Study of processes influencing bioavailability of pesticides in wood-soil systems: Effect of different factors.

Lignocellulosic wastes and by-products containing lignin are now available in large amounts from forestry and industrial activities, and could be promising organic materials for the biosorption of pesticides by soils in order to reduce point-source pollution. Adding these materials to soil requires understanding the process of pesticide sorption-desorption by wood-soils, as sorption capacity could increase, with changes in pesticide bioavailability and final fate. The objective of this work was to study the effect that pine and oak wood added to soils had on the sorption/desorption of the pesticides linuron, alachlor, and metalaxyl. Experiments were conducted with two sandy loam and sandy clay soils each amended with two wood doses (5% and 50%) after different incubation times (0, 5 and 12 months). A low wood dose (5%) had no significant impact on the sorption (Kf) of alachlor, but Kf increased for linuron (up to 5.4-1.7 times) and metalaxyl (up to 4.4 and 8.6 times) in all wood-soil systems. The results were not significantly different after different incubation times. The desorption results indicated that wood decreases the sorption irreversibility of alachlor, and increases that of linuron and metalaxyl, with a varying effect of the wood-soil incubation time. The addition of a high wood dose to soil (50%) was more significant for increasing the sorption of all the pesticides, and the sorbed amounts remaining after desorption (>49% for linuron, >33% for alachlor and >6% for metalaxyl), although there was no apparent discrimination between the two types of woods. The role of the nature of the organic carbón (Koc values) for sorption was evidenced for alachlor and metalaxyl, but not for linuron. These outcomes are of interest for extending wood application to soil as a barrier for avoiding environmental risk by point-source pollution due to the use and management of pesticides in farming systems.

Uptake, translocation, and elimination in sediment-rooted macrophytes: a model-supported analysis of whole sediment test data.

Understanding bioaccumulation in sediment-rooted macrophytes is crucial for the development of sediment toxicity tests using macrophytes. Here, we explore bioaccumulation in sediment-rooted macrophytes by tracking and modeling chemical flows of chlorpyrifos, linuron, and six PCBs in water-sediment-macrophyte systems. Chemical fluxes across the interfaces between pore water, overlying water, shoots, and roots were modeled using a novel multicompartment model. The modeling yielded the first mass-transfer parameter set reported for bioaccumulation by sediment-rooted macrophytes, with satisfactory narrow confidence limits for more than half of the estimated parameters. Exposure via the water column led to rapid uptake by Elodea canadensis and Myriophyllum spicatum shoots, followed by transport to the roots within 1-3 days, after which tissue concentrations gradually declined. Translocation played an important role in the exchange between shoots and roots. Exposure via spiked sediment led to gradual uptake by the roots, but subsequent transport to the shoots and overlying water remained limited for the chemicals studied. These contrasting patterns show that exposure is sensitive to test set up, chemical properties, and species traits. Although field-concentrations in water and sediment will differ from those in the tests, the model parameters can be assumed applicable for modeling exposure to macrophytes in the field.

Voltammetric determination of the herbicide Linuron using a tricresyl phosphate-based carbon paste electrode.

This paper summarises the results of voltammetric studies on the herbicide 3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Linuron), using a carbon paste electrode containing tricresyl phosphate (TCP-CPE) as liquid binder. The principal experimental conditions, such as the pH effect, investigated in Britton-Robinson buffer solutions (pH 2.0-7.0), the peak characteristics for the analyte of interest, or instrumental parameters for the differential pulse voltammetric mode were optimized for the method. As found out, the best electroanalytical performance of the TCP-CPE was achieved at pH 2.0, whereby the oxidation peak of Linuron appeared at ca. +1.3 V vs. SCE. The analytical procedure developed offers good linearity in the concentration range of 1.25-44.20 µg mL(-1) (1.77 × 10(-4)-5.05 × 10(-6) mol L(-1)), showing-for the first time-the applicability of the TCP-CPE for anodic oxidations in direct voltammetry (without accumulation). The method was then verified by determining Linuron in a spiked river water sample and a commercial formulation and the results obtained agreed well with those obtained by the reference HPLC/UV determination.

Occurrence and distribution of sulfonylurea and related herbicides in central Canadian surface waters 2006-2008.

