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Interactions between aqueous ferrous iron (Fe(II)) and secondary Fe oxyhydroxides catalyze mineral recrystallization and/or transformation processes in anoxic soils and sediments, where oxyanions, such as silicate, are abundant. However, the effect and the fate of silicate during Fe mineral recrystallization and transformation are not entirely understood and especially remain unclear for lepidocrocite. In this study, we reacted (Si-)ferrihydrite (Si/Fe = 0, 0.05, and 0.18) and (Si-)lepidocrocite (Si/Fe = 0 and 0.08) with isotopically labeled 57Fe(II) (Fe(II)/Fe(III) = 0.02 and 0.2) at pH 7 for up to 4 weeks. We followed Fe mineral transformations with X-ray diffraction and tracked Fe atom exchange by measuring aqueous and solid phase Fe isotope fractions. Our results show that the extent of ferrihydrite transformation in the presence of Fe(II) was strongly influenced by the solid phase Si/Fe ratio, while increasing the Fe(II)/Fe(III) ratio (from 0.02 to 0.2) had only a minor effect. The presence of silicate increased the thickness of newly formed lepidocrocite crystallites, and elemental distribution maps of Fe(II)-reacted Si-ferrihydrites revealed that much more Si was associated with the remaining ferrihydrite than with the newly formed lepidocrocite. Pure lepidocrocite underwent recrystallization in the low Fe(II) treatment and transformed to magnetite at the high Fe(II)/Fe(III) ratio. Adsorbed silicate inactivated the lepidocrocite surfaces, which strongly reduced Fe atom exchange and inhibited mineral transformation. Collectively, the results of this study demonstrate that Fe(II)-catalyzed Si-ferrihydrite transformation leads to the redistribution of silicate in the solid phase and the formation of thicker lepidocrocite platelets, while lepidocrocite transformation can be completely inhibited by adsorbed silicate. Therefore, silicate is an important factor to include when considering Fe mineral dynamics in soils under reducing conditions., Environmental Science & Technology, 56 (9), ISSN:0013-936X, ISSN:1520-5851

Under anoxic conditions, the interactions between As-bearing ferrihydrite (Fh) and As(V)-reducing bacteria are known to cause Fh transformations and As mobilization. However, the impact of different types of organic matter (OM) on microbial As/Fe transformation in As-bearing Fh-organic associations remains unclear. In our study, we therefore exposed arsenate-adsorbed ferrihydrite, ferrihydrite-PGA (polygalacturonic acid), and ferrihydrite-HA (humic acid) complexes to two typical Fe(III)- and As(V)-reducing bacteria, and followed the fate of Fe and As in the solid and aqueous phases. Results show that PGA and HA promoted the reductive dissolution of Fh, resulting in 0.7-1.6 and 0.8-1.9 times more As release than in the OM-free Fh, respectively. This was achieved by higher cell numbers in the presence of PGA, and through Fe-reduction via electron-shuttling facilitated by HA. Arsenic-XAS results showed that the solid-phase arsenite fraction in Fh-PGA and Fh-HA was 15-19% and 27-28% higher than in pure Fh, respectively. The solid-associated arsenite fraction likely increased because PGA promoted cell growth and As(V) reduction, while HA provided electron shuttling compounds for direct microbial As(V)-reduction. Collectively, our findings demonstrate that As speciation and partitioning during microbial reduction of Fh-organic associations are strongly influenced by PGA and HA, as well as the strains' abilities to utilize electron-shuttling compounds.

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 (

Ferrihydrite (Fh) is a poorly crystalline Fe(III)-oxyhydroxide found in abundance in soils and sediments. With a high specific surface area and sorption capacity at circumneutral pH, ferrihydrite is an important player in the biogeochemical cycling of nutrients and trace elements in redox-dynamic environments. Under reducing conditions, exposure to Fe(II) induces mineral transformations in ferrihydrite; the extent and trajectory of which may be greatly influenced by organic matter (OM). However, natural OM is heterogeneous and comprises a range of molecular weights (MWs) and varied functional group compositions. To date, the impact that the chemical composition of the associated OM has on Fe(II)-catalyzed mineral transformations is not clear. To address this knowledge gap, we coprecipitated ferrihydrite with model organic ligands selected to cover a range of MWs (25 000-50 000 vs200 Da) as well as carboxyl content (polygalacturonic acid (PGA)citric acid (CA)galacturonic acid (GA)). Coprecipitates (C:Fe ≈ 0.6) were reacted with 1 mM

