Fluorescence of sediment humic substance and its effect on the sorption of selected endocrine disruptors

Humic substances (HS) have a critical influence on the sorption of organic contaminants by soils and sediments. This paper describes investigations into the sorption behavior of three representative endocrine disruptors, bisphenol A (BPA), 17beta-estradiol (E2), and 17alpha-ethynylestradiol (EE2), onto sediments and HS extracted sediments using a batch technique. The organic carbon-normalized partition coefficients (K(oc)) for the extracted HS (K(oc)(hs)) were calculated, and the fluorescence spectra of the HS extraced from different sediment samples were gained using excitation/emission matrix (EEM). Particular attention was paid to the correlations between the fluorescence characteristics of HS and the log K(oc)(hs) of selected endocrine disruptors. The results show that the log K(oc)(hs) values range from 3.14 to 4.09 for BPA, from 3.47 to 4.33 for E2, and from 3.65 to 4.32 for EE2. Two characteristic excitation-emission peaks were observed for HS samples extracted from sediments. They are located at Ex/Em=250-260 nm/400-450 nm (peak alpha') and Ex/Em=310-330 nm/390-400 nm (peak alpha) respectively. The alpha' and alpha peak relative intensities I(alpha')/I(alpha) vary from 0.46 to 1.64 for different extracted HS samples. The similarity between fulvic acids (FA) Ex/Em pairs and those observed for HS indicates that FA is the predominant fraction of HS extracted from sediments. Moreover, the log K(oc)(hs) values of BPA, E2, and EE2 have a negative linear correlation to I(alpha')/I(alpha) values. Peak alpha is often attributed to relatively stable and high molecular weight aromatic fulvic-like matter. Therefore, the result presented here reveals that the abundance of aromatic rings in HS molecular structure plays a critical role in the sorption of selected endocrine disruptors.     

Biofilm controlled sorption of selected acidic drugs on river sediments characterized by different organic carbon content

The sorption process of selected non-steroidal anti-inflammatory drugs (ibuprofen, naproxen, ketoprofen, diclofenac) on biofilm covered river sediments were investigated in laboratory. In the course of the experiments, the effect of pH of aqueous phase, the effect of TOC (total organic carbon) content of biofilm on the sorption processes were studied. The determination of concentration of drugs was performed by gas chromatography mass spectrometry (GC-MS) both in liquid and solid phases. The pseudo-first-order rate constant of the sorption was found to be 83 min(-1). The effect of pH on the sorption of diclofenac was significantly lower than the obtained values in case of the other three drugs. The calculated K(d) (sorption coefficient) values increased in the sequence of ibuprofen, naproxen, ketoprofen and diclofenac and varied between 0.1-0.4; 0.2-0.7; 0.2-1.2; 0.2-1.4 kg L(-1) respectively, depending on the characteristics of the sediments. The value of K(d)×f(oc) showed a straight line as function of f(oc) (fraction of organic carbon) therefore, instead of the widely distributed normalization process (K(d)/f(oc)), an empirical equation (K(d)=A/f(oc)+B) was suggested for estimation of the K(d) values in case of different TOC content sediments.     

Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax)

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.     

Determination and partitioning behavior of perfluoroalkyl carboxylic acids and perfluorooctanesulfonate in water and sediment from Dianchi Lake, China

