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Fires in iron-rich seasonal wetlands can thermally transform Fe(III) minerals and alter their crystallinity. However, the fate of As associated with thermally transformed Fe(III) minerals is unclear, as are the consequences for As mobilization during subsequent reflooding and reductive cycles. Here, we subject As(V)-coprecipitated schwertmannite to thermal transformation (200, 400, 600 and 800 °C) followed by biotic reductive incubation (150 d) and examine aqueous- and solid-phase speciation of As, Fe and S. Heating to >400 °C caused transformation of schwertmannite to a nanocrystalline hematite with greater surface area and smaller particle size. Higher temperatures also caused the initially structurally incorporated As to become progressively more exchangeable, increasing surface-complexed As (AsEx) by up to 60-fold, thereby triggering enhanced As mobilization during incubation (~70-fold in the 800 °C treatment). Although more As was mobilized in biotic treatments than controls (~3-20?), in both cases it was directly proportional to initial AsEx and mainly due to abiotic desorption. Higher transformation temperatures also drove divergent pathways of Fe and S biomineralization and led to more As(V) and SO4 reduction relative to Fe(III) reduction. This study reveals thermal transformation of schwertmannite can greatly increase As mobility and has major consequences for As/Fe/S speciation under reducing conditions. Further research is warranted to unravel the wider implications for water quality in natural wetlands. [ABSTRACT FROM AUTHOR]

Abstract: Freshwater re-flooding is a relatively novel approach to remediate drained acid sulfate soil (ASS) wetlands. This study documents the geochemical consequences of restoring freshwater re-flooding for contemporary reduced inorganic sulfur (RIS) and iron species in two coastal floodplain ASS wetlands. Re-flooding has established predominantly reducing/suboxic conditions and encouraged organic carbon accumulation in surface sediments (~20–30%). The pH of former sulfuric horizons has increased by ~2–3 units, partly in response to alkalinity generation from anaerobic metabolism of organic carbon coupled with Fe(III) and SO4 2− reduction. Despite considerable sulfidisation, reactive Fe (FeR; sum of 1M HCl and citrate–dithionite extracts) and non-sulfidic Fe(II) remain abundant in both wetlands. High concentrations of Fe2+ (up to ~5mM) in wetland porewaters represent a considerable pool of labile net acidity and is partly a result of insufficient S(−II) to sequester excess Fe2+. Accumulation of iron sulfides appears to be constrained more by SO4 2− and carbon availability rather than FeR. Reformation and accumulation of RIS species is greatest in organic-rich surface horizons (~40–500μmolg−1), where time integrated RIS accumulation rates approximate 10–100nmolg−1 d−1. While pyrite is the dominant RIS species to have formed since re-flooding, there is anomalous accumulation of S(0) (up to 80μmolg−1), accounting for ~50% of the RIS pool in some samples. Greigite (Fe3S4) has formed in near-surface sediments and while AVS-S is a minor component of the RIS pool overall, at some locations maximum concentrations exceed 300μmolg−1. Contemporary near-surface pyrite is characterised by abundant small (200–300nm) crystals, in contrast to relic sedimentary pyrite of estuarine origin that is dominated by larger crystals with diverse habit. Although Fe and SO4 2− reduction are partly responsible for wetland-scale recovery from acute acidification, the resultant accumulation of diverse RIS species in surficial sediments indicates an oxidative component to the S-cycle and represents a hysteresis in S-cycling that contrasts markedly with the drained conditions existing before remediation. Analysis of seasonal climate fluctuations suggests that near-surface sediments containing contemporary RIS are vulnerable to oxidation and possible temporary re-acidification during future drought episodes. This study underscores the long-term legacy of ASS wetland drainage and highlights the need for both considered hydrological management of re-flooded wetlands and further study to quantify possible re-acidification risks associated with seasonal drought. [Copyright &y& Elsevier]