Surface water sampling in 2006-2008 measured the occurrence of sulfonylureas and related herbicides (SUs) during base flow conditions and wet weather events. Flumetsulam (29.2%), diuron (36.5%) and fomesafen (25.3%) were most frequently detected over the course of the study. Typical SU concentrations were in the low parts per trillion range; however, maximum concentrations of fomesafen (873 ng/L), linuron (856 ng/L) and diuron (2,900 ng/L) approached or exceeded 1 µg/L. The temporal trend in SUs showed a correlation with application periods. In general, detections of SUs were more frequent where rotation of row crops was more intense. Sampling during wet-weather events indicated potential for a range of SUs to be flushed into surface waters at relatively high concentrations.

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.

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.

A multi-lysimeter investigation on the mobility and persistence of pesticides in the loam soil of the Fucino Plain (Italy).

In order to evaluate the impact of intensive horticulture on the water resources of the Fucino Plain, one of the most important agricultural settlements of Central Italy, the mobility and persistence in the soil of five commonly used pesticides was investigated by means of multi-lysimeter experiments. The fate of simazine, carbaryl, dicloran, linuron and procymidone was evaluated in the laboratory under experimental conditions simulating as closely as possible both pesticide application and irrigation practices required by the local crops. An efficient extraction procedure followed by chromatographic analysis, allowing the simultaneous determination of the applied chemicals, was used to monitor the pesticide residues in the soil columns as a function of time from application and depth. The experiment, carried out for about 60 days, revealed that soil contamination apparently involves only the surface layer since none of the investigated pesticides was detected at depths greater than 20-30 cm. However, the five pollutants exhibit a quite different behaviour that can be related to their physico-chemical properties.

Measurement uncertainty arising from trueness of the analysis of two endocrine disruptors and their metabolites in environmental samples. Part II. Solid-phase extraction from environmental natural waters.

In this work, a preconcentration method for the simultaneous determination of the endocrine disrupting chemicals (EDCs), diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea), and linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea), as well as their metabolites DCPU (1-(3,4-dichlorophenyl) urea), DCPMU (1-(3,4-dichlorophenyl)-3-methylurea) and 3,4-DCA (3,4-dichloroaniline), present in natural waters was optimized and validated. Water was subjected to solid-phase extraction (SPE) and the influence of several experimental variables affecting the extraction efficiency of the target analytes was studied, including the sorbent material, elution solvents, pH and breakthrough volume, as well as some solution parameters that is, ionic strength and organic matter content. A high-performance liquid chromatography system coupled to UV-diode array detector (DAD) was used for the target analytes quantification at the optimum conditions described in Part I. The fully nested experimental design, adapted to the new experimental parameters, was used to study the measurement uncertainty arising from trueness by estimating proportional bias (in terms of recovery). The overall recoveries of the target analytes were in the range of 71.6-90.2%, except 3,4-DCA for which a low overall recovery of 51.4% was obtained. The analytical procedure was shown to be linear over the studied range of concentration (25-400 ng/l), exhibiting satisfactory repeatability and reaching limits of detection in the 1.3-11.2 ng/l range for all, quite different in nature, water types. The SPE method was further applied for the determination of the selected EDCs and their metabolites in water samples taken from selected study stations in the region of Epirus (N.W. Greece) corresponding to the sediment samples locations (Part I).

Measurement uncertainty arising from trueness of the analysis of two endocrine disruptors and their metabolites in environmental samples. Part I: ultrasonic extraction from diverse sediment matrices.

The validation of preconcentration strategies for the simultaneous determination of two endocrine disrupting compounds (EDCs) and their metabolites present in the aquatic environment including natural waters and freshwater sediments as well as the estimation of uncertainty arising from trueness using fully nested experimental designs are presented in a series of two papers. In this work, we present Part I of our ongoing study, the validation of an analytical method based on ultrasonic extraction of the target analytes from various freshwater sediments and the estimation of the method measurement uncertainty. The selected endocrine disruptors included two widely used herbicides, diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea) and linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and their common degradation products namely, 3,4-dichloroaniline (3,4-DCA), 1-(3,4-dichlorophenyl) urea (DCPU) and 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU). A high-performance liquid chromatography system coupled to UV-diode array detector (HPLC/UV-DAD) was used for the target analytes quantification. A fully nested experimental design was applied to study the measurement uncertainty arising from trueness by estimating proportional bias (in terms of recovery). The overall recoveries, that is, those determined by the nested experiments were in the range of 59.5-85.1%, except 3,4-DCA for which a low overall recovery of 29.0% was observed. The analytical method was shown to be linear over the studied range of concentrations (5-100 microg/kg), exhibiting satisfactory repeatability and reaching limits of detection usually in the 0.6-4.6 microg/kg range on dry sediment basis. The method used permitted the determination of the target EDCs and their metabolites in sediment samples collected from selected study stations in the region of Epirus (N.W. Greece) at the concentration levels demanded by current legislation.

