The process of sulfide oxidation in some acid sulfate soil materials

Soil Research ◽  
2004 ◽  
Vol 42 (4) ◽  
pp. 449 ◽  
Author(s):  
N. J. Ward ◽  
L. A. Sullivan ◽  
D. M. Fyfe ◽  
R.T. Bush ◽  
A. J. P. Ferguson
Keyword(s):  
Sulfide Oxidation ◽  
Water Soluble ◽  
Oxidation Products ◽  
Total Acid ◽  
Sulfur Species ◽  
Acid Sulfate ◽  
Incubation Experiments ◽  
O2 Concentration ◽  
Order Of Magnitude ◽  
Sulfate Soils

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.

Characteristics of the Acidity in Acid Sulfate Soil Drainage Waters, McLeods Creek, Northeastern NSW, Australia

2006 ◽  
Vol 3 (3) ◽  
pp. 225 ◽  
Author(s):  
Rosalind Green ◽  
T. David Waite ◽  
Michael D. Melville ◽  
Ben C. T. Macdonald
Keyword(s):  
Oxidation Products ◽  
Metal Species ◽  
Acid Sulfate Soils ◽  
Iron Sulfides ◽  
Dissolved Metals ◽  
Species Determination ◽  
Acid Sulfate ◽  
Direct Titration ◽  
Sulfate Soils ◽  
Drainage Waters

Environmental Context. Acid sulfate soils are found in many low-lying coastal areas, but they can also be encountered in inland areas of Australia and other parts of the world. These soils typically contain iron sulfides, primarily pyrite (FeS2) and mackinawite (FeS), and the products that result from oxidation of these iron minerals. Acidic and metal-rich waters can be produced when the pyrite in soil is oxidized by natural means or accelerated when the soil is drained, which typically occurs when it is developed for agriculture or urban use. In general, acid sulfate soils become a problem when oxidation products are transported from the soil profile into nearby streams and estuaries, which can severely affect the ecology, biodiversity, economic development, and the aesthetics of adjacent waterways. The key contributors to acidity in drainage waters from the site examined are Al3+, AlSO4– and, under particular circumstances, Mn2+ and Fe2+, but the principal species contributing to acidity are strongly time variant and would be expected to vary from site to site. Abstract. Catchments that contain acid sulfate soils can discharge large quantities of acid and dissolved metals into waterways. At McLeods Creek in far northern NSW, Australia, the acidity from the hydrolysis of dissolved metal species, particularly aluminium and iron, contributes to greater than 70% of the total acidity. Therefore, a poor relationship exists between both calculated and titrated acidity and pH because of the dominant influence of these hydrolyzable metal species. Determination of the so-called ‘cold acidity’ by direct titration with NaOH yields results that are difficult to replicate because of the buffering effects of suspended solids, carbon dioxide ingassing, and/or MnII and FeII oxidation in the sample as the titration end-point is approached. Samples that are pre-treated with sulfuric acid and hydrogen peroxide produce results (of ‘hot acidity’) that can be easily replicated and are similar to calculated acidities based on elemental analysis and speciation calculations. The cold acidity values for titrations of 105 water samples from the chosen field site are often higher than hot acidity values as a result of the loss of carbonate acidity during pre-treatment of samples for hot acidity analysis.

The response of partially oxidised acid sulfate soil materials to anoxia

Soil Research ◽  
2004 ◽  
Vol 42 (6) ◽  
pp. 515 ◽  
Author(s):  
Nicholas J. Ward ◽  
Leigh A. Sullivan ◽  
Richard T. Bush
Keyword(s):  
Organic Matter ◽  
Sulfide Oxidation ◽  
Management Strategies ◽  
Oxidation Products ◽  
Acid Sulfate Soil ◽  
Acid Sulfate ◽  
Anoxic Conditions ◽  
Inorganic Sulfur

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.

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

Soil Research ◽  
2002 ◽  
Vol 40 (6) ◽  
pp. 1057 ◽  
Author(s):  
Nicholas J. Ward ◽  
Leigh A. Sullivan ◽  
Richard T. Bush
Keyword(s):  
Sulfide Oxidation ◽  
Pyrite Oxidation ◽  
Application Rate ◽  
The Other ◽  
Optimal Rate ◽  
Initial Increase ◽  
Acid Sulfate Soil ◽  
Acid Sulfate ◽  
Application Rates ◽  
Incubation Experiments

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 (&gt;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.

