Determination of thermolabile urea pesticides after derivatization with HFBA using GC-ECD and confirmation by means of GC-MSD

Summary The determination of urea pesticides is difficult by means of gas chromatography because they undergo thermal decomposition when applying standardized chromatographic conditions as used in multiresidue analysis. A method is therefore described to make possible the detection of these compounds by gas chromatography after derivatization with HFBA using either electron capture and nitrogen-phosphorus detection or a mass spectrometer as detector.Part of this paper was presented at the Seventh International Congress of Pesticide Chemistry, Hamburg, August 5–10, 1990.     

Application of a micro multiphase laminar flow on a microchip for extraction and determination of derivatized carbamate pesticides.

Determination of carbamate pesticides such as carbaryl, carbofuran, propoxur and bendiocarb was demonstrated on a microchip with newly designed microchannels developed for efficient solvent extraction. The pesticides were hydrolyzed to corresponding naphthols, coupled with p-nitrobenzenediazonium fluoroborate reagent, and then extracted into 1-butanol as colored azo derivatives and detected with a thermal lens microscope. Optimum flow rates for the aqueous and organic phases were evaluated in the continuous-flow chemical process established in the microchip. The calibration lines showed good linearity in the range of concentrations of 0.03 - 3 ppm (10(-7) - 10(-5) M) and a mass detection limit down to a nanogram level was achieved that is at least two orders of magnitude lower than the LODs for conventional spectrophotometric methods. Azo derivatives of the pesticides were successfully separated and identified by micellar electrokinetic chromatography (MEKC) using a sample prepared on a bulk scale.     

Graphene-modified TiO2 nanotube arrays as an adsorbent in micro-solid phase extraction for determination of carbamate pesticides in water samples

Graphene is a good adsorbent for organic pollutants, especially for compounds containing benzene rings. When used in TiO₂ nanotube arrays for micro-solid phase extraction (μ-SPE), the combination of graphene’s strong adsorptive properties with its good separation capabilities results in excellent sample preconcentration performance. In the present study, graphene-modified TiO₂ nanotube arrays were prepared by electrodeposition using a cyclic voltammetric reduction method. Four carbamate pesticides, including metolcarb, carbaryl, isoprocarb, and diethofencarb, were used as model analytes to validate the enrichment properties of the prepared adsorbent in μ-SPE. Factors affecting the enrichment efficiency of the μ-SPE procedure were optimized and included sample pH, elution solvents, salting-out effect, adsorption time and desorption time. Under optimal conditions, graphene-modified TiO₂ nanotube arrays exhibited excellent enrichment efficiency for carbamate pesticides. The detection limits of these carbamate pesticides ranged from 2.27 to 3.26 μg L⁻¹. The proposed method was validated using four environmental water samples, and yields of pesticides recovered from spiked test samples of the four analytes were in the range of 83.9–108.8%. These results indicate that graphene-modified TiO₂ nanotube arrays exhibit good adsorption to the target pollutants, and the method described in this work could be used as a faster and easier alternative procedure for routine analysis of carbamate pesticides in real water samples.     

Concentration and determination of trace amounts of chlorinated pesticides in aqueous samples

Summary A method for the quantitative analysis of the organochloro-pesticides heptachlor, dieldrin, DDT and aldrin in water, using the HPLC technique of on-line trace enrichment, has been developed. A standard HPLC isocratic analytical system was employed the principle modification being the incorporation of a short pre-column across the sample loop connections of a Rheodyne 7125 valve to serve as the trace enrichment column. Pesticide recoveries of >95% were achieved at sample flow rate of 5–15 ml/min by employing stainless steel fittings throughout the system and with 5% methanol included in the pesticide sample reservoir. The pesticides were concentrated onto a 50 mm, 10 m Spherisorb ODS column; analysis was performed on a 25 cm, 5 m Spherisorb ODS column with methanol-water (7525) elution; detection was by UV absorption measurement at 220 mm and 0.64 AUFS.Resolution achieved was >=1.16 and selectivity >=1.14. 100 ml aqueous samples allow ppb detection of the named pesticides in real samples. Total analysis time including concentration and chromatography was less than 30 minutes.     

Electron Donor-Acceptor Complexing Reagents for the Detection of Pesticides on TLC

The formation of π-complexes to detect and identify a representative group of carbamate, anilide and urea pesticides was investigated. Results obtained with several electron-acceptor reagents used by previous workers are compared with those obtained with a group of nitro-substituted fluorene derivatives. The pesticides studied were chosen for their potential ability to act as electron donors. Detection limits after thin-layer chromatography ranged from 0.5 to 5.0 micrograms, depending upon the strength of the complex formed. Various chromatographic systems were studied and applications of in situ reflectance spectroscopy and mass spectrometry were investigated. The method combines a reasonable sensitivity with good selectivity and the pesticide may be recovered from the complex for further study. This non-destructive method of analysis should be of particular use in the separation and identification of these pesticides and their metabolites.     