Perfluorinated compounds (PFCs) have received much attention on their distribution in various matrices including water bodies, precipitations, sediment and biota in different areas globally, however, little attention has been paid to their occurrence and distribution in urban lakes. In this study, water and sediment samples collected from 26 sites in Dianchi Lake, a plateau urban lake in the southwestern part of China were analyzed via high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for ten analytes involving nine perfluoroalkyl carboxylic acids (PFOAs) and perfluorooctanesulfonate (PFOS). Total levels of PFCs were 30.98 ± 32.19 ng L(-1) in water and 0.95 ± 0.63 ng g(-1) in sediment. In water samples PFOA was the dominant PFC contaminant, with concentrations ranging from 3.41 to 35.44 ng L(-1), while in sediments PFOS was the main PFC contaminant at levels from 0.07-0.83 ng g(-1) dry weight. Field-based sediment water distribution coefficients (K(D)) were calculated and corrected for organic carbon content (K(oc)), which reduced variability among samples. The log K(oc) ranged from 2.54 to 3.57 for C8-C12 perfluorinated carboxylic acids, increasing by 0.1-0.4 log units with each additional CF2 moiety. The log K(oc) of PFOS was 3.35 ± 0.32. Magnitudes and trends in log K(D) or log K(oc) appeared to agree well with previously published laboratory data. Results showed that different PFC composition profiles were observed for samples from the lake water and sediments, indicating the presence of dissimilar characteristics of the PFCs compounds, which is important for PFC fate modeling and risk assessment.     

Acetamiprid, carbendazim, diuron and thiamethoxam sorption in two Brazilian tropical soils

Sorption of acetamiprid ((E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine), carbendazim (methyl benzimidazol-2-ylcarbamate), diuron (N-(3,4-dichlorophenyl)-N, N-dimethyl urea) and thiamethoxam (3-(2-chloro-thiazol-5-ylmethyl)-5-methyl-[1,3,5]oxadiazinan-4-ylidene-N-nitroamine) was evaluated in two Brazilian tropical soils, Oxisol and Entisol, from Primavera do Leste region, Mato Grosso State, Brazil. To describe the sorption process, batch experiments were carried out. Linear and Freundlich isotherm models were used to calculate the K(d) and K(f) coefficients from experimental data. The K(d) values were utilized to calculate the partition coefficient normalized to soil organic carbon (K(oc)). For the pesticides acetamiprid, carbendazim, diuron and thiamenthoxan the K(oc) (mL g(- 1)) values ranged in both soils from 98 - 3235, 1024 - 2644, 145 - 2631 and 104 - 2877, respectively. From the studied pesticides, only carbendazim presented correlation (r(2) = 0.82 and p < 0.01) with soil organic carbon (OC) content. Acetamiprid and thiamethoxam showed low sorption coefficients, representing a high risk of surface and ground water contamination.     

Correlations of nonlinear sorption of organic solutes with soil/sediment physicochemical properties

The estimation of solute sorptive behaviors is essential when direct sorption data are unavailable and will provide a convenient way to assess the fate and the biological activity of organic solutes in soil/sediment environments. In this study, the sorption of 2,4-dichlorophenol (2,4-DCP) on 19 soil/sediment samples and the sorption of 13 organic solutes on one sediment were investigated. All sorption isotherms are nonlinear and can be described satisfactorily by a simple dual-mode model (DMM): q(e)=KpCe+Q0 . bCe/(1+bCe), where Kp (mlg(-1)) is the partition coefficient; Ce (microgml(-1)) is the equilibrium concentration; Q0 (microgg(-1)) is the maximum adsorption capacity; Q0 . b (mlg(-1)) is the Langmuir-type isotherm slope in the low concentration (Henry's law) range and b (mlmicrog(-1)) is a constant related to the affinity of the surface for the solute. Based on these nonlinear sorption isotherms and similar other nonlinear isotherms, it is observed that, for both polar 2,4-DCP and nonpolar phenanthrene, Kp, Q0 and Q0 . b are linearly correlated with soil/sediment organic carbon content (f(oc) in the range of 0.118-53.7%). The results indicate that the nonlinear sorption of organic solutes results primarily from interactions with soil/sediment organic matter. The K*oc K*oc=Kp/f(oc)), Qoc (Qoc=Q0/f(oc)), Loc (Loc=Q0 . b/f(oc)) and b for a given organic solute with different soils/sediments are largely invariant. Furthermore, logK*oc, logb and logLoc for various organic solutes are correlated significantly with the solute logKow or logSw (logKow in the range of 0.9 to 5.13 and logSw in the range of -6.176 to -0.070). A fundamental empirical equation was then established to calculate approximately the nonlinear sorption from soil/sediment f(oc) and solute Sw for a given solute equilibrium concentration.     

