a b s t r a c tThe objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Febased coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

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The presence of mercury (Hg), particularly methylmercury (MeHg), is a concern for both human and ecological health as MeHg is a neurotoxin and can bioaccumulate to lethal levels in upper trophic level organisms. Recent research has demonstrated that coagulation with metal-based salts can effectively remove both inorganic mercury (IHg) and MeHg from solution through association with dissolved organic matter (DOM) and subsequent flocculation and precipitation. In this study, we sought to further examine interactions between Hg and DOM and the resulting organo-metallic precipitate (floc) to assess if (1) newly added IHg could be removed to the same extent as ambient IHg or whether the association between IHg and DOM requires time, and (2) once formed, if the floc has the capacity to remove additional Hg from solution. Agricultural drainage water samples containing ambient concentrations of both DOM and IHg were spiked with a traceable amount of isotopically enriched IHg and dosed with ferric sulfate after 0, 1, 5, and 30 days. Both ambient and newly added IHg were removed within hours, with 69-79 % removed. To a separate sample set, isotopically enriched IHg was added to solution after floc had formed. Under those conditions, 81-95 % of newly added Hg was removed even at Hg concentrations 1000-fold higher than ambient levels. Results of this study indicate coagulation with ferric sulfate effectively removes both ambient and newly added IHg entering a system and suggests rapid association between IHg and DOM. This work also provides new information regarding the ability of floc to remove additional Hg from solution even after it has formed.