Long-Term Uptake of Phenol-Water Vapor Follows Similar Sigmoid Kinetics on Prehydrated Organic Matter- and Clay-Rich Soil Sorbents.

Typical experimental time frames allowed for equilibrating water-organic vapors with soil sorbents might lead to overlooking slow chemical reactions finally controlling a thermodynamically stable state. In this work, long-term gravimetric examination of kinetics covering about 4000 h was performed for phenol-water vapor interacting with four materials pre-equilibrated at three levels of air relative humidity (RHs 52, 73, and 92%). The four contrasting sorbents included an organic matter (OM)-rich peat soil, an OM-poor clay soil, a hydrophilic Aldrich humic acid salt, and water-insoluble leonardite. Monitoring phenol-water vapor interactions with the prehydrated sorbents, as compared with the sorbent samples in phenol-free atmosphere at the same RH, showed, for the first time, a sigmoid kinetics of phenol-induced mass uptake typical for second-order autocatalytic reactions. The apparent rate constants were similar for all the sorbents, RHs and phenol activities studied. A significant part of sorbed phenol resisted extraction, which was attributed to its abiotic oxidative coupling. Phenol uptake by peat and clay soils was also associated with a significant enhancement of water retention. The delayed development of the sigmoidal kinetics in phenol-water uptake demonstrates that long-run abiotic interactions of water-organic vapor with soil may be overlooked, based on short-term examination.

Effects of γ-irradiation of original and organic matter-amended soils on the sorption of triclosan and diuron from aqueous solutions.

Soil γ-irradiation is a well-known method of inhibiting microbial activity in studies of the soil sorption of organic compounds. However, few studies have addressed the possible effect of γ-irradiation on the sorptive ability of soils enriched with different types of organic matter (OM). The objective of this study was to probe the effect of soil γ-irradiation on organic compound-soil interactions in two different situations representing adding OM to soils through land disposal of (a) OM-rich sewage sludge-originating biosolids and (b) olive mill wastewater (OMW). Both situations describe frequent environmental and agricultural scenarios. Comparisons of aqueous sorption on cobalt-60 γ-irradiated and non-irradiated soil sorbents were carried out for (a) triclosan (in a series of three soils and their lab-incubated mixtures with three different types of biosolids), and (b) the pesticide diuron (in two different untreated and OMW-affected soils). In each case, sodium azide was used as a biocide. Soil γ-irradiation affected the sorption of organic compounds by a factor generally not exceeding 2-3. Specifically, for triclosan, the sorbed concentration ratio between irradiated and non-irradiated soils when averaged over all the soil samples was 0.94. No significant effects of γ-irradiation on soil organic carbon or total nitrogen contents were observed. The effect of γ-irradiation on a soil sorbent may be less important when a rough estimate of a soil sorption coefficient of an organic compound is needed. However, it may need to be taken into account in mechanistic sorption studies, specifically, when the shape of sorption isotherms is of interest.

Sorption interactions of organic compounds with soils affected by agricultural olive mill wastewater.

The organic compound-soil interactions may be strongly influenced by changes in soil organic matter (OM) which affects the environmental fate of multiple organic pollutants. The soil OM changes may be caused by land disposal of various OM-containing wastes. One unique type of OM-rich waste is olive mill-related wastewater (OMW) characterized by high levels of OM, the presence of fatty aliphatics and polyphenolic aromatics. The systematic data on effects of the land-applied OMW on organic compound-soil interactions is lacking. Therefore, aqueous sorption of simazine and diuron, two herbicides, was examined in batch experiments onto three soils, including untreated and OMW-affected samples. Typically, the organic compound-soil interactions increased following the prior land application of OMW. This increase is associated with the changes in sorption mechanisms and cannot be attributed solely to the increase in soil organic carbon content. A novel observation is that the OMW application changes the soil-sorbent matrix in such a way that the solute uptake may become cooperative or the existing ability of a soil sorbent to cooperatively sorb organic molecules from water may become characterized by a larger affinity. The remarkable finding of this study was that in some cases a cooperative uptake of organic molecules by soils makes itself evident in distinct sigmoidal sorption isotherms rarely observed in soil sorption of non-ionized organic compounds; the cooperative herbicide-soil interactions may be characterized by the Hill model coefficients. However, no single trend was found for the effect of applied OMW on the mechanisms of organic compound-soil interactions.

