Fe(II)-Catalyzed Recrystallization Drives Phosphorus and Aluminum Release from Goethite.

Goethite often harbors impurities, such as phosphorus (P) and aluminum (Al), which are incorporated into its structure through direct substitution or coprecipitation with nanocrystalline phases. Understanding the processes that drive the release of P and Al from goethite is of paramount importance for the iron ore industry and for managing nutrient and pollutant behavior in the environment. This study investigates the impact of Fe(II)-catalyzed recrystallization on the release of P and Al from goethite. We evaluated the solubility and extractability of P and Al in suspensions of Al- and P-coprecipitated goethite, treated with 57Fe-enriched Fe(II)aq under oxygen-free conditions for 30 days at neutral pH and room temperatures. The addition of Fe(II)aq induced the recrystallization of goethite dominant initial synthetic phases (i.e., low P- and Al-containing phases) and the transformation of higher P- and/or Al-bearing starting material that was actually a mixture of goethite and minor amounts of lepidocrocite and feroxyhyte. Our results reveal that Fe(II)-catalyzed mineral and structural evolution led to the repartitioning of P and, to a lesser extent, Al throughout the crystal structure, mineral surface, and aqueous solution. Following a 30 day reaction with Fe(II)aq, we extracted approximately 80, 68.8, 73.9, and 83.2% of P from P-only, low, medium, and high P + Al goethite, respectively. Additionally, we observed total Al removals of approximately 17, 27, and 25% from low, medium, and high P + Al goethite, respectively. The results demonstrate that treating both P-only and P + Al goethite with Fe(II) at room temperature, followed by a 24 h extraction using 1 M NaOH, significantly enhances the overall extractability of P and Al, including both aqueous and surface-adsorbed fractions, compared to Fe(II)-free controls. These findings advance our understanding of the recrystallization process and impurity substitution in goethite, offering promising avenues for developing new environmentally friendly methods to extract P and other impurities from goethitic iron ores at lower temperatures.

Antimony sorption to schwertmannite in acid sulfate environments.

Schwertmannite is a poorly-crystalline Fe(III) oxyhydroxysulfate mineral that may control Sb(V) mobility in acid sulfate environments, including acid mine drainage and acid sulfate soils. However, the mechanisms that govern uptake of aqueous Sb(V) by schwertmannite in such environments are poorly understood. To address this issue, we examined Sb(V) sorption to schwertmannite across a range of environmentally-relevant Sb(V) loadings at pH 3 in sulfate-rich solutions. Antimony K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that Sb(V) sorption (at all loadings) involved edge and double-corner sharing linkages between SbVO6 and FeIIIO6 octahedra. The coordination numbers for these linkages indicate that sorption occurred by Sb(V) incorporation into the schwertmannite structure via heterovalent Sb(V)-for-Fe(III) substitution. As such, Sb(V) sorption to schwertmannite was not limited by the abundance of surface complexation sites and was strongly resistant to desorption when exposed to 0.1 M PO43-. Sorption of Sb(V) also conferred increased stability to schwertmannite, based on changes in the schwertmannite dissolution rate during extraction with an acidic ammonium oxalate solution. This study provides new insights into Sb(V) sorption to schwertmannite in acid sulfate environments, and highlights the role that schwertmannite can play in immobilizing Sb(V) within its crystal structure.

Floodplain morphology influences arsenic and antimony spatial distribution in a seasonal acid sulfate soil wetland.

Arsenic (As) and antimony (Sb) often co-occur in floodplain depositional environments that are contaminated by legacy mining activities. However, the distribution of As and Sb throughout floodplains is not uniform, adding complexity and expense to management or remediation processes. Identifying floodplain morphology predictor variables that help quantify and explain As and Sb spatial distribution on floodplains is useful for management and remediation. We developed As and Sb risk maps estimating concentration and availability at a coastal floodplain wetland impacted by upper-catchment mining. Significant predictors of As and Sb concentrations included i) distance from distributary channel-wetland intersection and ii) elevation. Distance from channel explained 53 % (P < 0.01) and 28 % (P < 0.01), while elevation explained 42 % (P < 0.01) and 47 % (P < 0.01) of the variability in near-total Sb and As respectively. As had a higher extractability than Sb across all tested soil extractions, suggesting that As is more environmentally available. As and Sb dry mass estimates to a depth of 0.1 m scaled to the lower coastal Macleay floodplain ranged from 113-192 tonnes and 14-24 tonnes respectively. Landscape-scale modelling of metalloid distribution, informed by morphology variables, presented here may be a useful framework for the development of risk maps in other regions impacted by contaminated upper-catchment sediments.

