Sorption of HOC in soils with carbonaceous contamination:: Influence of organic-matter composition

Detailed information about structure and composition of organic sorbents is required to understand their impact on sorption capacity and sorption kinetic of organic pollutants. Therefore, the chemical composition of organic material from 18 geosorbents was investigated by solid-state C-13 nuclear-magnetic-resonance (NMR) spectroscopy. Structural parameters such as aromaticity, polarity, and alkyl-C content were related to the Freundlich sorption exponent (1/n) and the sorption coefficient K-OC(degrees). The geosorbents included three natural and four combusted coals (carbonaceous material), three Histosols, five mineral soils from Germany containing inputs of technogenic carbonaceous material, derived from industrial activities, and four non-contaminated mineral soils from Germany. Equilibrium sorption was measured for five hydrophobic organic compounds and analyzed with the solubility-normalized Freundlich sorption isotherm. With increasing maturation degree, the proportion of polar constituents decreases from the natural soils to the coals. In contrast to the non-polluted mineral soils, the soils with technogenic input are characterized by high aromaticity and low polarity. A positive correlation between sorption coefficient K-OC degrees and aromaticity was found. The Freundlich exponent (1/n) is negatively correlated with the aromaticity, denoting an increase of adsorption processes with increasing aromaticity. Likewise, the contribution of partitioning decreases. This sorption mechanism predominates only if the organic matter in the samples contains a high proportion of polar compounds.