Effect of biosolid-derived dissolved organic matter on orthophosphate sorption to soils depends on clay mineralogy and solution composition.

Dissolved organic matter (DOM) from biosolids can alter the sorption of orthophosphate (inorganic phosphorus (IP)) to soils and, therefore, affect the bioavailability of IP. It is not clear how clay mineralogy and solution composition interfere with DOM effects on IP sorption by soils. Hence, we studied the effect of DOM on IP sorption to five semi-arid soils dominated by either illite/smectite (I/S) or kaolinite clays. IP sorption isotherms were constructed in either NaCl or CaCl2 background solution, with and without the addition of DOM. The IP sorption capacity maxima (SMAX, Langmuir model) of the I/S soils were 33-102% higher in the presence of CaCl2, as compared to NaCl. Although DOM had no effect on the IP-SMAX in the presence of CaCl2, it increased the IP-SMAX by 35-59% in the presence of the NaCl solution. Surprisingly, DOM sorption to the I/S soils was 30-90% greater in the presence of a Na+-dominated solution, as compared to a Ca2+-dominated solution. In contrast to the I/S soils, the SMAX of the kaolinitic soil was not affected by the background electrolyte (Na+, Ca2+) or the addition of DOM. Furthermore, the addition of IP reduced the sorption of DOM to the kaolinitic soil (by up to 50%) in both background electrolyte solutions. These results highlight the contrasting roles of divalent and monovalent cations in conjunction with DOM in IP sorption to semi-arid I/S soils. We propose a new approach based on two conceptual mechanisms to explain the DOM's enhancement of IP sorption to I/S soils. (1) Under dispersion conditions in the Na+-dominated solutions, Ca2+-mediated DOM-IP complexes bind to the clay's negative planar surfaces. (2) Under flocculation conditions in the Ca+-dominated solutions, the distance between adjacent platelets decreases, reducing both the electronegative charge spillover and Ca2+ bridge-mediated DOM sorption. In contrast, the addition of DOM to kaolinite, a multi-platelet clay with a low isomorphic negative charge, reduces IP sorption due to competitive sorption on the clay's broken edges.

Submicron polymer particles may mask the presence of toxicants in wastewater effluents probed by reporter gene containing bacteria.

Microplastics are ubiquitous in aquatic systems and break down into submicron particles that can interact with aquatic toxic chemicals. These interactions may affect the detection of toxicants when using bacteria as a biomonitoring tool. This study examined the effects of model polystyrene (PS)-based submicron particles on the detection of aqueous geno- and cytotoxicity by genetically modified bioluminescent (GMB) bacteria. The toxicities were tested in three treated wastewater (TWW) effluents before and after chlorination. The PS plastics included negatively charged sulfate-coated (S-PS) and pristine (P-PS) particles of different sizes (0.1, 0.5, and 1.0 µm) that were present at different concentrations. Chlorinated or not, the S-PS and P-PS particles per se were not toxic to the GMB bacteria. However, exposure of PS particles to TWW effluents can significantly reduce the measured geno- and cytotoxicity. Adsorption of toxic compounds to polymer particles can limit the ability of the bacteria to detect those compounds. This masking effect may be mitigated by TWW chlorination, possibly due to the formation of new toxic material. Due to interactions between toxic TWW constituents and the plastics particles, water samples containing particle-associated contaminants and/or their transformation products may be declared non-toxic, based on bacterial tests as a biomonitoring tool.

Water toxicity evaluations: Comparing genetically modified bioluminescent bacteria and CHO cells as biomonitoring tools.

The use of water for drinking and agriculture requires knowledge of its toxicity. In this study, we compared the use of genetically modified bioluminescent (GMB) bacteria whose luminescence increases in the presence of toxicants and Chinese Hamster Ovary (CHO) cells for the characterization of the toxicity of water samples collected from a lake and streams, hydroponic and aquaponic farms, and a wastewater treatment plant. GMB bacteria were used to probe genotoxicity, cytotoxicity and reactive oxygen species-induced effects in the whole water samples. Unlike GMB bacteria, the use of CHO cells requires XAD resin-based pre-concentration of toxic material present in water samples for the subsequent cytotoxicity assay. In addition to the examination of the toxicity of the water from the different sources, the GMB bacteria were also used to test the XAD extracts diluted to the concentrations causing 50% growth inhibition of the CHO cells. The two biomonitoring tools provided different results when they were used to test the above-mentioned diluted XAD extracts. A pre-concentration procedure based on adsorption by XAD resins with subsequent elution was not sufficient to represent the material responsible for the toxicity of the whole water samples toward the GMB bacteria. Therefore, the use of XAD resin extracts may lead to major underestimates of the toxicity of water samples. Although the toxicity findings obtained using the GMB bacteria and CHO cells may not correlate with each another, the GMB bacteria assay did provide a mechanism-specific biomonitoring tool to probe the toxicity of water samples without a need for the pre-concentration step.