Extreme iron cycling in a coastal lake-lagoon system driven by interactions between climate and entrance management.

Intermittently closed and open coastal lakes and lagoons (ICOLLs) are ecologically important and hydrologically sensitive estuarine systems. We explore how extreme drought and ICOLL entrance management intersect to influence the geochemical cycling of iron. Opening the ICOLL entrance just prior to an extreme drought in 2019 led to prolonged extremely low water levels, thereby exposing intertidal/subtidal sulfidic sediments and causing oxidation of sedimentary pyrite. Subsequent reflooding of exposed sediments for ∼4 months led to extremely elevated Fe2+(aq) (>10 mM) in intertidal hyporheic porewaters, consistent with Fe2+(aq) release via pyrite oxidation and via reductive dissolution of newly-formed Fe(III) phases. Re-opening the ICOLL entrance caused a rapid fall in water levels (∼1.5 m over 7 d), driving the development of effluent groundwater gradients in the intertidal zone, thereby transporting Fe2+-rich porewater into surface sediments and surface waters. This was accompanied by co-mobilisation of some trace metals and nutrients. On contact with oxic, circumneutral-pH estuarine water, the abundant Fe2+(aq) oxidised, forming a spatially extensive accumulation of poorly crystalline Fe(III) oxyhydroxide floc (up to 25 % Fe dry weight) in shallow intertidal zone benthic sediments throughout the ICOLL. Modelling estimates ∼4050 × 103 kg of poorly-crystalline Fe was translocated into surficial sediments. The newly formed Fe(III)-oxyhydroxides serve as a metastable sink encouraging enrichment of both phosphate and various trace metal(loid)s in near-surface sediments, which may have consequences for future cycling of nutrients, metals and ICOLL ecological function. The additional Fe also may enhance ICOLL sensitivity to similar future drought events by encouraging pyrite formation in shallow (<5 cm) benthic sediments. This system-wide translocation of Fe from deeper sediments into surficial benthic sediments represents a form of geochemical hysteresis with an uncertain recovery trajectory. This study demonstrates how climate extremes can interact with anthropogenic management to amplify ICOLL hydrological oscillations and influence biogeochemistry in complex ways.

Assessment of mercury distribution and bioavailability from informal coastal cinnabar mining - Risk to the marine environment.

Coastal cinnabar mining commenced in 2010 around Luhu on Seram (Ceram) Island, Indonesia. This study investigates the ore characteristics and environmental distribution and bioavailability of mercury in coastal sediments from eight sites adjacent to, and north and south of the mining area. Sediment and ore samples were digested using 1:3 HNO3:HCl for total extractable metal determination and separate samples were extracted with 1.0 HCl for bioavailable metals (Hg, Cu, Zn, Cr, Ni and Pb). Analysis was completed using inductively coupled plasma-mass spectrometry. Ore defined by miners as 'first class ore' was around 50 % cinnabar. Mercury concentrations were extremely elevated in near coastal sediments (up to 2796 mg/kg) with bioavailable concentrations exceeding 450 mg/kg. Marine sediments elevated in mercury extend to the north and south of the coastal mine site and cover in excess of 14 km. Total organic carbon in marine sediments was relatively low (predominately <0.6 %) suggesting mercury methylation will likely be slow, however, inorganic mercury is a known toxicant. Other metals of environmental concern (Cu, Zn, Cr, Ni and Pb) in sediments were not strongly associated with the mining operations, rather were elevated around coastal villages, but not at concentrations that raise immediate concerns.