Retention of pesticides in soil columns modified in situ and ex situ with a cationic surfactant.

A study of the effect of a clayey soil modified in situ and ex situ with the cationic surfactant octadecyltrimethylammonium bromide (ODTMA), on the retention of linuron, atrazine and metalaxyl was carried out. Leaching of these compounds was studied in columns of a natural clayey soil and the same clayey soil modified by direct injection of the surfactant in situ, and in columns of a natural sandy soil and the same sandy soil modified by intercalation of a barrier of the clayey soil saturated ex situ with the surfactant. Breakthrough curves indicated the total immobilization of linuron in modified soils and a decrease in the leaching kinetics of atrazine and metalaxyl compared to what was obtained in the natural soil. The results indicate the use of the clayey soil modified in situ or ex situ with the surfactant ODTMA could be of interest in the immobilization of pesticides of different hydrophobicities.

An accurate and robust LC-MS/MS method for the quantification of chlorfenvinphos, ethion and linuron in liver samples.

A method for the determination of chlorfenvinphos, ethion and linuron in liver samples by LC-MS/MS is described. Sample treatment was performed by using Sola™ polymeric reverse phase SPE cartridges after protein precipitation. Gradient elution using 10 mM ammonium formate in methanol (A) and 10 mM ammonium formate in water (B) was used for chromatographic separation of analytes on a Hypersil™ end-capped Gold PFP reverse phase column (100 mm × 2.1 mm, 3 µm). All analytes were quantified without interference, in positive ionization mode using multiple reaction monitoring (MRM) with chlorfenvinphos-d10 as internal standard. The whole procedure was validated according to the FDA guidelines for bioanalytical methods. The calibration curves for chlorfenvinphos, linuron and ethion compounds were linear over the concentration range of 0.005-2 µM (i.e. 0.0018-0.720 µg/mL, 0.0019-0.770 µg/mL and 0.0012-0.500 µg/mL respectively) with coefficients of determination higher than 0.998. A Lower limit of quantification of 0.005 µM was achieved for all analytes, i.e. 5.76, 6.08 and 3.84 µg/kg of liver for chlorfenvinphos, ethion and linuron respectively. Compounds extraction recovery rates ranged from 92.9 to 99.5% with a RSD of 2.3%. Intra- and inter-day accuracies were within 90.9 and 100%, and imprecision varied from 0.8 to 8.2%. Stability tests proved all analytes were stable in liver extracts during instrumental analysis (+12 °C in autosampler tray for 72 h) at the end of three successive freeze-thaw cycles and at -20 °C for up to 9 months. This accurate and robust analytical method is therefore suitable for contamination or metabolism studies.

Tillage system, application rate, and extreme event effects on herbicide losses in surface runoff.

Conservation tillage can reduce soil loss; however, the residual herbicides normally used to control weeds are often detected in surface runoff at high levels, particularly if runoff-producing storms occur shortly after application. Therefore, we measured losses of alachlor, atrazine, linuron, and metribuzin from seven small (0.45-0.79-ha) watersheds for 9 yr (1993-2001) to investigate whether a reduced-input system for corn (Zea mays L.) and soybean [Glycine max (L.) Merr.] production with light disking, cultivation, and half-rate herbicide applications could reduce losses compared with chisel and no-till. As a percentage of application, annual losses were highest for all herbicides for no-till and similar for chisel and reduced-input. Atrazine was the most frequently detected herbicide and yearly flow-weighted concentrations exceeded the drinking water standard of 3 microg L(-1) in 20 out of 27 watershed years that it was applied. Averaged for 9 corn yr, yearly flow-weighted atrazine concentrations were 26.3, 9.6, and 8.3 microg L(-1) for no-till, chisel, and reduced-input, respectively. Similarly, flow-weighted concentrations of alachlor exceeded the drinking water standard of 2 microg L(-1) in 23 out of 54 application years and in all treatments. Thus, while banding and half-rate applications as part of a reduced-input management practice reduced herbicide loss, concentrations of some herbicides may still be a concern. For all watersheds, 60 to 99% of herbicide loss was due to the five largest transport events during the 9-yr period. Thus, regardless of tillage practice, a small number of runoff events, usually shortly after herbicide application, dominated herbicide transport.

