Organic matter influences transformation products of ferrihydrite exposed to sulfide

Abstract

In redox-dynamic environments, sorption to poorly-crystalline, nanometer-sized Fe(III)-(oxyhydr)oxides like ferrihydrite influences the biogeochemical cycling of nutrients and trace elements. Under sulfate-reducing conditions, the reductive dissolution of ferrihydrite leads to the release of associated constituents, which may be re-immobilized via sorption to secondary Fe minerals. To date, studies following the kinetics and transformation pathways of Fe(III)-(oxyhydr)oxides upon exposure to dissolved sulfide (S(−II)) have largely focused on pure Fe minerals. However, in nature, Fe(III)-(oxyhydr)oxides are often found in association with organic matter (OM). Because ferrihydrite–OM associations exhibit characteristics and biogeochemical reactivity differing from those of pure ferrihydrite, in this study, we compared sulfidization kinetics and transformation pathways of a pure ferrihydrite to those of ferrihydrite coprecipitated with contrasting organic ligands; polygalacturonic acid, galacturonic acid, and citric acid (C/Fe molar ratio ∼0.55). Incorporating aqueous- and solid-phase S and Fe speciation analyses (via wet chemistry techniques and S and Fe X-ray absorption spectroscopy) in addition to X-ray diffraction and electron microscopy, we studied both rapid (<7 days) and long-term (12 months) mineral transformations as well as the impact of varying S(−II)/Fe molar ratios at neutral pH. Our results showed that at low S(−II)/Fe molar ratios (=0.1), poorly-crystalline Fe sulfide minerals (e.g. mackinawite) did not form in any (co)precipitate. In contrast, at higher S(−II)/Fe molar ratios (=0.5), mackinawite rapidly precipitated, with higher contributions detected in the coprecipitates than in the pure ferrihydrite. Aging of the samples led to further mineral transformations, including divergent pyrite and greigite precipitation, and an overall increase in the crystallinity of secondary mineral phases. Still, the fraction of residual ferrihydrite at 12 months was higher in the OM-containing coprecipitates, with the most ferrihydrite preservation observed in coprecipitates comprising carboxyl-poor ligands (galacturonic acid and citric acid). This suggests that the presence of OM inhibited S(−II)-induced ferrihydrite mineral transformations and that the composition of the associated OM influenced mineral transformation pathways. Collectively, these results suggest that further studies regarding sulfidization pathways should include OM in order to better represent environmental conditions.