Abundant stocks and mobilization of elements in boreal acid sulfate soils
- Authors: Yli-Halla, Markku , Virtanen, Seija , Mäkelä, Minna , Simojoki, Asko , Hirvi, Mirva , Innanen, Saila , Mäkelä, Jaakko , Sullivan, Leigh
- Date: 2017
- Type: Text , Journal article
- Relation: Geoderma Vol. 308, no. (2017), p. 333-340
- Full Text: false
- Reviewed:
- Description: Large amounts of sulfate and divalent iron (Fe) are released into the pore water of acid sulfate (AS) soils upon oxidation of sulfidic materials. The simultaneously produced acidity dissolves metals from the soil matrix. Reduced horizons of AS soils commonly have a large mineral nitrogen (N) stock in the form of NH4 +-N, which is a potential source of N leaching and gaseous emissions. This study was carried out at three AS soil sites in Finland. Cation composition of pore water was monitored in a monolithic lysimeter experiment. Timothy samples grown in an AS soil were analysed for mineral elements and the soil was investigated for zinc (Zn) distribution in different chemical species at four depths down to 85 cm. The composition of pipestems formed in previous root channels was investigated by SEM, X-ray EDX and XRD. Emissions of CO2 and N2O were measured in an AS field which had a peaty topsoil. Monitoring by closed chambers was carried out at three sites differing in the depth of peat layer (15, 30 and 60 cm). In the sulfuric horizon, large amounts of calcium and magnesium were mobilized. Reflooding stopped the mobilization of those elements but resulted in abundant dissolution of Fe, which became the dominant cation in the pore water. Timothy growing in an AS soil showed only small deviations from the average composition measured in Finland with the exception of Zn that was at the deficiency level. As Zn in the root zone had been dissolved and subsequently leached, it was recovered in easily soluble forms in the subsoil. Pipestem composition indicated accumulation of Fe and formation of a new solid phase probably mostly in the form of schwertmannite even though jarosite was also detected. The annual CO2 emissions from the peaty AS soil were about 6000 kg C ha− 1 but the N2O emissions were relatively small, with a magnitude more typical of mineral rather than organic soils. Thus, large N stock of an AS soil do not necessarily contribute to abundant gaseous N emissions. © 2017 Elsevier B.V.
Spatial and temporal changes in estuarine water quality during a post-flood hypoxic event
- Authors: Wong, Vanessa , Johnston, Scott , Bush, Richard , Sullivan, Leigh , Clay, Christina , Burton, Edward , Slavich, Peter
- Date: 2010
- Type: Text , Journal article
- Relation: Estuarine, Coastal and Shelf Science Vol. 87, no. 1 (2010), p. 73-82
- Full Text: false
- Reviewed:
- Description: A major fish kill occurred in the Richmond River estuary in January 2008 due to oxygen depletion following extensive overbank flooding. This paper examines spatial and temporal changes in the chemistry of main channel waters, thereby identifying the primary sources of deoxygenating water. Over 40 km of the mid- to lower estuary main channel was deoxygenated within seven days of the flood peak. Hypoxia was confined to downstream of the confluences with mid-estuary backswamp basins and occurred during the later phase of the flood recession. Water chemistry at key locations in the estuary indicated elevated concentrations of redox sensitive species associated with acid sulfate soils (ASS) during the hypoxic period. Peak concentrations of Fe
Iron and arsenic cycling in intertidal surface sediments during wetland remediation
- Authors: Johnston, Scott , Keene, Annabelle , Burton, Edward , Bush, Richard , Sullivan, Leigh
- Date: 2011
- Type: Text , Journal article
- Relation: Environmental Science and Technology Vol. 45, no. 6 (2011), p. 2179-2185
- Full Text: false
- Reviewed:
- Description: 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 Fe 2+ (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 Fe 2+ 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 Fe 2+. 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. © 2011 American Chemical Society.