Ionic liquid coated magnetic core/shell Fe3O4@SiO2 nanoparticles for the separation/analysis of linuron in food samples.

Three hydrophobic ionic liquids (ILs) including 1-butyl-3-methylimidazole hexafluorophosphate ([BMIM]PF6), 1-hexyl-3-methyl-imidazole hexafluorophosphate ([HMIM]PF6), and 1-octyl-3-methylimidazole hexafluoro-phosphate ([OMIM]PF6) coated Fe3O4@SiO2 nanoparticles with core-shell structure to prepare magnetic solid phase extraction agent (Fe3O4@SiO2@ILs) and establish a new method of magnetic solid phase extraction (MSPE) coupled with UV spectrometry for separation/analysis of linuron. The results showed that linuron was adsorbed rapidly by Fe3O4@SiO2@[OMIM]PF6 and eluanted by ethanol. Under the optimal conditions, preconcentration factor of the proposed method was 10-fold. The linear range, detection limit, correlation coefficient (R) and relative standard deviation (RSD) were found to be 0.04-20.00 µg mL(-1), 5.0 ng mL(-1), 0.9993 and 2.8% (n=3, c=4.00 µg mL(-1)), respectively. The Fe3O4@SiO2 nanoparticles could be used repeatedly for 10 times. This proposed method has been successfully applied to the determination of linuron in food samples.

Determination of linuron and related compounds in soil by microwave-assisted solvent extraction and reversed-phase liquid chromatography with UV detection.

The combination of microwave-assisted solvent extraction (MASE) and reversed-phase liquid chromatography (RPLC) with UV detection has been investigated for the efficient determination of phenylurea herbicides in soils involving the single-residue method (SRM) approach (linuron) and the multi-residue method (MRM) approach (monuron, monolinuron, isoproturon, metobromuron, diuron and linuron). Critical parameters of MASE, viz, extraction temperature, water content and extraction solvent were varied in order to optimise recoveries of the analytes while simultaneously minimising co-extraction of soil interferences. The optimised extraction procedure was applied to different types of soil with an organic carbon content of 0.4-16.7%. Besides freshly spiked soil samples, method validation included the analysis of samples with aged residues. A comparative study between the applicability of RPLC-UV without and with the use of column switching for the processing of uncleaned extracts, was carried out. For some of the tested analyte/matrix combinations the one-column approach (LC mode) is feasible. In comparison to LC, coupled-column LC (LC-LC mode) provides high selectivity in single-residue analysis (linuron) and, although less pronounced in multi-residue analysis (all six phenylurea herbicides), the clean-up performance of LC-LC improves both time of analysis and sample throughput. In the MRM approach the developed procedure involving MASE and LC-LC-UV provided acceptable recoveries (range, 80-120%) and RSDs (<12%) at levels of 10 microg/kg (n=9) and 50 microg/kg (n=7), respectively, for most analyte/matrix combinations. Recoveries from aged residue samples spiked at a level of 100 microg/kg (n=7) ranged, depending of the analyte/soil type combination, from 41-113% with RSDs ranging from 1-35%. In the SRM approach the developed LC-LC procedure was applied for the determination of linuron in 28 sandy soil samples collected in a field study. Linuron could be determined in soil with a limit of quantitation of 10 microg/kg.

Direct determination of monolinuron, linuron and chlorbromuron residues in potato samples by gas chromatography with nitrogen-phosphorus detection.

A gas chromatography with nitrogen-phosphorus detection direct method for methoxyurea herbicide determination in powdered potato and fresh potato samples has been developed. A previous study of the thermal stability of the phenylurea herbicides seems to confirm that the ones containing the methoxy radical, i.e. monolinuron, linuron and chlorbromuron, were stable. The herbicides were extracted from the sample through liquid-liquid extraction with dichloromethane-light petroleum (1:1), followed by solid-phase extraction in a C8 cartridge. The recoveries were in the range 84-95% for powdered potato and 86-101% for fresh potato. The RSD values were less than 10%, at 0.1 microg g(-1) concentration level (n = 4) for both types of samples. Detection limits of the method were 7.0-30 ng g(-1) for powdered potato and 6.0-50 ng g(-1) for fresh potato.

Determination of traces of pesticides in water by solid-phase extraction and liquid chromatography-ionspray mass spectrometry.

