Heterogeneous photocatalysed degradation of a herbicide derivative, isoproturon in aqueous suspension of titanium dioxide

Heterogeneous photocatalysed degradation of a herbicide derivative, N-(4-isopropylphenyl)-N',N'-dimethylurea (Isoproturon, 1) was investigated in aqueous suspensions of titanium dioxide by monitoring the change in absorption intensity and depletion in Total Organic Carbon content as a function of irradiation time. The degradation kinetics was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO(2) and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and potassium persulphate (K(2)S(2)O(8)) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts. An attempt was made to identify the degradation product through GC-MS analysis technique.     

Mineralization of soil-aged isoproturon and isoproturon metabolites by Sphingomonas sp. strain SRS2

The aim of the study was to determine the effect of aging of the herbicide isoproturon and its metabolites monodesmethyl-isoproturon and 4-isopropyl-aniline in agricultural soil on their availability to the degrading bacterium Sphingomonas sp. strain SRS2. The 14C-ring-labeled isoproturon, monodesmethyl-isoproturon, and 4-isopropyl-aniline were added to sterilized soil and stored for 1, 49, 71, or 131 d before inoculation with strain SRS2. The availability of the compounds was estimated from the initial mineralization and the amount of 14CO2 recovered after 120 d of incubation. Aging in soil for 131 d reduced the initial mineralization of isoproturon and monodesmethyl-isoproturon and, in the case of isoproturon, also reduced the recovery of 14CO2. Initial mineralization and recovery of 14CO2 from aged 4-isopropyl-aniline were slightly reduced, but less 14CO2 was generally produced than with isoproturon or monodesmethyl-isoproturon. Thus, recovery of 14CO2 from 14C-isoproturon and 14C-monodesmethyl-isoproturon was 50.7 to 64.4% of the initially added 14C, while recovery from 14C-4-isopropyl-aniline was only 11.7 to 17.0%. Sorption measurements revealed similar Freundlich constants (K(f)) for isoproturon and monodesmethyl-isoproturon, whereas K(f) for 4-isopropyl-aniline was more than fivefold greater. The findings imply that in soil, partial degradation of isoproturon to 4-isopropyl-aniline may lead to reduced mineralization of the herbicide due to sorption of the aniline moiety.     

Degradation and sorption of metribuzin and primary metabolites in a sandy soil

Leaching to the ground water of metabolites from the herbicide metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5-one] has been measured in a Danish field experiment in concentrations exceeding the European Union threshold limit for pesticides at 0.1 microg/L. In the present work, degradation and sorption of metribuzin and the metabolites desamino-metribuzin (DA), diketo-metribuzin (DK), and desamino-diketo-metribuzin (DADK) were studied in a Danish sandy loam topsoil and subsoil from the field in question, using accelerated solvent extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. Fast dissipation of metribuzin and the metabolites was observed in the topsoil, with 50% disappearance within 30 to 40 d. A two-compartment model described degradation of metribuzin and DA, whereas that of DADK could be described using first-order kinetics. Part of the dissipation was probably due to incorporation into soil organic matter. Degradation in subsoil occurred very slowly, with extrapolated half-lives of more than one year. Sorption in the topsoil followed the order DA > metribuzin > DK > DADK. Subsoil sorption was considerably lower, and was hardly measurable for metribuzin and DK. Abiotic degradation was considerably higher in the topsoil than the subsoil, especially concerning the de-amination step, indicating that organic matter may be related to the degradation process. The present results confirm observations of metribuzin and transformation product leaching made in the field experiment and demonstrate the need for knowledge on primary metabolites when assessing the risk for pesticide leaching.     

Degradation of soil fumigants as affected by initial concentration and temperature