Bulk and water-extractable organic matter from compost: evaluation of the selective dissolution in water using infrared absorbance ratios.

Land application of composts affects concentration and composition of dissolved organic matter (OM) which plays important roles in soil functioning and may have effects on spreading of environmental pollution. Linking between the composition of bulk compost OM and its water-soluble fraction may, therefore, allow better understanding and prediction of the environmental impact of compost added to soil. The objectives of this study were to (i) examine composition-based links between bulk compost OM and water-extractable OM (WEOM), and (ii) evaluate and quantify selectivity of bulk compost OM dissolution, based on infrared (IR) absorbing functional groups. For that, 8 different composts and their freeze-dried WEOMs were characterized by mid-IR transmission spectroscopy. Compositions of compost OM and of WEOM were characterized in terms of ratios (R) defined on the basis of both areas and heights of specific IR absorbance bands in relation to absorbance by aliphatic CH groups. A simple novel approach is suggested, whereby selective dissolution of compost OM components is quantified by relating the R values determined for WEOM to those associated with compost OM. Significant similarities of IR spectra found in a series of WEOMs (and, to a lesser extent, in a series of compost OMs) suggest significant contributions of OM carboxylic groups to various bands. IR absorbance of compost OM contributed by hydrophilic and, specifically, carboxyl and carboxylate groups, when related to absorbance by aliphatic CH groups, can be used for predicting the indices characterizing WEOM composition, such as IR absorbance-based R values and aromaticity estimated from specific UV absorbance.

Strengths of correlations with formation of chlorination disinfection byproducts: effects of predictor type and other factors.

Measurements of the UV-Vis absorbance (Abs) and intensity of fluorescence emission (Fluor), as well as of concentrations of total or dissolved organic carbon (OC) in aqueous samples are commonly used to estimate the potential for disinfection byproducts (DBPs) formation during water chlorination. In this work, based on 574 linear associations collected from 70 experimental research papers published over the period of 1997-2019, the strengths of the correlations of Abs, Fluor, and OC with DBPs concentrations are compared. The correlations were expressed as approximately normally distributed Z-scores using Fisher variance-stabilizing transformation. The effects of specific prediction method, chlorination agent, water source, and DBPs type, with consideration of possible effects due to the presence of bromide, are examined against Z-scores by ANOVA, testing main effects and some variables interactions. The performed analysis is a first attempt to expose differences and patterns in correlation strengths associated with DBPs formation, based on systematically covered broad existing literature. Abs and OC concentration of water samples tend to demonstrate the strongest correlations with DBPs formation as compared with specific UV absorbance (SUVA) or intensity of fluorescence emission. Correlations of DBPs formation during chloramination demonstrated weaker strengths as compared with other chlorination agents, suggesting more caution in predicting DBPs concentrations, based on simple descriptors such as Abs, OC, and Fluor. In a series of different water types, the correlations with DBPs formation are expected to be enhanced, when wastewater is chlorinated. Non-fluorescent matter may be an important contributor to DBPs formation during water chlorination. When fluorescence intensity is considered as a predicting tool, choosing humic-like rather than proteinaceous fluorescence may enhance the strengths of the correlations with DBPs formation. Different performances of Abs, OC, and Fluor in correlating with DBPs formation may be beneficial for their concurrent use helping to optimize removal of different DBPs precursors.

Quantification of bacteria in water using PLS analysis of emission spectra of fluorescence and excitation-emission matrices.

