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[3,4-dichloroaniline cometabolism by representatives of the genus Pseudomonas].

The effect of propanide, linuron and 3,4-dichloroaniline on soil organisms was studied. Two strains of Pseudomonas aurantiaca 1 and 7, were isolated from soil; they decomposed propanide yielding 3,4-dichloroaniline. These strains, as well as a number of collection cultures belonging to the Pseudomonas genus, could transform 3,4-dichloroaniline at a rate of 0-100 per cent during 48 hours. A certain correlation existed between this transformation ability and the level of total oxidase activity. All the strains of Pseudomonas studied in this work were characterized by a low peroxidase activity, and no strict correlation was detected between its level and the ability to transform 3,4-dichloroaniline.

Adsorption↗

The effect of herbicides on the qualitative properties of healing plants. Part 2: Content and composition of the essential oil from Salvia officinal is L. after application of Afalon 50 WP.

The aim of our work was to study the changes of the content and quality of volatile oil in Salvia officinalis L. being treated with Afalon 50 WP (the active substance linuron) in the major ontogenetic phases of the plant growth. The plants treatment with a herbicide in pre-emergence did not cause a dramatic change in the essential oil content or in the proportional representation of its individual components. During the investigation of the changes in quality of the essential oil after an application of Afalon during various plant growth phases there was found the same relationship when compared with those being untreated.

Chromatography, Thin Layer↗

Bacteria and pesticides: a new aspect of interaction--involvement of a new biofactor.

Positively charged hydrophobic pesticides of the dipyridyl family [diquat, paraquat, benzylviologen (BV++), etc.] were shown to provoke accumulation of 2-methylbutane-1,2,3,4-tetraol-2,4- cyclopyrophosphate in the cells Corynebacterium (Brevibacterium) ammoniagenes while neutral dipyridyls were not. Hydrophobicity was also an important factor in this phenomenon. Of the other pesticides tested, only linuron was effective. BV++ also induced biosynthesis of the compound in Rhodococcus rhodochrous, Rh.ruber, Rh.sp. (Nocardia corynebacteroides). These microorganisms as well as most of the previously identified oxidative stress activated producers of this new cyclopyrophosphate were able to synthesize free radical generating compounds. The microorganisms concerned belong mainly to the order Actinomycetales.

2,2'-Dipyridyl↗

Metabolism of twelve herbicides by Streptomyces.

Experiments were conducted to assess the ability of Streptomyces (strain PS1/5) to metabolize twelve herbicides representing several different classes including: acetanilides, triazines, ureas, uracils, and imidazoles. Incubations in aqueous culture with dextrin as carbon source and either ammonium or Casamino acids as nitrogen source resulted in transformations (> 50%) of eight of the herbicides tested: alachlor, metolachlor, atrazine, prometryne, ametryne, linuron, tebuthiuron, and bromacil; the remaining four herbicides (cyanazine, diuron, metribuzin, and imazapyr) were also transformed, but to a lesser extent. In most instances, biotransformations occurred concurrently with growth and results were consistent regardless of the nitrogen source (ammonium vs. Casamino acids). However, in some instances there were differences in rates of biotransformation as a consequence of the nitrogen source (e.g. alachlor, metribuzin), suggesting the selective induction of certain metabolic enzymes; in other instances biotransformations were not associated with growth, suggesting secondary metabolism. An experiment was also conducted to assess the ability of Streptomyces (strain PS1/5) to metabolize atrazine contaminated soil. Inoculation of soil amended with 20 micrograms/g of atrazine and 5% chitin as carbon source resulted in ca. 78% removal of atrazine within 28 days. These data suggest that Streptomyces species may be potential candidates for soil inoculation to bioremediate herbicide contaminated soils.

Biodegradation, Environmental↗

[Herbicide residues in some herbs (author's transl)].