Soil fumigation using shank injection creates high fumigant concentration gradients in soil from the injection point to the soil surface. A temperature gradient also exists along the soil profile. We studied the degradation of methyl isothiocyanate (MITC) and 1,3-dichloropropene (1,3-D) in an Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralf) at four temperatures and four initial concentrations. We then tested the applicability of first-order, half-order, and second-order kinetics, and the Michaelis-Menten model for describing fumigant degradation as affected by temperature and initial concentration. Overall, none of the models adequately described the degradation of MITC and 1,3-D isomers over the range of the initial concentrations. First-order and half-order kinetics adequately described the degradation of MITC and 1,3-D isomers at each initial concentration, with the correlation coefficients greater than 0.78 (r2> 0.78). However, the derived rate constant was dependent on the initial concentration. The first-order rate constants varied between 6 and 10x for MITC for the concentration range of 3 to 140 mg kg(-1), and between 1.5 and 4x for 1,3-D isomers for the concentration range of 0.6 to 60 mg kg(-1), depending on temperature. For the same initial concentration range, the variation in the half-order rate constants was between 1.4 and 1.7x for MITC and between 3.1 and 6.1x for 1,3-D isomers, depending on temperature. Second-order kinetics and the Michaelis-Menten model did not satisfactorily describe the degradation at all initial concentrations. The degradation of MITC and 1,3-D was primarily biodegradation, which was affected by temperature between 20 and 40 degrees C, following the Arrhenius equation (r2 > 0.74).     

Ecological scenarios analyzed and evaluated by a shallow lake model

We applied the complex ecosystem model EMMO, which was adopted to the shallow lake Müggelsee (Germany), in order to evaluate a large set of ecological scenarios. By means of EMMO, 33 scenarios and 17 indicators were defined to characterize their effects on the lake ecosystem. The indicators were based on model outputs of EMMO and can be separated into biological indicators, such as chlorophyll-a and cyanobacteria, and hydro-chemical indicators, such as phosphorus. The question to be solved was, what is the ranking of the scenarios based on their characterization by these 17 indicators? And how can we handle high quantities of complex data within evaluation procedures? The scenario evaluation was performed by partial order theory which, however, did not provide a clear result. By subsequently applying the hierarchical cluster analysis (complete linkage) it was possible to reduce the data matrix to indicator and scenario representatives. Even though this step implies losses of information, it simplifies the application of partial order theory and the post processing by METEOR. METEOR is derived from partial order theory and allows the stepwise aggregation of indicators, which subsequently leads to a distinct and clear decision. In the final evaluation result the best scenario was the one which defines a minimum nutrient input and no phosphorus release from the sediment while the worst scenario is characterized by a maximum nutrient input and extensive phosphorus release from the sediment. The reasonable and comprehensive results show that the combination of partial order, cluster analysis and METEOR can handle big amounts of data in a very clear and transparent way, and therefore is ideal in the context of complex ecosystem models, like that we applied.     

Degradation of polycyclic aromatic hydrocarbons by combined chemical pre-oxidation and bioremediation in creosote contaminated soil

The ability of pre-oxidation to overcome polycyclic aromatic hydrocarbons (PAH) recalcitrance to biodegradation was investigated in creosote contaminated soil. Sand and peat artificially spiked with creosote (quality WEI C) were used as model systems. Ozonation and Fenton-like treatment were proved to be feasible technologies for PAH degradation in soil. The efficiency of ozonation was strongly dependent on the water content of treated soil samples. The removal of PAH by Fenton-like treatment depended on the applied H2O2/soil weight ratio and ferrous ions addition. It was determined that the application of chemical oxidation in sand resulted in a higher PAH removal and required lower oxidant (ozone, hydrogen peroxide) doses. The enhancement of PAH biodegradability by different pre-treatment technologies also depended on the soil matrix. It was ascertained that combined chemical and biological treatment was more efficient in PAH elimination in creosote contaminated soil than either one alone. Thus, the combination of Fenton-like and the subsequent biological treatment resulted in the highest removal of PAH in creosote contaminated sand, and biodegradation with pre-ozonation was found to be the most effective technology for PAH elimination in peat.     

Phosphorus movement and speciation in a sandy soil profile after long-term animal manure applications

Long-term application of phosphorus (P) with animal manure in amounts exceeding removal with crops leads to buildup of P in soil and to increasing risk of P loss to surface water and eutrophication. In most manures, the majority of P is held within inorganic forms, but in soil leachates organic P forms often dominate. We investigated the mobility of both inorganic and organic P in profile samples from a noncalcareous sandy soil treated for 11 yr with excessive amounts of pig slurry, poultry manure, or poultry manure mixed with litter. Solution 31P nuclear magnetic resonance spectroscopy was used to characterize NaOH-EDTA-extractable forms of P, corresponding to 64 to 93% of the total P concentration in soil. Orthophosphate and orthophosphate monoesters were the main P forms detected in the NaOH-EDTA extracts. A strong accumulation of orthophosphate monoesters was found in the upper layers of the manure-treated soils. For orthophosphate, however, increased concentrations were found down to the 40- to 50-cm soil layers, indicating a strong downward movement of this P form. This was ascribed to the strong retention of orthophosphate monoesters by the solid phase of the soil, preventing orthophosphate sorption and facilitating downward movement of orthophosphate. Alternatively, mineralization of organic P in the upper layers of the manure-treated soils may have generated orthophosphate, which could have contributed to the downward movement of the latter. Leaching of inorganic P should thus be considered for the assessment and the future management of the long-term risk of P loss from soils receiving large amounts of manure.     

