Solubilization And Biodegradation Of Hydrophobic Organic Compounds In Soil PDF Download

Volatile hydrophobic compounds (HOCs) brought into soil and sediment systems represent a serious threat to the environment. Dissolved organic carbon (DOC) may exert an important influence over the total aqueous solubility and mobility of organic pollutants through their incorporation into micelles or the formation of soluble complexes. To date, however, it is not clear whether DOC interacts with nonionic volatile HOCs under natural conditions. Also, very little is known about the influence of DOC-type and other environmental parameters. A static headspace analysis technique was used in combination with gas chromatography to determine the extent of interactions between DOC and benzene, toluene, and chlorobenzene. Three different types of DOC were compared: a natural water-soluble extract (WSE) obtained from a Cumulic Humaquept (Labish Series), a commercial humic acid (HA), and a high purity fulvic acid (FA). In factorial experiments, the effect of type and concentration of DOC, solution pH, preparative treatment of DOC solutions, and hydrophobicity of HOCs was examined. DOC concentrations in the experiments ranged from 1.3 to 36.5 mmol-L−1, the ionic background was made up by 0.10 M KC1, and the temperature was held constant at 25 °C. The solution pH in different experiments was 4.0, 6.5, and 9.0. The acidity of classes of DOC functional groups, the influence of solution pH on the degree of DOC-protonation, and the maximum number of protons complexed per mol DOC were determined for WSE, HA, and FA through continuous potentiometric titrations. Basic solutions 9.36 mM in DOC were titrated with HC1 under N2 in a 0.1 M KC1 ionic background at 25 °C. At DOC concentrations ≥ 9.3 mmol-L−1, a small percentage of HOC molecules associated with DOC. However, no statistically significant linear relation between DOC concentration and DOC-HOC interaction was observed. Differences in the association of benzene, toluene, and chlorobenzene with DOC were inconsistent with different DOC-sources. Toluene exhibited a higher affinity for unfiltered and aged WSE- and HA-solutions when compared with freshly prepared, filtered solutions of the same materials. Most HOC molecules associated with DOC at pH 6.5. HA and FA showed a significantly greater affinity for HOCs than WSE. This reflects the acidic functional group properties of the three DOC-sources. WSE displayed the greatest capacity to complex protons, although the FA and HA functional groups were more acidic. WSE, FA, and HA complexed a maximum number of 0.196, 0.158, and 0.136 mol H-mol−1 DOC, respectively. Formation functions of WSE, HA, and FA calculated from titration data were fitted to a chemical model through a non-linear least-squares minimization program in order to obtain conditional protonation constants (cK) for classes of functional groups. Log cK values were 5.52 and 9.12 for WSE, 4.87 and 8.77 for FA, and 4.75, 7.62, and 9.39 for HA. These values were in agreement with protonation constants obtained through a graphical procedure. A comparison of the data obtained for WSE, HA, and FA from association and titration experiments shows that the capacity to complex protons and the affinity for HOCs are inversely related. The relatively high functional group content of WSE corresponds to a relatively low hydrophobicity, as expressed in the small extent of WSE-HOC interactions when compared with HA and FA.