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.
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
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- 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.
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.
Quantifying alkalinity generating processes in a tidally remediating acidic wetland
- Authors: Johnston, Scott , Keene, Annabelle , Burton, Edward , Bush, Richard , Sullivan, Leigh
- Date: 2012
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 304-305, no. (2012), p. 106-116
- Full Text: false
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- Description: 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 HCO 3 - 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 SO 4 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 H 2S. 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 HCO 3 - pool. © 2012 Elsevier B.V.
Enrichment and heterogeneity of trace elements at the redox-interface of Fe-rich intertidal sediments
- Authors: Keene, Annabelle , Johnston, Scott , Bush, Richard , Burton, Edward , Sullivan, Leigh , Dundon, Matthew , McElnea, Angus , Smith, C. Douglas , Ahern, Col , Powell, Bernard
- Date: 2014
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 383, no. (2014), p. 1-12
- Full Text: false
- Reviewed:
- Description: Redox-interfacial sediments can undergo radical geochemical changes with oscillating tides. In this study, we examine trace element enrichment and availability, at both landscape and pedon-scales, in the surface sediments of a remediating acidic tidal wetland. Fe-rich sediments at the surface-water interface (0-10. mm in depth) were collected across an elevation gradient spanning the supratidal to subtidal range. These sediments were analysed for solid phase Fe fractions and trace elements (As, Pb, Cr, Cu, Mn, Ni, Zn, V, B, Co, Mo, Ba and U) via dilute HCl-extractions and total digests. Their concentrations were compared with those of underlying (0.05-0.65. m in depth) former sulfuric horizon sediments of a coastal acid sulfate soil (CASS). Reactive Fe was enriched at the redox interface by up to 16 times (197. g. Fe/kg) that of the former sulfuric horizon. The proportion of total trace elements associated with reactive phases was high in interfacial sediments, representing over 90% of B and U and 50% of Pb, Cu, Zn, V and Ba extractable by dilute HCl. The interfacial sediments were particularly enriched in reactive Cr, Cu, Ni, Zn, B, Mo and U, with reactive B, Mo and U concentrations between 5 and 10 times greater than in the former sulfuric horizon. Surface enrichment of trace elements is strongly co-associated with Fe(III) mineralisation, likely via sorption and co-precipitation processes. Enrichment is highly spatially heterogeneous and is strongly influenced by elevation and tidal zonation at a landscape-scale and by sediment micro-topography and preferential advective transport via surface connected macropores at the pedon-scale. The results from this study provide new insights to the processes influencing trace element enrichment in Fe-rich redox-interfacial sediments across a remediating acidic tidal wetland. © 2014 Elsevier B.V.
Seawater inundation of coastal floodplain sediments : Short-term changes in surface water and sediment geochemistry
- Authors: Wong, Vanessa , Johnston, Scott , Burton, Edward , Hirst, Phillip , Sullivan, Leigh , Bush, Richard , Blackford, Mark
- Date: 2015
- Type: Text , Journal article
- Relation: Chemical Geology Vol. 398, no. (2015), p. 32-45
- Full Text: false
- Reviewed:
- Description: Coastal floodplains are highly vulnerable to seawater inundation as a result of storm surge and sea-level rise due to their low elevation and proximity to the coastline. Intact soil cores from a levee, acid-sulfate soil scald and four backswamp sites on a coastal floodplain in eastern Australia were inundated with artificial seawater treatments (0%, 50% and 100%) for 14days to examine the short term consequences for surface water and floodplain sediment geochemistry. All sites displayed an initial decrease in surface water pH following inundation with 50% and 100% seawater. In addition, higher concentrations of trace metals (Al, Fe, Mn, Ni and Zn) were observed in most sites inundated with 50% or 100% seawater. This was generally attributed to competitive exchange and desorption of trace metals from sediments due to the higher ionic strength of the seawater solutions and upward diffusive flux of metals from the sediments to surface waters. At one backswamp site, reductive processes had established by day 7, which also resulted in elevated Fe2+ concentrations in the overlying surface waters. Transmission electron microscopy (TEM) identified the presence of poorly crystalline ferrihydrite and schwertmannite, and goethite and jarosite. These meta-stable Fe(III) minerals can act as a source of metals for desorption and can also be readily reduced and act as a source of Fe2+ to surface waters. Importantly, inundation with either 50% or 100% seawater resulted in a similar magnitude of acidity and trace metal mobilisation. The data suggest that an inundation event of ~0.2m depth with either 50% or 100% seawater could cause a pulse mobilisation of up to 64.8 and 9.1kgha-1 of Fe and Al, respectively - quantities of similar magnitude to previous estimates of annual drainage fluxes from similar backswamps. This study suggests that the short term inundation of coastal floodplain sediments by either brackish water or seawater will result in rapid declines in surface water quality as a result of increased liberation of acidity and trace metals. © 2015 .