Degradation of endosulfan in a clay soil from cotton farms of western Queensland.

The persistence and degradation of endosulfan isomers and their primary degradation product, endosulfan-sulfate, were studied in a clay soil from cotton farms of western Queensland. Endosulfan degradation in relation to soil moisture, temperature, day and night temperature fluctuation, waterlogging and re-application were studied. The results show that the degradation rates of both endosulfan isomers were greatly affected by changes in soil water content and temperature. Under a high water content-high temperature regime the concentration of alpha-endosulfan in the soil fell rapidly during the first 4 weeks of application, followed by a prolonged period of slower rate of degradation. Alpha endosulfan showed a bi-exponential form of degradation for all water content-temperature experiments except for extremes in both these two factors. In the submerged soils (and also in low-water content, low temperature, non-submerged experiments) no such rapid initial degradation of alpha-endosulfan was observed, and a single first-order rate equation describes the data. Degradation of beta-endosulfan was significantly slower than for the alpha-isomer under all conditions studied. A half-life of more than a year was recorded for the beta-isomer when both water content and temperature were low. The degradation of beta-endosulfan showed no sign of the bi-exponential function observed for alpha-isomer, and a single first order rate equation described the data obtained for each factor studied. Endosulfan-sulfate was the major degradation product in all non-submerged experiments. Its build up in the soil very closely followed the disappearance of alpha-endosulfan. Its highest build-up was in the high water content-low temperature experiments, but its persistence was primarily influenced by soil temperature. Both alpha and beta-isomers, and endosulfan sulfate, persisted longer in the submerged soil. Re-application of endosulfan, and day and night fluctuation of temperature had contrasting effects on the degradation of the two isomers. Both factors slowed down the degradation of alpha-endosulfan and enhanced that of beta-endosulfan, but their net effect was to prolong the overall persistence of this chemical in the soil. Submerged conditions reduced the net formation of endosulfan-sulfate and enhanced its degradation rate.     

Degradation and mobility of linear alkylbenzene sulfonate and nonylphenol in sludge-amended soil

Degradation and mobility of the surfactants linear alkylbenzene sulfonate (LAS) and nonylphenol (NP) were investigated in a lysimeter study using a sandy loam soil and 45-cm soil columns. Anaerobically digested sewage sludge was incorporated in the top-15-cm soil layer to an initial content of 38 mg LAS and 0.56 mg NP kg(-1) dry wt., respectively. Spring barley (Hordeum vulgare L.) was sown onto the columns. The lysimeters were placed outdoors and therefore received natural precipitation, but were also irrigated to a total amount of water equivalent to 700 mm of precipitation. Leachate and soil samples from three soil layers were collected continuously during a growth period of 110 d. Leachate samples and soil extracts were concentrated by solid-phase extraction (SPE) and analyzed using high performance liquid chromatography (HPLC) with fluorescence detection. The concentrations in the top-15-cm soil layer declined to 25 and 45% of the initial contents for LAS and NP, respectively, within the first 10 d of the study. At the end of the study, less than 1% LAS was left, while the NP content was below the detection limit. Assuming first-order degradation kinetics, half-lives of 20 and 37 d were estimated for LAS and NP, respectively. The surfactants were not measured in leachate samples in concentrations above the analytical detection limits of 4.0 and 0.5 microg L(-1) for LAS and NP, respectively. In addition, neither LAS nor NP were measured in concentrations above the detection limits of 150 and 50 microg kg(-1) dry wt., respectively, in soil layers below the 15 cm of sludge incorporation, indicating negligible downward transport of the surfactants in the lysimeters.     