Liberation of acidity and arsenic from schwertmannite : Effect of fulvic acid
- Authors: Vithana, Chamindra , Sullivan, Leigh , Burton, Edward , Bush, Richard
- Date: 2014
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 372, no. (2014), p. 1-11
- Full Text: false
- Reviewed:
- Description: Schwertmannite is one of the major components that produces acidity in acid mine drainage (AMD) and acid sulfate soils (ASS) and is also known to be an effective scavenger of Arsenic (As) in such environments. Fulvic acid (FA) is an active component of natural organic matter (NOM) and is known to interact strongly with both schwertmannite and As. Two main environmental hazards related to schwertmannite are acidity liberation and potential re-mobilization of adsorbed or co-precipitated As upon hydrolysis. This study focused on understanding the behaviour of As-substituted schwertmannite with regard to the potential of acidity liberation, the effect of FA on acidity liberation from both pure and As-substituted synthetic schwertmannites, and the effect of FA on arsenic mobilization from As-substituted synthetic schwertmannite. This was investigated by means of short-term (48. h) titrations. The liberation of acidity from As-substituted schwertmannite and the effect of FA were examined at two pH values (i.e. 4.5 and 6.5) typical for ASS environments.As-substituted schwertmannite liberated a greater amount of acidity in comparison to pure schwertmannite at both pHs. Concentration of FA and pH each showed a strong influence on the liberation of acidity from both pure and As-schwertmannite. At the acidic pH (4.5), FA inhibited acidity liberation from schwertmannite. At the near neutral pH of 6.5, the concentration of FA played a critical role in affecting the liberation of acidity from schwertmannite. The initial liberation of acidity was enhanced from pure schwertmannite at pH6.5 by low FA concentration (1mgL-1) and from As-schwertmannite by both low (1mgL-1) and moderate (10mgL-1) FA concentrations. Interestingly, higher FA concentrations (25mgL-1) inhibited acidity liberation from both types of schwertmannite in comparison to the control (pure/As-schwertmannite titrated without added FA). FA enhanced the liberation of As from the As-schwertmannite at both pHs under oxidising conditions and the rate of As liberation was greater at the near neutral pH. The present study provides new insights on the effect of As-substitution on acidity liberation from schwertmannite and the role of FA on: a) liberation of acidity, and b) As mobilization, from schwertmannite. © 2014.
Raman, infrared and XPS study of bamboo phytoliths after chemical digestion
- Authors: Watling, Kym , Parr, Jeffrey , Rintoul, Llew , Brown, Christopher , Sullivan, Leigh
- Date: 2011
- Type: Text , Journal article
- Relation: Spectrochimica Acta - Part A : Molecular and Biomolecular Spectroscopy Vol. 80, no. 1 (2011), p. 106-111
- Full Text: false
- Reviewed:
- Description: Raman, infrared and X-ray photoelectron spectroscopies have been used to examine the effect of various chemical digestion methods on the composition of bamboo phytoliths. Intact bilobate phytoliths, suitable for interrogation by Raman microprobe analysis, were isolated by a microwave wet ashing technique using hydrogen peroxide with nitric and hydrochloric acids. The occluded phytolith carbon presented evidence of cellulose, lignin and carboxylic acids. Nitrate from the nitric acid used in the digestion was observed in homogenized samples of the isolated phytoliths; in addition to nitrogen of plant origin occluded within the phytolith, which was observed as amine nitrogen and ammonia. Intact bilobate phytoliths were not observed following an exothermic hydrogen peroxide/sulfuric acid digest, suggesting that these structures ruptured during this digestion procedure. The silicate network was significantly altered during isolation using the exothermic hydrogen peroxide/sulfuric digest, with surface hydroxyls undergoing condensation to form a SiO 3 ring structure. © 2011 Elsevier B.V. All rights reserved.
Mobility of arsenic and selected metals during re-flooding of iron- and organic-rich acid-sulfate soil
- Authors: Burton, Edward , Bush, Richard , Sullivan, Leigh , Johnston, Scott , Hocking, Rosalie
- Date: 2008
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 253, no. 1-2 (2008), p. 64-73
- Full Text: false
- Reviewed:
- Description: 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. © 2008 Elsevier B.V. All rights reserved.