Enantioselective determination of persistent and partly degradable toxaphene congeners in high trophic level biota

Enantiomer separation of chiral toxaphene components in biological samples was studied by application of different chiral stationary phases based on modified cyclodextrins. Several pairs of enantiomers were resolved on permethylated beta-cyclodextrin (beta-PMCD), among them 2-endo,3-exo,5-endo,6-exo,8,8,9,10-octachlorobornane (B8-1412), which was not enantiomerically resolved on tert-butyldimethylsilylated beta-cyclodextrin (beta-BSCD). The latter column was applied to determine the enantiomer ratios (ERs) of 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P-26) in brain tissue of three seal species. The ER of B8-1413 (P-26) in brain was virtually racemic as well as those of the two persistent and chiral components of technical chlordane, 1-exo,2,2,4,5,6,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-metha noindane (trans-nonachlor III or MC 6) and 1-exo,2-endo,3-exo,4,5,6,8,8-octachloro-3a,7,7a-tetrahydro-4,7- methanoindane (U82). In contrast, B8-1412 and 2-exo,5,5,8,9,9,10,10-octachlorobornane (B8-2229 or P-44) were significantly enantiomerically enriched in several samples of high trophic level biota. 2,2,5,5,8,9,9,10,10-Nonachlorobornane (B9-1025 or P-62), a chlorobornane metabolisable by seals and the presumable precursor of B8-2229 (P-44), was also enantiomerically enriched in seal blubber. These results confirm the assumption that some less persistent toxaphene components may be significantly degraded in biological samples. Enantioselective gas chromatography provides the information that such a degradation is happening by the characteristic change of the ratio of the two enantiomers in the respective tissues.     

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in suspended sediments, dissolved phase and bottom sediment in the Houston Ship Channel

Spatial distributions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the water column and bottom sediments of the Houston Ship Channel in Texas were measured three times over a 1-year period. Total TEQ concentrations in water ranged from 0.01 to 0.25 pg/l for the dissolved phase and from 0.09 to 2.91 pg/l for the suspended phase, while TEQ concentrations in bottom sediments varied from 0.9 to 139.8 ng/kg dry wt. The dissolved concentrations were lower than their respective suspended concentrations, with average dissolved/suspended ratios between 0.11 and 0.59 for individual congeners. More than 89% of the total concentration of 2378-substituted PCDD/PCDFs was attributable to OCDD but 2378-TCDD was the major contributor to total TEQ for the three sampled media. Average logs of organic carbon-normalized suspended sediment-dissolved partitioning coefficients (logK(oc)(obs)) varied between 4.92 and 8.59 l/kg-oc; while in the bottom sediment-dissolved interface, logK(oc)(obs) values ranged from 5.48 to 8.48 l/kg-oc. Observed logK(oc)values varied within a factor of 0.64-1.26 from equilibrium logK(oc) values, suggesting fluxes of PCDD/PCDFs across the interfaces. It was found that in the HSC, on average, the tendency of a compound to move from the particulate phase to the dissolved phase decreases with increasing K(ow).     