A multi-residue analytical method for six pesticides (atrazine, hydroxyatrazine, carbofuran, promecarb, linuron and monolinuron) in drinking water has been developed. The method combines liquid chromatography and mass spectrometry using an ionspray interface. The linearity domain, as well as the limits of detection and quantification, were determined for each compound. Although satisfactory performance could be achieved, present drinking water regulations (0.1 microgram l-1 for single pesticide) requires a pre-concentration step. This was performed using solid-phase extraction with octadecyl-bonded silica cartridges. The analytical procedure was tested on water samples spiked at the 0.04 and 0.08 microgram l-1 levels, and allowed the determination of the investigated pesticides (except hydroxyatrazine) at these trace concentrations.

Simultaneous determination of linuron and trifluralin residues in carrots and their pulp by liquid chromatography and gas chromatography.

A simple method is described for determining trifluralin and linuron in carrots and their pulp. Samples are extracted with hexane-ethyl ether (1 + 1), cleaned up with a disposable Florisil cartridge, and eluted first with hexane-ethyl ether (99 + 1) (for trifluralin), and then with hexane-ethyl ether (3 + 7) (for linuron). Trifluralin is then analyzed by electron capture gas chromatography (GC/ECD), and linuron by GC/ECD and liquid chromatography with ultraviolet detection (LC/UV). Recoveries were determined by spiking untreated carrot and carrot pulp homogenates with trifluralin and linuron at 0.04, 0.16, and 0.32 micrograms/g. Six determinations were performed at each level for both compounds. GC/ECD average recoveries were 87.1% for trifluralin and 93.6% for linuron in carrots and 89.9% for trifluralin and 94.2% for linuron in carrot pulp. LC/UV recoveries for linuron were 91.5% for carrots and 92.8% for carrot pulp.

A comparison of electron-capture GLC, electrolytic-conductivity GLC and UV-absorption HPLC for the analysis of some herbicides in foods.

A comparison of gas chromatography with electron-capture or electrolytic-conductivity (nitrogen mode) detection, and high-pressure liquid chromatography (HPLC) with UV-absorption detection (254 nm) was carried out for the analysis of several herbicides in foods. Linuron, propanil, terbacil, benzoylprop-ethyl, and the fungicide DCNA in samples of cabbage, corn, potato, and wheat spiked at 2 and 0.2 ppm were examined. The pesticides were extracted with acetone, partitioned into petroleum ether-methylene chloride, and cleaned up on a 2% deactivated Florisil column before direct chromatographic analysis. Electron-capture gas-liquid chromatography (GLC) was most suitable for DCNA and benzoylprop-ethyl while UV-absorption HPLC was best for terbacil analysis. Linuron and propanil gave similar results for both electron-capture GLC and HPLC. Electrolytic-conductivity GLC could detect all pesticides at the 0.2 ppm level and exhibited the least number of extraneous peaks in the chromatograms.

Tetrachloroazobenzene in 3,4-dichloroaniline and its herbicidal derivatives: propanil, diuron, linuron, and neburon.

The presence of 3,3', 4,4'-tetrachloroazobenzene (TCAB) was determined by high performance liquid chromatography in 3, 4-dichloroaniline and herbicides made therefrom. The concentrations of TCAB in 3, 4-dichloroanilines and in different herbicides from a variety of manufacturers ranged from 9 to 1400 micrograms/g (ppm). The chloracnegenic potential of these products, as determined by rabbit ear test, suggests that it is in the same range of 2, 3, 7, 8-tetrachlorodibenzodioxin, a known potent chloracnegenic agent.

["More is not better"--evaluation of toxicologic risks of the heavy metals, lead and cadmium, and the herbicides, linuron, fluazifop-P-butyl and cycloxydim in dried Chamomile flowers (Chamomilla recutita L. Rauschert)]. / "Vise nije bolje"--prilog procjeni toksikoloskog rizika teskih metala olova i kadmija te herbicida linuron, fluazifop-P-butyl i cycloxydim u osusenom cvijetu kamilice (Chamomilla recutita L. Rauschert).

Cadmium and all three enumerated herbicide residues in dried samples of industrially grown true chamomile were found to be above the suggested and accepted tolerance values. The results are discussed with regard to the current Croatian regulation and FAO/WHO recommendations on herbicides and to human toxicology risk assessment. The paper gives a critical evaluation of the herbicide overuse in agricultural practice and strongly discouraged such practice. The authors advocate prospective use of plants as natural indicators of environmental contamination and toxicological burden of the human food chain.