Bacterial contamination of drinking water is a considerable concern for public health. Tryptophan-like fluorescence (TLF) has been widely suggested to enable fast and inexpensive monitoring and quantification of bacterial contamination of water. Typically, TLF is determined at a certain excitation (ex)/emission (em) wavelengths pair. The aim of this study was to assess fluorescence spectroscopy supported with partial least squares (PLS) algorithms as a tool for a rapid evaluation of the microbial quality of water, by comparing the use of a single ex/em wavelengths pair, of the spectrum of emission obtained at a single excitation wavelength to that of whole excitation-emission matrices (EEMs). For that, laboratory-grown Escherichia coli, Bacillus subtilis and Pseudomonas aeruginosa were studied as the model systems, as well as 90 groundwater samples from 6 different wells in Israel. The groundwater samples were characterized for fluorescence emission, coliforms, fecal coliforms, fecal streptococci and heterotrophic plate counts. The PLS analysis of emission spectra and, especially, of EEMs was capable of meaningfully reducing the detection limit of microorganisms in model systems, as compared with the single ex/em wavelengths pair-based determination commonly used, reaching a detection threshold as low as 10 CFU/ml. Use of PLS-analyzed EEMs becomes beneficial also in terms of correlation and similarity between the actual and predicted bacterial concentrations. Similarly, improved detection of bacteria was also achieved in groundwater samples. Furthermore, at a level of >104 CFU/ml, use of EEMs coupled with PLS enabled discrimination between E. coli, B. subtilis and P. aeruginosa.

Toxicity of chlorinated and ozonated wastewater effluents probed by genetically modified bioluminescent bacteria and cyanobacteria Spirulina sp.

Chlorination and ozonation of various waters may be associated with the formation of toxic disinfection byproducts (DBPs) and cause health risks to humans. Monitoring the toxicity of chlorinated and ozonated water and identification of different toxicity mechanisms are therefore required. This study is one of its kind to examine the toxic effects of chlorinated and ozonated wastewater effluents on three genetically modified bioluminescent bacteria, in comparison to the naturally isolated cyanobacteria, Spirulina strains as test systems. Three different secondary wastewater effluents were collected from treatment plants, chlorinated using sodium hypochlorite (at 1 and 10 mg L-1 of chlorine) or treated using 3-4 mg L-1 of ozone at different contact times. As compared to cyanobacterial Spirulina sp., the genetically modified bacteria enhancing bioluminescence at the presence of stress agents demonstrated greater sensitivity to the toxicity induction and have also provided mechanism-specific responses associated with genotoxicity, cytotoxicity and reactive oxygen species (ROS) generation in wastewater effluents. Effects of effluent chlorination time and chlorine concentration revealed by means of bioluminescent bacteria suggest the formation of genotoxic and cytotoxic DBPs followed with their possible disappearance at longer times. Ozonation could degrade genotoxic compounds in some effluents, but the cytotoxic potential of wastewater effluents may certainly increase with ozonation time. No induction of ROS-related toxicity was detected in either chlorinated or ozonated wastewater effluents. UV absorbance- and fluorescence emission-based spectroscopic characteristics may be variously correlated with changes in genotoxicity in ozonated effluents, however, no associations were obtained in chlorinated wastewater effluents. The bacterial response to the developed mechanism-specific toxicity differs among wastewater effluents, reflecting variability in effluent compositions.

Pesticide distribution and depletion kinetic determination in honey and beeswax: Model for pesticide occurrence and distribution in beehive products.

Beehive products such as honey, beeswax and recently pollen have been regarded for many years as appropriate sentinels for environmental pesticide pollutions. However, despite yearly application of hundreds of approved pesticides in agricultural fields, only a minor fraction of these organic compounds were actually detected in honey and beeswax samples. This observation has led us to question the general suitability of beehive products as a sentinel for synthetic organic pesticides applied in the field. The aim of the present study was to experimentally determine the distribution (logarithmic ratio of beeswax to honey pesticide concentration, LogD) and depletion kinetics (half-life) of selected pesticides in honey and beeswax as a measure of the latter matrixes to serve as a pesticide sentinel. The obtained parameters were used to extrapolate to pesticide burden in honey and beeswax samples collected from German and Israeli apiaries. In addition, we aimed to establish a mathematical model, enabling us to predict distribution of selected pesticides between honey to beeswax, by utilizing simple substance descriptors, namely, octanol/water partitioning coefficient, molar weight and Henry coefficient. Based on the present results, it appears that pesticides with LogD values > 1 and half-life in beeswax > 1 day, were likely to accumulate and detected in beeswax samples, and less likely to be found in honey. On the other hand, pesticides with negative LogD values were highly likely to be found in honey and less so in beeswax samples. Finally, pesticides with LogD values between 0-1 were expected to be found in both matrixes. The developed model was successfully applied to predict LogD values, thereby identifying octanol/water partitioning and molar weight as the most prominent substance descriptors, which affect pesticide distribution between honey and beeswax.

