Determination of azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their commercially available pesticide formulations by liquid chromatography.

A rapid, simple, precise and accurate high performance liquid chromatographic (HPLC) analytical method was developed and validated for the determination of the active substances (a.s.) azoxystrobin, topramezone, acetamiprid, fluometuron and folpet in their respective commercially available formulations. The method was used for the analysis of samples under the frame of the national quality control program of plant protection products in the Greek market. Chromatographic separation of the active substances from additives and co-formulants is achieved using isocratic elution with acetonitrile and 0.1% phosphoric acid solution (60:40 v/v) at a flow rate of 0.4 mL min-1 on a C18 monolithic column (Chromolith Performance-RP18e 100 × 4.6 mm) and UV detection at 230 nm. Validation parameters of the method fulfilled acceptability criteria. Recovery of all individual compounds was in the range 97.8-100.9%. Precision expressed as relative standard deviation was lower than the theoretical values of the modified Horwitz equation. Correlation coefficients of linearity of response were better than 0.999. The benefits of the proposed method are significant reduction in analysis time and total cost since all analytes were determined with the same extraction procedures and chromatographic system. Analysis of real samples for all active ingredients confirmed fitness for purpose of the suggested method.

An effective configuration for automated magnetic micro solid-phase extraction of phenylurea herbicides from water samples followed by high-performance liquid chromatography.

In this study, a new automated magnetic micro solid-phase extraction was introduced. A Tygon tube was folded and fixed around the pole of a cylindrical magnet. Nanosized magnetic sorbents modified with diphenyldichlorosilane were uniformly immobilized on one side of the inner wall of the tube. Sample solution and desorption solvent were passed through the tube using a peristaltic pump. Four phenylurea herbicides (tebuthiuron, monolinuron, isoproturon, and monuron) were used as the model compounds to evaluate the method performance. HPLC-UV was used to separate and quantify the analytes. The effective parameters influencing the performance of the extraction process (i.e., extraction and desorption flow rates, eluent and sample volumes, type of eluent and sample ionic strength) were investigated. The limit of detection was 0.04 µg L-1 for all studied compounds. Calibration curves were linear in the range of 0.1-500 µg L-1 with a determination coefficient between 0.9988 and 0.9999. Intra-day, inter-day and batch-to-batch precisions expressed as relative standard deviation were less than 7%. Several environmental water samples were investigated to assess the applicability of the method for real sample analysis.

Residue investigation of some phenylureas and tebuthiuron herbicides in vegetables by ultra-performance liquid chromatography coupled with integrated selective accelerated solvent extraction-clean up in situ.

BACKGROUND: Some trace amounts of urea herbicide residues can be transferred to humans via the food chain, thereby being potentially harmful to human health. The development of a robust analytical methodology for effective sample preparation and simultaneous determination of herbicide residues in vegetable samples is required for achieving food safety. RESULTS: The diuron-molecularly imprinted polymers (MIPs) synthesized have excellent affinity and high selectivity to phenylureas (monolinuron, isoproturon, diuron and linuron) and tebuthiuron. A novel automated procedure with better selectivity for vegetable sample treatment was developed by integrated matrix solid-phase dispersion-accelerated solvent extraction clean-up in situ. Five herbicides can be baseline separated with runtime down to 5 min by ultra-performance liquid chromatography, and good linearity was obtained with a correlation coefficient (r) of 0.9999. The limit of quantification of the method was in the range of 0.8-2.3 µg kg-1 . Diuron residue in cherry tomato sample was found to be 40 µg kg-1 . CONCLUSION: The developed method has satisfactory selectivity, good linearity, high sensitivity and accuracy as well as speediness, and can ensure rapid selective extraction and sensitive multi-residue analysis at low microgram per kilogram levels of the herbicides in vegetable food. © 2018 Society of Chemical Industry.

Dissipation, occurrence and risk assessment of a phenylurea herbicide tebuthiuron in sugarcane and aquatic ecosystems in South China.