Interactions of triclosan, gemfibrozil and galaxolide with biosolid-amended soils: Effects of the level and nature of soil organic matter.

Triclosan, gemfibrozil and galaxolide, representing acidic and non-ionized hydrophobic organic compounds, are biologically active and can be accumulated during wastewater treatment in sewage sludge. The interactions of these substances with the soils amended by sewage sludge-originating biosolids may control their environmental fate. Therefore, the sorption of three organic compounds was studied in dune sand, loess soil, clay soil and mixtures of these media with three different sewage sludge-originating biosolids that were incubated under aerobic conditions for 6 months. For each compound, 15 sorption isotherms were produced at pH 7.8-8.0. The sorption of triclosan and gemfibrozil on sand-containing sorbents was examined also under acidic conditions. In some soil series, the compound's Freundlich constants (KF) are linearly related to the soil organic carbon (OC) content. Notably, for a given OC content, the sand-containing sorbents tend to demonstrate enhanced interactions with triclosan and galaxolide. This may be related with more hydrophobic and/or less rigid soil organic matter (SOM) as compared with the clay-containing soils, implying indirect effects of minerals. Generally the OC-normalized KF vary among different soil-biosolid combinations which is explained by the differences in the composition and properties of SOM, and is also contributed by the non-zero intercepts of the linear KF upon soil OC dependencies. The negative intercepts suggest that below a certain OC level no considerable organic compound-soil interactions would occur. Interactions of molecular and anionic forms of triclosan with a sand-containing sorbent may be comparable, but interactions involving gemfibrozil molecules could be stronger than interactions involving its anion.

Spatial and seasonal patterns of fluorescent organic matter in Lake Kinneret (Sea of Galilee) and its catchment basin.

Lake Kinneret (Sea of Galilee) is one of the major water resources in Israel. The origin and characteristics of natural organic matter (NOM) in the lake and its tributary rivers were studied using fluorescence excitation emission matrices (EEM) and parallel factor analysis. Two humic-like and one proteinous components were sufficient to describe EEM variability among 167 water samples collected between 2/2005 and 9/2006. The two humic-like components showed different relations in lake and riverine samples. Their vertical distribution in the lake was affected by seasonal stratification and distance from water surface, presumably reflecting the release of humic-like matter from sediments, its production via NOM transformation in the bottom layers, and its photodegradation in the upper layers. Vertical distribution of the proteinous component, indicating biological activity at upper water layers, did not correlate with that of the humic-like components. Dissolved organic carbon concentrations did not show any vertical stratification, emphasizing the power of EEM to explore NOM dynamics.

Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter.

Using fluorescence intensity measurements, pyrene interactions with different types of effluent dissolved organic matter (EDOM) originated from treated municipal wastewater are examined. Multiple observations show that fluorescence intensity of pyrene-EDOM solutions is non-linearly related to pyrene concentration, with distinct concave-up dependence. Testing the effect of pyrene concentration on fluorescence intensity of pyrene-EDOM solutions provides a tool to examine whether binding of an organic compound to EDOM follows linear or non-linear isotherm. Possible coupling between static and dynamic quenching effects was addressed while analyzing fluorescence data. Limited number of EDOM binding sites results in a non-linear binding isotherm such that the concept of pyrene "partitioning" between aqueous phase and "bulky" EDOM organic phase is hardly relevant. Maximal EDOM capacity for pyrene binding is estimated approximately as 0.1% ww(-1). Examination of the differences between the total fluorescence intensity of pyrene-EDOM solution and the fluorescence intensities of separated constituents (pyrene and EDOM) was used to illustrate the accumulation of pyrene-EDOM complexes and saturation of some EDOM binding sites. Strong interactions between pyrene and EDOM binding sites may result in pyrene distribution coefficients differing at least by a factor 3.5-7 at varying pyrene concentrations.