Abstract: Sulfur biogeochemical cycling and associated Fe–S mineralization processes exert a major influence over acidity dynamics, electron flow and contaminant mobility in wetlands, benthic sediments and groundwater systems. While S biogeochemical cycling has been studied intensively in many environmental settings, relatively little direct information exists on S cycling in formerly drained wetlands that have been remediated via tidal re-flooding. This study focuses on a tidal wetland that was drained in the 1970s (causing severe soil and water acidification), and subsequently remediated by controlled re-flooding in 2002. We examine reduction rates and Fe–S mineralization at the tidal fringe, 7years after the commencement of re-flooding. The initial drainage of the wetland examined here caused in-situ pyrite (FeS2) oxidation, resulting in the drained soil layers being highly acidic and rich in -bearing Fe(III) minerals, including jarosite (KFe3(SO4)2(OH)6). Tidal re-flooding has neutralized much of the previous acidity, with the pore-water pH now mostly spanning pH 5–7. The fastest rates of in-situ reduction (up to ∼300nmolcm−3 day−1) occur within the inter-tidal zone in the near-surface soil layers (to ∼60cm below ground surface). The reduction rates correlate with pore-water dissolved organic C concentrations, thereby suggesting that electron donor supply was the predominant rate determining factor. Elemental S was a major short-term product of reduction, comprising up to 69% of reduced inorganic S in the near-surface soil layers. This enrichment in elemental S can be partly attributed to interactions between biogenic H2S and jarosite – a process that also contributed to enrichment in pore-water Fe2+ (up to 55mM) and (up to 50mM). The iron sulfide thiospinel, greigite (Fe3S4), was abundant in near-surface soil layers within the inter- to sub-tidal zone where tidal water level fluctuations created oscillatory redox conditions. There was evidence for relatively rapid pyrite re-formation within the re-flooded soil layers. However, the results indicate that pyrite re-formation has occurred mainly in the lower formerly drained soil layers, whereas the accumulation of elemental S and greigite has been confined towards the soil surface. The discovery that pyrite formation was spatially decoupled from that of elemental S and greigite challenges the concept that greigite is an essential precursor required for sedimentary pyrite formation. In fact, the results suggest that greigite and pyrite may represent distinct end-points of divergent Fe–S mineralization pathways. Overall, this study highlights novel aspects of Fe–S mineralization within tidal wetlands that have been drained and re-flooded, in contrast to normal, undisturbed tidal wetlands. As such, the long-term biogeochemical trajectory of drained and acidified wetlands that are remediated by tidal re-flooding cannot be predicted from the well-studied behaviour of normal tidal wetlands. [Copyright &y& Elsevier]

Abstract: Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe2+ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe2+ was transported with advecting groundwater, facilitating the downstream Fe2+-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe2+-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings show that microbial sulfidogenesis can trigger significant As mobilization in subsurface environments with advective groundwater flow. The results also demonstrate that formation of mackinawite by sulfidization of ferric (hydr)oxides is not effective for the immobilization of As, whereas the Fe2+-catalyzed transformation of ferrihydrite to goethite under mildly acidic conditions may mitigate As mobility. [Copyright &y& Elsevier]

Solid phase Fe and S fractions were examined in an acid sulfate soil (ASS) wetland undergoing remediation via tidal inundation. Considerable diagenetic enrichment of reactive Fe(III) oxides (HCl- and dithionite-extractable) occurred near the soil surface (0-0.05 m depth), where extremely large concentrations up to 3534 μmol/g accounted for ~90% of the total Fe pool. This major source of reactive Fe exerts a substantial influence on S cycling and the formation, speciation and transformation of reduced inorganic S (RIS) in tidally inundated ASS. Under these geochemical conditions, acid volatile sulfide (AVS; up to 57 μmol/g) and elemental sulfur (S; up to 41 μmol/g) were the dominant fractions of RIS in near surface soils. AVS-S to pyrite-S ratios exceeded 2.9 near the surface, indicating that abundant reactive Fe favoured the accumulation of AVS minerals and S over pyrite. This is supported by the significant correlation of poorly crystalline Fe with AVS-S and S-S contents ( r = 0.83 and r = 0.85, respectively, P < 0.01). XANES spectroscopy provided direct evidence for the presence of a greigite-like phase in AVS-S measured by chemical extraction. While the abundant reactive Fe may limit the transformation of AVS minerals and S to pyrite during early diagenesis (~5 years), continued sulfidisation over longer time scales is likely to eventually lead to enhanced sequestration of S within pyrite (with a predicted 8% pyrite by mass). These findings provide an important understanding of sulfidisation processes occurring in reactive Fe-enriched, tidally inundated ASS landscapes. [ABSTRACT FROM AUTHOR]

Abstract: This study examines the abundance of trace elements in surface sediments of a former acid sulfate soil (ASS) wetland subjected to marine tidal inundation. Sediment properties of this highly modified study site are compared with those of an adjacent unmodified, intertidal mangrove forest. Whilst some trace elements (Al, Cd, Mn, Ni and Zn) were clearly depleted due to mobilisation and leaching in the previous oxic–acidic phase, other trace elements (As and Cr) displayed significant enrichment in the tidally inundated ASS. Many trace elements were strongly associated with the reactive Fe and acid volatile sulfide (AVS) fractions, suggesting that trace elements may be adsorbed to abundant reactive Fe phases or sequestered as sulfide minerals. These findings provide an important understanding of the fate and mobility of reactive iron, AVS and trace elements during tidal remediation of a formerly acidified Great Barrier Reef (GBR) catchment. [Copyright &y& Elsevier]

The article presents a study on equilibrium dialysis device. It aims to depict the design, deployment and application of the device in pore water sampling. It states that the device is made of high-density polyethylene rod to attain inflexibility and has less ability to absorb molecular oxygen and has removable cells. The device is inserted to sediments wherein a stainless steel is placed to protect cell membranes. It finds that the method of using the device is simple and effective and is fitted in sampling of pore water in acid sulfate soil and other firm wetland soils. Moreover, its advantages are the long housing structure, removable cells and the ability to remove the filter membrane.