In this study, a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method coupled with UPLC-QqQ-MS/MS analysis was developed to detect tebuthiuron in sugarcane fields and the surrounding aquatic ecosystems. Methodological validation showed the method developed was of favorable sensitivity, reproducibility and accuracy. For assessment of its dietary and ecological risks, dissipation and occurrence of tebuthiuron in situ were further investigated through a supervised field trial and an aquatic environment monitoring carried out in six dominant sugarcane production regions in South China. After application at the range of recommended dose, tebuthiuron dominantly distributed in soil, and then dissipated in accordance with the first-order rate model with the half-lives of 12.2-21.5 d. At pre-harvest intervals (PHI), occurrence of tebuthiuron was found to be 0.718-1.366 mg/kg and 0.016-0.034 mg/kg, in sugarcane and soil, respectively. The supervised trials median residue (STMR) of tebuthiuron in sugarcane was thus 0.024 mg/kg and the dietary Risk Quotient (RQd) was accordingly calculated as 2.34 × 10-4, indicating safety on long-term consumption of sugarcane with tebuthiuron residues. Yet high risks of tebuthiuron towards soil ecosystems was noticed as it possessed maximum ecological Risk Quotient (RQe) at 1.97 to earthworms. In sugarcane field-surrounding aquatic environment, distribution of tebuthiuron was found to range from 0.007 mg/L to 0.022 mg/L, leading to high risk towards the aquatic ecosystem due to the maximum RQe at 440 to algae, irrespective of its low risks to invertebrate and fish. Taken together, our approach serve as an effective tool for monitoring residual tebuthiuron environmentally and also advance in-depth understanding of dietary and ecological risks posed by the phenylurea herbicide.

Comprehensive two-dimensional liquid chromatography-tandem mass spectrometry for the simultaneous determination of wine polyphenols and target contaminants.

A novel system for comprehensive two-dimensional liquid chromatography coupled to a triple quadrupole mass spectrometer is described for the analysis of wine components. The first dimension consisted of a 250-mm microbore cyano column utilizing 5µm diameter particles, interfaced to a 50-mm superficially-porous particle C18 column with 2.7µm diameter particles. Both columns were operated under reversed-phase conditions. Correlation between the two chromatographic separation modes was decreased by designing a 60-s shift gradient program in the second dimension, and the increase in orthogonality was evaluated quantitatively utilizing a number of orthogonality metrics. The system was employed for the analysis of a red wine sample, without preliminary clean-up procedures, and a total of 43 polyphenols were separated and identified. Comparison with a one-dimensional LC system showed a large increase in the number of identified components with the two-dimensional system. Optimized multiple reaction monitoring experiments allowed for the determination of trans-resveratrol, which is one of the most active antioxidant component of wine, and for monuron, a plant protection product (herbicide) of interest to regulatory agencies. The estimated limits of detection and of quantification were 0.3µgL(-1) and 1µgL(-1), respectively, well below the minimum detection limit (10µgL(-1)) set by current regulation.

Dry-wet cycles increase pesticide residue release from soil.

Soil drying and rewetting may alter the release and availability of aged pesticide residues in soils. A laboratory experiment was conducted to evaluate the influence of soil drying and wetting on the release of pesticide residues. Soil containing environmentally long-term aged (9-17 years) (14) C-labeled residues of the herbicides ethidimuron (ETD) and methabenzthiazuron (MBT) and the fungicide anilazine (ANI) showed a significantly higher release of (14) C activity in water extracts of previously dried soil compared to constantly moistened soil throughout all samples (ETD: p < 0.1, MBT and ANI: p < 0.01). The extracted (14) C activity accounted for 44% (ETD), 15% (MBT), and 20% (ANI) of total residual (14) C activity in the samples after 20 successive dry-wet cycles, in contrast to 15% (ETD), 5% (MBT), and 6% (ANI) in extracts of constantly moistened soils. In the dry-wet soils, the dissolved organic carbon (DOC) content correlated with the measured (14) C activity in the aqueous liquids and indicated a potential association of DOC with the pesticide molecules. Liquid chromatography MS/MS analyses of the water extracts of dry-wet soils revealed ETD and MBT in detectable amounts, accounting for 1.83 and 0.01%, respectively, of total applied water-extractable parent compound per soil layer. These findings demonstrate a potential remobilization of environmentally aged pesticide residue fractions from soils due to abiotic stresses such as wet-dry cycles.

Long-term persistence of various 14C-labeled pesticides in soils.

The fate of the 14C-labeled herbicides ethidimuron (ETD), methabenzthiazuron (MBT), and the fungicide anilazine (ANI) in soils was evaluated after long-term aging (9-17 years) in field based lysimeters subject to crop rotation. Analysis of residual 14C activity in the soils revealed 19% (ETD soil; 0-10 cm depth), 35% (MBT soil; 0-30), and 43% (ANI soil; 0-30) of the total initially applied. Accelerated solvent extraction yielded 90% (ETD soil), 26% (MBT soil), and 41% (ANI soil) of residual pesticide 14C activity in the samples. LC-MS/MS analysis revealed the parent compounds ETD and MBT, accounting for 3% and 2% of applied active ingredient in the soil layer, as well as dihydroxy-anilazine as the primary ANI metabolite. The results for ETD and MBT were matching with values obtained from samples of a 12 year old field plot experiment. The data demonstrate the long-term persistence of these pesticides in soils based on outdoor trials.