Sorption of phenanthrene by soils contaminated with heavy metals

The fate of polycyclic aromatic hydrocarbons (PAHs) in soils with co-contaminants of heavy metals has yet to be elucidated. This study examined sorption of phenanthrene as a representative of PAHs by three soils contaminated with Pb, Zn or Cu. Phenanthrene sorption was clearly higher after the addition of heavy metals. The distribution coefficient (K(d)) and the organic carbon-normalized distribution coefficient (K(oc)) for phenanthrene sorption by soils spiked with Pb, Zn or Cu (0-1000 mg kg(-1)) were approximately 24% larger than those by unspiked ones, and the higher contents of heavy metals added into soils resulted in the larger K(d) and K(oc) values. The enhanced sorption of phenanthrene in the case of heavy metal-contaminated soils could be ascribed to the decreased dissolved organic matter (DOM) in solution and increased soil organic matter (SOM) as a consequence of DOM sorption onto soil solids. Concentrations of DOM in equilibrium solution for phenanthrene sorption were lower in the case of the heavy metal-spiked than unspiked soils. However, the decreased DOM in solution contributed little to the enhanced sorption of phenanthrene in the presence of metals. On the other hand, the sorbed DOM on soil solids after the addition of heavy metals in soils was found to be much more reactive and have far stronger capacity of phenanthrene uptake than the inherent SOM. The distribution coefficients of phenanthrene between water and the sorbed DOM on soil solids (K(ph/soc)) were about 2-3 magnitude larger than K(d) between water and inherent SOM, which may be the dominant mechanism of the enhanced sorption of phenanthrene by soils with the addition of heavy metals.     

Sorption, degradation and mobility of microcystins in Chinese agriculture soils: Risk assessment for groundwater protection

In the present paper, sorption, persistence, and leaching behavior of three microcystin variants in Chinese agriculture soils were examined. Based on this study, the values of capacity factor and slope for three MCs variants in three soils ranged from 0.69 to 6.00, and 1.01 to 1.54, respectively. The adsorption of MCs in the soils decreased in the following order: RR > Dha7 LR > LR. Furthermore, for each MC variant in the three soils, the adsorption rate in the soils decreased in the following order: soil A > soil C > soil B. The calculated half-time ranged between 7.9 and 17.8 days for MC-RR, 6.0-17.1 days for MC-LR, and 7.1-10.2 days for MC-Dha7 LR. Results from leaching experiments demonstrated that recoveries of toxins in leachates ranged from 0-16.7% for RR, 73.2-88.9% for LR, and 8.9-73.1% for Dha7 LR. The GUS value ranged from 1.48 to 2.06 for RR, 1.82-2.88 for LR, and 1.76-2.09 for Dha7 LR. Results demonstrated the use of cyanobacterial collections as plant fertilizer is likely to be unsafe in soils.     

Sorption of imidazolium-based ionic liquids to aquatic sediments

Ionic liquids (ILs) have received much attention as "green" alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K(d)) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7l kg(-1) at an initial concentration of 0.5mM and were positively related to sediment organic matter (SOM) content. These K(d) values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.     

The effect of landuse on soil organic carbon chemistry and sorption of pesticides and metabolites

Earlier studies had shown significant differences in sorption of nine pesticides in soils collected from two landuses (native vegetation and market gardens), which could not be explained on the basis of organic carbon content alone. Consequently it was hypothesised that the differences in sorption behaviour between the two landuses may be due to variation in the chemistry of the organic carbon. In this study the relationship between sorption behaviour of the nine chemicals and soil organic carbon chemistry, as determined by solid-state (13)C NMR spectroscopy, was investigated. No significant differences were found between the two landuses in the distribution of the four main spectral regions of the (13)C NMR spectra of soil OC, except for the carbonyl fraction (165-220ppm), which may reflect the low OC content of the soils from both landuses. For all chemicals, except prometryne, the most significant (P<0.01 or P<0.001) relationship between K(d) values and types of OC was found with the aromatic (110-165ppm) or the alkyl (0-45ppm) fraction. A comparison was made of the variability of K(d) values normalized over OC (i.e. K(oc)), alkyl, aromatic and alkyl+aromatic fractions. Expressing K(d) values for all chemicals, except azinphos methyl, in soils under native vegetation as K(alkyl) or K(aromatic) greatly decreased the variability compared with the K(oc) value. However in the cultivated soils only the sorption coefficients for DEA, DIA and fenamiphos showed a decrease in variability when expressed as K(alkyl) or K(aromatic). This reflected the stronger relationship between sorption coefficients and the alkyl and aromatic fraction of soil OC in soils from native vegetation compared with those determined from the market garden soils. The different relationships between sorption coefficients and types of OC of the two landuses also suggests that the type of aromatic and alkyl carbon under the two landuses is different and NMR characterisation of the OC was not sufficient to distinguish these differences.     

