Exploring the affinity and selectivity of sedimentary mackinawite (FeS) towards natural organic matter

While iron oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) in sediments, the role of iron sulfide (Fe-S) minerals in the long-term sequestration of OC remains poorly defined. In this study, we assessed the affinity of different types of natural organic matter (NOM) towards synthetic Fe-S minerals using sorption isotherms. We found affinities and sorption capacities varying in the following order: plankton NOM > corn leaves NOM > aged terrestrial NOM. Scanning electron microscopy showed that NOM increases the size and surface area of Fe-S aggregates, likely also influencing their surface reactivity. High NOM contents in Fe-S minerals protected Fe(II) from oxidation after exposure to atmospheric oxygen. Analysis of the synthetically prepared Fe-S-NOM complexes by synchrotron scanning transmission X-ray microscopy (STXM) coupled to near-edge X-ray absorption fine-edge structure (NEXAFS) spectroscopy revealed strong interactions between Fe-S minerals and NOM extracted from plankton, specifically with amide and carboxylic functional groups. We also attempted to identify and characterize interactions between OC and Fe-S minerals in natural sulfidic sediments from the St. Lawrence Estuary and the Saguenay Fjord, hence linking our work on synthetic iron sulfides to what is occurring in natural environments, although this effort proved more challenging owing to the presence of Fe(III) minerals even at depth and the difficulty in distinguishing FeS from other Fe(II) minerals. We present depth concentration profiles of dissolved OC, iron, and sulfur in the liquid-phase (pore water) along with speciation data from sequential extractions of sulfur in the solid-phase collected from sediment cores. We found a clear association between mixed Fe(II)/Fe(III) minerals and OC in sediments, which, combined with the results of the synthetic FeS experiment, suggests that Fe-S minerals can promote OC sequestration in sediments.