Acid Sulfate Soil Materials Research Articles

Sulfide oxidation and acidification of acid sulfate soil materials treated with CaCO3 and seawater-neutralised bauxite refinery residue

Acid sulfate soil (ASS) materials that are subject to oxidation are often treated with neutralising agents to minimise the export of acidity that may result from pyrite oxidation. The effects of additions of both CaCO3 and seawater-neutralised bauxite refinery residue (SNBRR) on the oxidation of sulfides and acidification were assessed for 4 ASS materials using laboratory incubation experiments. As the application of sub-optimal rates of neutralising materials can occur for a variety of reasons, the effect of application rates were also examined. Two application rates were chosen; a sub-optimal rate [approximately 20% of the theoretical neutralising requirement (NR)] and an excessive application rate (>250% of the NR). There was minimal sulfide oxidation and no acidification after the addition of excess CaCO3 over the 180 days of incubation. The addition of excess SNBRR prevented acidification, but substantial sulfide oxidation still occurred. Following a brief initial increase in pH when sub-optimal rates of CaCO3 and SNBRR were applied, the treated ASS materials rapidly acidified. For three of the ASS materials the addition of sub-optimal amounts of CaCO3 had little impact on the rate of sulfide oxidation. However, for the other ASS material (a peat) both the rates of sulfide oxidation and acidification were accelerated by the addition of sub-optimal rates of CaCO3, resulting in higher soluble Fe and Al concentrations than in the untreated ASS materials. For some of the ASS materials, sub-optimal applications of SNBRR resulted in elevated soluble Al.

Assessment of peroxide oxidation for acid sulfate soil analysis. 1. Reduced inorganic sulfur

The reduced inorganic sulfur fraction of 4 acid sulfate soil (ASS) materials was quantified using a variety of peroxide oxidation procedures. The temperature and duration of the peroxide oxidation were found to markedly affect the peroxide oxidisable sulfur determination. For 3 ASS materials with low total carbon content (i.e. <2.5% C), peroxide oxidisable sulfur underestimated the reduced inorganic sulfur fraction, with the peroxide oxidisable sulfur determinations being as low as 42% of those determined using chromium reducible sulfur technique. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation of reduced inorganic sulfur in these materials. Apparent losses of sulfur of approximately 25% on average occurred during peroxide oxidation budget accounting; this also contributed towards the observed underestimation of reduced inorganic sulfur. It is most likely that these unaccounted losses are due to atmospheric losses of sulfur. In a peat ASS, one of the peroxide oxidation methods overestimated the reduced inorganic sulfur fraction and was attributed to the release of a large reserve of organic sulfur in this material by the peroxide. This study shows the peroxide oxidation methods examined here are subject to substantial interferences. Consequently these peroxide oxidation methods are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction in ASS materials. pyritic sulfur, peroxide oxidisable sulfur, chromium reducible sulfur, jarosite, sulfur budget.

Assessment of peroxide oxidation for acid sulfate soil analysis. 2. Acidity determination

Total sulfidic acidity (TSA) and total potential acidity (TPA) are derived from peroxide oxidation of acid sulfate soil materials (ASS), and are measures of the sulfidic acidity and the net acidity (net acidity = sulfidic acidity + actual acidity – acid neutralising capacity), respectively. The TSA and TPA of 4 ASS materials were determined using a variety of peroxide oxidation procedures and compared with the sulfidic acidity and net acidity derived from the use of an acid–base accounting model. TSA and TPA values both varied greatly with each peroxide oxidation method used, and both measures were found to substantially underestimate (i.e. by 23–85%) both sulfidic acidity (as determined from the chromium reducible sulfur content) and net acidity (as determined by acid–base accounting). A major cause of this underestimation of acidity was the retention of acidity through the precipitation of jarosite during peroxide oxidation. Substantial clay mineral dissolution appears to have occurred during peroxide oxidation of the ASS materials, as indicated by increased soluble aluminium. Such dissolution may contribute to the underestimation of both sulfidic and net acidity for the ASS materials using peroxide oxidation methods. The loss of acidity to the atmosphere was identified as a possible additional interference. This study shows the peroxide oxidation methods examined here are subject to substantial interferences, which caused large underestimations of acidity, and consequently, are unable to reliably provide accurate measurements of sulfidic and net acidity in ASS materials. pyritic sulfur, total potential acidity, total sulfidic acidity, net acidity, jarosite, acid budget, acid neutralising capacity.

A modified chromium-reducible sulfur method for reduced inorganic sulfur: optimum reaction time for acid sulfate soil

Reaction times for 16 acid sulfate soil materials analysed using a modified chromium-reducible sulfur method varied between 10 and 15 min, regardless of whether the samples had been dried and ground prior to analysis or were analysed without pretreatment. The reaction time for a ground (<63 mm) pyritic rock sample was 20 min. An optimum reaction time of 20 min is recommended for analysing acid sulfate soil using the modified method; this reaction time is much less than the 1 h reaction time used in previous methods.