Sorption of hydrophobic compounds to aliphatic components of soil organic matter (SOM) is poorly understood even though these aliphatic carbons are a major fraction of SOM. The main source of aliphatic compounds in SOM is above- and below-ground plant cuticular materials (cutin, cutan and suberin). As decomposition proceeds, these aliphatic moieties tend to accumulate in soils. Therefore, if we consider that cuticular material contributes significantly to SOM, we can hypothesize that the cuticular materials play an important role in the sorption processes of hydrophobic compounds (including pesticides) in soils, which has not yet been studied. The overall goal of this research was to illustrate the mechanism and significance of the refractory aliphatic structures of SOM in sorbing hydrophobic compounds (nonionic and weakly polar pesticides). The importance of this study is related to our ability to demonstrate the sorption relationship between key pesticides and an important fraction of SOM. The specific objectives of the project were: (1) To isolate and characterize cuticular fractions from selected plants; (2) To investigate the sorption mechanism of key hydrophobic pesticides and model compounds to cuticular plant materials; (3) To examine the sorption mechanisms at the molecular level using spectroscopic techniques; (4) To investigate the sorption of key hydrophobic pesticides to synthetic polymers; (5) To evaluate the content of cuticular materials in agricultural soils; and (6) To study the effect of incubation of plant cuticular materials in soils on their sorptive capabilities. This project demonstrates the markedly high sorption capacity of various plant cuticular fractions for hydrophobic organic compounds (HOCs) and polar organic pollutants. Both cutin (the main polymer of the cuticle) and cutan biopolymers exhibit high sorption capability even though both sorbents are highly aliphatic in nature. Sorption by plant cuticular matter occurs via hydrophobic interactions and H-bonding interactions with polar sorbates. The cutin biopolymer seems to facilitate reversible and noncompetitive sorption, probably due to its rubbery nature. On the other hand, the epicuticular waxes facilitate enhance desorption in a bi-solute system. These processes are possibly related to phase transition (melting) of the waxes that occur in the presence of high solute loading. Moreover, our data highlight the significance of polarity and accessibility of organic matter in the uptake of nonpolar and polar organic pollutants by regulating the compatibility of sorbate to sorbent. In summary, our data collected in the BARD project suggest that both cutin and cutan play important roles in the sorption of HOCs in soils; however, with decomposition the more condensed structure of the cutin and mainly the cutan biopolymer dominated sorption to the cuticle residues. Since cutin and cutan have been identified as part of SOM and humic substances, it is suggested that retention of HOCs in soils is also controlled by these aliphatic domains and not only by the aromaticrich fractions of SOM.
DISTINCTIVE SORPTION MECHANISMS OF SOIL ORGANIC MATTER AND MINERAL COMPONENTS AS ELUCIDATED BY ORGANIC VAPOR UPTAKE KINETICS