Coupling of Dissolved Organic Matter Molecular Fractionation with Iron and Sulfur Transformations during Sulfidation-Reoxidation Cycling.

Iron (oxyhydr)oxides and organic matter (OM) are intimately associated in natural environments, and their fate might be linked to sulfur during sulfidation-reoxidation cycling. However, the coupling of DOM molecular fractionation with Fe and S transformations following a full sulfidation-reoxidation cycle remains poorly understood. Here, we reacted Fh and Fh-OM associations with S(-II) anaerobically and then exposed the sulfidic systems to air. S(-II) preferentially reacted with Fh to form inorganic S (e.g., mackinawite, S0, and S22-) over being incorporated into OM as organic S and therefore indirectly affected OM fate by altering Fe speciation. Fh sulfidation was inhibited by associated OM, and the main secondary Fe species were mackinawite, Fe(II)-OM compounds, and lepidocrocite. Concomitantly, organic molecules high in unsaturation, aromaticity, and molecular weight were detached from solid-phase Fe species due to their lower affinities for secondary Fe species than for Fh. During the reoxidation stage, the previously formed Fe(II) species were reoxidized to Fh with a stronger aggregation, which recaptured formerly released OM with higher selectivity. Additionally, •OH was generated from Fe(II) oxygenation and degraded a portion of the DOM molecules. Overall, these results have significant implications for Fe, C, and S cycling in S-rich environments characterized by oscillating redox conditions.

Mechanisms of Arsenic and Antimony Co-sorption onto Jarosite: An X-ray Absorption Spectroscopic Study.

Jarosite, a common mineral in acidic sulfur-rich environments, can strongly sorb both As(V) and Sb(V). However, little is known regarding the mechanisms that control simultaneous co-sorption of As(V) and Sb(V) to jarosite. We investigated the mechanisms controlling As(V) and Sb(V) sorption to jarosite at pH 3 (in dual and single metalloid treatments). Jarosite was found to sorb Sb(V) to a greater extent than As(V) in both single and dual metalloid treatments. Relative to single metalloid treatments, the dual presence of both As(V) and Sb(V) decreased the sorption of both metalloids by almost 50%. Antimony K-edge EXAFS spectroscopy revealed that surface precipitation of an Sb(V) oxide species was the predominant sorption mechanism for Sb(V). In contrast, As K-edge EXAFS spectroscopy showed that As(V) sorption occurred via bidentate corner-sharing complexes on the jarosite surface when Sb(V) was absent or present at low loadings or by formation of similar complexes on the Sb(V) oxide surface precipitate when Sb(V) was present at high loadings. These results point to a novel mechanism by which Sb(V) impacts the co-sorption of As(V). Overall, these findings highlight a strong contrast in the sorption mechanisms of Sb(V) versus As(V) to jarosite under acidic environmental conditions.

Porous titania beads for remediation of arsenic contamination from acid mine drainage.

Hierarchically porous titania beads with and without amine functionalisation have been developed and tested as adsorbents for removal of highly toxic As(V) from environments affected by acid mine drainage (AMD). The unique acid stability of the titania framework enables these adsorbents to function in highly acidified environments and their granular form facilitates practical deployment under continuous flow conditions. Herein, both non-functionalised and amine-functionalised titania beads have been demonstrated to selectively remove As(V) from simulated and real AMD solutions at pH 2.6. Novel selectivity for As(V) over Na(I), Mg(II), Al(III), Si(VI), Ca(II), Co(II), Cu(II), Zn(II), Nd(III) and Ho(III) was achieved, with competing element concentrations similar to or up to an order of magnitude greater than that of As(V). Although Fe(III) and some Fe(II) were also adsorbed by the titania beads, Fe adsorption did not inhibit As(V) adsorption, indicating different adsorption mechanisms for these two elements. The As(V) adsorption capacity of the titania beads decreased from ∼20 mg/g from pure As(V) solution to ∼10 mg/g from real AMD solution, demonstrating the importance of adsorbent testing under applied conditions. Amine functionalisation increased the kinetics of adsorption, but the non-functionalised titania beads showed greater selectivity for As(V) over Fe(II) and Fe(III) and hence were considered preferable for As remediation applications. Nevertheless, the functionalisation ability of the porous titania beads makes them a promising, flexible technology for remediation of a wide range of AMD affected environments.