In soils and sediments, short-range order (SRO) iron minerals constitute one of the most abundant and reactive mineral components. With high surface areas and points of zero charge near pH 7-8, SRO minerals like ferrihydrite (Fe10O14(OH)2+mH2O) are often linked to high adsorption of nutrients (C, N, P, S) and trace elements (e.g. As, Zn). However, under oxygen-limiting conditions, microbially derived sulfide (S(−II)) may cause the rapid reductive dissolution of ferrihydrite and the release of associated nutrients and trace elements, thus influencing the biogeochemical cycling of trace elements and nutrients, particularly in redox dynamic environments.Sulfidization of ferrihydrite occurs rapidly, whereby electron transfer between surface complexed sulfide and the ferrihydrite surface results in (partially) oxidized sulfur species and Fe(II). Depending on the S(-II):Fe molar ratios, secondary reactions then lead to mackinawite (FeS) or pyrite (FeS2) precipitation. In nature, however, ferrihydrite is often found associated with natural organic matter (NOM). Because coprecipitation of ferrihydrite with NOM decreases particle size, alters the surface charge, and may block surface sorption sites, we speculated that kinetics and pathways of sulfidization of organic-associated ferrihydrite may differ from those of the pure mineral. Therefore, in this study, we followed iron mineral transformations and sulfur speciation during sulfidization of a pure ferrihydrite over one year and compared this to ferrihydrite coprecipitated with model organic ligands (polygalacturonic acid, galacturonic acid, and citric acid). Using a combination of solid- and aqueous phase Fe and S speciation techniques, we show that the impact of OM on ferrihydrite sulfidization kinetics and pathways varies with the chemical structure of the organic ligand, and that secondary reactions continue well past the initial rapid consumption of S(-II).

In freshwater wetlands, redox interfaces characterized by circumneutral pH, steep gradients in O2, and a continual supply of Fe(II) form ecological niches favorable to microaerophilic iron(II) oxidizing bacteria (FeOB) and the formation of flocs; associations of (a)biotic mineral phases, microorganisms, and (microbially-derived) organic matter. On the volcanic island of Iceland, wetlands are replenished with Fe-rich surface-, ground- and springwater. Combined with extensive drainage of lowland wetlands, which forms artificial redox gradients, accumulations of bright orange (a)biotically-derived Fe-rich flocs are common features of Icelandic wetlands. These loosely consolidated flocs are easily mobilized, and, considering the proximity of Iceland's lowland wetlands to the coast, are likely to contribute to the suspended sediment load transported to coastal waters. To date, however, little is known regarding (Fe) mineral and elemental composition of the flocs. In this study, flocs from wetlands (n = 16) across Iceland were analyzed using X-ray diffraction and spectroscopic techniques (X-ray absorption and 57Fe Mössbauer) combined with chemical extractions and (electron) microscopy to comprehensively characterize floc mineral, elemental, and structural composition. All flocs were rich in Fe (229–414 mg/g), and floc Fe minerals comprised primarily ferrihydrite and nano-crystalline lepidocrocite, with a single floc sample containing nano-crystalline goethite. Floc mineralogy also included Fe in clay minerals and appreciable poorly-crystalline aluminosilicates, most likely allophane and/or imogolite. Microscopy images revealed that floc (bio)organics largely comprised mineral encrusted microbially-derived components (i.e. sheaths, stalks, and EPS) indicative of common FeOB Leptothrix spp. and Gallionella spp. Trace element contents in the flocs were in the low μg/g range, however nearly all trace elements were extracted with hydroxylamine hydrochloride. This finding suggests that the (a)biotic reductive dissolution of floc Fe minerals, plausibly driven by exposure to the varied geochemical conditions of coastal waters following floc mobilization, could lead to the release of associated trace elements. Thus, the flocs should be considered vectors for transport of Fe, organic carbon, and trace elements from Icelandic wetlands to coastal waters., Science of The Total Environment, 816, ISSN:0048-9697, ISSN:1879-1026

