Surface reactivity of poorly-ordered minerals in podzol B horizons

The surface reactivity of mineral soil horizons from three podzolised forest soils in Scandinavia was examined. The amount of accumulated C was low, between 1.8 and 2.3% in the top of the B horizons. Selective extractions in combination with infrared (IR) spectroscopy and transmission electron microscopy (TEM) indicated a predominance of poorly-ordered imogolite-type materials (ITM) in the oxalate extractable fraction in an examined B horizons. The presence of well-ordered imogolite was only indicated in the Nyanget B3 horizon. A large proportion of free Fe was removed by ammonium oxalate. Comparisons of Mossbauer spectra (both at room temperature and at 4.2 K) before and after treatment with ammonium oxalate showed that the oxalate treatment resulted in a removal of a (super)paramagnetic Fe3+ phase? probably ferrihydrite. A comparison of the Mossbauer Fe3+ parameters at room temperature and 4.2 K indicated a close intergrowth of a ferrihydrite-like oxide with a magnetically neutral matrix, e.g., allophane. The specific surface area (SSA) was determined by N-2 adsorption before and after treatment of the samples with acid ammonium oxalate. The loss of SSA after oxalate treatment was considerable in the B horizon where only between 3.8 to 13.38 of the original SSA remained after treatment. The point of zero charge salt effect (PZSE) increased with depth in the B horizon from between 4.4 and 5.1 in the upper horizons to between 5.7 and 7.7 in the lower part of the B horizon. The increased PZSE with depth paralleled a decrease in the ratio of pyrophosphate soluble C to oxalate soluble Fe + Al. The affinity for SO42-. a goad indicator of the presence of active surface hydroxyls, was measured by comparing the H+ buffering capacity of a sample titrated in 2.5 mM Na2SO4 with a sample titrated in 5 mh I NaNO3,. The buffering capacity of the soil in the Na2SO4, electrolyte was well correlated with the amount of oxalate minus pyrophosphate soluble Fe + Al (r(2) = 0.88). The sulphate exchange capacity was considerably higher than CEC, especially in lower parts of the B horizon. The calculated surface area of the oxalate soluble material (OSM) ranged between 74 and 289 m(2) g(-1) and the calculated surface site density of the same material ranged between 0.6 to 3.3 site nm(-2). It was concluded that the surface reactivity in the B horizons is dominated by the poorly-ordered variable-charge oxides resulting in a low capacity to retain cations but a high capacity for adsorption of weak acid anions like SO42- and organic acids. (C) 2000 Elsevier Science B.V. All rights reserved.