Iron Isotopes in Acid Mine Drainage: Extreme and Divergent Fractionation between Solid (Schwertmannite, Jarosite, and Ferric Arsenate) and Aqueous Species.

Examination of stable Fe isotopes is a powerful tool to explore Fe cycling in a range of environments. However, the isotopic fractionation of Fe in acid mine drainage (AMD) has received little attention and is poorly understood. Here, we analyze Fe isotopes in waters and Fe(III)-rich solids along an AMD flow-path. Aqueous Fe spanned a concentration and δ56Fe range of ∼420 mg L-1 and + 0.04‰ at the AMD source to ∼100 mg L-1 and -0.81‰ at ∼450 m downstream. Aqueous As (up to ∼33 mg L-1) and SO42- (up to ∼2000 mg L-1), like aqueous Fe, decreased in concentration down the flow-path. X-ray absorption spectroscopy indicated that downstream attenuation in aqueous Fe, As, and SO42- was due to the precipitation of amorphous ferric arsenate (AFA), schwertmannite, and jarosite. The Fe(III) in these solids displayed extreme variability in δ56Fe, spanning +3.95‰ in AFA near the AMD source to -1.34‰ in schwertmannite at ∼450 m downstream. Similarly, the isotopic contrast between solid Fe(III) precipitates and aqueous Fe (Δ56Feppt-aq) dropped along the flow-path from about +4.1 to -1.1‰. The shift from positive to negative Δ56Feppt-aq reflects divergence between competing equilibrium versus kinetic fractionation processes.

Antimony(V) Incorporation into Schwertmannite: Critical Insights on Antimony Retention in Acidic Environments.

This study examines incorporation of Sb(V) into schwertmannite─an Fe(III) oxyhydroxysulfate mineral that can be an important Sb host phase in acidic environments. Schwertmannite was synthesized from solutions containing a range of Sb(V)/Fe(III) ratios, and the resulting solids were investigated using geochemical analysis, powder X-ray diffraction (XRD), dissolution kinetic experiments, and extended X-ray absorption fine structure (EXAFS) spectroscopy. Shell-fitting and wavelet transform analyses of Sb K-edge EXAFS data, together with congruent Sb and Fe release during schwertmannite dissolution, indicate that schwertmannite incorporates Sb(V) via heterovalent substitution for Fe(III). Elemental analysis combined with XRD and Fe K-edge EXAFS spectroscopy shows that schwertmannite can incorporate Sb(V) via this mechanism at up to about 8 mol % substitution when formed from solutions having Sb/Fe ratios ≤0.04 (higher ratios inhibit schwertmannite formation). Incorporation of Sb(V) into schwertmannite involves formation of edge and double-corner sharing linkages between SbVO6 and FeIII(O,OH)6 octahedra which strongly stabilize schwertmannite against dissolution. This implies that Sb(V)-coprecipitated schwertmannite may represent a potential long-term sink for Sb in acidic environments.

Tooeleite Transformation and Coupled As(III) Mobilization Are Induced by Fe(II) under Anoxic, Circumneutral Conditions.