Arsenic-contaminated waters affect millions of people on a daily basis. Because the toxicity of As is dependent on the redox state, understanding As biogeochemistry, particularly in reducing environments, is critical to addressing the environmental risk that As poses. Sorption of As to Fe(III)-(oxyhydr)oxides is an important mechanism for As removal from solution under anoxic conditions. However, dissolved ferrous Fe (Fe(II)) also occurs under anoxic conditions, and the impact that Fe(II)-catalyzed recrystallization of crystalline Fe minerals has on As sorption mechanisms is not clear. Our research investigates the potential for non-stoichiometric magnetite, a commonly occurring mixed-valence Fe oxide in anoxic aquifers, to adsorb and/or incorporate inorganic As species during Fe(II)-catalyzed recrystallization at neutral pH, with particular focus on the impact of mineral stoichiometry (Fe(II):Fe(III) = 0.23 and 0.0) and varying Fe(II) concentrations. By following aqueous As concentrations and speciation over time coupled with As K-edge X-ray absorption spectroscopy, our results demonstrate that the presence of Fe(II) substantially enhanced As removal from solution. In addition, we highlight a Fe(II)-induced mechanism through which highly mobile, toxic As(III) species are oxidized on the mineral surface to form As(V). Furthermore, the presence of Fe(II) promotes the structural incorporation of As(V) into the non-stoichiometric magnetite and maghemite structures. These results highlight the potential of Fe(II)-reacted non-stoichiometric magnetite or maghemite as pathways for long-term As sequestration in anoxic environments., Journal of Hazardous Materials, 402, ISSN:0304-3894, ISSN:1873-3336

In soils and sediments, poorly-crystalline, short-range order (SRO) iron minerals constitute one of the most abundant and reactive components. With high surface areas, SRO minerals like ferrihydrite (Fe10O14(OH)2+mH2O) influence the biogeochemical cycling of trace elements and nutrients, particularly in redox dynamic environments. While under oxic conditions SRO iron mineral adsorption capacity is high, in the absence of O2, FeIII acts as an electron acceptor during microbial respiration. Electron transfer induces transformations in pure iron minerals, impacting the release and re-distribution of SRO-associated trace elements and nutrients.In nature, however, pure SRO iron minerals rarely form. Rather, the ubiquitous presence of natural organic matter (OM) in soils and sediments promotes the formation mineral-organic associations. Coprecipitation of ferrihydrite with OM decreases particle size and alters the mineral susceptibility towards microbial reduction. Thus, under reducing conditions, an increased rate and extent of mineral transformation could be expected for OM-associated ferrihydrite. However, in the presence of abiotic reductants, mineral transformation rates and extents in OM-associated ferrihydrite are markedly inhibited when compared to that of a pure ferrihydrite. Using polygalacturonic acid (PGA) as a proxy for acid carbohydrate fraction found in exopolymeric substances, we reacted ferrihydrite-PGA coprecipitates of varying C:Fe molar ratios (0-2.5) with ferrous Fe (Fe(II), 0.5-5.0 mM) at neutral pH for up to 5 weeks. Through a combination of XRD and 57Fe Mössbauer spectroscopy, we showed that at all Fe(II) concentrations, the kinetics and extent of mineral transformation decreased with increasing C content of the coprecipitates. Similarly, ferrihydrite-OM coprecipitates comprising PGA, citric acid (CA), or galacturonic acid (GA) of similar C:Fe molar ratios (~0.6) also showed inhibited mineral transformations compared to a pure ferrihydrite, whereby the extent of inhibition of mineral transformations followed the order GA>>CA>PGA. In addition, electron microscopy imaging showed that the crystal morphology of the secondary mineral phases varied with the varying chemical structure of the coprecipitating organic ligands. Despite this, applications of stable Fe isotope tracers revealed that all OM-associated ferrihydrite actively partook in iron atom exchange, suggesting that the presence of OM inhibited crystal growth of more crystalline phases, therefore again leading to SRO phases during iron atom exchange. Collectively, the stabilization of high surface-area ferrihydrite under reducing conditions via recrystallization has implications for the release and re-distribution of ferrihydrite-associated trace elements and nutrients in redox-dynamic environments.

