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Ward, NJ 2004, 'Sulfide oxidation in some acid sulfate soil materials', PhD thesis, Southern Cross University, Lismore, NSW.

Copyright NJ Ward 2004


This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.