Degradation of 14C-atrazine bound residues in brown soil and rendzina fractions

The remobilization and the fate of 14C-ring labeled atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) bound residues was examined in relation with the turnover of natural soil organic matter. Soil fractions of a brown soil and a rendzina were incubated under controled laboratory conditions. The mineralization of natural organic matter and atrazine-bound residues was respectively estimated by the amounts of CO2 and 14CO2 evolved during the incubation. The remobilization and distribution of 14C residues among the soil organic fractions were achieved after physical-chemical extractions of the samples. Comparisons of samples in abiotic and biotic conditions allowed us to assess the influence of microbial activity on the fate of atrazine-bound residues. The mineralization curves showed that natural organic matter and atrazine-bound residues had similar decomposition patterns. After 100 d of incubation, 0.8 to 3.6% of total organic C was evolved as CO2, while only 0.1% of the initial radioactivity was mineralized as CO2, and 7 to 15% was becoming extractable with water and methanol. Few differences were observed in the distribution of residues within organic compounds for both fractions of the rendzina, except a decrease of the 14C radioactivity of the 50- to 5000-microm fraction and a slight increase of that of humin. For the 0- to 5000-microm brown soil fraction, increased radioactivity in humin at the expense of humic (HA) and fulvic (FA) acids was detected after incubation, while for the 0- to 50-microm fraction more radioactivity was recovered with FA.     

Relative movement and soil fixation of soluble organic and inorganic phosphorus

There is considerable concern about pollution of surface waters with P. Although most of the research has focused on inorganic P in surface runoff, it has recently become possible to easily follow the fate of soluble organic P forms in soils and waters. Two experiments were performed to compare the relative mobility and soil fixation affinity of orthophosphate monoesters, orthophosphate diesters, and soluble inorganic P. We used three P substrates, 4-methylumbelliferyl phosphate (MUP), deoxyribonucleic acid (DNA), and KH(2)PO(4) in (i) a soil column experiment and (ii) a soil P adsorption test tube experiment. Shortly after columns were prepared, approximately two pore volumes of 0.005 M CaCl(2) were passed through 25 cm length columns containing 10 cm of loamy sand amended with approximately 10 mg P as MUP, DNA, or KH(2)PO(4) above 15 cm of nonamended loamy sand. The total net quantity of 757.8 microg P 2L(-1) of orthophosphate diesters in the leachate from the DNA columns exceeded the net quantity of orthophosphate monoesters in leachate from the MUP columns (4.6 microg P 2L(-1)) and soluble inorganic P from the KH(2)PO(4) columns (34.0 microg P 2L(-1)). Adsorption of soluble organic and inorganic P in the test tube experiment yielded similar results: DNA, containing orthophosphate diesters, had a relatively low affinity for soils. In both experiments, high concentrations of other P compounds were identified in samples treated with organic P substrates, suggesting enzymatic hydrolysis by native soil phosphatase enzymes. These findings indicate that repeated application of organic forms of P could lead to significant leaching of P to ground water.     

Decolorization and Complete Degradation of Methyl Red by a Mixed Culture

Synthetic dyes, azo dyes in particular, are widely found in the effluents from textile industries. The persistence and toxicity of these compounds cause adverse impacts in the receiving streams. A mixed culture isolated from a domestic wastewater treatment plant was found to remove the colour of the azo dye, methyl red, efficiently. Total decolorization and degradation occurred within 18 h. The mixed culture could degrade 700 mgl^–1 of methyl red efficiently in the presence of 200 mgl^–1 of glucose, whereas in the absence of glucose it could degrade only 100 mgl^–1 of methyl red. The mixed culture, when suspended in phosphate buffer along with methyl red at 100 mgl^–1 concentration could degrade methyl red efficiently within 2 h of incubation. The pH of the medium decreased continuously during degradation. After the complete removal of initial methyl red, another 100 mgl^–1 was added to the culture filtrate and incubated further. The mixed microbial cultures could degrade methyl red efficiently through three cycles but further degradation was not possible as the pH of the medium decreased to 3.5.     