Metal partitioning dynamics during the oxidation and acidification of sulfidic soil
- Authors: Claff, Salirian , Burton, Edward , Sullivan, Leigh , Bush, Richard
- Date: 2011
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 286, no. 3-4 (2011), p. 146-157
- Full Text: false
- Reviewed:
- Description: The oxidation and acidification of sulfidic soil can lead to changes to metal mobility that can have far-reaching environmental consequences. In this study, we examined changes in the partitioning and mobility of Fe, Cr, Cu, Mn, Ni and Zn in four sulfidic soils, due to sulphide oxidation driven acidification, over a 90. day period. These changes were examined using a novel six-step sequential extraction procedure specifically developed for acid sulphate soil materials. The results demonstrate two distinct steps for the mobilisation of metals in disturbed acid sulphate soil materials, associated with (i) oxidation and (ii) acidification. Initially, oxidation causes metals to be redistributed from the "pyritic" and "organic" fractions to the "acid-soluble" fraction. Subsequent acidification, due to exceedance of the acid neutralising capacity of the soil, drives the release of metals to the "labile" fraction. This study demonstrates the importance of these metal pools in understanding the short-term processes which mobilise metals in sulfidic soils. © 2011 Elsevier B.V.
A sequential extraction procedure for acid sulfate soils : Partitioning of iron
- Authors: Claff, Salirian , Sullivan, Leigh , Burton, Edward , Bush, Richard
- Date: 2010
- Type: Text , Journal article
- Relation: Geoderma Vol. 155, no. 3-4 (2010), p. 224-230
- Full Text: false
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- Description: A new sequential extraction scheme for acid sulfate soil materials has been evaluated for iron partitioning in a range of synthetic iron-bearing minerals and natural acid sulfate soil materials. This sequential extraction procedure employs six steps to quantify (1) exchangeable (magnesium chloride extractable), (2) acid (hydrochloric acid) soluble, (3) reactive organic-bound (pyrophosphate extractable), (4) crystalline oxide (citrate buffered dithionite (CBD)) extractable, (5) pyrite-bound (nitric acid extractable) and (6) residual (acid/peroxide digestible) forms of iron. Given its intended use for acid sulfate soil materials that frequently contain pyrite, a primary aim of this new sequential extraction procedure was to differentiate iron bound in pyrite from iron contained in other minerals. The results demonstrated that dissolution of pyrite was effectively isolated in the pyrite-bound extraction step, with dissolution of other iron mineral phases (i.e. akaganeite, ferrihydrite, goethite, hematite, jarosite, magnetite, and schwertmannite) occurring within the other five extraction steps. Following a systematic examination of these synthetic iron mineral phases, the sequential extraction scheme was applied to an acid sulfate soil profile, with detailed data presented for two soil layers: one representative of the sulfidic (unoxidised) conditions, and the other sulfuric (oxidised) conditions. Partitioning data for pyrite-bound iron in the acid sulfate soil profile showed good agreement with that calculated via the independently measured pyrite-bound reduced sulfur. This study indicates that the new sequential extraction procedure is suitable for the assessment of iron partitioning in acid sulfate soil materials. © 2009 Elsevier B.V. All rights reserved.
Effect of sample pretreatment on the fractionation of Fe, Cr, Ni, Cu, Mn, and Zn in acid sulfate soil materials
- Authors: Claff, Salirian , Burton, Edward , Sullivan, Leigh , Bush, Richard
- Date: 2010
- Type: Text , Journal article
- Relation: Geoderma Vol. 159, no. 1-2 (2010), p. 156-164
- Full Text: false
- Reviewed:
- Description: A sequential extraction procedure was applied to acid sulfate soil materials from a soil profile to investigate the effect of sample pretreatment on the geochemical fractionation of selected metals. The samples were prepared for analysis by oven-drying, sieving and grinding the soil, or were examined as collected in field condition. The soil profile encompassed oxidising conditions near the surface, through to reducing conditions at depth. Six metals (Fe, Cr, Ni, Mn, Cu, and Zn) were measured during the sequential extraction procedure, and their fractionation determined in the oxidised and in the reduced zone. Although cumulative totals (the sum of all steps in the sequential extraction procedure) for the metals extracted from both the field condition and dried/ground samples were similar, some significant differences in fractionation within individual extraction steps were observed. Of particular interest was the redistribution of metals from the sulfide-bearing (pyrite-bound) fraction to the more readily available fractions (i.e. labile and acid-soluble), as a result of oven-drying and grinding. The results indicate that when assessing metal fractionation in acid sulfate soil materials, samples should be analysed in field condition in order to avoid the considerable metal fractionation artifacts that are induced by drying and grinding. © 2010 Elsevier B.V.
