Exchangeable and secondary mineral reactive pools of aluminium in coastal lowland acid sulfate soils

The use of coastal floodplain sulfidic sediments for agricultural activities has resulted in the environmental degradation of many areas worldwide. The generation of acidity and transport of aluminium (Al) and other metals to adjacent aquatic systems are the main causes of adverse effects. Here, a five-step sequential extraction procedure (SEP) was applied to 30 coastal lowland acid sulfate soils (CLASS) from north-eastern New South Wales, Australia. This enabled quantification of the proportion of aluminium present in 'water-soluble', 'exchangeable', 'organically-complexed', 'reducible iron(III) (oxyhydr)oxide/hydroxysulfate-incorporated' and 'amorphous Al mineral' fractions. The first three extractions represented an average of 5% of 'aqua regia' extractable Al and their cumulative concentrations were extremely high, reaching up to 4000 mg·kg− 1. Comparison of Al concentrations in the final two extractions indicated that 'amorphous Al minerals' are quantitatively a much more important sink for the removal of aqueous Al derived from the acidic weathering of these soils than reducible Fe(III) minerals. Correlations were observed between soil pH, dissolved and total organic carbon (DOC and TOC) and Al concentrations in organic carbon-rich CLASS soil horizons. These results suggest that complexation of Al by dissolved organic matter significantly increases soluble Al concentrations at pH values > 5.0. As such, present land management practices would benefit with redefinition of an 'optimal' soil from pH ≥ 5.5 to ~ 4.8 for the preservation of aquatic environments adjacent to organic-rich CLASS where Al is the sole or principle inorganic contaminant of concern. Furthermore, it was observed that currently-accepted standard procedures (i.e. 1 M KCl extraction) to measure exchangeable Al concentrations in these types of soils severely underestimate exchangeable Al and a more accurate representation may be obtained through the use of 0.2 M CuCl2.