Angus E McElnea

Arsenic Mobilization in a Seawater Inundated Acid Sulfate Soil

Tidal seawater inundation of coastal acid sulfate soils can generate Fe- and S0(4)-reducing conditions in previously oxic-acidic sediments. This creates potential for mobilization of As during the redox transition. We explore the consequences for As by investigating the hydrology, porewater geochemistry, solid-phase speciation, and mineralogical partitioning of As across two tidal fringe toposequences. Seawater inundation induced a tidally controlled redox gradient Maximum porewater As (~400 μg/L) occurred in the shallow (<1 m), intertidal, redox transition zone between Fe-oxidizing and S0(4)-reducing conditions. Primary mechanisms of As mobilization include the reduction of solid-phase As(V) to As(lll), reductive dissolution of As(V)-bearing secondary Fe(lll) minerals and competitive anion desorption. Porewater As concentrations decreased in the zone of contemporary pyrite reformation. Oscillating hydraulic gradients caused by tidal pumping promote upward advection of As and Fe(2+)-enriched porewater in the intertidal zone, leading to accumulation of As(V)-enriched Fe(lll) (hydr)oxides at the oxic sediment-water interface. While this provides a natural reactive-Fe barrier, it does not completely retard the flux of porewater As to overtopping surface waters. Furthermore, the accumulated Fe minerals may be prone to future reductive dissolution. A conceptual model describing As hydro-geochemical coupling across an intertidal fringe is presented.

The measurement of actual acidity in acid sulfate soils and the determination of sulfidic acidity in suspension after peroxide oxidation

Improvements to the routine methods for the determination of actual acidity in suspension for acid sulfate soils (ASS) are introduced. The titratable sulfidic acidity (TSA) results using an improved peroxide-based method were compared with the theoretical acidity predicted by the chromium reducible sulfur method for 9 acid sulfate soils. The regression between these 2 measures of sulfidic acidity was highly significant, the slope of the regression line not significantly different from unity (P = 0.05) and the intercept not significantly different from zero. This contrasts with results of other workers using earlier peroxide oxidation methods, where TSA substantially underestimated the theoretical acidity predicted by reduced inorganic sulfur analysis. Comparison was made between the 2 principal measurements from the improved peroxide method (TSA and S-POS), with S-POS converted to theoretical sulfidic acidity to allow comparison. The relationship between these 2 measurements was highly significant. The effects of titration in suspension, as well as raising titration end points to pH 6.5, were investigated, principally with respect to the titratable actual acidity (TAA) result. TAA results obtained by KCl extraction were compared with those obtained using BaCl2, MgCl2, and water extraction. TAA in 1 M KCl suspensions titrated to pH 6.5 agreed well with titratable actual acidity measured using the 25-h extraction approach of the Lin et al. (2000a) BaCl2 method. Both BaCl2 and KCl solutions were ineffective at fully recovering acidity from synthetic jarosite without repeated extraction and titration. The application of correction factors for the estimation of total actual acidity in ASS is not supported by the results of this investigation. Acid sulfate soils that contain substantial quantities of jarosite or other acid-producing but relatively insoluble sulfate minerals continue to prove problematic to chemically analyse; however, an approach for estimating this component is discussed.

Improvements to peroxide oxidation methods for analysing sulfur in acid sulfate soils

Improvements to peroxide oxidation methods for analysing acid sulfate soils (ASS) are introduced. The soil solution ratio has been increased to 1 : 40, titrations are performed in suspension, and the duration of the peroxide digest stage is substantially shortened. For 9 acid sulfate soils, the peroxide oxidisable sulfur value obtained using the improved method was compared with the reduced inorganic sulfur result obtained using the chromium reducible sulfur method. Their regression was highly significant, the slope of the regression line was not significantly different (P = 0.05) from unity, and the intercept not significantly different from zero. A complete sulfur budget for the improved method showed there was no loss of sulfur as has been reported for earlier peroxide oxidation techniques. When soils were very finely ground, efficient oxidation of sulfides was achieved, despite the milder digestion conditions. Highly sulfidic and organic soils were shown to be the most difficult to analyse using either the improved method or the chromium method. No single analytical method can be universally applied to all ASS, rather a suite of methods is necessary for a thorough understanding of many ASS. The improved peroxide method, in combination with the chromium method and the 4 M HCl extraction, form a sound platform for informed decision making on the management of acid sulfate soils.

Accounting for Carbon Stocks in Soils and Measuring GHGs Emission Fluxes from Soils: Do We Have the Necessary Standards?

Soil is a key compartment for climate regulation as a source of greenhouse gases (GHGs) emissions and as a sink of carbon. Thus, soil carbon sequestration strategies should be considered alongside reduction strategies for other greenhouse gas emissions. Taking this into account, several international and European policies on climate change are now acknowledging the importance of soils, which means that proper, comparable and reliable information is needed to report on carbon stocks and GHGs emissions from soil. It also implies a need for consensus on the adoption and verification of mitigation options that soil can provide. Where consensus is a key aspect, formal standards and guidelines come into play. This paper describes the existing ISO soil quality standards that can be used in this context, and calls for new ones to be developed through (international) collaboration. Available standards cover the relevant basic soil parameters including carbon and nitrogen content but do not yet consider the dynamics of those elements. Such methods have to be developed together with guidelines consistent with the scale to be investigated and the specific use of the collected data. We argue that this standardization strategy will improve the reliability of the reporting procedures and results of the different climate models that rely on soil quality data.

Ultra-fine grinding is not essential for acid sulfate soil tests

Australian Standard methods for acid sulfate soils (ASS) require the grinding of soil to <0.075 mm. A ring-mill or similar grinding apparatus is therefore needed. We investigated whether ring-mill grinding is required for accurate and reproducible test results and associated calculations (such as acid–base accounting), or if more conventional fine-grinding (i.e. <0.5 mm) is sufficient to obtain acceptable results. An initial experiment (unreplicated) was conducted on 52 soils comparing ring-mill and fine-grinding treatments, and this information was used to formulate final, more detailed experimental work on five soils from the same dataset. Soils from an ASS survey in coastal central Queensland were chosen to reflect the range of chemical properties found in ASS. Soils were analysed by the Chromium and SPOCAS suite of tests for the two grinding treatments. For those tests that follow a relatively vigorous extraction carried out with heating [such as chromium-reducible S, peroxide-oxidisable S and acid-neutralising capacity by back titration (ANCBT)], results were similar for the two grinding treatments. However, for those tests that follow a relatively mild extraction without heating (such as KCl-extractable S, HCl-extractable S and titratable actual acidity), significantly higher values (P < 0.05) were obtained for ring-mill ground soil. There was no significant difference in calculated net acidity between ring-mill grinding and fine-grinding for soils without excess ANC. For self-neutralising soils, fine-grinding gave significantly lower values of ANC than ring-mill grinding. It is uncertain whether ring-mill grinding gives a true reflection of the ANC available in the natural environment.