Enhancing phytolith carbon sequestration in rice ecosystems through basalt powder amendment
- Authors: Guo, Fengshan , Song, Zhaoliang , Sullivan, Leigh , Wang, Hailong , Liu, Xueyan , Wang, Xudong , Li, Zimin , Zhao, Yuying
- Date: 2015
- Type: Text , Journal article
- Relation: Science Bulletin Vol. 60, no. 6 (2015), p. 591-597
- Full Text: false
- Reviewed:
- Description: Global warming as a result of rapid increase in atmospheric CO
Iron geochemical zonation in a tidally inundated acid sulfate soil wetland
- Authors: Johnston, Scott , Keene, Annabelle , Bush, Richard , Burton, Edward , Sullivan, Leigh , Isaacson, Lloyd , McElnea, Angus , Ahern, Col , Smith, C. Douglas , Powell, Bernard
- Date: 2011
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 280, no. 3-4 (2011), p. 257-270
- Full Text: false
- Reviewed:
- Description: 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. © 2010 Elsevier B.V.
Decoupling between water column oxygenation and benthic phosphate dynamics in a shallow eutrophic estuary
- Authors: Kraal, Peter , Burton, Edward , Rose, Andrew , Cheetham, Michael , Bush, Richard , Sullivan, Leigh
- Date: 2013
- Type: Text , Journal article
- Relation: Environmental Science and Technology Vol. 47, no. 7 (2013), p. 3114-3121
- Full Text: false
- Reviewed:
- Description: Estuaries are crucial biogeochemical filters at the land-ocean interface that are strongly impacted by anthropogenic nutrient inputs. Here, we investigate benthic nitrogen (N) and phosphorus (P) dynamics in relation to physicochemical surface sediment properties and bottom water mixing in the shallow, eutrophic Peel-Harvey Estuary. Our results show the strong dependence of sedimentary P release on Fe and S redox cycling. The estuary contains surface sediments that are strongly reducing and act as net P source, despite physical sediment mixing under an oxygenated water column. This decoupling between water column oxygenation and benthic P dynamics is of great importance to understand the evolution of nutrient dynamics in marine systems in response to increasing nutrient loadings. In addition, the findings show that the relationship between P burial efficiency and bottom water oxygenation depends on local conditions; sediment properties rather than oxygen availability may control benthic P recycling. Overall, our results illustrate the complex response of an estuary to environmental change because of interacting physical and biogeochemical processes. © 2013 American Chemical Society.
Contemporary pedogenesis of severely degraded tropical acid sulfate soils after introduction of regular tidal inundation
- Authors: Johnston, Scott , Keene, Annabelle , Bush, Richard , Burton, Edward , Sullivan, Leigh , Smith, Douglas , McElnea, Angus , Martens, Michelle , Wilbraham, Steve
- Date: 2009
- Type: Text , Journal article
- Relation: Geoderma Vol. 149, no. 3-4 (2009), p. 335-346
- Full Text: false
- Reviewed:
- Description: Marine tidal inundation was partially restored to a severely degraded tropical acid sulfate soil landscape after having been excluded for over 30 years. The effects on soil acidity and iron-sulfide mineral reformation were investigated by comparing the geochemistry of soils before and after five years of regular tidal inundation. The soil pH increased by 2-3 units and titratable actual acidity (TAA) decreased by ∼ 40-50 μmol H+ g- 1 within former sulfuric horizons. Relict acidity remained at depth (> 1 m) in the underlying sulfidic horizons. δ34S data indicate that tidal inundation caused exchange of marine solutes within former sulfuric horizons, but not within underlying sulfidic material. There was considerable reformation of pyrite within former sulfuric horizons after tidal inundation with reduced inorganic sulfur increasing by ∼ 60 μmol g- 1. Acid-volatile sulfide also accumulated, but mainly near the soil surface (up to 16 μmol g- 1). Reduction of Fe(III) minerals strongly influences the geochemistry of the tidally inundated soils. After tidal inundation the soil pH and Eh closely followed the iron redox couple and there was non-sulfidic solid-phase Fe(II) up to 600 μmol g- 1. There was also substantial diagenetic enrichment of poorly crystalline Fe-oxides near the soil surface following tidal inundation, with reactive Fe spanning 400-1800 μmol g- 1. While the decreases in soil acidity documented here are likely due to a combination of marine alkalinity inputs and reduction of both Fe and SO42-, the relative importance of each process remains to be determined. This study demonstrates that marine tidal inundation can be an effective landscape-scale strategy for ameliorating severe acidity associated with drained acid sulfate soils. © 2008 Elsevier B.V. All rights reserved.
