Iron and phosphorus speciations in DSDP Leg 92 sediments

We present a detailed study of the co-diagenesis of Fe and P in hydrothermal plume fallout sediments from ~19°S on the southern East Pacific Rise. Three distal sediment cores from 340-1130 km from the ridge crest, collected during DSDP Leg 92, were analysed for solid phase Fe and P associations using sequential chemical extraction techniques. The sediments at all sites are enriched in hydrothermal Fe (oxyhydr)oxides, but during diagenesis a large proportion of the primary ferrihydrite precipitates are transformed to the more stable mineral form of goethite and to a lesser extent to clay minerals, resulting in the release to solution of scavenged P. However, a significant proportion of this P is retained within the sediment, by incorporation into secondary goethite, by precipitation as authigenic apatite, and by readsorption to Fe (oxyhydr)oxides. Molar P/Fe ratios for these sediments are significantly lower than those measured in plume particles from more northern localities along the southern East Pacific Rise, and show a distinct downcore decrease to a depth of ~12 m. Molar P/Fe ratios are then relatively constant to a depth of ~35 m. The Fe and P speciation data indicate that diagenetic modification of the sediments is largely complete by a depth of 2.5 m, and thus depth trends in molar P/Fe ratios can not solely be explained by losses of P from the sediment by diffusion to the overlying water column during early diagenesis. Instead, these sediments are likely recording changes in dissolved P concentrations off the SEPR, possibly as a result of redistribution of nutrients in response to changes in oceanic circulation over the last 10 million years. Furthermore, the relatively low molar P/Fe ratios observed throughout these sediments are not necessarily solely due to losses of scavenged P by diffusion to the overlying water column during diagenesis, but may also reflect post-depositional oxidation of pyrite originating from the volatile-rich vents of the southern East Pacific Rise. This study suggests that the molar P/Fe ratio of oxic Fe-rich sediments may serve as a proxy of relative changes in paleoseawater phosphate concentrations, particularly if Fe sulfide minerals are not an important component during transport and deposition.

Iron analysis in bottle profiles off Mauritania

Iron solubility measurements in the Mauritanian upwelling and the adjacent Open Ocean of the Tropical Atlantic show for all stations lower values in the surface mixed layer than at depth below the pycnocline. We attribute this distribution to a combination of loss terms, chiefly photo-oxidation of organic ligands in the surface, and supply terms, predominantly from the release of ligands from the decomposition of organic matter. Significant correlations with pH, oxygen and phosphate for all samples below the surface mixed layer indicate that biogenic remineralisation of organic matter results in the release of iron binding ligands into the dissolved phase. The comparison of the cFeS/PO4**3- ratio with other published data from intermediate and deep waters in the Pacific suggests an enhanced release of iron chelators in the more productive Mauritanian upwelling zone.

The sedimentary fingerprint of an open-marine iron shuttle

We present iron (Fe) concentration and Fe isotope data for a sediment core transect across the Peru upwelling area, which hosts one of the ocean's most pronounced oxygen minimum zones (OMZs). The lateral progression of total Fe to aluminum ratios (FeT/Al) across the continental margin indicates that sediments within the OMZ are depleted in Fe whereas sediments below the OMZ are enriched in Fe relative to the lithogenic background. Rates of Fe loss within the OMZ, as inferred from FeT/Al ratios and sedimentation rates, are in agreement with benthic flux data that were calculated from pore water concentration gradients. The mass of Fe lost from sediments within the OMZ is within the same order of magnitude as the mass of Fe accumulating below the OMZ. Taken together, our data are in agreement with a shuttle scenario where Fe is reductively remobilized from sediments within the OMZ, laterally transported within the anoxic water column and re-precipitated within the more oxic water below the OMZ. Sediments within the OMZ have increased 56Fe/54Fe isotope ratios relative to the lithogenic background, which is consistent with the general notion of benthic release of dissolved Fe with a relatively low 56Fe/54Fe isotope ratio. The Fe isotope ratios increase across the margin and the highest values coincide with the greatest Fe enrichment in sediments below the OMZ. The apparent mismatch in isotope composition between the Fe that is released within the OMZ and Fe that is re-precipitated below the OMZ implies that only a fraction of the sediment-derived Fe is retained near-shore whereas another fraction is transported further offshore. We suggest that a similar open-marine shuttle is likely to operate along many ocean margins. The observed sedimentary fingerprint of the open-marine Fe shuttle differs from a related transport mechanism in isolated euxinic basins (e.g., the Black Sea) where the laterally supplied, reactive Fe is quantitatively captured within the basin sediments. We suggest that our findings are useful to identify OMZ-type Fe cycling in the geological record.