Residue occurrence is discussed with use of 14 herbicides (Alachlor, Chloridazone, Chlorpropham, Chloroxuron, Chlorthal-methyl, Desmetryne, Lenacil, Linuron, Methabenzthiazuron, Monolinuron, Na-propamide, Pendimethalin, Phenmedipham and Terbutryne) on 6 herbs (borage, dill, garden-chervil, garden cress, anise and sorrel) in the light of residue analyses (from field trials over two seasons with analyses carried out in two laboratories). The methods are outlined; limits of the determinations and recoveries are given.

Carbamates↗

Effect of pesticides on blue-green algae and nitrogen-fixation.

The effects of the pesticides, amitrol, a derivative of amitrol (viz. 3,5-diamino-1,2,4-triazole), diquat, paraquat, linuron, MCPA, malathion, and monuron, were studied on the nitrogen-fixing algae, Anabaena cylindrica, Aulosira sp., Calothrix elenkenii. Chlorogloeae frischii, Cylindrospermum muscicola, Nostoc sp. from Collema tenax, Nostoc muscorum Tolypothrix tenuis, and Westiellopsis sp. In general, two types of response were discernible; an initial period of depression succeeded by an increased activity and an initial period of depression followed by a distinct decrease on prolonged incubation. The results indicate that some pesticidal compounds can severely limit the nitrogen-fixing capacities of blue-green algae, thereby affecting the overall nitrogen economy of soils in general.

Culture Media↗

The role of organic colloids in herbicide transfer to rivers: a quantitative study of triazine and phenylurea interactions with colloids.

For moderately hydrophobic compounds such as most pesticides adsorption on colloids (<0.2 microm) may play a key role in pesticide mobility as well as in their degradation by chemical and microbiological processes. However, until now, pesticide-organic colloid interactions are poorly understood. Quantitative data for sorption equilibria on colloids of two series of herbicides including triazines (atrazine, simazine, terbutylazine, prometryne, desethylatrazine, and desisopropylatrazine) and phenylureas (isoproturon, linuron, neburon, and diuron) sampled in the Seine river (urban zone) and the Marne river (agricultural zone) are presented. Partition coefficient of herbicides on colloids (K(com)), were evaluated by solid-phase extraction coupled with high-performance liquid chromatography-UV diode-array detection (SPE-HPLC-UV/DAD). In the case of triazines a satisfactory log-log correlation was found between K(com) and octanol-water coefficient (K(ow)) values. Phenylureas did not obey this correlation, with K(com) values being about two times higher than those of triazines. The existence of two distinct types of adsorption behaviour on colloids partly explains the different occurrence of triazines and phenylureas in surface waters.

Adsorption↗

A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites.

The extensive use of pesticides to protect agricultural crops can result in the transfer of these compounds into the atmosphere and their diffusion towards urban areas. Precise evaluation of the geographic impact of this type of pollution is important environmentally. In this paper, analytical methods for the sampling, characterization, and determination of agricultural pesticides in air were developed; the methods were then applied in the Paris and Champagne regions. Sixteen pesticides belonging to nine chemical families were monitored. Sampling was carried out in urban (Paris) and rural (Aube district) sites, utilizing either a high-volume pump (12.5 m3 h(-1)) (urban site) or a low-volume pump (2.3 m3 h(-1)) for the rural site. Quartz filters and polyurethane foams (PUF) were used for sampling in all cases. After extracting the samples and concentrating the recovered solutions, high-performance liquid chromatography (HPLC) analysis with UV detection was performed. Identification of the pesticides was confirmed by applying to the HPLC measurements a novel UV-detection procedure based on the normalized absorbance variation with wavelength (Noravawa procedure). The presence of metsulfuron methyl, isoproturon, linuron, deltamethrin (and/or malathion), and chlorophenoxy acids (2,4-D and MCPP) was found at the urban sampling site at levels ranging from about 1 to 1130 ng m(-3) of air, depending on the compound and sampling period. On the rural sampling site residues of isoproturon, deltamethrin (and/or malathion), MCPP, and 2,4-D were generally detected at higher levels (19-5130 ng m(-3)) than on the urban site, as expected. The effects of the weather conditions and agricultural activity on the atmospheric concentrations of pesticides are discussed, as are long-range atmospheric transfer processes for these pesticides.

