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  • 1
    Electronic Resource
    Electronic Resource
    Oxford, UK : Blackwell Science Ltd
    European journal of soil science 51 (2000), S. 0 
    ISSN: 1365-2389
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl2 or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl2 than in NaCl of the same ionic strength. Apparently Ca2+ ions were more effective than Na+ ions in screening the negative charge on HA. In CaCl2 the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl2 sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co-sorption of extraneous cations (Ca2+ or Na+) for charge balance. The Ca2+ co-sorbed can attract more HA to the complex possibly by a cation-bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca2+ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1365-2389
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: 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.
    Type of Medium: Electronic Resource
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