Photochemistry and photoinduced toxicity of acifluorfen, a diphenyl-ether herbicide

Photochemistry studies can be helpful in assessing the environmental fate of chemicals. Photochemical reactions lead to the formation of by-products that can exhibit different toxicological properties from the original compound. For this reason the photochemical behavior of the herbicide acifluorfen (5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid) in the presence of different solvents was studied. Photochemical reactions were carried out using a high-pressure mercury arc and a solar simulator. Kinetic parameters and quantum yields were determined. The identification of photoproducts was performed by mass spectrometry and [1H] nuclear magnetic resonance (NMR). Nitrofluorfen, hydroxy-nitrofluorfen, 2-chloro-4-(trifluoromethyl)phenol, 5-trifluoromethyl-5'-nitrodibenzofuran, and other derivatives were identified. The photochemical reactions were also carried out in the presence of either a singlet or a triplet quencher, and in the presence of either a radical initiator or a radical inhibitor. Substances used as inhibitors of the excited levels T1 and S1 showed that photodegradation of acifluorfen begins from a singlet state S1 through a pi,pi* transition. The role of free radicals in the photodegradation of acifluorfen was determined and a radical mechanism was proposed. Toxicity tests against Daphnia magna Strauss showed that acifluorfen was not toxic at a concentration of 0.1 mM; however, photoproducts formed after 36 h of UV exposure of the herbicide induced a remarkable toxicity to the test organism.     

Imidacloprid movement in soils and impacts on soil microarthropods in southern Appalachian eastern hemlock stands

Imidacloprid is a systemic insecticide effective in controlling the exotic pest (hemlock woolly adelgid) in eastern hemlock () trees. Concerns over imidacloprid impacts on nontarget species have limited its application in southern Appalachian ecosystems. We quantified the movement and adsorption of imidacloprid in forest soils after soil injection in two sites at Coweeta Hydrologic Laboratory in western North Carolina. Soils differed in profile depth, total carbon and nitrogen content, and effective cation exchange capacity. We injected imidacloprid 5 cm into mineral soil, 1.5 m from infested trees, using a Kioritz soil injector. We tracked the horizontal and vertical movement of imidacloprid by collecting soil solution and soil samples at 1 m, 2 m, and at the drip line from each tree periodically for 1 yr. Soil solution was collected 20 cm below the surface and just above the saprolite, and acetonitrile-extractable imidacloprid was determined through the profile. Soil solution and extractable imidacloprid concentrations were determined by high-performance liquid chromatography. Soil solution and extractable imidacloprid concentrations were greater in the site with greater soil organic matter. Imidacloprid moved vertically and horizontally in both sites; concentrations generally declined downward in the soil profile, but preferential flow paths allowed rapid vertical movement. Horizontal movement was limited, and imidacloprid did not move to the tree drip line. We found a negative relationship between adsorbed imidacloprid concentrations and soil microarthropod populations largely in the low-organic-matter site; however, population counts were similar to other studies at Coweeta.     

Lateral movement of soil fumigants 1,3-dichloropropene and chloropicrin from treated agricultural fields

The soil fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are often used for controlling soil-borne plant pathogens and parasitic nematodes before reestablishing new vineyards and orchards. To evaluate crop safety and environmental risks with the replant fumigation, four field experiments were performed over 2 yr to examine 1,3-D and CP lateral movement away from the treated fields. Shank injection with or without a virtually impermeable film (V1F) was used in two vineyard fumigation experiments, and spot drip application without tarp cover was used in two orchard experiments. Results showed that 1,3-D and CP gases moved laterally to 6 m from the treated fields when the fumigants were applied by shank injection. The maximum 1,3-D or CP soil gas concentration at 6 m was approximately 10 ng cm(-3) when the fumigated plot was not cover with a tarp. With VIF, the measured maximum concentration increased to approximately 100 ng cm(-3). In the spot drip application, maximum 1,3-D and CP gas concentrations reached approximately 100 ng cm(-3) but at 1.5 m radial distance from the point of fumigant injection.     