Journal Article↗

Sorption of Nine Pesticides to Three Aquatic Macrophytes.

The sorption of nine pesticides to the aquatic macrophytes Chara globularis, Elodea nuttallii, and Lemna gibba was studied. A batch equilibrium method was used to study the sorption at five concentration levels to fresh shoots of the macrophytes. The results for the herbicides atrazine and linuron were described by nonlinear Freundlich equations, with Freundlich exponents ranging from 0.53 to 0.60. The results for the other compounds showed almost linear sorption isotherms, with Freundlich exponents ranging from 0.9 to 1.1. The highest sorption was measured for chlorpyrifos, with sorption coefficients ranging from 1,660 to 2,150 L/kg. Sorption coefficients for C. globularis tended to be lower than those for the other two macrophytes. Correlation (R(2) = 0.80) was found for the relation between the sorption coefficient (K(d)) of six pesticides and their solubility in water (S). The equation log K(d) = 3.20 - 0.65 log S can be used for a first estimate of the sorption coefficient of a pesticide to aquatic macrophytes.http://link.springer-ny.com/link/service/journals/00244/bibs/37n3p310.html

Journal Article↗

Solid-phase extraction followed by high-performance liquid chromatographic analysis for monitoring herbicides in drinking water.

A multiresidue analytical method based on C18 solid-phase extraction and one-run HPLC determination has been developed for the analysis of eleven acidic, neutral and weak basic herbicides in drinking water. A 1-1 sample of water was preconcentrated by passage through a 500-mg C18 solid phase extraction column. The retained compounds were eluted from the column with 1 ml of methanol. After concentration of the extract the pesticides were separated and quantified by reversed-phase HPLC with UV detection. Bentazone, 2,4-D, MCPA, fluazifop-acid, metoxuron, monolinuron, metobromuron, diuron, linuron, atrazine and simazine were determined simultaneously in a single run on a C18 HPLC column. Reanalyses of the sample extracts on a second cyano column were used to confirm the identity of the neutral and basic compounds. The limit of determination, defined as four times the baseline noise, varied between 0.01 microgram/l and 0.1 microgram/l depending on the compound, the detection sensitivity of the instrument and the type of HPLC column used.

Chromatography, High Pressure Liquid↗

Separation and detection of herbicides in water by micellar electrokinetic capillary chromatography.

The herbicides linuron, metolachlor, atrazine and metsulfuron were analysed using micellar electrokinetic capillary chromatography (MECC) after a 1000-fold concentration step by solid-phase extraction (SPE). Recoveries ranged from 80 to 92%, depending on the concentration and the number of active substances in the sample. Furthermore, the hydrolysis products of metsulfuron were analysed by MECC and by gas chromatography-mass spectrometry (GC-MS). Representative MECC and GC-MS profiles are shown and the structures of the hydrolysis products are proposed on the basis of their chromatographic and mass spectra features. A tentative pathway for the degradation of metsulfuron is proposed.

Chromatography↗

Solid-phase extraction and sample stacking-micellar electrokinetic capillary chromatography for the determination of multiresidues of herbicides and metabolites.

Micellar electrokinetic capillary chromatography (MEKC) with diode array detection was used for the separation of 13 compounds (eight herbicides widely used in agriculture: metribuzin, lenacil, ethofumesate, atrazine, terbutryn, isoproturon, chlorotoluron and linuron, and five of their principal degradation products; namely, deethylatrazine, 2-hydroxyatrazine, deethyl-2-hydroxyatrazine, deisopropylatrazine and 3-chloro-4-methylphenylurea). Peak separation for the 13 analytes was not successful when a single surfactant system was employed, neither sodium dodecyl sulfate (SDS) nor dioctyl sulfosuccinate (DOSS) sodium salt. However, a mixture of these herbicides was successfully separated using a mixed micellar system involving SDS-DOSS in less than 14 min. An application study of an on-line concentration technique for MEKC was carried out to enhance sensitivity. The optimized on-line stacking procedure consisted simply of the addition of 50 mM of sodium chloride to the injection sample, the stacking effect being more intensive as analyte polarity increased. When this stacking procedure was combined with an off-line sample preconcentration step, based on solid-phase extraction, analytes could be detected in the ppb range. The whole method was applied to ultra-high-quality and natural waters. Linear relationships between the analytical signal and the initial analyte concentration were found to be independent of the type of water, except for the more polar analytes for which small differences were observed.

