Occurrences, distribution and risk assessment of polar pesticides in Niger River valley and its tributary the Mekrou River (Niger Republic).

The increase in food needs due to high population growth in Niger has led to the intensification of urban agriculture and the increased use of pesticides. The objective of this study is primarily to assess the polar pesticide contamination (mainly herbicides) of the Niger River and its tributary, the Mekrou River, in Niger, using both grab sampling and POCIS (Polar Organic Chemical Integrative Samplers), and then to evaluate the risk to the aquatic environment. Two water sampling campaigns were carried out during the wet and dry seasons. The polar pesticides were analyzed by liquid chromatography coupled with tandem mass spectrometry, which allowed the identification of compounds with concentrations in the grab samples above the WHO guide values and the EU directive: diuron with 2221 ng/L (EU quality guideline: 200 ng/L), atrazine with 742 ng/L (EU quality guideline: 600 ng/L) and acetochlor with 238 ng/L (EU quality guideline: 100 ng/L). The risk assessment study indicated that diuron and atrazine present a high risk for the aquatic environment during the wet season. The main source of water contamination is the intensive use of pesticides in urban agriculture near the city of Niamey, and the intensive cotton farming in the Benin. Moreover, the surveys (30 producers interviewed) showed that 70% of the pesticides used are not approved by the Interstate Committee for Drought Control in the Sahel (CILSS) and some are prohibited in Niger. The inventory of pesticides sold in the zone showed that active ingredients used by producers are 48% insecticides, 45% herbicides, and 7% fungicides.

Development of monoclonal antibodies for the detection of diuron in water and sugarcane and their application in immunochromatographic strips.

Diuron (DR) as a chemical herbicide persists in soil and water for a long time and causes extensive harm to humans. We have produced an excellent monoclonal antibody (mAb) with the ability to sensitively and specifically recognize DR in water and sugarcane samples. The semi-inhibitory concentration (IC50) of this mAb was 0.28 ng mL-1, and the limit of detection (LOD) was 0.07 ng mL-1. Based on the mAb, an immunochromatographic assay (ICA) strip was developed. The visual detection limits of the strip assay were estimated, and the critical values of DR in water and sugarcane samples were determined to be 5 and 10 ng mL-1, respectively, when assessed by the naked eye. The ICA strip was validated by HPLC-MS for water and sugarcane samples which had been spiked with DR. This ICA strip could be a useful tool for in-site and rapid detection of DR in water and sugarcane samples.

Contamination, dynamics, and health risk assessment of pesticides in seawater and marine samples from the Seto Inland Sea, Japan.

We assessed the contamination, dynamics, and health risks of the pesticides cyanazine, simetryn, fenarimol, isoprothiolane, diazinon, irgarol, fenitrothion, and diuron in marine samples (seawater, sediments, plankton, fish, and other edible organisms) at various locations in the Seto Inland Sea in Japan in 2016 and 2017. Pesticide concentrations were highest at sampling sites close to the coastline, and mean concentrations in seawater were slightly higher in surface water than in bottom water. All eight pesticides were detected in plankton. Diazinon concentrations (77-387 ng/g dw) were highest in sediments and cyanazine was the most frequently detected pesticide (88%, n = 17) in sediments. Only cyanazine (2.7-41.9 ng/g dw), simetryn (1.0-34.3 ng/g dw), and diazinon (6.3-308.8 ng/g dw) were detected in fish and other edible marine organisms. Based on the calculated bioconcentration factor, the results showed that plankton, fish, and marine animals bioaccumulated pesticides. The highest hazard quotients were calculated for diazinon in red seabream and greenling, indicating a possible risk to consumers. It is, therefore, imperative to promote strict implementation of pollution control, integrated pest management practices, and policy formulation on pesticides. Usage of diazinon must be controlled and monitored to ensure large residues do not reach aquatic ecosystems and marine coastlines.

Simultaneous multi-residue pesticide analysis in southern Brazilian soil based on chemometric tools and QuEChERS-LC-DAD/FLD method.