Tooeleite [FeIII6(AsIIIO3)4SO4(OH)4.4H2O] is an important As(III) host phase in diverse mining-impacted environments. Tooeleite has also received attention as a target phase for immobilizing As(III) in environmental and engineered settings. However, little is known regarding tooeleite's environmental stability, with no previous research examining the possible role of Fe(II) in inducing tooeleite transformation (as occurs for Fe(III) oxide minerals). We investigated shifts in solid-phase Fe and As speciation and associated As mobilization into the aqueous phase during exposure of tooeleite to aqueous Fe(II) under anoxic conditions at pH 4 to 8. Our results demonstrate that environmentally relevant concentrations of aqueous Fe(II) (i.e., 1 to 10 mM) induce significant mobilization of As(III) from tooeleite under near-neutral pH conditions, with greater As(III) mobilization occurring at higher pH. Extended X-ray absorption fine structure spectroscopy at both the As and Fe K-edge reveals that the observed As(III) mobilization was coupled with partial Fe(II)-induced transformation of tooeleite to As(III)-bearing ferrihydrite at pH 6 to 8. These results provide new insights into the environmental stability of tooeleite and demonstrate a novel pathway for As(III) mobilization in tooeleite-bearing systems.

Remediation of Pb-contaminated soil using modified bauxite refinery residue.

This study examines amendment of Pb-contaminated soil with modified bauxite refinery residue (MBRR) to decrease soil Pb mobility and bioaccessibility. Amendment experiments were conducted using four soils contaminated with Pb from various sources, including smelting, shooting-range activities and Pb-based paint waste. Lead L3-edge X-ray absorption spectroscopy (XAS) indicated that Pb speciation in these soils was a mixture of Pb sorbed to Fe (hydr)oxide and clay minerals, along with Pb bound to organic matter. Amendment with MBRR decreased water-soluble Pb and/or Toxicity Characteristic Leachate Procedure (TCLP) Pb concentrations. Lead L3-edge XAS and X-ray diffraction (XRD) indicated that Pb retention by MBRR occurred via sorption to Fe- and Al-(hydr)oxides at low Pb loadings, in addition to formation of hydrocerussite (Pb3(CO3)2(OH)2) at high loadings. Soil amendment with MBRR had relatively little effect on gastric-phase Pb bioaccessibility; as quantified via the Solubility/Bioavailability Research Consortium, SBRC, in vitro assay. In contrast, amendment with MBRR caused substantial decreases in relative intestinal-phase Pb bioaccessibility (Rel-SBRC-I) due to increased Pb sorption by MBRR's Fe- and Al-hydr(oxide) minerals as simulated GI tract conditions shifted from the gastric- to the intestinal-phase. These decreases in Rel-SBRC-I point to the potential efficacy of using amendment with MBRR to decrease soil Pb bioavailability.

An X-ray absorption spectroscopic study of the Fe(II)-induced transformation of Cr(VI)-substituted schwertmannite.

The environmental chemistry of Cr is of widespread interest due to the hazardous nature of Cr(VI). Because of similar atomic size and charge, CrVIO42- can substitute for SO42- within schwertmannite - an Fe(III) oxyhydroxysulfate mineral that occurs widely in acidic and sulfate-rich systems. The presence of aqueous Fe(II) can induce transformation of schwertmannite to more stable Fe(III) phases (e.g. goethite) which may potentially impact the behaviour of co-associated Cr(VI). Here, we investigate the Fe(II)-induced transformation of Cr(VI)-substituted schwertmannite as a function of pH (4-8) and the degree of Cr(VI) substitution (0.16-13 mol% CrVIO42--for-SO42- substitution). Iron K-edge EXAFS spectroscopy revealed that higher levels of Cr(VI) substitution inhibited Fe(II)-induced schwertmannite transformation. Chromium K-edge XANES spectroscopy indicated that this outcome could be partly attributed to consumption of Fe(II) by reaction with Cr(VI), and the resulting formation of a passivating Cr(III)-Fe(III) hydroxide phase which stabilizes schwertmannite at greater levels of Cr(VI) substitution and at higher pH while also decreasing further reduction of structural Cr(VI). Overall, this study enriches our understanding of interactions between hazardous Cr(VI) and schwertmannite in environmental and engineered systems.

Antimony speciation, phytochelatin stimulation and toxicity in plants.

