. Here, positive fluxes (to the water column) estimated from pore water concentrations of several elements were observed (Ba, Co, Ni, Fe and Mn). The less reduced environment at this site produces authigenic enrichment of Cu associated with the formation of oxides in the oxic surface sediment layer, and the reduction of U within deeper sediment sections occur consistently with negative estimated pore water fluxes. In the outer shelf sediments (permanent suboxia, OMZ site), negative fluxes (to the sediment) were estimated for all elements, but these sediments showed authigenic enrichments only for Cd, Cu and U. The short oxygenation period during the winter season did not affect the accumulation of these metals on the shelf. The distribution of Cu, Cd and U have been preserved within the sediments and the authigenic accumulation rates estimated showed a decrease from the deep sections of the core to the surface sediments. This could be explained by a gradual decrease in the strength of the OMZ in the last 100 years, in combination with periods of strong oxygenations during El Niño events.

▶ High organic flux does not imply nutrient type TM enrichment due to seasonal oxygenation. ▶ Reduced conditions prevail in outer shelf sediments even during seasonal oxygenation. ▶ U enrichment responds to the low O2 conditions maintained by the OMZ on the bottom. ▶ Cd and Cu enrichment were associated with primary productivity and low O2 in the OMZ. ▶ TM enrichments indicated diminishing OMZ strength during recent times.