Experimental variability in characterization of cyfluthrin sorption to soil

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-alpha -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, Koc, obtained using different experimental methodologies with one soil can be comparable to the variation in Koc values obtained for soils with different physical and chemical properties using one method. Koc values for cyfluthrin ranged from 56,000 to 300,000 L kg-1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.     

Determination of sorption coefficients of pharmaceutically active substances carbamazepine, diclofenac, and ibuprofen, in sandy sediments

Laboratory batch studies were conducted to characterize the sorption behavior of three pharmaceutically active substances (carbamazepine, diclofenac, and ibuprofen) in different sediment types. The sediments were natural sandy sediments from the water saturated zone and the unsaturated zone in the Berlin (Germany) area. They are characterized as medium and fine-grained sands, both with low organic carbon content. The results of the experiments show that sorption coefficients were generally quite low. Distribution coefficients (K(d) values) determined by the batch experiments varied from 0.21 to 5.32 for carbamazepine, 0.55 to 4.66 for diclofenac, and 0.18 to 1.69 for ibuprofen. Comparison of the organic carbon normalized sorption coefficient K(OC) values based on correlation equations with actual experimental data revealed that the calculated data for carbamazepine is of the same order as the experimental data. For diclofenac and ibuprofen the calculated values are much higher than the experimental data, showing a much higher mobility of diclofenac and ibuprofen in natural aquifer sediments than indicated by correlation equations based on octanol water distribution coefficients.     

Adsorption and desorption processes of MCPA in Polish mineral soils

Studies on the adsorption and desorption of MCPA (4-chloro-2-methylophenoxyacetic acid) were performed in soil horizons of three representative Polish agricultural soils. The Hyperdystric Arenosol, the Haplic Luvisol and the Hypereutric Cambisol were investigated in laboratory batch experiments. Initially, both the adsorption and desorption proceeded rapidly, and either the equilibrium was reached after approximately 30 min or the process slowed down and continued at a slow rate. In the latter case, the equilibrium was reached after 8 hours. Data on the adsorption/desorption kinetics fitted well to the two-site kinetic model. The measured sorption and desorption isotherms were of L-type. The sorption distribution coefficients (K(ads) (d)) were in the range of 0.75--0.97 for Ap soil horizons and significantly lower in deeper soil layers. The corresponding desorption coefficients (K(des) (d)) were higher and ranged from 1.02 to 2.01. Both the adsorption and desorption of MCPA in all soil horizons was strongly and negatively related to soil pH. It appears that hydrophobic sorption plays a dominant role in the MCPA retention in topsoils whereas hydrophilic sorption of MCPA anions is the dominant adsorption mechanism in subsoils.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Effect of fly ash on sorption behavior of metribuzin in agricultural soils

This investigation was undertaken to determine the effect of two different fly ashes [Kota and Inderprastha (IP)] amendment on the sorption behavior of metribuzin in three Indian soil types. The IP fly ash was very effective in increasing the metribuzin sorption in the soils. The sorption with IP amendment was increased by 15-92%, whereas with the Kota fly ash an increase in sorption by 13-38% was noted. The adsorption isotherms fitted very well to the Freundlich adsorption equation and, in general, slope (1/n) values less then unity were observed. Although both the fly ashes significantly decreased metribuzin desorption, the IP fly ash was comparatively more effective in retaining metribuzin in the soils. Metribuzin sorption in the IP fly ash-amended soils showed strong correlation with the fly ash content and compared to K(f)/K(d) values, K(FA) values (sorption normalized to fly ash content) showed less variation. Metribuzin sorption-desorption did not correlate to the organic carbon content of the soil-fly ash mixture. The study demonstrates that all coal fly ashes may not be effective in enhancing the sorption of metribuzin in soils to the same extent. However, among the fly ashes used in this study, the IP fly ash was observed to be significantly effective in enhancing the sorption of metribuzin in soils. This may play an important role in reducing the run off and leaching losses of the herbicide by retaining it in the soil.     