Agricultural acid sulfate soils: a potential source of volatile sulfur compounds?

2007 ◽  
Vol 4 (1) ◽  
pp. 18 ◽  
Author(s):  
Andrew S. Kinsela ◽  
Jason K. Reynolds ◽  
Mike D. Melville
Keyword(s):  
Sulfur Dioxide ◽  
Sulfur Compounds ◽  
Water Soluble ◽  
Acid Sulfate Soils ◽  
Acid Sulfate Soil ◽  
Acid Sulfate ◽  
Volatile Sulfur Compounds ◽  
Potential Source ◽  
Sulfate Soils ◽  
Volatile Sulfur

Environmental context. Acid sulfate soils are important contributors to global environmental problems. Agricultural acid sulfate soils have recently been shown to emit sulfur dioxide, an important gas in global issues of acid rain, cloud formation and climate change. This emission is surprising because these soils tend to be wet and the gas is extremely water-soluble. The potential origins of this gas are not yet understood within the context of acid sulfate soils. Our new study reports the measurement of two potential precursors of sulfur dioxide, dimethylsulfide and ethanethiol, from both a natural and an agricultural acid sulfate soil in eastern Australia. Abstract. Most agricultural soils are generally considered to be a sink for sulfur gases rather than a source; however, recent studies have shown significant emissions of sulfur dioxide and hydrogen sulfide from acid sulfate soils. In the current study, acid sulfate soil samples were taken in northern New South Wales from under sugarcane cropping, as well as from an undisturbed nature reserve. Using gas chromatography/flame photometric detection in conjunction with headspace solid-phase microextraction, we have now determined that these soils are a potential source of the low molecular weight volatile sulfur compounds, dimethylsulfide and ethanethiol. Although the mechanism for their production remains unclear, both compounds are important in the transfer and interconversions of atmospheric and terrestrial sulfur. Therefore, these novel findings have important implications for refining local and regional atmospheric sulfur budgets, as well as for expanding our understanding of sulfur cycling within acid sulfate soils and other sediments.

Effect of season and landscape position on the aluminium geochemistry of tropical acid sulfate soil leachate

Soil Research ◽  
2009 ◽  
Vol 47 (2) ◽  
pp. 137 ◽  
Author(s):  
W. S. Hicks ◽  
G. M. Bowman ◽  
R. W. Fitzpatrick
Keyword(s):  
Process Model ◽  
Iron Oxidation ◽  
Oxidation Products ◽  
Wet Season ◽  
Soil Leachate ◽  
Acid Sulfate ◽  
Seasonal Factors ◽  
Water Ph ◽  
Drying Conditions ◽  
Sulfate Soils

Acid sulfate soils (ASS) occupy an estimated 5.8 × 106 ha of coastal Australia. In tropical Australia, the processes operating in these soils, and their environmental hazards, are poorly understood. Drainage of a tropical estuarine wetland containing extensive ASS deposits left the area in a highly degraded condition. Surface and soil water pH values from the site were consistently <5 and commonly <3.5. Aluminium activity was several orders of magnitude greater than the level set for the protection of aquatic ecosystems, with a seasonal variation of 3 orders of magnitude. Aluminium behaved conservatively at the discharge point to receiving waters. In drainage lines and soil solution, aluminium activity was limited by elevated sulfate activity. Aluminium was commonly supersaturated with respect to alunite and behaved as though an aluminium species with the stoichiometry Al:OH:SO4 regulated its activity, which was 2–5 orders of magnitude lower than if gibbsite or amorphous aluminium hydroxide solubility was the control. While jurbanite (AlOHSO4.5H2O) is no longer considered a potential mineral in ASS, these data again raise the question of a satisfactory explanation of aluminium activity. Sulfate activity was influenced by seasonal factors. Wet season conditions were reducing and favoured the dissolution of acid iron oxidation products. The dry season oxidising and drying conditions favoured their precipitation, resulting in seasonal cycling. Based on our findings we developed a landscape geochemical process model for the site.