1株乙羧氟草醚降解菌的分离鉴定与降解特性研究

本研究从某农药厂污水处理池的活性污泥中分离得到1株能以乙羧氟草醚为唯一碳源生长的菌株。经生理生化鉴定和16SrRNA基因序列同源性分析,将此菌株初步鉴定为腐生葡萄球茵（Staphylococcussaprophyticus）,并命名为YSC．1。对菌株YSC．1的生长特性研究表明：茵株的最佳生长温度和pH分别为30℃、7．0;NaCI浓度对菌株YSC-1生长有较大的影响。菌株在20℃-40℃之间均能降解乙羧氟草醚,在30％1、pH7．0的条件下对乙羧氟草醚的降解率最高;增加乙羧氟草醚的浓度会对菌株产生毒害作用,降低其降解率;提高接种量可以加快乙羧氟草醚的降解。在乙羧氟草醚终浓度为100mg／L的工业废水经7d处理后,乙羧氟草醚的去除率达91．62％,说明菌株YSC-1在废水处理中具有很好的应用前景。     

Application of two organic wastes in a soil polluted by lead: effects on the soil enzymatic activities

The effects of adding a crushed cotton gin compost (CCGC) and a poultry manure (PM) on the enzymatic activities of a Typic Xerofluvent soil polluted with Pb were studied in the laboratory. Three hundred grams of sieved soil (<2 mm) were mixed with PM at a rate of 10% or CCGC at a rate of 17.2%, applying to the soil the same amount of organic matter with each organic amendment. Urease, protease-BBA, beta-glucosidase, alkaline phosphatase, and arylsulfatase activities were measured at four different incubation times (1, 7, 15, and 45 d) in soils containing seven concentrations (100, 250, 500, 1000, 2500, 5000, and 8000 mg kg-1) of Pb, and in the same soils amended with CCGC and PM. In all treatments and incubation times, the inhibition percentage of soil enzyme activities by Pb was lower in soils amended with the PM and CCGC than in nonamended soils, and it differed with the organic amendment. In this respect, the in the 8000 mg Pb kg-1 treatment at the end of the incubation period, the protease-BBA activity inhibition percentage was lower (14.7 and 33.9% lower, respectively) in CCGC- than in PM-amended soils. Since the adsorption capacity of Pb was higher in CCGC- than the PM-amended soils, the addition of organic wastes with higher humic acid concentration is more beneficial for remediation of soils polluted with Pb.     

高效海洋溢油降解菌降解海洋溢油条件的优化研究

针对海洋溢油污染问题,采用实验室筛选的海洋溢油降解菌HJ01和HJ02开展海洋溢油微生物降解优化研究,采用单因素实验和多因素正交实验进行降解率测定。结果表明,单因素实验条件下,当pH值为7、培养温度35℃、石油初始浓度7 500mg/L、NaCl含量20 000mg/L时,HJ01和HJ02对海洋溢油的降解效果最佳。正交实验条件下,HJ01在pH值为7、培养温度35℃、石油初始浓度7 500mg/L、NaCl含量10 000mg/L时降解效果最佳;HJ02在pH值为7、培养温度30℃、石油初始浓度11 000 mg/L、NaCl含量10 000mg/L时降解效果最佳。     

Prediction of soil organic partition coefficients by a soil leaching column chromatographic method

The soil organic partition coefficient (Koc) is one of the most important parameters to depict the transfer and fate of a chemical in the soil-water system. Predicting Koc by using a chromatographic technique has been developing into a convenient and low-cost method. In this paper, a soil leaching column chromatograpy (SLCC) method employing the soil column packed with reference soil GSE 17201 (obtained from Bayer Landwirtschaftszentrum, Monheim, Germany) and methanol-water eluents was developed to predict the Koc of hydrophobic organic chemicals (HOCs), over a log Koc range of 4.8 orders of magnitude, from their capacity factors. The capacity factor with water as an eluent (k'w) could be obtained by linearly extrapolating capacity factors in methanol-water eluents (k'w) with various volume fractions of methanol (symbol in text). The important effects of solute activity coefficients in water on k'w and Koc were illustrated. Hence, the correlation between log Koc and log k'w (and log k') exists in the soil. The correlation coefficient (r) of the log Koc vs. log k'w correlation for 58 apolar and polar compounds could reach 0.987, while the correlation coefficients of the log Koc -log k' correlations were no less than 0.968, with (symbol in text)ranging from 0 to 0.50. The smaller the (symbol in text), the higher the r. Therefore, it is recommended that the eluent of smaller (symbol in text), such as water, be used for accurately estimating Koc. Correspondingly, the r value of the log Koc -log k'w correlation on a reversed-phase Hypersil ODS (Thermo Hypersil, Kleinostheim, Germany) column was less than 0.940 for the same solutes. The SLCC method could provide a more reliable route to predict Koc indirectly from a correlation with k'w than the reversed-phase liquid chromatographic (RPLC) one.     

Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.