A simple and straightforward QuEChERS extraction method was proposed for the simultaneous determination of atrazine (ATZ), desethylatrazine (DEA), desisopropylatrazine (DIA), carbaryl (CBL), carbendazim (CBD), and diuron (DIU) in soil with high agricultural activity from southeastern Brazil, using high-performance liquid chromatography-diode-array detection/fluorescence detection. Screening studies carried out by 24 factorial design indicate better recoveries when less sample (1.0 g) and the volume of solvent (2.0 mL of ACN) were applied, compared to the original QuEChERS method. Furthermore, interactions between factors were not negligible in the experimental set, except for ATZ and DIU, in which only water volume influenced their recovery. The influence of the type (primary secondary amine (PSA), C18, and Florisil) and the sorbent amount ratio to the compounds' concentration were also considered. PSA (25 mg) was selected as the best sorbent without losing analytical response. The limits of quantification (LOQ) were estimated to be 5.0 to 15 µg kg-1 in the soil matrix. Analytical performances were consistent with linearity (R2 ≥ 0.998), recovery from 74.7 to 108%, and relative standard deviations (RSD) between 2.6 and 20.2%. Robustness was assessed by fractional factorial Plackett-Burman design. The method is recommended for chemicals that are soluble in water, and it was successfully applied in the analysis of real soil samples containing the analytes in the range of µg kg-1, proving to be suitable for the study of soils strongly impacted by agricultural activity.

Pesticides in the surface waters of the Camanducaia River watershed, Brazil.

Camanducaia River is part of the Piracicaba watershed responsible for pumping water into the Cantareira System, which is one of the main water sources for the metropolis of São Paulo and Campinas, Brazil. Intensive use of pesticides and hilly topography represents a situation of high risk for river water contamination. Therefore, water samples from 12 locations were collected along the Camanducaia River and its tributaries, over a period of 4 mo during the rainy season, and analyzed by GC-MS/MS or UPLC- MS/MS for the presence of 46 pesticides. Seven pesticides (fipronil, methyl parathion, metolachlor, atrazine, carbofuran, diuron, and simazine) were positively detected. Only atrazine (the most frequently detected) and diuron were present at concentrations above the limit of quantification of the analytical method (0.32 and 0.57 µg L-1 for atrazine and diuron, respectively). Pesticides detection frequency was higher than expected for a river system where only 11.8% of the land area is under agriculture. The vulnerability of the Camanducaia basin to pesticide contamination is attributed to the high annual precipitation (> 1.5 m y-1 in the headwaters), associated with topographical features (steep terrain) and soil types that favor surface runoff, which has been exacerbated by poor soil management practices.

Combined Approach for Determining Diuron in Sugarcane and Soil: Ultrasound-Assisted Extraction, Carbon Nanotube-Mediated Purification, and Gas Chromatography-Electron Capture Detection.

Diuron is a urea herbicide that is frequently detected in surface water, groundwater, and marine waters. However, there are few methods or guidelines reported on ensuring the quality of sugarcane and soil. In this study, a method was developed for detecting diuron to ensure the quality and safety of food and sugar. Mass spectrometry was used to identify 3,4-dichloroaniline as a marker for the thermal decomposition of diuron, and thus, as a representative component for quantitative diuron analysis. This approach can be used to rapidly detect trace amounts of diuron. In addition, ultrasound-assisted extraction (UAE) and carbon nanotube column purification were used in conjunction with gas chromatography-electron capture detection to detect diuron. The method was then evaluated for its accuracy, detection limit, and viability. The effects of extraction solvent, ultrasound time, and ultrasound power on the extraction efficiency of the analyte from sugarcane and soil were also investigated. The efficiency and optimum conditions of UAE were examined through single-factor experiments and Box-Behnken design (BBD). The optimal extraction conditions were identified as follows: acetonitrile as the extraction solvent, extraction temperature of 27 °C, extraction time of 3.4 min, and ultrasound power of 70 W. Under these conditions, high linearity was achieved for diuron concentrations of 0.01 to 5.0 mg/L, and the purification correlation coefficient was consistently greater than 0.998. Hence, gas chromatography, combined with UAE and BBD, offers superior efficiency extraction, which is sufficiently accurate and precise for pesticide residue analysis. PRACTICAL APPLICATION: We developed an accurate and cost-effective method for detecting diuron (a commonly used herbicide) in soil and sugar samples. We performed experiments to determine the optimum detection conditions for our method. This method can be used for online monitoring of sugar manufacturing processes to ensure food safety and quality.

