The low-temperature geochemical cycle of iron: From continental fluxes to marine sediment deposition

Abstract

Suspended sediments from 34 major rivers (geographically widespread)and 36 glacial meltwater streams have been examined for their variations in different operationally-defined iron fractions; FeHR (iron oxides soluble in dithionite), FePR (iron soluble in boiling HCl but not in dithionite) and FeU (total iron less that soluble in boiling HCl). River particulates show a close association between FeHR and total iron (FeT), reflecting the effects of chemical weathering which derive oxide iron from, and retain it in close association with, total iron. Consistent with this, continentalscale average FeHR/FeT ratios vary with runoff ratios (average river runoff per unit area/average precipitation per unit area). By contrast, the diminished effects of chemical weathering produce no recognizable association of FeHR with FeT in glacial particulates, and instead both FePR and FeU are closely correlated with FeT, reflecting essentially pristine mineralogy. A comparison of the globally-averaged compositions of riverine particulates and marine sediments reveals that the latter are depleted in FeHR, FePR and FeT but enriched in FeU. The river and glacial particulate data are combined with estimates of authigenic, hydrothermal, atmospheric and coastal erosive iron fluxes from the literature to produce a global budget for FeHR, FePR, FeU and FeT. This budget suggests that the differences between riverine particulates and marine sediments can be explained by; (i) preferentially removing FeHR from the riverine particulate flux by deposition into inner shore reservoirs such as floodplains, salt marshes and estuaries; and (ii) mixing the resulting riverine particulates with FeHRdepleted glacial particulates. Preliminary measurements of inner shore sediments are consistent with (i) above. Phanerozoic and modern normal marine sediments have similar iron speciation characteristics, which implies the existence of a long-term steady state for the iron cycle. This steady state could be maintained by a glacioeustatic feedback, where FeHR-enriched riverine particulates are either more effectively trapped when sealevel is high (small ice masses, diminished glacial erosion), or are mixed with greater masses of FeHR-depleted glacial particulates when sealevel is low (large ice masses, enhanced glacial erosion). Further important controls on the steady state for FeHR operate through the formation of euxinic sediments and ironstones, which also provide sealevel-dependent sinks for FeHR-enriched sediment