Abstract: The drainage-induced oxidation of iron-sulfide minerals in acid-sulfate soils has adversely affected large areas of coastal floodplains. Re-flooding of these soils, via the re-establishment of more natural drainage regimes, is a potential remediation approach. Here we describe the mobility of Al, As, Fe, Mn, Ni and Zn during controlled re-flooding of an Fe- and organic-rich acid-sulfate soil material. Soil re-flooding caused the onset of microbially-mediated Fe(III)-reduction, which raised the pH of the initially acidic (pH 3.4) soil to pH 6.0 to 6.5, thereby immobilizing Al. The process of Fe(III)-reduction released high concentrations of FeII and was associated with significant mobilization of As. During the early stages of re-flooding, FeII mobility was controlled by dissolution of schwertmannite (Fe8O8(OH)6SO4) with an ion activity product (IAP) of 1019±2. The mobility of FeII was subsequently controlled by the precipitation of siderite (FeCO3) with an IAP spanning 10−10 to 10−7.5. The formation of acid-volatile sulfide (AVS), as a product of SO4-reduction, further retarded the mobility of FeII. Interactions with AVS also strongly immobilized Mn, Ni and Zn, yet had little effect on As which remained relatively mobile in the re-flooded soil. This study shows that the mobilization of As and Fe during soil re-flooding should be considered when planning remediation approaches for acid-sulfate soils. [Copyright &y& Elsevier]

Restoration of acid sulfate soil (ASS) wetlands by freshwater re-flooding can lead to the reformation of various Fe(II) and reduced inorganic sulfur (RIS) species in surface soil layers. However, in many locations, wetland water levels undergo large seasonal fluctuations that drive extreme redox oscillations. Newly formed RIS species [e.g. greigite, mackinawite, nano-pyrite and S(0)] and Fe(II) are vulnerable to rapid oxidation during dry periods and may generate substantial acidity. Rainfall following a dry period may then mobilise acidity and metal cations in surface waters prior to eventual recovery in pH by re-establishment of reducing conditions. We explore this dry-wet transition by subjecting soil samples from two freshwater re-flooded ASS wetlands to oxidative incubation for up to 130 days followed by re-flooding simulation for 84 days. During very early stages of re-flooding (up to 7 days) there was an initial pulse-release of acidity, and trace metals/metalloids (Al, Mn, Zn and As). This was followed by a rapid reversion to anoxia, and Fe(III) and SO 4 reducing conditions which generated alkalinity, ameliorated acidity and sequestered Fe, S, Zn, Mn and As. Field-observations of surface water quality in an ASS wetland at a sub-catchment scale also confirms re-establishment of SO 4 reducing conditions and recovery of pH within ~ 4–8 weeks of re-flooding after dry periods. These observations suggest that retaining surface water in ASS wetlands for ~ 8 weeks after a dry-wet transition will allow sufficient time for alkalinity producing reductive processes to ameliorate most surface water acidity. Although management of freshwater re-flooded ASS wetlands in a highly dynamic climate will remain challenging over the long term and the post-remediation effectiveness of the method depends on initial soil characteristics, knowledge of the timing of redox oscillations and the associated changes in water geochemistry can be helpful for mitigating the risks to downstream estuarine water quality. [ABSTRACT FROM AUTHOR]