Antifouling booster biocide extraction from marine sediments: a fast and simple method based on vortex-assisted matrix solid-phase extraction.

This paper reports the development of an analytical method employing vortex-assisted matrix solid-phase dispersion (MSPD) for the extraction of diuron, Irgarol 1051, TCMTB (2-thiocyanomethylthiobenzothiazole), DCOIT (4,5-dichloro-2-n-octyl-3-(2H)-isothiazolin-3-one), and dichlofluanid from sediment samples. Separation and determination were performed by liquid chromatography tandem-mass spectrometry. Important MSPD parameters, such as sample mass, mass of C18, and type and volume of extraction solvent, were investigated by response surface methodology. Quantitative recoveries were obtained with 2.0 g of sediment sample, 0.25 g of C18 as the solid support, and 10 mL of methanol as the extraction solvent. The MSPD method was suitable for the extraction and determination of antifouling biocides in sediment samples, with recoveries between 61 and 103% and a relative standard deviation lower than 19%. Limits of quantification between 0.5 and 5 ng g-1 were obtained. Vortex-assisted MPSD was shown to be fast and easy to use, with the advantages of low cost and reduced solvent consumption compared to the commonly employed techniques for the extraction of booster biocides from sediment samples. Finally, the developed method was applied to real samples. Results revealed that the developed extraction method is effective and simple, thus allowing the determination of biocides in sediment samples.

[Evaluation of human health risk for a population from Cali, Colombia, by exposure to lead, cadmium, mercury, 2,4-dichloro-phenoxyacetic acid and diuron associated with water and food consumption]. / Valoración del riesgo en salud en un grupo de población de Cali, Colombia, por exposición a plomo, cadmio, mercurio, ácido 2,4-diclorofenoxiacético y diuron, asociada al consumo de agua potable y alimentos.

INTRODUCTION: Exposure to pollutants such as pesticides and heavy metals has been linked to health problems. Several studies have revealed the presence of these contaminants in Cali; however, there is no information available about the main routes of exposure and risk of these contaminants. OBJECTIVE: To estimate the risk associated with the intake of cadmium, lead and mercury, and pesticides 2,4-D and diuron through the consumption of water and food in a population in Cali. MATERIALS AND METHODS: Population and environmental data were obtained, and a risk assessment was performed using United States Environmental Protection Agency guidelines. RESULTS: The concentrations of the evaluated pollutants were below permissible levels as established by the Colombian Ministerio de Ambiente, Vivienda y Desarrollo Territorial (3 µg/L -1 of cadmium; 10 µg/L -1 of lead; 1 µg/L -1 of mercury; 1 µg/L -1 of 2,4 D; 1 µg/L -1 of diuron). Salema butterfish ( Peprilus snyderi ) samples contained levels of cadmium between 20 and 80 µg/kg -1 , which are below the permissible limit set by the World Health Organization (100 µg/kg -1 ). The results of the risk assessment indicated that the carcinogenic and non-carcinogenic attributable risk to population health from the intake of food contaminants was below the maximum level permitted by the United States Environmental Protection Agency. CONCLUSIONS: It is believed that the findings in previous studies on pollutants may have been due to specific contamination events; therefore, monitoring and early warning about water intake is recommended. Furthermore, the report of cadmium being found in fish consumed as food suggests the need for quality control by regulators.