Phylogenetically diverse species of bacteria can mediate anaerobic oxidation of ferrous iron [Fe(II)] and/or arsenite [As(III)] coupled to nitrate reduction, impacting the biogeochemical cycles of Fe and As. However, the mechanisms for nitrate-dependent anaerobic oxidation of Fe(II) and As(III) remain unclear. In this study, we isolated two bacterial strains from arsenic-contaminated paddy soils, Ensifer sp. ST2 and Paracoccus sp. QY30. Both strains were capable of anaerobic As(III) oxidation, but only QY30 could oxidize Fe(II) under nitrate-reducing conditions. Both strains contain the As(III) oxidase gene aioA, whose expression was induced greatly by As(III) exposure. Both strains contain the whole suite of genes for complete denitrification, but the nitrite reductase gene nirK was not expressed in QY30 and nitrite accumulated under nitrate-reducing conditions. When the functional nirK gene was knocked out in strain ST2, its nitrite reduction ability was completely abolished and nitrite accumulated in the medium. Moreover, the ST2ΔnirK mutant gained the ability to oxidize Fe(II). When nirK gene from ST2 was introduced to QY30, the recombinant strain QY30::nirK gained the ability to reduce nitrite but lost the ability to oxidize Fe(II). These genetic manipulations did not affect the ability of both strains to oxidize As(III). Our results indicate that nitrite accumulation is required for anaerobic oxidation of Fe(II) but not for As(III) oxidation in these strains. The results suggest that anaerobic Fe(II) oxidation in the two bacterial strains is primarily driven by abiotic reaction of Fe(II) with nitrite, while reduction of nitrate to nitrite is sufficient for redox coupling with anaerobic As(III) oxidation catalyzed by Aio. Deletion of nirK gene in denitrifiers can enhance anaerobic Fe(II) oxidation.

In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57Fe Mossbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, r...

In submerged soils and sediments, clay minerals are often exposed to anoxic waters containing ferrous iron (Fe2+). Here, we investigated the sorption of Fe2+ onto a synthetic montmorillonite (Syn-1) low in structural Fe (

Phosphorus (P) is often a limiting nutrient in soils and aquatic systems, but excessive concentrations can lead to eutrophication. The chemical forms in which P is retained in soils and sediments determine its bioavailability. Under reducing conditions, the ferrous phosphate mineral vivianite has been shown to be a major P burial phase in various environments such as coastal sediments. Depending on the local environmental geochemistry, ferrous iron (Fe2+) can be substituted by other divalent cations such as magnesium (Mg2+) and manganese (Mn2+). The substitution of Fe2+ could alter mineralogical characteristics of vivianite, which influences its further reactivity and thus the P and iron (Fe) cycle. Despite the importance of divalent cation substitution in vivianite in the environment, questions remain if certain divalent cations are preferentially incorporated and how they compete for substitution.Here, we assessed the competitive incorporation of Mn2+ and Mg2+ into vivianite by carrying out vivianite precipitation experiments in anoxic aqueous solutions at pH 7. Additionally, we explored how varying salinity simulating an estuarine gradient influences the incorporation of Mn2+ and Mg2+. Changes in mineralogy with different degrees of Mn2+/ Mg2+ substitution were studied with X-ray powder diffraction, Raman spectroscopy, total elemental dissolution and other techniques.Based on 19 different vivianites, our results demonstrate that Fe2+ is replaced by up to 50% by Mn2+/ Mg2+ in the vivianite structure, with preferential incorporation of Mn2+ over Mg2+. Increases in salinity seem to slightly enhance divalent cation incorporation. Following from our results, we will discuss the factors influencing divalent cation incorporation into vivianite, and how divalent cation substitution alters mineralogical characteristics. Finally, we will highlight how the substitution of Fe2+ by other divalent cations potentially enhances P fixation in form of vivianite under Fe-limiting conditions.