Abstract: Lime-assisted tidal exchange (LATE) is a new remediation technique that is demonstrably effective at decreasing acidity in coastal acid sulfate soils (CASS). However, the relative magnitude of the major in situ alkalinity generating processes and external alkalinity inputs that dominate neutralization of acidity during LATE have not been quantified. Here, we combine investigations of porewater and solid-phase geochemistry from a remediating CASS wetland to derive first-order estimates of alkalinity generating processes and inputs after 6years of LATE. Quantified inputs include: marine derived HCO3 − from tidal exchange; hydrated lime additions; and in situ alkalinity from anaerobic metabolism of organic carbon coupled with reduction of iron and sulfate. A progressive increase in tidal inundation led to the development of significant relationships (α=0.01) between topography and both non-sulfidic, solid-phase Fe(II) and solid-phase reduced inorganic sulfur species. These topographic relationships were conjoined with a digital elevation model, enabling up-scaling of alkalinity estimates to a sub-catchment level. Estimates indicate the relative order of importance of alkalinity generating processes and inputs is Fe reduction (50–64%)>tidal exchange (25–42%)>sulfate reduction (7–13%)>>hydrated lime addition (<1%). Accurately attributing the relative contributions due to Fe and SO4 2− reduction was limited by an inability to distinguish between non-sulfidic, solid-phase Fe(II) generated by microbial dissimilatory reduction of Fe(III) or chemical reduction of Fe(III) by H2S. Nevertheless, the combined alkalinity contribution of these two electron accepting processes accounts for between 58 and 74% of the total. The majority (>99%) of net alkalinity generation was due to either tides or microbial metabolism. This indicates that the LATE remediation technique is both a cost effective means of decreasing soil acidity and is readily transferable to similar CASS landscapes - provided there is adequate supply of suitable electron donors and sufficient regenerative capacity in the adjacent estuarine/marine tidal HCO3 − pool. [Copyright &y& Elsevier]

The accumulation and behavior of arsenic at the redox interface of Fe-rich sediments is strongly influenced by Fe(III) precipitate mineralogy, As speciation, and pH. In this study, we examined the behavior of Fe and As during aeration of natural groundwater from the intertidal fringe of a wetland being remediated by tidal inundation. The groundwater was initially rich in Fe2+ (32 mmol L-1) and As (1.81 μmol L-1) with a circum-neutral pH (6,05). We explore changes in the solid/solution partitioning, speciation and mineralogy of Fe and As during long-term continuous groundwater aeration using a combination of chemical extractions, SEM, XRD, and synchrotron XAS. Initial rapid Fe2+ oxidation led to the formation of As(III)-bearing ferrihydrite and sorption of >95% of the As(aq) within the first 4 h of aeration. Ferrihydrite transformed to schwertmannite within 23 days, although sorbed/coprecipitated As(III) remained unoxidized during this period. Schwertmannite subsequently transformed to jarosite at low pH (2-3), accompanied by oxidation of remaining Fe2+. This coincided with a repartitioning of some sorbed As back into the aqueous phase as well as oxidation of sorbed/coprecipitated As(III) to As(V). Fe(III) precipitates formed via groundwater aeration were highly prone to reductive dissolution, thereby posing a high risk of mobilizing sorbed/coprecipitated As during any future upward migration of redox boundaries. Longer-term investigations are warranted to examine the potential pathways and magnitude of arsenic mobilization into surface waters in tidally reflooded wetlands. [ABSTRACT FROM AUTHOR]

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups). [ABSTRACT FROM AUTHOR]

Abstract: Tidal inundation is a new technique for remediating coastal acid sulfate soils (CASS). Here, we examine the effects of this technique on the geochemical zonation and cycling of Fe across a tidally inundated CASS toposequence, by investigating toposequence hydrology, in situ porewater geochemistry, solid-phase Fe fractions and Fe mineralogy. Interactions between topography and tides exerted a fundamental hydrological control on the geochemical zonation, redistribution and subsequent mineralogical transformations of Fe within the landscape. Reductive dissolution of Fe(III) minerals, including jarosite (KFe3(SO4)2(OH)6), resulted in elevated concentrations of porewater Fe2+ (>30mmol L−1) in former sulfuric horizons in the upper-intertidal zone. Tidal forcing generated oscillating hydraulic gradients, driving upward advection of this Fe2+-enriched porewater along the intertidal slope. Subsequent oxidation of Fe2+ led to substantial accumulation of reactive Fe(III) fractions (up to 8000μmol g−1) in redox-interfacial, tidal zone sediments. These Fe(III)-precipitates were poorly crystalline and displayed a distinct mineralisation sequence related to tidal zonation. Schwertmannite (Fe8O8(OH)6SO4) was the dominant Fe mineral phase in the upper-intertidal zone at mainly low pH (3–4). This was followed by increasing lepidocrocite (γ-FeOOH) and goethite (α-FeOOH) at circumneutral pH within lower-intertidal and subtidal zones. Relationships were evident between Fe fractions and topography. There was increasing precipitation of Fe-sulfide minerals and non-sulfidic solid-phase Fe(II) in the lower intertidal and subtidal zones. Precipitation of Fe-sulfide minerals was spatially co-incident with decreases in porewater Fe2+. A conceptual model is presented to explain the observed landscape-scale patterns of Fe mineralisation and hydro-geochemical zonation. This study provides valuable insights into the hydro-geochemical processes caused by saline tidal inundation of low lying CASS landscapes, regardless of whether inundation is an intentional strategy or due to sea-level rise. [Copyright &y& Elsevier]