scholarly journals EFFECT OF DIFFERENT REMEDIATION TECHNIQUES AND DOSAGES OF PHOSPHORUS FERTILIZER ON SOIL QUALITY AND KLEKAP PRODUCTION IN ACID SULFATE SOIL AFFECTED AQUACULTURE PONDS

2007 ◽  
Vol 2 (2) ◽  
pp. 141 ◽  
Author(s):  
Akhmad Mustafa ◽  
Jesmond Sammut
Keyword(s):  
Soil Improvement ◽  
Oxidation Products ◽  
Available P ◽  
Poor Growth ◽  
Acid Sulfate ◽  
Soil Variables ◽  
Aquaculture Ponds ◽  
Two Factors ◽  
Forced Oxidation ◽  
Sulfate Soils

<p>Acid sulfate soils (ASS) contain sufficient pyrite which, when oxidised following excavation for brackishwater aquaculture ponds, will generate acid and mobilise toxic metals. Production in affected ponds can be low due to poor growth of shrimp and fish, mass mortalities of stock and low plankton blooms. The resultant low soil pH can also cause poor klekap production due to the retention of phosphorus associated with elevated concentrations of Fe and Al in the pond soils. A series of experiments was conducted to determine the effects of different soil amelioration techniques and dosage of phosphorus (P) on soil and klekap production under laboratory conditions. The treatments consisted of two factors. The first factor tested was different techniques for ASS improvement (non-improvement, improvement through liming and improvement through remediation involving forced oxidation of pyrite, flooding and flushing of oxidation products). The second factor tested was phosphorus dosages, that is, with phosphorus and without phosphorus-based fertilizer. Each treatment had three replications. The experiment showed that liming and remediation had the same effect on several soil variables; they raised the soi pH (pHF, pHFOX, pHKCl) and decreased SPOS, Fe and Al. Remediation of ASS decreased retention of P and increased available-P of soil, whereas liming did not show a significant effect on retention of P and available-P in the doses used for this experiment. The interaction between the different soil improvement techniques and phosphorus fertilising showed a significant effect on klekap production with the highest klekap production of 23.21 mg/cm2 found in remediated soil and with a phosphorus fertiliser dosage of 75 kg/ha.</p>

The acid flux dynamics of two artificial drains in acid sulfate soil backswamps on the Clarence River floodplain, Australia

Soil Research ◽  
2004 ◽  
Vol 42 (6) ◽  
pp. 623 ◽  
Author(s):  
S. G. Johnston ◽  
P. Slavich ◽  
P. Hirst
Keyword(s):  
Temporal Dynamics ◽  
Sulfide Oxidation ◽  
Soil Surface ◽  
Drainage Density ◽  
Oxidation Products ◽  
Acid Sulfate Soil ◽  
Flux Dynamics ◽  
Acid Sulfate ◽  
High K ◽  
Very High

The export of acidity, iron, aluminium, and sulfate to an estuary from 2 drains in acid sulfate soil backswamps was monitored over 18 months. The backswamps had similar geomorphology, stratigraphy, and drainage density, and comparable soil and groundwater acidity. However, the flux rates, temporal dynamics, and export pathways of acid and other sulfide oxidation products varied greatly and were controlled to first order by (i) the saturated hydraulic conductivity (K) of sulfuric horizons and (ii) the tidally influenced groundwater gradients. The site with very high K and large tidally influenced groundwater gradients had high acid flux rates (5300 mol H+/ha.year), chronic acid discharge, high drain water acid and metal concentrations, and the primary flux pathway was direct groundwater seepage (interflow/bypass flow) to the drain. The site with lower K and smaller groundwater gradients displayed low acid flux rates (50 mol H+/ha.year), infrequent, highly episodic discharge, and the primary flux pathway was dilute surface runoff following dissolution of sulfide oxidation products accumulated on the soil surface. Importantly, the majority of acid export at both sites occurred while the backswamp groundwater level was within a very narrow elevation range.