Iron-monosulfide oxidation in natural sediments : Resolving microbially mediated S transformations using XANES, electron microscopy, and selective extractions
- Authors: Burton, Edward , Bush, Richard , Sullivan, Leigh , Hocking, Rosalie , Mitchell, David , Johnston, Scott , Fitzpatrick, Rob W. , Raven, Mark , McClure, Stuart , Jang, Lingyun
- Date: 2009
- Type: Text , Journal article
- Relation: Environmental Science and Technology Vol. 43, no. 9 (2009), p. 3128-3134
- Full Text: false
- Reviewed:
- Description: Iron-monosulfide oxidation and associated S transformations in a natural sediment were examined by combining selective extractions, electron microscopy and S K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The sediment examined in this study was collected from a waterway receiving acid-sulfate soil drainage. It contained a high acid-volatile sulfide content (1031 μ mol g-1), reflecting an abundance of iron-monosulfide. The iron-monosulfide speciation in the initial sediment sample was dominated by nanocrystalline mackinawite (tetragonal FeS). At near-neutral pH and an O 2 partial pressure of ∼0.2 atm, the mackinawite was found to oxidize rapidly, with a half-time of 29 ± 2 min. This oxidation rate did not differ significantly (P < 0.05) between abiotic versus biotic conditions, demonstrating that oxidation of nanocrystalline mackinawite was not microbially mediated. The extraction results suggested that elemental S (S0 8) was a key intermediate S oxidation product. Transmission electron microscopy showed the S0 8 to be amorphous nanoglobules, 100-200 nm in diameter. The quantitative importance of S0 8 was confirmed by linear combination XANES spectroscopy, after accounting for the inherent effect of the nanoscale S0 8 particle-size on the corresponding XANES spectrum. Both the selective extraction and XANES data showed that oxidation of S0 8 SO4 2- was madiated by microbial activity. In addition to directly revealing important S transformations, the XANES results support the accuracy of the selective extraction scheme employed here. © 2009 American Chemical Society.
Effect of schwertmannite and jarosite on the formation of hypoxic blackwater during inundation of grass material
- Authors: Vithana, Chamindra , Sullivan, Leigh , Shepherd, Troy
- Date: 2017
- Type: Text , Journal article
- Relation: Water Research Vol. 124, no. (2017), p. 1-10
- Full Text: false
- Reviewed:
- Description: This study focused on understanding the effect of schwertmannite and jarosite, commonly found in floodplains containing acid sulfate soil materials, on the characteristics of the hypoxic blackwaters that can form when floodplain vegetation experiences prolonged inundation. The formation of these ‘blackwaters’ was simulated in the laboratory by inundating flood-intolerant pasture grass leaf material in both the presence of schwertmannite/jarosite (schwertmannite and jarosite treatments) minerals and their absence (control treatment) at 27.5 °C for 32 days. The presence of either schwertmannite or jarosite was able to decrease the concentrations of DOC, nutrients (e.g. NH3 and PO4 3−) and the biological oxygen demand (BOD) in the incubating water compared to the control treatment. Being fresh and labile, the pasture grass material liberated DOC immediately following inundation with a concomitant decrease in dissolved O2 thereby resulting in anoxic and reducing conditions in the incubating water. With the onset of anoxic and reducing conditions, the biogeochemical cycling of DOC in schwertmannite and jarosite treatments might have proceeded via microbially mediated iron(III) and sulfate reduction and electron shuttling processes. Under anoxic, slightly acidic conditions, microbially mediated iron(III) reduction and subsequent dissolution of schwertmannite and jarosite were triggered by liberating Fe2+, SO4 2− and alkalinity to the incubating water. The resultant increase in pH led to SO4 2− reduction in schwertmannite, and the Fe2+ catalysed transformation of both schwertmannite and jarosite to goethite. Schwertmannite almost completely transformed to goethite within two weeks of incubation. Iron(III) in goethite (formed from schwertmannie transformation) was also reduced and likely proceeded via direct microbial reduction or via electron shuttling using the humic acids in the incubating water derived from pasture grass. These findings are highly useful in managing the coastal low lying acid sulfate soils landscapes which are subject to frequent flooding during wet seasons. © 2017 Elsevier Ltd
