A global reassessment of the controls on iron speciation in modern sediments and sedimentary rocks: A dominant role for diagenesis

The speciation of iron in sediments and sedimentary rocks is a widely used proxy for the chemistry and oxidation state of ancient water bodies. Specifically, the fraction of reactive iron out of the total iron (Fe_HR/Fe_T) and the fraction of pyrite iron out of the reactive iron pool (Fe_PYR/Fe_HR) are thought to constrain the oxidation state and the presence of sulfide in the water column, respectively. This approach was developed and tested against modern core-top sediments, but application to sedimentary rocks requires consideration of the effects of diagenesis and lithification on iron speciation. Furthermore, the effects of deep burial, metamorphism, and late-stage alteration during exhumation or sampling (e.g., oxidative weathering) have not been systematically explored. To bridge this gap, we combined new data from four sediment cores (n = 54) with an extensive literature compilation of modern sediments (2936 measurements from 316 cores) and ancient sedimentary rocks (12,173 measurements spanning the Neoarchean to Quaternary). The modern data include both surface and buried sediments, allowing an investigation of the effects of diagenesis on iron speciation. Depending on the thresholds used to distinguish oxic from anoxic environments and ferruginous from euxinic environments, interpretation of the modern sedimentary iron speciation data within the existing framework yields incorrect environmental classifications up to ≈70% of the time. In modern sediments, diagenesis is the main reason that iron speciation does not represent the chemistry and oxidation state of the water column. We find that iron speciation correlates with porewater chemistry and that it changes with progressive burial along three distinctive Fe_HR/Fe_T–Fe_PYR/Fe_HR arrays, each of which represents a different set of diagenetic processes. We suggest that similarly to modern sediments, stratigraphic variation in iron speciation in sedimentary rocks primarily reflects progressive burial diagenesis or variation in depositional conditions rather than temporal variation in water-column chemistry and oxidation state. Indeed, analysis of the geologic iron speciation data reveals no statistically significant trends in either Fe_HR/Fe_T or Fe_PYR/Fe_HR from the Archean to the present day. The diagenetic Fe_HR/Fe_T–Fe_PYR/Fe_HR arrays that we identified in modern marine sediments suggest that under certain conditions, iron speciation analyses may be used to constrain Fe_HR/Fe_T in the local sediment source(s). Hence, we suggest that iron speciation data, together with complementary petrographic, mineralogical and geochemical constraints, may be used to constrain the local iron source(s) and early and late diagenetic processes, but rarely the chemistry or oxidation state of ancient water columns.