Effect of olive-mill waste addition to soil on sorption, persistence, and mobility of herbicides used in Mediterranean olive groves.

Laboratory and field experiments were conducted to evaluate the effect of olive-mill waste (OMW) addition to a Mediterranean olive grove soil on sorption, persistence, and mobility of two herbicides which are simultaneously applied for weed control in olive groves: terbuthylazine (TA) and fluometuron (FM). Laboratory batch sorption experiments showed that OMW addition to the soil at rates of 5 and 10% (w/w) greatly enhanced the sorption of both herbicides, thus suggesting that amendment with OMW could be useful to enhance the retention and reduce the mobility of FM and TA in the soil. Incubation experiments showed that OMW increased the persistence of FM and had little effect on the long persistence of TA in the soil studied. A demonstration field experiment was also conducted in field plots with a slope of about 5%, either unamended or amended with OMW at a rate of 10 kg m⁻², and then treated with a commercial formulation containing a mixture of TA and FM. Extraction of field soil samples, taken from different soil depths (0-5, 5-10, 10-20, and 20-30 cm) at different times after herbicide application, showed that both TA and FM moved deeper in unamended soil than in OMW-amended soil, and that OMW addition affected the persistence of FM in the toplayer, increasing its half-life from 24 to 58 days, while having little effect on the persistence of TA. Thus, data obtained under real field conditions were consistent with those obtained under controlled laboratory conditions. Preliminary herbicide runoff data indicated that the total herbicide runoff losses were also reduced upon OMW addition. Addition of OMW could be beneficial in reducing the mobility of TA and FM in olive grove soils, and also in increasing the persistence of FM in soils where this herbicide could be rapidly degraded.

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrodes.

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30,000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(app) close to 3.2 × 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities ≥ 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition.

Photocatalytic oxidation of monuron in the suspension of WO3 under the irradiation of UV-visible light.

A comprehensive study of the degradation of monuron, one of the phenylurea herbicides, was conducted by UV-Vis/WO(3) process. It was found that hydroxyl radicals played a major role in the decay of monuron while other radicals (e.g. superoxide) and hole might also contribute to the decomposition of monuron. The oxidation path likely plays a major role in the generation of hydroxyl radicals. The effects of initial pH level, initial concentration of monuron, and inorganic oxidants on the performance of UV-Vis/WO(3) process were also investigated and optimized. Comparison between monuron decay pathways by UV-Vis/WO(3) and UV/TiO(2) was conducted. The decay mechanisms, including N-terminus demethylation, dechlorination and direct hydroxylation on benzene ring, were observed to be involved in the oxidation of monuron in these two processes. Sixteen intermediates were identified during the photodegradation of monuron and degradation pathways were proposed accordingly.

Constructed wetlands as a component of the agricultural landscape: mitigation of herbicides in simulated runoff from upland drainage areas.

Constructed wetlands are a recommended practice for buffering pollutant source areas and receiving waters. A wetland consisting of a sediment trap and two treatment cells was constructed in a Mississippi Delta lake watershed. A 3-h simulated runoff event was initiated (2003) to evaluate fate and transport of atrazine and fluometuron through the wetland. Water samples were collected during a runoff simulation and then afterward at selected intervals for 21d, and analyzed for the herbicides. Breakthrough patterns for herbicide concentrations in water samples during the first 20h after simulated runoff showed peak concentrations in the first 6h, with gradual tailing as the herbicide pulse was diluted in the second, excavated (deeper) cell. Atrazine and fluometuron concentrations in the first (shallower, non-excavated) cell averaged 12- and 20-fold greater, respectively, than those in the second cell following simulated runoff, indicating entrapment in the first cell. Atrazine and fluometuron concentrations in the shallower cell decreased 32% and 22%, respectively, 9d following simulated runoff, indicating either degradation or sorption to soil or wetland flora. In the excavated cell, concentrations were even lower, and atrazine declined more rapidly than fluometuron. Results indicate constructed wetlands can improve downstream water quality though sequestration or processing of pollutants.

Determination of benzoylurea insecticides in food by pressurized liquid extraction and LC-MS.