Tidally driven water column hydro-geochemistry in a remediating acidic wetland
- Authors: Johnston, Scott , Keene, Annabelle , Bush, Richard , Sullivan, Leigh , Wong, Vanessa
- Date: 2011
- Type: Text , Journal article
- Relation: Journal of Hydrology Vol. 409, no. 1-2 (2011), p. 128-139
- Full Text: false
- Reviewed:
- Description: Managed tidal inundation is a newly evolved technique for remediating coastal acid sulphate soil (CASS) wetlands. However, there remains considerable uncertainty regarding the hydro-geochemical pathways and spatiotemporal dynamics of residual H+ and metal(loid) mobilisation into the tidal fringe surface waters of these uniquely iron-rich landscapes. Here, we examine the hydrology and water column chemistry across the intertidal slope of a remediating CASS wetland during several tide cycles. There was extreme spatial and temporal dynamism in water column chemistry, with pH fluctuating by ∼3 units (∼3.5-6.5) during a single tide cycle. Acute acidity was spatially confined to the upper intertidal slope, reflecting surface sediment properties, and tidal overtopping is an important pathway for mobilisation of residual H+ and Al3+ to the water column. Marine derived HCO3- was depleted from surface waters migrating across the intertidal slope and a strong gradient in HCO3- was observed from the tidal fringe to the adjacent tributary channel and nearby estuary. Tidal forcing generated oscillating hydraulic gradients in the shallow fringing aquifer, favouring ebb-tide seepage and driving rapid, heterogeneous advection of groundwater on the lower intertidal slope via surface connected macropores. A combination of diffusive and advective flux across the sediment-water interface led to persistent, elevated surface water Fe2+ (∼10-1000μM). The geochemical processes associated with Fe2+ mobilisation displayed distinct spatial zonation, with low pH, proton-promoted desorption occurring on the upper intertidal slope, whilst circum-neutral pH, Fe(III)-reducing processes dominated the lower intertidal slope. Arsenic was also mobilised into surface waters on the lower intertidal slope under moderate pH (∼6.0) conditions and was strongly positively correlated with Fe2+. Saturation index values for aragonite were substantially depressed (-1 to -5) and significantly negatively correlated with elevation, thereby presenting a barrier to re-colonisation of the upper intertidal slope by calcifying benthic organisms. These findings highlight the spatially complex hydrological and geochemical controls on surface water quality that can occur in tidally inundated acid sulphate soil environments. © 2011 Elsevier B.V.
Phytolith occluded carbon and silica variability in wheat cultivars
- Authors: Parr, Jeffrey , Sullivan, Leigh
- Date: 2010
- Type: Text , Journal article
- Relation: Plant and Soil Vol. 342, no. 1-2 (2010), p. 165-171
- Full Text: false
- Reviewed:
- Description: Phytolith Occluded Carbon (PhytOC) has recently been demonstrated to be an important long-term terrestrial carbon fraction. The aim of this study was to examine the rates of silica accumulation and carbon bio-sequestered within the silica phytoliths of the leaf and stem material of wheat (Triticum sp.) cultivars. The phytolith content of 53 wheat cultivars sourced from 25 countries around the world and grown on a single trial site was first isolated and the PhytOC content then determined. The data shows that the phytolith occluded carbon content of the wheat cultivars ranged from 0.06% to 0.60% of dry leaf and stem biomass: a range of 1,000%. The data also demonstrates that it is the efficiency by which carbon is encapsulated within silica rather than the quantity of silica accumulated by the plant that is the most important factor in determining the relative PhytOC yields. The potential phytolith carbon bio-sequestration rates in the leaf and stem components of these wheat cultivars ranged up to 0.246 t-e-CO2 ha-1y-1. These phytolith carbon bio-sequestration rates indicate a substantial potential (~50 million t-e-CO2 y-1) exists for increasing the rate of secure carbon bio-sequestration in wheat crops using existing cultivars. © 2010 Springer Science+Business Media B.V.
