Nicholas J Ward

Alkalinity conversion of bauxite refinery residues by neutralization

Red mud remains the largest environmental issue for the alumina industry due to its high pH (>13), fine-grained nature (>90% is <10 microm), elevated sodium concentration (>50 g/kg), and soluble alkalinity (approximately 30 g/kg as equivalent CaCO(3)), which reduce the transport and reuse options of red mud. The neutralization of red mud provides potential reuse options because neutralization lowers pH, increases grain-size (e.g., coagulation), and precipitates or converts alkalinity. This paper investigates the geochemistry of 3 treatments of a red mud to affect neutralization and potentially convert materials from a waste material to a resource. This study investigates two commonly used neutralization techniques, a CO(2)-neutralized red mud (CNRM), a Basecon-neutralized red mud (Basecon), and a more novel approach of a CO(2)-neutralization followed by a Basecon-neutralization (Hybrid) to understand the effects that these treatments have on neutralization process. Data indicate that the neutralization techniques form two distinct geochemical groups when discriminated on total alkalinity alone, that is treatments with, and treatments without alkalinity precipitation. However, each treatment has distinct alkalinity speciation (hydroxide-dominant or carbonate/bicarbonate dominant) and residual Ca, Mg and Al in the treatment solution. Similarly, solids produced differ in their reaction pH and ANC, and contrary pH and ANC, a contrary to other studies, Dawsonite was not seen to precipitate during any neutralization. However, despite this approximately 17 g/kg CO(2) was sequestered during CNRM and hybrid neutralizations and all treatments increased either the transport or reuse options of red mud in some way.

The process of sulfide oxidation in some acid sulfate soil materials

The process of sulfide oxidation in acid sulfate soils (ASS) is complex, involving the formation of numerous oxidation products. In this study the sulfide oxidation process was examined in 2 ASS materials over a period of 36 days using laboratory incubation experiments. Both ASS materials experienced substantial sulfide oxidation and acidification during incubation. The oxidation of pyrite was the primary cause of acidification in these ASS materials. Although a decrease in magnetic susceptibility (χ) over the initial 4 days of incubation suggested the rapid oxidation of ferromagnetic iron monosulfide greigite (Fe3S4), the total acid volatile sulfur (SAV) fraction increased in concentration by an order of magnitude over the initial 8 days of incubation. Oxygen (O2) concentration profiles indicated the presence of anoxic conditions in the centre of the incubating materials even after 16 days of exposure to the atmosphere enabling SAV formation to occur. The oxidation of the SAV fraction did not result in substantial acidification. A large proportion of the water-soluble iron released by sulfide oxidation was precipitated as iron oxides and hydroxides. Sulfate (SO42–) was the dominant sulfur species produced from sulfide oxidation in both ASS materials, although water-soluble SO42– was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates, thiosulfate (S2O32–) and tetrathionate (S4O62–), were detected only in the early stages of incubation, with minimal amounts being detected after the initial 4 days. The relative abundance of these 2 intermediate sulfur species appeared to be dependent on the soil pH, with S4O62– dominating S2O32– in the more acidic ASS material (i.e. pH <6) as has been observed in previous studies. The diminishing presence of sulfoxyanion intermediates as oxidation progressed was indicative that ferric ion (Fe3+) and bacterial catalysis were driving the oxidation processes. While these sulfoxyanion intermediates only constituted a small percentage of the reduced inorganic sulfur (RIS) fraction, they accounted for up to 9.3% of the total soluble sulfur fraction. Elemental sulfur (S0) was not an important sulfide oxidation product in the ASS materials examined in this study.

Sulfide oxidation and acidification of acid sulfate soil materials treated with CaCO 3 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.

Effects of Bauxsol on the immobilisation of soluble acid and environmentally significant metals in acid sulfate soils

The effects of Bauxsol, an abundant industrial by-product, on the immobilisation of soluble acid and a range of potentially environmentally toxic metals in artificial and natural acid sulfate soils were investigated. The acid neutralising capacity of Bauxsol increased with decreasing pH, which is probably provided not only by basic metal hydroxides, carbonates, and hydroxycarbonates but also by protonation of variably charged particles (e.g. gibbsite and hematite) present in Bauxsol. Simulation experiment results show that the removal of 9 tested environmentally significant heavy metals can be enhanced by addition of BauxsolTM; an exception was Co. The removal of the added soluble heavy metals by the BauxsolTM-soil mixtures shows a preferential order of Pb > Fe > Cr > Cu > Zn > Ni > Cd > Co > Mn. For the natural acid sulfate soil without added synthesised metal solution, the retention of the investigated environmentally significant metals is in the following decreasing order : Al > Zn > Fe > Co > Mn.

Soil pH, oxygen availability, and the rate of sulfide oxidation in acid sulfate soil materials: implications for environmental hazard assessment

The potential environmental hazard of acid sulfate soil (ASS) materials is directly related to both the net acidity and the rate that actual acidity is released from these soil materials into the environment. While current environmental hazard assessment techniques for ASS materials are able to quantify the net acidity, they do not take account of differences in the rate of sulfide oxidation (the dominant source of actual acidity) and differences in the rate of acidification. In this study the rate of sulfide oxidation during incubation was examined for 4 ASS materials. The effect of pH and oxygen availability on the rate of sulfide oxidation was assessed. The ASS materials were incubated in: (i) gauze where oxygen diffusion was not restricted, and (ii) sealed 100-µm-thick plastic bags which greatly limited oxygen diffusion. When oxygen diffusion was not restricted, an accelerated oxidation of sulfide occurred when the pH decreased below pH 4.0. The accelerated rate of sulfide oxidation at such low pH did not occur when oxygen diffusion was limited. This study indicates that the initial pH of an ASS material is a useful additional indicator 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.