A method based on pressurized liquid extraction and LC-MS/MS has been developed for determining nine benzoylureas (BUs) in fruit, vegetable, cereals, and animal products. Samples (5 g) were homogenized with diatomaceous earth and extracted in a 22 mL cell with 22 mL of ethyl acetate at 80 degrees C and 1500 psi. After solvent concentration and exchange to methanol, BUs were analyzed by LC-MS/MS using an IT mass analyzer, which achieved several transitions of precursor ions that increase selectivity providing identification. LOQs were between 0.002 and 0.01 mg/kg, which are equal or lower than maximum residue limits established by the Codex Alimentarius. Excellent linearity was achieved over a range of concentrations from 0.01 to 1 mg/kg with correlation coefficients 0.995-0.999 (n=7). Validation of the total method was performed by analyzing in quintuplicate seven different commodities (milk, eggs, meat, rice, lettuce, avocado, and lemon) at three concentration levels (0.01, 0.1, and 1 mg/kg). The recoveries ranged from 58 to 97% and the RSDs from 5 to 19% depending on the compound and the commodity. The combination of pressurized liquid extraction with LC-MS/MS provides a sensitive and selective method for the determination of BUs in food.

Rate of loss of simazine, terbuthylazine, isoproturon, and methabenzthiazuron during soil solarization.

This paper reports the use of solar heating by polyethylene mulching for decontamination of a silty clay-loam soil polluted with herbicides. Soil solarization, a natural and hydrothermal method commonly used for disinfesting soils, was tested during the summer season on a Hipercalcic Calcisol located in Murcia (southeast Spain) for dissipation of s-triazine (simazine and terbuthylazine) and phenylurea (isoproturon and methabenzthiazuron) herbicides using low-density (LD) and high-density (HD) polyethylene (PE) film as a cover. A well-established influence of the film was observed on the dissipation of all herbicides from the soil, although the density (0.92-0.95 g/cm(3)) of the film used (LDPE and HDPE) was not significant in terms of the rate of loss. In all cases, a quick depletion during the first 2 weeks was observed, mainly for terbuthylazine. The first-order model satisfactorily explained the dissipation process, but the Hoerl and biexponential equations were more appropriate, mainly for simazine, isoproturon, and methabenzthiazuron. In all cases, herbicides disappeared at faster rates in solarized soils (DT(50) = 4-29 days) than in nonmulched soils (DT(50) = 11-35 days), especially for terbuthylazine and isoproturon.

Leaching of Diuron, Linuron and their main metabolites in undisturbed field lysimeters.

The increasing use of pesticides in Morocco raises the potential risk of groundwater contamination, notably in the Gharb area, which has a shallow groundwater table. Thus, the leaching of two phenyl-ureas, diuron and linuron and their metabolites through undisturbed soil columns was studied under outdoor conditions. The soil chosen is a loamy clay soil, representative of the Gharb agricultural area. After four irrigation events were applied from 31/03/2005 to 15/05/2005, leachates contained higher amounts of linuron (from 0.08% to 6.96% of applied linuron) than diuron (from 0% to 0.27%). The greater mobility of linuron might be related to its higher water solubility (64 mg x L(- 1) compared with 42 mg x L(- 1) for diuron) and smaller adsorption coefficient (K(oc) of 400 L x kg(- 1), compared with 480 L x kg(- 1) for diuron). Concerning their metabolites, greater amounts of, N'-(3,4-dichlorophenyl)-N, (DCPMU) than N'-3,4-dichlorophenylurea (DCPU) were detected N-dimethylurea in the percolates, from 0% to 0.046% and from 0% to 0.008%, respectively. At the end of the monitoring period, more linuron residues than diuron residues were recovered in the soil profiles, 25.02% and 16.41%, respectively. The diuron residues were found mainly in the 0-20 cm soil layer, whereas linuron residues reached the 20-40 cm soil layer. Under such experimental conditions, linuron leaching, and thus its potential to contaminate groundwater, is greater than that of diuron.

Assessing the toxicity of herbicide isoproturon on Aporrectodea caliginosa (Oligochaeta) and its fate in soil ecosystem.

This study was conducted to determine the residues of isoproturon and its metabolites, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl) urea, and 4-isopropylanilin in soil and mature earthworms under laboratory conditions. Mature earthworms (Aporrectodea caliginosa) were exposed for various durations (7, 15, 30, and 60 days) to soils contaminated with isoproturon concentrations (2, 4, 6, 8, and 10 mg kg(-1) soil). The decrease in isoproturon concentration in the soil was inversely correlated to it's initial concentration. The highest concentration detected for isoproturon in earthworms was observed during the first 15 days and decreased thereafter. Acute toxicity of isoproturon was investigated; total soluble protein content and glycogen of the worms were evaluated. Levels of these parameters were related to isoproturon concentration in soil and earthworms. No lethal effect of isoproturon was observed even at the concentration of 1200 mg kg(-1) soil after 60 days of exposure. A reduction of total soluble protein was observed in all treated worms (maximum 59.54%). This study suggests the use of the total soluble protein content and glycogen of earthworms as biomarkers of exposure to isoproturon.

