The application of a spectrophotometric method to determine pH in acidic (pH<5) soils.

pH is a "master variable" controlling many biogeochemical processes in soils. Acid sulfate soils undergo rapid and large pH changes from circumneutral pH under anaerobic soil conditions to sulfuric soils with ultra (pH < 3.5) and extremely (pH 3.5-4.4) acidic properties following oxidation. Measuring soil pH using a glass electrode has several potential drawbacks including liquid junction errors, drift, suspension effects and clogging. Spectrophotometric pH measurement, involving addition of an indicator dye to the sample, is widely used in seawater and has recently been developed for soil extracts at circumneutral pH ranges. The aim of this study was to extend the spectrophotometric method for application in ultra and extremely acidic soils. The acid dissociation constant (pKa = 5.02) and molar absorptivities of the indicator dye bromocresol green were determined and shown to enable spectrophotometric pH measurement between pH 3 - 5.3. To demonstrate the performance and application of the method, pH and metal availability (Fe, Al, Zn) were measured during the incubation of two acid sulfate soils, which both classified as hypersulfidic soils (pH > 4) and transformed to sulfuric soils (pH < 4) after incubation for 12 weeks. The method compared well (r2 > 0.99) to glass electrode measurements under acidic conditions with high metal availability. The method has potential to improve understanding of biogeochemical processes in ultra and extremely acidic soils.

Porewater geochemistry of inland Acid sulfate soils with sulfuric horizons following postdrought reflooding with freshwater.

Following the break of a severe drought in the Murray-Darling Basin, rising water levels restored subaqueous conditions to dried inland acid sulfate soils with sulfuric horizons (pH <3.5). Equilibrium dialysis membrane samplers were used to investigate in situ changes to soil acidity and abundance of metals and metalloids following the first 24 mo of restored subaqueous conditions. The rewetted sulfuric horizons remained severely acidified (pH ∼4) or had retained acidity with jarosite visibly present after 5 mo of continuous subaqueous conditions. A further 19 mo of subaqueous conditions resulted in only small additional increases in pH (∼0.5-1 pH units), with the largest increases occurring within the uppermost 10 cm of the soil profile. Substantial decreases in concentrations of some metal(loid)s were observed with time most likely owing to lower solubility and sorption as a consequence of the increase in pH. In deeper parts of the profiles, porewater remained strongly buffered at low pH values (pH <4.5) and experienced little progression toward anoxic circumneutral pH conditions over the 24 mo of subaqueous conditions. It is proposed that low pH conditions inhibited the activity of SO-reducing bacteria and, in turn, the in situ generation of alkalinity through pyrite production. The limited supply of alkalinity in freshwater systems and the initial highly buffered low pH conditions were also thought to be slowing recovery. The timescales involved for a sulfuric horizon rewetted by a freshwater body to recover from acidic conditions could therefore be in the order of several years.

Changes in acidity and metal geochemistry in soils, groundwater, drain and river water in the Lower Murray River after a severe drought.

Acid sulfate soils with sulfuric material (pH<4) can have significant impacts on surface water quality and aquatic ecosystems due to low pH and high soluble metal concentrations in runoff and drainage discharges. There has been limited research on the complex geochemical transformations that occur along flow pathways from the soil acidity source to receiving waters. We studied the integrated geochemistry of metals in acid sulfate soils with sulfuric material, groundwater, drain and river water in the Lower Murray River (South Australia) over a 2 year period. The oxidation of an estimated 3500 ha of acid sulfate soils with sulfidic material (pH>4) underlying this former floodplain occurred due to falling river and groundwater levels during the 2006-2010 extreme "millennium" drought. A low pH (<4.5) soil layer was found approximately 1-2.5m below ground level with substantial amounts (up to 0.2 mol H(+)/kg dry weight) of available/soluble acidity and retained acidity in the form of the Fe oxyhydroxy sulfate mineral jarosite. The jarosite appears to be dissolving over time and buffering the sub-surface soil layers at pH≈4. Metal (Fe, Al, Mn) and metalloid (As) lability was greatly increased in the acidic soil layer. Highly acidic and metal rich groundwater (median pH 4.3, Fe, Al, Mn of 0.04-0.52 mmol/L) was observed at the same depths as the acidic soil layers. Nearly all of the dissolved Fe in the groundwater was present as Fe(2+). In the drains, increases in pH and redox potential promoted formation of the Fe oxyhydroxysulfate mineral schwertmannite. This mineral precipitation transferred a portion of the dissolved acidity to the drain sediments. Upon discharge to, and dilution of, the acid drainage in the river, pH neutralisation and rapid oxidation, hydrolysis, and precipitation of solid Al and Fe phases occurred in a localised area. Acidity is persisting (>3 years) following a return to pre-drought water levels.