Valoración del riesgo en salud en un grupo de población de Cali, Colombia, por exposición a plomo, cadmio, mercurio, ácido 2,4-diclorofenoxiacético y diuron, asociada al consumo de agua potable y alimentos / Evaluation of human health risk for a population from Cali, Colombia, by exposure to lead, cadmium, mercury, 2,4-dichloro-phenoxyacetic acid and diuron associated with water and food consumption

Introducción. La exposición a contaminantes como plaguicidas y metales pesados, se asocia a problemas de salud. Diversos estudios revelan la presencia de estos contaminantes en Cali; sin embargo, no existe información sobre las rutas principales de esa exposición y su riesgo implícito. Objetivo. Estimar los riesgos asociados a la exposición a cadmio, plomo y mercurio, y a los plaguicidas ácido 2,4-diclorofenoxiacético y diuron, debida al consumo de agua potable y alimentos en un grupo de población de Cali. Materiales y métodos. Se obtuvieron datos ambientales e información sobre la población, y se valoró el riesgo empleando los modelos de la Environmental Protection Agency (EPA) de los Estados Unidos. Resultados. Las concentraciones de los contaminantes evaluados estuvieron por debajo de las permisibles establecidas por el Ministerio de Ambiente, Vivienda y Desarrollo Territorial de Colombia (3 µg/L -1 de cadmio; 10 µg/L -1 de plomo; 1 µg/L -1 de mercurio; 1 µg/L - 1 de ácido 2,4 diclorofenoxiacético; 1 µg/L -1 de diuron). En las muestras de pescado "manteco" ( Peprilus snyderi ), se detectaron concentraciones de cadmio entre 20 y 80 µg/kg -1 por debajo del límite permisible establecido por la Organización Mundial de la Salud (100 µg/kg -1 ). Los resultados de la valoración mostraron que el riesgo cancerígeno y no cancerígeno atribuible a la ingestión de alimentos y de agua potable con presencia de los contaminantes evaluados, estaba por debajo de los valores máximos admisibles según la EPA. Conclusiones. Se cree que los hallazgos sobre contaminantes en estudios anteriores, pueden deberse a eventos puntuales de contaminación y se recomienda vigilar la bocatoma de agua y emitir alertas tempranas. El reporte sobre la presencia de cadmio en las muestras de pescado, sugiere que el control de la calidad de los alimentos por parte de las entidades reguladoras debe mejorar.

Introduction: Exposure to pollutants such as pesticides and heavy metals has been linked to health problems. Several studies have revealed the presence of these contaminants in Cali; however, there is no information available about the main routes of exposure and risk of these contaminants. Objective: To estimate the risk associated with the intake of cadmium, lead and mercury, and pesticides 2,4-D and diuron through the consumption of water and food in a population in Cali. Materials and methods: Population and environmental data were obtained, and a risk assessment was performed using United States Environmental Protection Agency guidelines. Results: The concentrations of the evaluated pollutants were below permissible levels as established by the Colombian Ministerio de Ambiente, Vivienda y Desarrollo Territorial (3 µg/L -1 of cadmium; 10 µg/L -1 of lead; 1 µg/L -1 of mercury; 1 µg/L -1 of 2,4 D; 1 µg/L -1 of diuron). Salema butterfish ( Peprilus snyderi ) samples contained levels of cadmium between 20 and 80 µg/kg -1 , which are below the permissible limit set by the World Health Organization (100 µg/kg -1 ). The results of the risk assessment indicated that the carcinogenic and non-carcinogenic attributable risk to population health from the intake of food contaminants was below the maximum level permitted by the United States Environmental Protection Agency. Conclusions: It is believed that the findings in previous studies on pollutants may have been due to specific contamination events; therefore, monitoring and early warning about water intake is recommended. Furthermore, the report of cadmium being found in fish consumed as food suggests the need for quality control by regulators.

Occurrence and behavior of pesticides in wastewater treatment plants and their environmental impact.