Accelerated solvent extraction of fluometuron from selected soils.

Accelerated solvent extraction (ASE) is a recently developed extraction technique that is more rapid and produces less waste than do conventional liquid/liquid extraction methods. Optimal conditions were determined for ASE of fluometuron from 2 Weswood clay loam soils. Two solvents (acetonitrile and methanol), 2 temperatures (50 and 100 degrees C), and the number of static cycles (1, 2, and 3) were evaluated. The most efficient and reproducible extractions were obtained when methanol was combined with a 50 degrees C extraction temperature and the static cycle was repeated 3 times. These experiments indicated that existing extraction methods for fluometuron can easily be adapted for ASE.

Leaching and half-life of the herbicide tebuthiuron on a recharge area of Guarany aquifer in sugarcane fields in Brazil.

This study was undertaken to evaluate the degradation and mobility of the herbicide tebuthiuron (N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea) in soil under field conditions, and its potential for leaching and groundwater contamination. A watershed, Espraiado, located over a recharge area in Brazil, was chosen for soil and water studies. At Espraiado, water samples were collected from seven wells at intervals of three months from March 2004 to June 2006 and analyzed for tebuthiuron. Other samples were taken from city wells located outside of the recharge area. To assess the potential movement to the aquifer, tebuthiuron was also applied to trial plots at the recommended label rate of 1.0 kg/ha a.i. in May of 2004, with and without sugarcane coverage, on sandy soil. Soil samples were collected during the years of 2004 and 2005, at depths intervals of 20 cm from soil surface down to 120 cm and analyzed for tebuthiuron at zero, 3, 30, 60, 90, 120, 150, 180, 240, and 300 days after application. There was no clear effect of sugarcane coverage on the tebuthiuron degradation in soils, but it moved faster into the soil where there was no cover. After 180 days there were no measurable residues in the soil, and tebuthiuron was not found below 40 cm depth in any time. Tebuthiuron had a half-life of 20 days under those conditions. No tebuthiuron residue was found in ground water samples at any sampling time.

Photolysis of fluometuron in the presence of natural water constituents.

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.

Performance evaluation of elemental analysis/isotope ratio mass spectrometry methods for the determination of the D/H ratio in tetramethylurea and other compounds--results of a laboratory inter-comparison.

Tetramethylurea (TMU) with a certified D/H ratio is the internal standard for Site-specific Natural Isotope Fractionation measured by Nuclear Magnetic Resonance (SNIF-NMR) analysis of wine ethanol for detection of possible adulterations (Commission Regulation 2676/90). A new batch of a TMU certified reference material (CRM) is currently being prepared. Whereas SNIF-NMR has been employed up to now, Elemental Analysis/Isotope Ratio Mass Spectrometry ((2)H-EA-IRMS) was envisaged as the method of choice for value assignment of the new CRM, as more precise (better repeatable) data might be obtained, resulting in lower uncertainty of the certified value. In order to evaluate the accuracy and intra- and inter-laboratory reproducibility of (2)H-EA-IRMS methods, a laboratory inter-comparison was carried out by analysing TMU and other organic compounds, as well as some waters. The results revealed that experienced laboratories are capable of generating robust and well comparable data, which highlights the emerging potential of IRMS in food authenticity testing. However, a systematic bias between IRMS and SNIF-NMR reference data was observed for TMU; this lack of data consistency rules out the (2)H-IRMS technique for the characterisation measurement of the new TMU CRM.

Photo-induced fluorescence of fluometuron in a continuous-flow multicommutation assembly.

This paper deals with the photo-induced fluorimetric determination of the herbicide Fluometuron with the aid of a continuous-flow assembly of the emergent and new methodology known as Multicommutation which was provided with an on-line photoreactor. Maximum fluorescence intensity was observed at basic pH solutions, 1x 10(-4) mol l(-1) NaOH, after 1.4 min of irradiation and being the maximum at lambda(exc) 247.0 nm and lambda(em) 325.0 nm. The influence of different experimental parameters either chemical (pH, surfactants presence, solvent polarity and temperature) or hydrodynamic (time of photo-degradation, size and number of different segments and flow-rate) was tested. The linear dynamic range was from 0.01 to 4.0 mg l(-1) of Fluometuron; the inter-day reproducibility (as R.S.D.) of the slope was 0.001% and 1.7% from the peaks intra-day reproducibility. A large series of potential interferents was studied and finally the method was applied to human urine, soil, formulation and water samples.