Antimony (Sb) is a toxic metalloid that has been listed as a priority pollutant. The environmental impacts of Sb have recently attracted attention, but its phytotoxicity and biological transformation remain poorly understood. In this study, Sb speciation and transformation in plant roots was quantified by Sb K-edge X-ray absorption spectroscopy. In addition, the phytotoxicity of antimonate (SbV) on six plant species was assessed by measuring plant photosynthesis, growth, and phytochelatin production induced by SbV. Linear combination fitting of the Sb K-edge X-ray absorption near-edge structure (XANES) spectra indicated reduction of SbV was limited to ∼5-33% of Sb. The data confirmed that Sb-polygalacturonic acid was the predominant chemical form in all plant species (up to 95%), indicating Sb was primarily bound to the cell walls of plant roots. Shell fitting of Sb K-edge X-ray absorption fine-structure (EXAFS) spectra confirmed Sb-O and Sb-C were the dominant scattering paths. The fitting indicated that SbV was bound to hydroxyl functional groups of cell walls, via development of a local coordination environment analogous to Sb-polygalacturonic acid. This is the first study to demonstrate the key role of plant cell walls in Sb metabolism.

Antimonate Controls Manganese(II)-Induced Transformation of Birnessite at a Circumneutral pH.

Manganese (Mn) oxides, such as birnessite (δ-MnO2), are ubiquitous mineral phases in soils and sediments that can interact strongly with antimony (Sb). The reaction between birnessite and aqueous Mn(II) can induce the formation of secondary Mn oxides. Here, we studied to what extent different loadings of antimonate (herein termed Sb(V)) sorbed to birnessite determine the products formed during Mn(II)-induced transformation (at pH 7.5) and corresponding changes in Sb behavior. In the presence of 10 mM Mn(II)aq, low Sb(V)aq (10 µmol L-1) triggered the transformation of birnessite to a feitknechtite (ß-Mn(III)OOH) intermediary phase within 1 day, which further transformed into manganite (γ-Mn(III)OOH) over 30 days. Medium and high concentrations of Sb(V)aq (200 and 600 µmol L-1, respectively) led to the formation of manganite, hausmannite (Mn(II)Mn(III)2O4), and groutite (αMn(III)OOH). The reaction of Mn(II) with birnessite enhanced Sb(V)aq removal compared to Mn(II)-free treatments. Antimony K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that heterovalent substitution of Sb(V) for Mn(III) occurred within the secondary Mn oxides, which formed via the Mn(II)-induced transformation of Sb(V)-sorbed birnessite. Overall, Sb(V) strongly influenced the products of the Mn(II)-induced transformation of birnessite, which in turn attenuated Sb mobility via incorporation of Sb(V) within the secondary Mn oxide phases.

Impact of Antimony(V) on Iron(II)-Catalyzed Ferrihydrite Transformation Pathways: A Novel Mineral Switch for Feroxyhyte Formation.

The environmental mobility of antimony (Sb) is controlled by interactions with iron (Fe) oxides, such as ferrihydrite. Under near-neutral pH conditions, Fe(II) catalyzes the transformation of ferrihydrite to more stable phases, thereby potentially altering the partitioning and speciation of associated Sb. Although largely unexplored, Sb itself may also influence ferrihydrite transformation pathways. Here, we investigated the impact of Sb on the Fe(II)-induced transformation of ferrihydrite at pH 7 across a range of Sb(V) loadings (Sb:Fe(III) molar ratios of 0, 0.003, 0.016, and 0.08). At low and medium Sb loadings, Fe(II) induced rapid transformation of ferrihydrite to goethite, with some lepidocrocite forming as an intermediate phase. In contrast, the highest Sb:Fe(III) ratio inhibited lepidocrocite formation, decreased the extent of goethite formation, and instead resulted in substantial formation of feroxyhyte, a rarely reported FeOOH polymorph. At all Sb loadings, the transformation of ferrihydrite was paralleled by a decrease in aqueous and phosphate-extractable Sb concentrations. Extended X-ray absorption fine structure spectroscopy showed that this Sb immobilization was attributable to incorporation of Sb into Fe(III) octahedral sites of the neo-formed minerals. Our results suggest that Fe oxide transformation pathways in Sb-contaminated systems may strongly differ from the well-known pathways under Sb-free conditions.