Reports on pesticides elimination during wastewater treatment are rare since these substances are typically considered of agricultural rather than of urban origin. In this context, the aim of this work was to evaluate the presence, removal and environmental relevance of 22 selected pesticides in three different wastewater treatment plants (WWTPs), paying attention not only to their occurrence and elimination but also to the toxicity of each pesticide against three aquatic micro organisms (algae, daphnia and fish) through the calculation of the so-named Environmental Relevance of Pesticides from Wastewater treatment plants Index (ERPWI). For this purpose, an analytical method based on isotope dilution on-line solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was optimized, allowing the determination of the 22 target pesticides in wastewater with satisfactory sensitivity (limits of detection below 30 ng/L), accuracy and precision. Concerning the results, total pesticide levels were in most instances below 1 µg/L but removal in the WWTPs was variable and often poor, with concentrations in the effluent sometimes higher than in the corresponding influent. Possible explanations for these poor or negative removal rates are, among many others considered (e.g. sampling, sample preservation, method biases, atmospheric deposition), deconjugation of metabolites and/or transformation products of the pesticides, hydrolysis, and desorption from particulate matter during wastewater treatment. The most significant pesticides in terms of concentration and frequency of detection were diazinon and diuron. These two pesticides, followed by atrazine, simazine and malathion, were also the most relevant from the environmental point of view, according to the calculated ERPWI.

An experimental design approach employing artificial neural networks for the determination of potential endocrine disruptors in food using matrix solid-phase dispersion.

Matrix solid-phase dispersion (MSPD) as a sample preparation method for the determination of two potential endocrine disruptors, linuron and diuron and their common metabolites, 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl) urea (DCPU) and 3,4-dichloroaniline (3,4-DCA) in food commodities has been developed. The influence of the main factors on the extraction process yield was thoroughly evaluated. For that purpose, a 3 fractional factorial design in further combination with artificial neural networks (ANNs) was employed. The optimal networks found were afterwards used to identify the optimum region corresponding to the highest average recovery displaying at the same time the lowest standard deviation for all analytes. Under final optimal conditions, potato samples (0.5 g) were mixed and dispersed on the same amount of Florisil. The blend was transferred on a polypropylene cartridge and analytes were eluted using 10 ml of methanol. The extract was concentrated to 50 microl of acetonitrile/water (50:50) and injected in a high performance liquid chromatography coupled to UV-diode array detector system (HPLC/UV-DAD). Recoveries ranging from 55 to 96% and quantification limits between 5.3 and 15.2 ng/g were achieved. The method was also applied to other selected food commodities such as apple, carrot, cereals/wheat flour and orange juice demonstrating very good overall performance.

Level of contamination and impact of pesticides in cupped oyster, Crassostrea gigas, reared in a shellfish production area in Normandy (France).

Over the last decade, oysters in the Bay of Veys (Northwest France) have sporadically experienced significant summer mortality events which appear to be due to a combination of extrinsic and intrinsic factors. In the present work, the involvement of pesticides (as additional stressors) was investigated using both artificial exposure and field studies (at two sites). Six herbicides were detected in seawater following tests for a total of 15 herbicides. The most estuarine site was the most contaminated, showing relatively high values compared with those recorded in a neighboring river. No pesticides were detected in the flesh of oysters in the field but exposure experiments led to an accumulation of two substituted ureas (diuron and isoproturon, from 0.5 micro g/L and 1 micro gL(- 1) respectively). Some physiological effects were observed in terms of reproduction (partial spawning) and histopathology (atrophy of the digestive tubule epithelium) but results related to other tissue alterations and to neutral red retention (NRR) assays were not conclusive and require further investigation.

Particle-size dependent sorption and desorption of pesticides within a water-soil-nonionic surfactant system.