Sample pre-treatment and the determination of some chemical properties of acid sulfate soil materials

This study provides a systematic analysis of the effect of common acid sulfate soil (ASS) sample pre-treatments (namely freezing, oven drying, and grinding) on chromium-reducible sulfur (SCR) and water-soluble sulfate determinations. The results show that oven drying and hand grinding of the samples prior to analysis resulted in a decrease in SCR (i.e. up to 20% compared to those of frozen samples). This lower SCR value was partly due to the oxidation of sulfides in the oven. For oven-dried ASS materials, more intensive grinding in a ring mill increased SCR values, most likely by abrading coatings from pyrite grains. For oven-dried mineral ASS materials the highest SCR values were obtained with 1 min of ring mill grinding, but for soils with appreciable organic matter (such as peat), 5 min of ring mill grinding gave the highest values. The results indicate that for some ASS materials, oven drying, regardless of the ensuing grinding procedure, results in underestimated SCR values. This study also demonstrates that an artifact of oven drying ASS materials can be greatly increased water-soluble sulfate contents.

Monosulfidic black ooze accumulations in sediments of the Geographe Bay area, Western Australia

Mobilisation of sedimentary monosulfidic black ooze (MBO) may result in rapid deoxygenation and acidification of surface waters, and release of potentially toxic metals. This study examines the extent and nature of MBO accumulation in the Geographe Bay area, Western Australia. MBO accumulations were found to be widespread in benthic sediments of the Geographe Bay area with acid-volatile sulfide (AVS) contents as high as 320 μmol g(-1). The MBO materials often had unusually high dissolved sulfide (S(-II)) concentrations in their pore-waters (up to 610 mg L(-1)) and elevated elemental sulfur (S(0)) contents (up to 51 μmol g(-1)). Dissolved S(-II) is able to accumulate due to limited iron availability and S(0) is largely its partial oxidation product. The availability of organic carbon and Fe limited MBO accumulation at many sites. A comparison of AVS and simultaneously extracted metal (SEM) concentrations has shown that metals are likely to be bound in sulfide complexes.

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 p 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 23–85p) 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.

Air–water CO2 outgassing in the Lower Lakes (Alexandrina and Albert, Australia) following a millennium drought

Lakes are an important source and sink of atmospheric CO2, and thus are a vital component of the global carbon cycle. However, with scarce data on potentially important subtropical and tropical areas for whole continents such as Australia, the magnitude of large-scale lake CO2 emissions is unclear. This study presents spatiotemporal changes of dissolved inorganic carbon and water - to - air interface CO2 flux in the two of Australias largest connected, yet geomorphically different freshwater lakes (Lake Alexandrina and Lake Albert, South Australia), during drought (2007 to September-2010) and post-drought (October 2010 to 2013). Lake levels in the extreme drought were on average approximately 1m lower than long-term average (0.71 m AHD). Drought was associated with an increase in the concentrations of dissolved inorganic species, organic carbon, nitrogen, Chl-a and major ions, as well as water acidification as a consequence of acid sulfate soil (ASS) exposure, and hence, had profound effects on lake pCO2 concentrations. Lakes Alexandrina and Albert were a source of CO2 to the atmosphere during the drought period, with efflux ranging from 0.3 to 7.0 mmol/m(2)/d. The lake air-water CO2 flux was negative in the post-drought, ranging between -16.4 and 0.9 mmol/m(2)/d. The average annual CO2 emission was estimated at 615.5×10(6) mol CO2/y during the drought period. These calculated emission rates are in the lower range for lakes, despite the potential for drought conditions that shift the lakes from sink to net source for atmospheric CO2. These observations have significant implications in the context of predicted increasing frequency and intensity of drought as a result of climate change. Further information on the spatial and temporal variability in CO2 flux from Australian lakes is urgently warranted to revise the global carbon budget for lakes.

The response of partially oxidised acid sulfate soil materials to anoxia

Four acid sulfate soil (ASS) materials were subjected to anoxia after varying periods of oxidation to determine the geochemical response of these types of soils to flooding. The response of the partially oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification, and the production of soluble oxidation products such as sulfate, iron, and aluminium generally decreased markedly when subjected to anoxia. However, especially in the highly acidic ASS materials (i.e. pH <3.5), sulfide oxidation and acidification generally continued (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. This substantial sulfide re-formation was accompanied by only a slight increase in pH. Minimal sulfide re-formation occurred in 2 of the ASS materials when placed in anoxic conditions, most likely due to a lack of readily available organic matter in these materials. The results show that the imposition of anoxic conditions on partially oxidised ASS materials is generally effective in decreasing the rates of further sulfide oxidation, acidification, and the production of soluble sulfide oxidation products. Biogeochemical sulfide formation consumes acidity; however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The results indicate that the treatment of sites containing actual ASS materials by management strategies relying on oxygen exclusion need to be accompanied by other strategies that include acidty neutralisation or containment.