Sorption of nonpolar neutral organic compounds to humic acid-coated sands: contributions of organic and mineral components

The contributions of organic matter and the mineral surface to the overall sorption of six nonpolar neutral organic compounds (1,2,4-trichlorobenzene, 1,4-dichlorobenzene, chlorobenzene, m-xylene, toluene, benzene) by five humic acid (HA)-coated sands with different fractions of organic carbon (f(oc)) ranging from 0.024% to 0.154% were evaluated on the basis of measured data and four different sorption models. Sorption of all six sorbates to both uncoated and heated sands was nearly linear due to the coverage of hydrophilic mineral surface with the ordered vicinal water region. Sorption of all six sorbates to the HA-coated sands was also essentially linear, and resulted from a combination of sorption to both organic matter and the mineral surface, with the dominance of either contribution depending on the properties of the sorbents (e.g., f(oc)) and the sorbates (e.g., K(ow)). A proposed two-component model for sorption including blocking effect was appropriate for quantifying the contributions of organic matter and the mineral surface to the overall sorption. However, conventional sorption models considering the contributions of both organic matter and the mineral surface provided essentially as good agreement between predicted and measured distribution coefficients as the more complicated, two-component model for sorption that takes into account mineral surface blocking by HA.     

Sorption behaviour of acetochlor,atrazine, carbendazim,diazinon, imidacloprid and isoproturon on Hungarian agricultural soil

Laboratory studies were conducted to determine the sorption behaviour of six commonly used pesticides (acetochlor, atrazine, carbendazim, diazinon, imidacloprid and isoproturon) on Hungarian brown forest soil with clay alluviation (Luvisol) using the batch equilibrium technique. The sorption isotherms could be described by the Freundlich equation in non-linear form (n < 1) for all compounds, however in case of diazinon using the extended Freundlich equation proved to be a better approach. The adsorption constant related soil organic carbon content (Koc) calculated from Freundlich equation were 314 for acetochlor, 133 for atrazine, 2805 for carbendazim, 1589 for diazinon, 210 for imidacloprid and 174 for isoproturon. The octanol-water partition coefficients (Pow), which can be a useful parameter to predict of adsorption behaviour of a chemical on soil, and dissociation coefficients of these pesticides were calculated based on the chemical structure of them using a computerized expert system. The octanol-water partition coefficients were determined experimentally from high performance liquid chromatographic parameters as well. Good agreement was observed between experimental and the computer expert system estimated data. Computer estimated log Pow values ranged 0.5 and 3.86 for the examined pesticides, with imidacloprid and diazinon being the least and most hydrophobic respectively. Experimentally determined logPow ranged between 0.92 and 3.81 with the same tendency. It can be concluded that the Freundlich adsorption constants (Kf) are slightly related to the octanol-water partition coefficients of investigated chemicals, nevertheless no close correlation could be established because of the influence of further characteristics of solutes and soil.     

Structure elucidation of the three most important toxaphene congeners by X-ray analysis

Three of the most frequently detected toxaphene components in environmental samples are the chlorobornanes 2-exo,3-endo,5-exo,6-endo,8b,8c,10a,10b-octachlorobornane (Parlar No. 26); 2-exo,3-endo,5-exo,6-endo,8b,8c,9c,10a,10b-nonachlorobornane (Parlar No. 50), and 2,2,5,5,8b,8c,9c,10a,10b-nonachlorobornane (Parlar No. 62), whose structures could not be completely elucidated by spectroscopical methods. This paper now describes the X-ray structure analysis of the three compounds and presents their exact crystal structure.