Reductive transformation of birnessite and the mobility of co-associated antimony.

Manganese (Mn) oxide minerals, such as birnessite, are thought to play an important role in affecting the mobility and fate of antimony (Sb) in the environment. In this study, we investigate Sb partitioning and speciation during anoxic incubation of Sb(V)-coprecipitated birnessite in the presence and absence of Mn(II)aq at pH 5.5 and 7.5. Antimony K-edge XANES spectroscopy revealed that Sb(V) persisted as the only solid-phase Sb species for all experimental treatments. Manganese K-edge EXAFS and XRD results showed that, in the absence of Mn(II), the Sb(V)-bearing birnessite underwent no detectable mineralogical transformation during 7 days. In contrast, the addition of 10 mM Mn(II) at pH 7.5 induced relatively rapid (within 24 h) transformation of birnessite to manganite (~93%) and hausmannite (~7%). Importantly, no detectable Sb was measured in the aqueous phase for this treatment (compared with up to ∼90 µmol L-1 Sb in the corresponding Mn(II)-free treatment). At pH 5.5 , birnessite reacted with 10 mM Mn(II)aq displayed no detectable mineralogical transformation, yet had substantially increased Sb retention in the solid phase, relative to the corresponding Mn(II)-free treatment. These findings suggest that the Mn(II)-induced transformation and recrystallization of birnessite can exert an important control on the mobility of co-associated Sb.

Antimony and arsenic speciation, redox-cycling and contrasting mobility in a mining-impacted river system.

The Macleay River in eastern Australia is severely impacted by historic stibnite- and arsenopyrite-rich mine-tailings. We explore the partitioning, speciation, redox-cycling, mineral associations and mobility of antimony and arsenic along >70 km reach of the upper Macleay River. Elevated Sb/As occur throughout the active channel-zone and in floodplain pockets up to the regolith margin, indicating broad dispersal during floods. Sb concentrations in bulk-sediments decay exponentially downstream more efficiently than As, likely reflecting sediment dilution, hydraulic sorting and comparatively greater leaching of (more mobile) Sb(V) species. However, Sb in bulk-sediments becomes proportionally more bio-available downstream. Sb(V) and As(V) species dominate stream fine-grained (<180 µm) bulk-sediments, reflecting oxidative weathering downstream. Increasing poorly-crystalline Fe(III) [Fe(III)HCl] in bulk-sediments also indicates progressive oxidative weathering of Fe(II)-bearing minerals downstream and significant (P < .05) correlations exist between PO4-3-exchangeable As and Sb fractions and Fe(III)HCl. Accumulations of poorly-crystalline Fe(III) precipitates (mainly ferrihydrite/feroxyhyte) occur intermittently in hyporheic-zone seeps and are enriched in As relative to Sb and contain some As(III) and Sb(III) (~30-40%). There is dynamic in-stream redox-cycling of both Sb and As, with localised S-coordinated As and Sb species re-forming in organic-rich, hyporheic sediments subject to contemporary sulfidogenesis. Sb [mainly Sb(V)] is comparatively more mobile in hyporheic and surface waters under oxic conditions, whereas As [mainly As(III)] is more mobile in hyporheic porewaters subject to reducing/sulfidogenic conditions. Repeat water-leaching of bulk-sediments confirms that Sb is proportionally more mobile than As. Mean concentrations of Sb in river water 168 km downstream from the mine are significantly (P < .05) higher than As, while Kd data indicate Sb is more strongly partitioned to the aqueous phase than As. Although the (mainly) oxic flow path of this river favours aqueous Sb mobility compared to As, localised redox-driven shifts in speciation of both elements strongly influence their respective mobility and partitioning.

Antimony speciation and mobility during Fe(II)-induced transformation of humic acid-antimony(V)-iron(III) coprecipitates.