Poorly crystalline Fe(III) (oxyhydr)oxides like ferrihydrite are abundant in soils and sediments and are often associated with organic matter (OM) in the form of mineral-organic aggregates. Under anoxic conditions, interactions between aqueous Fe(II) and ferrihydrite lead to the formation of crystalline secondary minerals, like lepidocrocite, goethite, or magnetite. However, the extent to which Fe(II)-catalyzed mineral transformations are influenced by ferrihydrite-associated OM is not well understood. We therefore reacted ferrihydrite-PGA coprecipitates (PGA = polygalacturonic acid, C:Fe molar ratios = 0–2.5) and natural Fe-rich organic flocs (C:Fe molar ratio = 2.2) with 0.5–5.0 mM isotopically labeled 57Fe(II) at pH 7 for 5 weeks. Relying on the combination of stable Fe isotope tracers, a novel application of the PONKCS method to Rietveld fitting of X-ray diffraction (XRD) patterns, and 57Fe Mossbauer spectroscopy, we sought to follow the temporal evolution in Fe mineralogy and elucidate the fate of ad...

Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. To date, spectroscopic speciation analyses of Fe and trace elements in these mineral-organic matter (OM) associations are missing. In this study, we investigated the speciation and distribution of Fe and As in flocs collected from low-flow streams (pH 5.3-6.3) of the naturally As-enriched peatland Gola di Lago (Switzerland) using (57)Fe Mössbauer spectroscopy and synchrotron X-ray techniques. The flocs were rich in acid carbohydrates and contained up to 22.1 wt % Fe, 34.9 wt % C, and 2620 mg/kg As. Mössbauer analyses revealed small quantities (5%) of Fe(II) and Fe(III)-OM complexes and the predominance of ferrihydrite (∼ Fe(5)HO(8) · 4H2O, 51-59%) and lepidocrocite (γ-FeOOH, 34-46%). The latter was not observed by synchrotron X-ray diffraction, implying a coherent scattering domain size of10 nm. Iron X-ray absorption spectroscopy (XAS) confirmed the Mössbauer results, and bulk As XAS indicated the prevalence of arsenate (71-84%) in the flocs. Shell-fit analyses showed that As was entirely sorbed to Fe(III)-(oxyhydr)oxides and that both arsenate and arsenite exclusively formed monodentate-binuclear ("bridging") complexes (R(As-Fe) = 3.31-3.34 Å). Microfocused X-ray fluorescence spectrometry documented a strong correlation between As and Fe in the flocs. These analyses also revealed intense As hotspots coinciding with abundant freshwater green algae (Closterium spp.). Microfocused As X-ray absorption near-edge structure spectra collected at algae-specific points identified up to 29% As(III), which, in combination with ∼ 5% As(III) detected at Fe-rich points, suggests As(V) bioreduction in the algae. Our findings imply that floc (bio)organics serve primarily as nucleation sites for the precipitation of nanocrystalline Fe(III)-(oxyhydr)oxides, rendering flocs effective sorbents for trace metal(loid)s. Thus, Fe-rich freshwater flocs likely play a pivotal role for the speciation and cycling of trace elements in wetlands.

Iron rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low flow stream conditions flocs may settle become buried and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study we reacted freshwater flocs (704 1280 mg As/kg) from a minerotrophic peatland (Gola di Lago Switzerland) with sulfide (5.2 mM S( II)(spike)/Fe = 0.75 1.62 mol/mol) at neutral pH and studied the speciation changes of Fe S and As at 25 +/ 1 degrees C over 1 week through a combination of synchrotron X ray techniques and wet chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52 81 of Fe solid at day 7) as well as solid phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide ieacted flocs contained primarily arsenate (47 72) which preferentially adsorbed to Fe(III) (oxyhydr)oxides despite abundant mackinawite precipitation. At higher S( II)(spike)/Fe molar ratios (>= 1.0) the formation of an orpiment like phase accounted for up to 35 of solid phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III) (oxyhydr)wddes mobilization of As was recorded in all samples (As aq = 0.45 7.0 mu M at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33 of As aq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate reducing conditions and emphasize the pivotal role Fe rich organic freshwater flocs play in trace metal(loid) cycling in S rich wetlands characterized by oscillating redox conditions.