Although nonionic surfactants have been considered in surfactant-aided soil washing systems, there is little information on the particle-size dependence of these processes, and this may have significant implications for the design of these systems. In this study, Triton-100 (TX) was selected to study its effect on the sorption and desorption of two pesticides (Atrazine and Diuron) from different primary soil size fractions (clay, silt, and sand fractions) under equilibrium sorption and sequential desorption. Soil properties, TX sorption, and pesticide sorption and desorption all exhibited significant particle-size dependence. The cation exchange capacity (CEC) of the bulk soils and the soil fractions determined TX sorption capacity, which in turn determined the desorption efficiency. Desorption of pesticide out of the clay raction is the limiting factor in a surfactant-aided washing system. The solubilization efficiency of the individual surfactant micelles decreased as the amount of surfactant added to the systems increased. Thus, instead of attempting to wash the bulk soil, a better strategy might be to either (1) use only the amount of surfactant that is sufficient to clean the coarse fraction, then separate the fine fraction, and dispose or treat it separately, or (2) to separate the coarse fractions mechanically and then treatthe coarse and fine fractions separately. These results may be applicable to many other hydrophobic organic compounds such as polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) strongly sorbed onto soils and sediments.

Fate of diuron and terbuthylazine in soils amended with two-phase olive oil mill waste.

The addition of organic amendments to soil increases soil organic matter content and stimulates soil microbial activity. Thus, processes affecting herbicide fate in the soil should be affected. The objective of this work was to investigate the effect of olive oil production industry organic waste (alperujo) on soil sorption-desorption, degradation, and leaching of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] and terbuthylazine [N2-tert-butyl-6-chloro-N4-ethyl-1,3,5-triazine-2,4-diamine], two herbicides widely used in olive crops. The soils used in this study were a sandy soil and a silty clay soil from two different olive groves. The sandy soil was amended in the laboratory with fresh (uncomposted) alperujo at the rate of 10% w/w, and the silty clay soil was amended in the field with fresh alperujo at the rate of 256 kg per tree during 4 years and in the laboratory with fresh or composted alperujo. Sorption of both herbicides increased in laboratory-amended soils as compared to unamended or field-amended soils, and this process was less reversible in laboratory-amended soils, except for diuron in amended sandy soil. Addition of alperujo to soils increased half-lives of the herbicides in most of the soils. Diuron and terbuthylazine leached through unamended sandy soil, but no herbicide was detected in laboratory-amended soil. Diuron did not leach through amended or unamended silty clay soil, whereas small amounts of terbuthylazine were detected in leachates from unamended soil. Despite their higher sorption capacity, greater amounts of terbuthylazine were found in the leachates from amended silty clay soils. The amounts of dissolved organic matter from alperujo and the degree of humification can affect sorption, degradation, and leaching of these two classes of herbicides in soils. It appears that adding alperujo to soil would not have adverse impacts on the behavior of herbicides in olive production.

Analysis of trace levels of pesticides in rainwater by SPME and GC-tandem mass spectrometry after derivatisation with PFBBr.

Solid-phase microextraction (SPME) was used for the analysis of some pesticides (bromoxynil, chlorotoluron, diuron, isoproturon, 2,4-MCPA, MCPP and 2,4-D) in rainwater after derivatisation with PFBBr and gas chromatography-ion trap mass spectrometry. The derivatisation procedure was optimized by testing different methods: direct derivatisation in the aqueous phase followed by SPME extraction, on-fibre derivatisation and derivatisation in the injector. The best result was obtained by headspace coating the PDMS/DVB fibre with PFBBr for 10 min followed by direct SPME extraction for 60 min at 68 degrees C (pH 2 and 75% NaCl). Good detection limits were obtained for all the compounds: these ranged between 10 and 1,000 ng L-1 with a relatively high uncertainty due to the combination of derivatisation and SPME extraction steps. The optimized procedure was applied to the analysis of pesticides in rainwater and results obtained shows that this method is a fast and simple technique to assess the spatial and temporal variations of concentrations of pesticides in rainwater.

Analysis of herbicides in olive oil by liquid chromatography time-of-flight mass spectrometry.