PEUBAH KUALITAS AIR YANG MEMPENGARUHI PERTUMBUHAN RUMPUT LAUT (Gracilaria verrucosa) DI TAMBAK TANAH SULFAT MASAM KECAMATAN ANGKONA KABUPATEN LUWU TIMUR PROVINSI SULAWESI SELATAN

2009 ◽  
Vol 4 (1) ◽  
pp. 125
Author(s):  
Akhmad Mustafa ◽  
Rachmansyah Rachmansyah ◽  
Dody Dharmawan Trijuno ◽  
Ruslaini Ruslaini
Keyword(s):  
Water Quality ◽  
Growth Rate ◽  
Ammonium Phosphate ◽  
Gracilaria Verrucosa ◽  
Acid Sulfate Soils ◽  
Acid Sulfate Soil ◽  
Acid Sulfate ◽  
Independent Variables ◽  
Water Quality Variables ◽  
Sulfate Soils

Rumput laut (Gracilaria verrucosa) telah dibudidayakan di tambak tanah sulfat masam dengan kualitas dan kuantitas produksi yang relatif tinggi. Oleh karena itu, dilakukan penelitian yang bertujuan untuk mengetahui peubah kualitas air yang mempengaruhi laju pertumbuhan rumput laut di tambak tanah sulfat masam Kecamatan Angkona Kabupaten Luwu Timur Provinsi Sulawesi Selatan. Pemeliharaan rumput laut dilakukan di 30 petak tambak  terpilih selama 6 minggu. Bibit rumput laut dengan bobot 100 g basah ditebar dalam hapa berukuran 1,0 m x 1,0 m x 1,2 m. Peubah tidak bebas yang diamati adalah laju pertumbuhan relatif, sedangkan peubah bebas adalah peubah kualitas air yang meliputi: intensitas cahaya, salinitas, suhu, pH, karbondioksida, nitrat, amonium, fosfat, dan besi. Analisis regresi berganda digunakan untuk menentukan peubah bebas yang dapat digunakan untuk memprediksi peubah tidak bebas. Hasil penelitian menunjukkan bahwa laju pertumbuhan relatif rumput laut di tambak tanah sulfat masam berkisar antara 1,52% dan 3,63%/hari dengan rata-rata 2,88% ± 0,56%/hari. Di antara 9 peubah kualitas air yang diamati ternyata hanya 5 peubah kualitas air yaitu: nitrat, salinitas, amonium, besi, dan fosfat yang mempengaruhi pertumbuhan rumput laut secara nyata. Untuk meningkatkan pertumbuhan rumput laut di tambak tanah sulfat masam Kecamatan Angkona Kabupaten Luwu Timur dapat dilakukan dengan pemberian pupuk yang mengandung nitrogen untuk meningkatkan kandungan amonium dan nitrat serta pemberian pupuk yang mengandung fosfor untuk meningkatkan kandungan fosfat sampai pada nilai tertentu, melakukan remediasi untuk menurunkan kandungan besi serta memelihara rumput laut pada salinitas air yang lebih tinggi, tetapi tidak melebihi 30 ppt.Seaweed (Gracilaria verrucosa) has been cultivated in acid sulfate soil-affected ponds with relatively high quality and quantity of seaweed production. A research has been conducted to study water quality variables that influence the growth of seaweed in acid sulfate soil-affected ponds of Angkona Sub-district East Luwu Regency South Sulawesi Province. Cultivation of seaweed was done for six weeks in 30 selected brackishwater ponds. Seeds of seaweed with weight of 100 g were stocked in hapa sized 1.0 m x 1.0 m x 1.2 m. Dependent variable that was observed was specific growth rate, whereas independent variables were water quality variables including light intensity, salinity, temperature, pH, carbondioxide, nitrate, ammonium, phosphate, and iron. Analyses of multiple regressions were used to determine the independent variables which could be used to predict the dependent variable. Research result indicated that relative growth rate of seaweed in acid sulfate soils-affected brackishwater ponds ranged from 1.52% to 3.63%/day with 2.88% ± 0.56%/day in average. Among nine observed water quality variables, only five variables namely: nitrate, salinity, ammonium, phosphate and iron influence significantly on the growth of seaweed in acid sulfate soils-affected brackishwater ponds. The growth of seaweed in acid sulfate soils-affected brackishwater ponds of Angkona District East Luwu Regency, can be improved by using nitrogen-based fertilizers to increase ammonium and nitrate contents and also fertilizers which contain phosphorus to improve phosphate content to a certain level. Pond remediation to decrease iron content and also rearing seaweed at higher salinity (but less than 30 ppt) can also be alternatives to increase the growth of seaweed.

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