Sulfur biogeochemical cycling and novel Fe-S mineralization pathways in a tidally re-flooded wetland
- Authors: Burton, Edward , Bush, Richard , Johnston, Scott , Sullivan, Leigh , Keene, Annabelle
- Date: 2011
- Type: Text , Journal article
- Relation: Geochimica et Cosmochimica Acta Vol. 75, no. 12 (2011), p. 3434-3451
- Full Text: false
- Reviewed:
- Description: 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 SO42- 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 SO42--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 SO42- reduction (up to ~300nmolcm-3day-1) occur within the inter-tidal zone in the near-surface soil layers (to ~60cm below ground surface). The SO42- 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 SO42- 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 SO42- (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. © 2011 Elsevier Ltd.
Simultaneous redox conversion of chromium(VI) and arsenic(III) under acidic conditions
- Authors: Wang, Zhaohui , Bush, Richard , Sullivan, Leigh , Liu, Jianshe
- Date: 2013
- Type: Text , Journal article
- Relation: Environmental Science and Technology Vol. 47, no. 12 (2013), p. 6486-6492
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- Description: Arsenic and chromium are often abundant constituents of acid mine drainage (AMD) and are most harmful as arsenite (As(III)) and hexavalent (Cr(VI)). To simultaneously change their oxidation state from As(III) to As(V), and Cr(VI) to Cr(III), is a potentially effective and attractive strategy for environmental remediation. The coabundance of As(III) and Cr(VI) in natural environments indicates their negligible direct interaction. The addition of H 2O2 enables and greatly accelerates the simultaneous oxidation of As(III) and reduction of Cr(VI). These reactions are further enhanced at acidic pH and higher concentrations of Cr(VI). However, the presence of ligands (i.e., oxalate, citrate, pyrophosphate) greatly retards the oxidation of As(III), even though it enhances the reduction of Cr(VI). To explain these results we propose a reaction mechanism where Cr(VI) is primarily reduced to Cr(III) by H2O2, via the intermediate tetraperoxochromate Cr(V). Cr(V) is then involved in the formation of •OH radicals. In the presence of ligands, the capacity of Cr(V) to form •OH radicals, which are primarily responsible for As(III) oxidation, is practically inhibited. Our findings demonstrate the feasibility for the coconversion of As(III) and Cr(VI) in AMD and real-world constraints to this strategy for environmental remediation. © 2013 American Chemical Society.
Selective oxidation of arsenite by peroxymonosulfate with high utilization efficiency of oxidant
- Authors: Wang, Zhaohui , Bush, Richard , Sullivan, Leigh , Chen, Chuncheng , Liu, Jianshe
- Date: 2014
- Type: Text , Journal article
- Relation: Environmental Science and Technology Vol. 48, no. 7 (2014), p. 3978-3985
- Full Text: false
- Reviewed:
- Description: Oxidation of arsenite (As(III)) is a critical yet often weak link in many current technologies for remediating contaminated groundwater. We report a novel, efficient oxidation reaction for As(III) conversion to As(V) using commercial available peroxymonosulfate (PMS). As(III) is rapidly oxidized by PMS with a utilization efficiency larger than 90%. Increasing PMS concentrations and pH accelerate oxidation of As(III), independent to the availability of dissolved oxygen the addition of PMS enables As(III) to oxidize completely to As(V) within 24 h, even in the presence of high concentrations of radical scavengers. On the basis of these observations and theoretical calculations, a two-electron transfer (i.e., oxygen atom transfer) reaction pathway is proposed. Direct oxidation of As(III) by PMS avoids the formation of nonselective reactive radicals, thus minimizing the adverse impact of coexisting organic matter and maximizing the utilization efficiency of PMS therefore, this simple approach is considered a cost-effective water treatment method for the oxidation of As(III) to As(V). © 2014 American Chemical Society.