The application of liquid chromatography time-of-flight mass spectrometry (LC/TOF-MS) for the identification and quantitation of four herbicides (simazine, atrazine, diuron, and terbuthylazine) in olive oil samples is reported here. The method includes a sample treatment step based on a preliminary liquid-liquid extraction followed by matrix solid-phase dispersion (MSPD) using aminopropyl as a sorbent material. A final cleanup step is performed with florisil using acetonitrile as an eluting solvent. The identification by LC/TOF-MS is accomplished with the accurate mass (and the subsequent generated empirical formula) of the protonated molecules [M + H]+, along with the accurate mass of the main fragment ion and the characteristic chlorine isotope cluster present in all of them. Accurate mass measurements are highly useful in this type of complex sample analyses since they allow us to achieve a high degree of specificity, often needed when other interferents are present in the matrix. The mass accuracy typically obtained is routinely better than 2 ppm. The sensitivity, linearity, precision, mass accuracy, and matrix effects are studied as well, illustrating the potential of this technique for routine quantitative analyses of herbicides in olive oil. Limits of detection (LODs) range from 1 to 5 microg/kg, which are far below the required maximum residue level (MRL) of 100 microg/kg for these herbicides in olive oil.

Source and persistence of pesticides in a semi-confined chalk aquifer of southeast England.

Pesticide contamination in groundwater is an increasing problem that poses a significant long-term threat to water quality. Following the detection of elevated concentrations of diuron in boreholes in a semi-confined chalk aquifer from southeast England, a sampling programme was undertaken. Between 2003 and 2004 diuron was observed in 90% of groundwaters analysed. In 60% of groundwater samples metabolites of diuron were more prevalent than the parent compound. Longer-term (1989-2005) monitoring shows that pollution of the aquifer by atrazine, simazine, and more recently diuron, shows a positive correlation with periods of high groundwater levels. Results from groundwater residence time indicators suggest that the highest diuron concentrations are associated with waters containing the greatest proportion of recent recharge. There is some evidence to indicate that diuron occurrence can be spatially related to areas of urban and industrial development and is probably correlated with amenity usage.

Electrically driven microseparation methods for pesticides and metabolites. II: on-line and off-line preconcentration of urea herbicides in capillary electrochromatography.

Capillary electrochromatography (CEC) was introduced to the separation of nine important urea herbicides using octadecyl-silica (ODS) capillary columns that were specially designed to allow the realization of a relatively strong electroosmotic flow (EOF) and, in turn, fast separations. The ODS stationary phase was intentionally prepared to have a low surface coverage in octadecyl ligands in order to ensure a strong EOF. This ODS stationary phase of low surface coverage exhibited the usual reversed-phase chromatographic behavior as was manifested by the linearity of plots of log kappa versus the percent organic modifier in the mobile phase. The nature of the organic modifier of the mobile phase influenced the order of elution as well as the separation efficiency of the nine urea herbicides. Mobile phases containing acetonitrile yielded higher separation efficiency (by a factor of 1.5) than methanol-containing mobile phases. This was attributed to the higher mass transfer resistances of the solute in and out of the pores in the presence of the more viscous methanol-containing mobile phases. Due to the relatively strong affinity of the urea herbicides to the ODS stationary phase, on-line preconcentration consisting of prolonged injections allowed the determination of 10(-5) M urea herbicide samples using a UV detector without sacrificing separation efficiency. This was further decreased to 10(-7) M when the prolonged injection was preceded by the injection of a plug of water. The plug of water (the more retentive mobile phase) brought about an enhanced accumulation of the dilute samples into a narrow band at the inlet of the CEC column. When this on-column sample enrichment approach was combined with an off-line sample preconcentration step, which consisted of a solid-phase extraction process, ultra dilute samples of 10(-10) M (0.1 ppb) could be detected.

Gas chromatography mass spectrometry of some thermally labile urea pesticides.

The application of gas chromatography/mass spectrometry to three thermally labile phenylurea pesticides is reported. Using alcohols as solvents the decomposition of the pesticides is followed by a reaction in which esters of N-(3,4-dichlorophenyl)carbamic acid are formed. As these reactions occur during the gas chromatographic analysis, it is the esters which are identified in the mass spectrometer. The methyl ester is itself a pesticide so an erroneous conclusion about the original pesticide could be reached when methanol is the solvent.