Chromatography, Micellar Electrokinetic Capillary↗

Determination of herbicides, including thermally labile phenylureas, by solid-phase microextraction and gas chromatography-mass spectrometry.

A method for the determination of 10 herbicides, including thermally unstable compounds, has been developed. The method uses solid-phase microextraction (SPME) with a polyacrylate fibre. Separation, identification and quantification were accomplished with gas chromatography-mass spectrometry. The herbicides chosen belong to different chemical groups and were alachlor, atrazine, chlorotoluron, diclofop, diflufenicam, ethofumesate, isoproturon, linuron, terbutryn and trifluralin. In the present work we studied the chromatographic behaviour of three phenylureas as a function of the medium and injection mode employed. The compounds generated as a function of the solvent used in direct injection of the phenylureas (ethyl acetate, methanol and methanol-water) and those obtained when injection was accomplished using the polyacrylate fibre were determined. The results allow us to propose a method for the determination of stable and thermally unstable herbicides as long as a preconcentration step involving SPME is carried out. In the proposed method, the limits of detection varied between 0.02 microg/l for ethofumesate and 0.11 microg/l for chlorotoluron. The method was applied to the determination of these herbicides in surface and ground water samples, performing quantification by standard addition calibration. The contents of chlorotoluron and atrazine found were significantly equal to those obtained using HPLC after a preconcentration stepwith styrene-divinylbenzene sorbents.

Gas Chromatography-Mass Spectrometry↗

Simultaneous quantitative determination of thirteen urea pesticides at sub-ppb levels on a Zorbax SB-C18 column.

A simple multi-residue method is described for simultaneously determining ten urea and three benzoylurea pesticides residues in drinking water with quantitation limits below the European regulatory limit of 0.1 microgram/l. The residues were extracted from drinking water with dichloromethane and analysed by HPLC on a Zorbax 5 microns SB-C18 column with diode array detection (DAD) at 240 nm. Recoveries were determined by spiking drinking water with 13 pesticides (benzthiazuron, metoxuron, monuron, fluometuron, isoproturon, diuron, linuron, chloroxuron, chlorbromuron, diflubenzuron, neburon, triflumuron and flucycloxuron) at the 0.05-0.50 microgram/l level.

Chromatography, High Pressure Liquid↗

Evaluation of pesticide uptake by Lupinus seeds.

Pesticide uptake by seeds depends on the properties of the chemical, such as structure, stability, log k(ow) and diffusion rate, type of water, pH, temperature, content of organic matter and composition, and on seed characteristics such as permeability of the seed coat. The efficiency with which Lupinus angustifolius seeds retain different herbicides (simazine, atrazine, isoproturon, linuron,) and insecticides (carbaryl, fenamiphos, permethrin) was evaluated using both a batch and a continuous system. Factors which affect pesticide uptake by seeds, such as flow rate, seed biomass, pesticide concentration, contact time, pH, seed saturation and also the speed of the retention process for 17 days, were tested. L. angustifolius showed a high retention capacity for the above mentioned pesticides. The extraction of pesticides from seeds using different organic solvents, such as methanol, acetonitrile, ethyl acetate and n-hexane was evaluated and no pesticide residues were detected in any of the solvents tested. This could be attributed to the capacity of the seed to degrade the pesticides. From the results obtained, L. angustifolius seems to be a promising seed to be applied for phytoremediation of industrial effluents or contaminated water.

Biodegradation, Environmental↗

Evaluation of ELISA microtiter plate-based assays for the direct determination of isoproturon in water samples and soil extracts.

