Predicting the release of metals from ombrotrophic peat due to drought-induced acidification.

Ombrotrophic peats in northern England and Scotland, close to industrial areas, have substantial contents of potentially toxic metals (Al, Ni, Cu, Zn, Cd and Pb) and of pollutant sulphur, all derived from atmospheric deposition. The peat sulphur, ordinarily in reduced form, may be converted to sulphuric acid under drought conditions, due to the entry of oxygen into the peats. The consequent lowering of soil solution pH is predicted to cause the release of metals held on ligand sites of the peat organic matter. The purpose of the present study was to explore, by simulation modelling, the extent of the metal response. Chemical variables (elemental composition, pH, metal contents) were measured for samples of ombrotrophic peats from three locations. Water extracts of the peats, and samples of local surface water, were also analysed, for pH, dissolved organic carbon (DOC) and metals. Metal release from peats due to acidification was demonstrated experimentally, and could be accounted for reasonably well using a speciation code (WHAM/Model VI). These data, together with information on metal and S deposition, and meteorology, were used to construct a simple description of peat hydrochemistry, based on WHAM/Model VI, that takes into account ion-binding by humic substances (assumed to be the "active" constituents of the peat with respect to ion-binding). The model was used to simulate steady state situations that approximated the observed soil pH, metal pools and dissolved metal concentrations. Then, drought conditions were imposed, to generate increased concentrations of H2SO4, in line with those observed during the drought of 1995. The model calculations suggest that the pH will decrease from the initial steady state value of 4.3 to 3.3-3.6 during rewetting periods following droughts, depending upon assumptions about the amount of potentially mobile soil S. The pH decreases will be accompanied by increases in concentrations of dissolved metals (Mg, Al, Ca, Ni, Cu, Zn, Cd, Pb) of an order of magnitude or more, depending upon assumptions about the replenishment of soil metal pools by deposition. In the most realistic scenario for present conditions, the severity of pH depressions will gradually decline due to the relatively slow depletion of the soil S pool by droughts. However, the magnitudes of heavy metal pulses will decline quite rapidly (over two or three droughts) because current and future metal deposition is unable to compensate for leaching losses from the soil pools.