Antimony, as the Sb(V) species, often occurs in oxic soils and sediments as coprecipitates with poorly-crystalline Fe(III)-bearing minerals. It is common for these Sb(V)-Fe(III) coprecipitates to also contain varying quantities of co-occurring humic acid (HA). When exposed to reducing conditions, the production of Fe(II) may cause the initial metastable HA-Sb(V)-Fe(III) phases to undergo rapid transformations to more stable phases, thereby potentially influencing the geochemical behavior of coprecipitated Sb(V). However, little is known about the impacts of this transformation on the mobility and speciation of Sb. In this study, we reacted synthetic HA-Sb(V)-Fe(III) coprecipitates (Fe:Sb ratio = 4, and C:Fe molar ratios = 0, 0.3, 0.8 and 1.3) with 0, 1 or 10 mM Fe(II) under O2-free conditions at pH 7.0 for 15 days. Fe K-edge EXAFS spectroscopy revealed that solid-phase Fe(III) in the initial coprecipitates contained a mixture of ∼4/5 ferrihydrite (Fe10O14(OH)2) and ∼1/5 tripuhyite (FeSbO4), regardless of the corresponding amount of coprecipitated HA. Tripuhyite persisted throughout the full experiment duration, while ferrihydrite was partially replaced by goethite (FeOOH) when either 1 or 10 mM Fe(II)aq was added to the coprecipitates. The greatest level of goethite formation (∼55% of solid-phase Fe) was observed in the HA-free/10 mM Fe(II)aq treatment, with ferrihydrite transformation being partially attenuated at higher levels of HA. Mobilisation of aqueous Sb was the greatest for 1 mM Fe(II) treatments at high HA:Fe ratios. Sb K-edge XANES spectroscopy showed that the largest reduction of Sb(V) to Sb(III) (∼37%) and the greatest repartitioning of Sb to the mineral surface (∼7.9-9.8%) occurred in the coprecipitates with the highest HA contents in the presence of 10 mM Fe(II). The results indicate that the amount of HA in HA-Sb(V)-Fe(III) coprecipitates can greatly influence mobility and speciation of Sb in Fe(II)-rich conditions. The results of this study provide new insights into alterations in Sb mobility and retention in response to Fe cycling under organic matter-rich reducing conditions.

Humic acid impacts antimony partitioning and speciation during iron(II)-induced ferrihydrite transformation.

The Fe(II)-induced transformation of ferrihydrite, a potent scavenger for antimony (Sb), can considerably influence Sb mobility in reducing soils, sediments and groundwater systems. In these environments, humic acids (HA) are prevalent, yet their influence on Sb behaviour during ferrihydrite transformation is poorly understood. In this study, we investigated the effect of HA on (1) Sb partitioning between solid, colloidal and dissolved phases and (2) Sb redox speciation during the Fe(II)-induced transformation of Sb(V)-bearing ferrihydrite at pH 6.0 and 8.0 and Fe(II) concentrations of 0, 1 and 10 mM. The results show that, at pH 8.0 and in the presence of 10 mM Fe(II), ferrihydrite was replaced by goethite, lepidocrocite and magnetite across a wide range of HA concentrations. At pH 6.0 in the 10 mM Fe(II) treatments, ferrihydrite transformed to mainly lepidocrocite and goethite in both HA-free and low HA treatments. In contrast, high HA concentrations retarded the rate and extent of ferrihydrite transformation at both pH 6.0 and 8.0 in the 1 mM Fe(II) treatments. Antimony K-edge XANES spectroscopy revealed up to 60% reduction of solid-phase Sb(V) to Sb(III), which corresponded with an increase in the PO43--extractable fraction of solid-phase Sb in HA- and Fe(II)-rich conditions at pH 8.0. In contrast to the observations at pH 8.0, minimal reduction of solid-phase Sb(V) was observed in the pH 6.0 treatments with the highest HA content, yet some reduction of Sb(V) occurred (~30-40%) at intermediate HA concentrations. Humic acid-rich conditions were also found to promote the formation of substantial amounts of colloidal Sb in the <0.45 µm to 3 kDa size range at both pH 6.0 and 8.0. Our results demonstrate that HA can exert an important control on the partitioning, mobility and speciation of Sb during Fe(II)-induced transformation of ferrihydrite in sub-surface environments.