Trials were carried out on the commercially available Millipore isoproturon ELISA microtiter plate tests and on laboratory assays developed by Hirst as part of a Joint European Union research project (BIOPTICAS). The lowest detectable dose (LDD) was determined as three times the standard deviation of the blanks. Depending on the calibration curves obtained on different days with different plates, the LDD varied from 0.020 to 0.064 microgram/L for the Millipore test and from 0.080 to 0.329 microgram/L for the Hirst test. The mean coefficients of variation within a single plate for triplicate determinations of standard solutions in the 0.05 to 0.5 microgram/L range were 5.5 and 3.6% for Millipore and Hirst respectively. Cross-reactivity was studied for mono- and di-demethylated isoproturon, chlortoluron, diuron and linuron. The highest cross-reactivity with both tests was that of mono-demethylated isoproturon (22% for Millipore, 4% for Hirst). This molecule was the only one to show significant cross-reactivity in the Hirst test, whereas in the Millipore test, the di-demethylated isoproturon also cross-reacted (4%). Natural water samples, 19 ground-, 53 lysimetric plate and 47 suction cup water samples, and 32 soil samples were also analysed with the ELISA tests. HPLC with a diode array detector was used as a validated control technique for the natural samples. For each water type, ELISA concentrations of both tests were significantly correlated with the HPLC values (r > or = 0.937; p < 0.001). For the soil extracts, the correlations were also significant (p < 0.001), but the scatter in the data was greater. Overall, the Millipore correlation coefficients were higher than those of Hirst.

Antibodies↗

A field study to compare performance of stainless steel research monitoring wells with existing on-farm drinking water wells in measuring pesticide and nitrate concentrations.

Existing drinking water wells are widely used for the collection of ground water samples to evaluate chemical contamination. A well comparison study was conducted to compare pesticide and nitrate-N data from specially designed stainless steel research monitoring wells with data from nearby existing on-farm drinking water wells. Results could help to determine whether adequate information concerning ground water contamination can be obtained from existing drinking water wells for use in making pollutant control decisions. The study was conducted during 1993-1994 in the Little Coharie Watershed, a 158 square mile area located in the coastal plain of eastern North Carolina. Statistical analysis indicated that research monitoring wells provided a greater probability of detecting pesticides in ground water than existing on-farm wells. Atrazine was the most frequently detected pesticide found in all wells, followed in order by fluometuron, carbofuran, metolachlor, alachlor, carbaryl, butylate, chlorothalonil, linuron and simazine. Ninety-seven percent of all wells had observed concentrations of nitrate-N, ranging from 0.1 to 30.1 mg/L. There was not a significant difference between research wells and existing wells for monitoring nitrate-N. Based on results of this study, existing drinking water wells can be used for monitoring nitrate; however, specialized stainless steel monitoring wells should be used for monitoring pesticides in ground water.

Databases, Factual↗

The distribution of micro-organic contaminants in river bed-sediment cores.

There is little information available on the distributions of micro-organic contaminants in river bed-sediments below a depth of 5 cm. The aim of this study is to determine the concentrations and distributions of contaminants in river bed-sediments up to 1 m depth and to make an assessment of the results. The approach taken was to collect five cores from each of two lowland rivers in southern England, the first a rural river and the second a dominantly urban catchment. The cores were analysed for micro-organic compounds and sediment/sediment porewater characteristics. Compounds detected were polyaromatic hydrocarbons (naphthalene, fluoranthene and pyrene), pesticides (carbaryl, linuron, fenpropimorph, the synthetic pyrethroids, and prometryn), and non-ionic surfactant residue (nonylphenol). A particularly important finding was that some micro-organic contaminants penetrated to depths of 1 m, and in one of the rivers they were detected in undisturbed Eocene substrata. The more hydrophobic contaminants showed a clear depth distribution with higher concentrations towards the top of the cores. The less hydrophobic contaminants demonstrated no systematic trend suggesting they had become soluble in porewaters and subsequently travelled within the cores. Partition between the porewater and sediment appeared to be controlling the distribution of the compounds with depth.

England↗