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Summary Measuring the specific surface area (SSA) of soils that contain much organic matter (OM) is problematic. The adsorption of p‐nitrophenol (pNP) from xylene at room temperature yielded realistic values for the SSA of a wide range of clays, oxides and subsoils. Here we have extended the same measurement to some topsoils with varied OM content, texture and clay mineral composition. Specifically, we have compared the surface areas measured by adsorption of N2, and, applying the BET equation, with the values obtained by adsorption of pNP, before and after treatment of the samples with hydrogen peroxide. In all instances, the removal by H2O2 of organic matter – albeit in part only – led to a marked increase in the SSAs measured by nitrogen because of the exposure of micropores previously blocked or covered by OM. The surface areas measured by pNP were appreciably larger than those obtained by the standard BET equation, and showed little change after removal of organic matter. However, the surface area of two smectite‐rich samples measured by pNP increased substantially after peroxidation, presumably because smectite crystals decomposed during treatment with H2O2. The results suggest that, under the experimental conditions used, pNP could diffuse without hindrance into and through organic matter, enabling it to adsorb on to micropore surfaces within clay aggregates (domains). In keeping with this suggestion, the relation between the surface areas measured by pNP and the corresponding values calculated from the clay and OM contents, and clay mineral composition, of the soils was close to 1:1. An even stronger relation was observed between the measured and calculated values for cation exchange capacity.

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Adsorption and catalytic decomposition of 4-nitrobenzenesulphonylmethylcarbamate (herbicide Nisulam) on Upton, Wyoming, bentonite saturated with different cations was studied using thin-layer chromatography and infrared spectroscopy. Nisulam is adsorbed at room temperature by coordination through the NO~ group to the exchange cation regardless of the cation's nature. On moderate heating (75~176 this molecule decomposes to 4-nitrobenzenesulphonamide whereas a similar compound (herbicide Asulam) containing the NHz functional group instead of NOz is adsorbed by protonation at room temperature and decomposes into different products. For cations having a high polarizing power, a coordination bond between the Asulam molecule's C=O group and the exchange cation is established, and the molecule decomposes to sulphanilic and carbamic acid. In contrast, for cations having a low polarizing power there is no coordination, and the molecule decomposes mainly into sulphanilamide. Nisulam's coordination to the exchange cation through the NO2 group instead of C=O is ascribed to inductive and conjugation effects, typical of the nitro group.

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