Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Abstract

Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline-acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline-acidic conditions (pH 1-4; ionic strengths=0.01 and 0.25M; 25°C) and over a range of temperatures (25-45°C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2-4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45°C (-9.07molg-1s-1), while the lowest log RSi value was obtained at pH 4 and 25°C (-11.20molg-1s-1). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6kJmol-1 (pH 1) to 37.7kJmol-1 (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 (I=0.25M, 25°C) compared to an ANC of 0.21kg H2SO4/tonne clay/day at pH 4 (I=0.25M, 25°C). The highest ANC of 6.91kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 and at 45°C (I=0.25M), which is more than three times higher than the ANC provided under the similar solution conditions at 25°C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.