Accumulated Gibbs free energy as a quantitative measure of desorption hysteresis associated with the formation of metastable states.

The persistence of metastable states was proposed in the literature as one explanation for sorption-desorption hysteresis (SDH) of organic compounds on soils and sediments. When such metastable states freely exchange sorbate molecules with the surroundings and there is no spontaneous exit of a whole system from that state, it is possible to determine the extra Gibbs free energy (ΔGext) accumulated in a system due to the persistence of metastable states. A novel contribution of this paper is the characterization of SDH, in which the sorption isotherm (SI) and desorption isotherm (DI) do not close a loop, in terms of free energy needed to create "frozen", metastable states. To that end, liquid phase sorption of non-ionized sorbates is considered and by integrating over the sorption-desorption sequence, ΔGext and an integral hysteresis index (IHI) were obtained. Experimental data collected from the literature on aqueous sorption and desorption of polyaromatic hydrocarbons, triazines and ureas were examined on soils, sediments, organic matter-rich sorbents, montmorillonites and fullerene. Positive ΔGext values were obtained to quantify the thermodynamic potential for spontaneous exit from a metastable state that is not implemented due to the kinetic barriers. Relating the ΔGext values to sorbate molecular structure and sorbent properties may allow the prediction of SDH for various chemicals on sorbents in which the sorbate-induced perturbation of a sorbent matrix is believed to be a cause for the formation of persistent metastable states and the appearance of a non-closed sorption-desorption sequence.

Spectroscopic Indicators for Cytotoxicity of Chlorinated and Ozonated Effluents from Wastewater Stabilization Ponds and Activated Sludge.

We investigated chronic mammalian cell cytotoxicity of wastewaters from four sources and their optical spectroscopic properties with or without chlorination or ozonation. Samples from effluents of activated sludge, nitrification tower, facultative waste stabilization pond, and maturation waste stabilization pond were either chlorinated or ozonated. The wastewater samples were analyzed for fluorescence excitation emission matrix, specific fluorescence index (SFI), and specific UV absorbance at 254 nm (SUVA). Before and after disinfection the wastewater samples were quantitatively analyzed for in vitro mammalian cell cytotoxicity. We found that the organic extracts from the ozonated samples induced lower cytotoxicity responses than those from the chlorinated or the nondisinfected samples. To develop correlations between SFI, SUVA, and cytotoxicity, we analyzed 21 independent samples. Significant linear correlations found among these samples suggest that under the tested conditions, cytotoxicity was preferentially influenced by the fluorescence and SUVA of their composite organic agents. These two spectroscopic parameters may be used as indicators for the potential cytotoxicity of nondisinfected, ozonated, or chlorinated municipal wastewaters.

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.

Fluorescent components of organic matter in wastewater: efficacy and selectivity of the water treatment.

