Changes in surface reactivity and organic matter composition of clay subfractions with duration of fertilizer deprivation

Preservation of organic matter in soils depends on the chemical structure of organic compounds and on the surface properties of the mineral matrix. We tested the effect of mineral surface reactivity on organic matter decomposition by (i) investigating changes of organic matter composition in clay subfractions of an illitic Haplic Chernozem along a time series of fertilizer deprivation and (ii) simultaneously characterizing the reactivity of mineral surfaces. The soil was subjected to fertilizer deprivation for 18, 44 and 98 years, respectively. Mineral surface properties were characterized by selective dissolution of pedogenic oxides. The number of hydroxyls released after exposure to sodium fluoride was taken as an index for mineral surface reactivity. Organic soil constituents were determined by C-13 cross-polarization magic-angle spinning nuclear magnetic resonance (C-13 CPMAS NMR). Clay subfractions had different mineral surface properties. The coarse fractions have more reactive surfaces and contain more organic carbon than the fine clay fractions. Mineral surface properties are constant over time and are not affected by fertilizer deprivation. Surface reactivity is a function of iron oxide density and controls carbon concentrations in the clay subfractions. Within the time frame of our investigation, alkyl C and aromatic C responded to the duration of fertilizer deprivation, but were indifferent to mineral surface reactivity. O-alkyl C seems to be protected by interactions with pedogenic oxides.