The mechanism whereby acid deposition can cause acidification of surface waters via equilibrium processes in soil solution was investigated using chemical equilibrium models. These models show that for soils with low to moderately low exchangeable bases (15% Ca2+ saturation), the soil solution pH is only slightly affected by CO2 partial pressures over the range likely to be found in soils (1–5% CO2), but the alkalinity (defined as alkalinity = 2[CO32−] + [HCO3−] + [OH−] − [H+] − [Al3+] − [Al(OH)2+] − [Al(OH)22+] of the soil solution increases rapidly with increasing CO2 partial pressure (the brackets denote molar concentrations). In contrast, solutions that are not in contact with the soil's cation exchange complex maintain alkalinity independently of CO2 partial pressure. If alkalinity is positive, the pH in such solutions rapidly increases in response to decreasing CO2 pressure. Waters having positive alkalinity will undergo a rapid rise in pH when released from the soil due to CO2 degassing, while waters with negative alkalinity (net acidity) remain acid when degassed.The effect on the soil of precipitation containing H2SO4 is to increase the SO42− concentration. In acid soils, ion exchange reactions that take place in response to increasing SO42− from 25 to 250 µmol (e−) L−1 can be expected to depress soil solution pH by 0.2 to 0.4 units. This depression is sufficient to cause a switch from positive to negative alkalinity in many soil solutions and when waters with negative alkalinity are released from the soil they remain acid when degassed. This mechanism could easily account for a change in pH of surface waters from 6.25 to 5.0 or less, while the associated change in soil solution would be < 0.3 units. This mechanism does not depend on soil acidification in the sense of a reduction in base saturation. It is completely reversible and responses to changes in SO42− concentration is instantaneous, so that lags in response to changes in sulfate input levels would be controlled only by processes such as soil sulfate adsorption and biological cycling that tend to buffer changes in SO42− concentration.
Calcium‐aluminum exchange isotherms were generated for three common ion exchange equilibrium equations, and their implications relative to the probable effects of acid rainfall are examined. The equations examined were those of Gaines and Thomas (1953), Vanselow (1932), and Gapon (1933), using selectivity coefficients Kgt, Kv nd Kgp, respectively, covering the range likely to be found in soils. These isotherms, shown as fraction Al in solution as a function of the charge fraction compensated by exchangeable Ca2+ (E*Ca), are affected by solution concentration but are independent of cation exchange capacity. At least within the range of log Kgt values from 1 to 3, the isotherms generated from the Gaines‐Thomas and Vanselow equations are almost identical when Kv = 0.316 Kgt. The shape of the isotherm generated by the Gapon equation, however, is somewhat different. Using the Gaines‐Thomas equation, the system was expanded to include the Al(OH) 2+, Al(OH)2+, and H+ ions. Examination of these curves suggests that for most soils, solutions will be dominated by Ca2+ or other basic cations, as long as E*Ca is above ≈0.15. The change from Ca2+ to Al3+ domination is quite abrupt and will usually occur at E*Ca values between 0.05 and 0.15. These results are useful in predicting the changes in Ca‐Al balance in soil solutions and leachates over time as a result of H2SO4 and/or SO2 impacts.
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