Characterization of organic matter (OM) present in treated wastewater (TWW) after various treatment stages is important for optimizing wastewater recycling. The general aim of this research was to carry out a long-term examination of OM in wastewater along the treatment, by applying excitation-emission matrices (EEM) fluorescence spectroscopy and parallel factor analysis (PARAFAC). Fluorescent OM was examined in water samples obtained from four wastewater treatment plants (WWTPs) in Israel for 20 months. The PARAFAC analysis of EEMs of water samples from the four WWTPs yielded six components. The fluorescent components included proteinaceous tryptophan-like matter (C1), three humic-like components (C2-C4), a component (C5) that was characterized by excitation and emission with a distinct vibrational structure similar to that of pyrene and a component (C6) that was characterized by the excitation and emission spectra demonstrating two peaks where the appearance of two emission peaks was suggested to reflect the formation of an intra-molecular exyplex. The biological treatment strongly reduced the concentration of component C1 thus increasing the overall fraction of humic-like OM over the proteinaceous OM in the treated water. The fluorescence of component C1 could therefore be used as an indicator of the biological treatment efficacy. The concentration of the humic-like component C2 characterized by excitation and emission maxima at <240,305/422 nm, respectively, was also sensitive to biological treatment. The soil aquifer treatment was not effective in completely eliminating the fingerprints of the initial wastewater. The concentrations of the fluorescent components in wastewater after the biological treatment were only slightly affected by filtration (0.45 µm) of the samples. For water sampled prior to the biological treatment, the 0.45 µm filtration had the most pronounced effect on concentrations of the proteinaceous matter and component C6. Strong positive correlations were found between concentrations of component C1 and total carbon (TC) in wastewater samples from the WWTPs thus suggesting the proteinaceous fluorescence in wastewater as an indicator for TC reduction. Chemical oxygen demand (COD) and the fluorescein diacetate hydrolyzing activity (a measure for the total microbial activity) were strongly positively correlated with the concentrations of components C1-C3 thus suggesting the fluorescence of these components as indicators for reduction in COD and the total microbial activity in wastewater.

Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: a case study with carbamazepine.

Natural organic matter (NOM) in soils and sediments is recognized to strongly affect environmental distributions of organic compounds. Water associated with NOM may have a significant impact on NOM-organic compound interactions. The objectives of this research were (1) to determine the effect of hydration of a model NOM sorbent on interactions with a probe organic compound, carbamazepine (CBZ), and (2) based on the comparison with the literature data, to evaluate the effect of organic compound structure on the cooperative participation of water molecules in organic sorbate-NOM interactions. CBZ is one of the most widely reported water pollutants from the pharmaceutical and personal care products family. Therefore, CBZ sorption on Pahokee peat was compared from water and from n-hexadecane, using solubility-normalized solute concentrations. CBZ-NOM interactions were enhanced by one to two orders of magnitudes when NOM became fully hydrated. This enhancement is associated with the distinct ability of CBZ to undergo strong, specific interactions with NOM which was revealed by comparing the transfer of CBZ and another model sorbate, phenanthrene, from solution in n-hexadecane to the hydrated NOM sorbent. The enhancing effect of NOM hydration on CBZ-NOM interactions was also observed when CBZ sorption was examined on partially hydrated NOM. In comparison with a smaller-size organic sorbate such as phenol, CBZ needs more NOM-associated water in order to demonstrate the strengthening of interactions with NOM. Therefore, for penetration of the larger sorbate molecules into the NOM interior, a greater number of water molecules are needed to compensate for the local NOM disintegration thus suggesting the greater extent of the cooperativity in an involvement of water molecules in the CBZ-NOM interactions.

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.

Organic sorbate-organoclay interactions in aqueous and hydrophobic environments: sorbate-water competition.

Sorption of nitrobenzene, phenol, and m-nitrophenol from water and n-hexadecane was measured on Na-montmorillonite and organoclays in which 41 and 90% of the exchange capacity of the Na-clay was occupied by hexadecyltrimethylammonium. The strength of sorbate-sorbent interactions in n-hexadecane for all three sorbents was in the following order: nitrobenzene < phenol < m-nitrophenol. The magnitude of the distribution coefficients suggests that the contribution to solute uptake of partitioning between n-hexadecane and the organic pseudophase of the dried organoclays is minor, whereas the major contribution is from adsorptive sorbate-sorbent interactions. Sorption isotherms obtained in different solvents were compared using a sorbate activity scale. In the organoclays, the stronger the tendency of a sorbate to interact with sorption sites, the less pronounced is the reduction in the activity-based sorption due to competition with water. The order of this reduction for the different sorbates is nitrobenzene > phenol > m-nitrophenol. The weakening of sorbate-sorbent interactions resulting from water-sorbate competition might be mitigated by interaction between the organic sorbate and sorbed water molecules. Since the more strongly interacting organic compounds are less susceptible to suppression of sorption in the presence of water, hydrating organoclays may result in an increased differentiation between "weakly" and "strongly" interacting ("nonpolar" and "polar") compounds in the organoclay phase.

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.

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements.

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.