Derivatization reactions of carbamate pesticides in supercritical carbon dioxide

Supercritical fluid carbon dioxide (SC-CO(2)) has been used to dissolve derivatizing agents (e.g. heptafluorobutyric anhydride, HFBA, and pyridine), which also act as a modifier in the fluid phase, for simultaneous extraction and derivatization of carbamates from the sample matrix. The derivatized carbamate pesticides (carbaryl, 3-hydroxycarbofuran, carbofuran, aldicarb, methiocarb) were then analyzed by GC-ECD or GC-MS with excellent sensitivity. Extraction and conversion of the carbamates was complete, as indicated by HPLC with post-column hydrolysis and o-phthalaldehyde derivatization then fluorescence detection. GC-MS (ion trap) was also used to confirm the formation of the carbamate derivatives. Compared with the same HFBA reaction in an organic solvent the derivatization reaction time was considerably shorter in SC-CO(2.) The described approach, combining both extraction and derivatization, simplifies the analysis of carbamate pesticides and eliminates the use of organic solvents associated with the derivatization step.     

Solubility of some pesticides in supercritical CO2

Summary The solubility limits of some pesticides (Linuron, Methoxychlor, Diclofopmethyl, Diclofop and 2,4-D) and of 3,4-dichloroaniline have been determined in supercritical CO₂ at 200 bar and 40° C, using the Milton Roy sample preparation accessory SPA^TM. Depending on the polarity and vapour pressure of the investigated compounds, the solubility was found to be between 0.3 and 12 gl^–1.

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Löslichkeit einiger Pesticide in überkritischem CO₂

     

Determination of polar pesticides in water, vegetables, and fruits by high performance liquid chromatography

The methods for determining 25 combined pesticides (neonicotinoids, imidazole derivatives, urea derivatives, sim-triazines, triazoles, carbamates, organophosphorous compounds, pirethroids) in water, vegetables, and fruits in the concentration range of 0.005–10 mg/L (mg/kg) have been developed by the HPLC method with diode matrix detection at 220 nm. The determination of pesticides in water was carried out without the preparation or concentration of the sample. In the analysis of vegetables and fruits (pestcides extraction and extract purification), the preparation of the sample was performed by the QuEChERS method. The duration of analysis is 0.5–1.0 h, and the relative standard deviation of analysis results does not stand out above 0.05.     

Determination of polar pesticides in soil by micellar electrokinetic chromatography using QuEChERS sample preparation

The optimal conditions for the separation of pesticides of the following classes: phenoxy carboxylic acids, sim-triazines, triazinones, chloroacetamides, urea derivatives, neonicotinoids, carbamates, triazoles, imidazoles, benzimidazoles, and phosphorus organic compounds by micellar electrokinetic chromatography have been selected. A method for determining 27 polar pesticides in soil using QuEChERS sample preparation has been developed. The recovery of pesticides was from 31 to 104%. The lower limits of the found pesticide concentrations in soil taking into account preconcentration were 0.01–0.4 mg/kg. The relative standard deviation of the results of analysis does not exceed 10%.     

Multiresidue method for the determination of 227 pesticides in hot pepper (Capsicum annuum L.) by liquid chromatography with tandem mass spectrometry†

A high‐throughput, rapid, and efficient modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method with a simple cleanup procedure has been developed for simultaneously determining 227 pesticides in pepper samples by liquid chromatography with tandem mass spectrometry (running time: 10 min). Pesticide residues were extracted/partitioned with an acetonitrile/DisQuE QuEChERS pouch, and the resulting samples were cleaned up with different methods: dispersive solid‐phase extraction with primary secondary amines or multiwalled carbon nanotubes and graphitized carbon solid mini cartridge column. The results indicated that multiwalled carbon nanotubes dispersive sorbents achieved the best recoveries and had less matrix interference. The numbers of pesticides with a recovery in the range of 70–120% were 199 at a spiked level of 40 μg/kg. The correlation coefficients (r²) for 227 pesticides were above 0.99, while the limits of quantitation of pesticides in pepper samples ranged from 0.13 to 13.51 μg/kg (S/N = 10), and the limits of detection ranged from 0.04 to 4.05 μg/kg (S/N = 3). The relative standard deviations of approximately 197 pesticides were below 20% at spiked levels of 40 μg/kg. Based on these results, the proposed method was chosen as the most suitable cleanup procedure for the determination of multiresidue pesticides in pepper samples.     

Cholinesterase-based dipstick assay for the detection of organophosphate and carbamate pesticides

A cholinesterase (ChE)-based dipstick-type assay for the class-specific detection of organophosphate (OP) and carbamate (CM) pesticides was developed. The principle of the assay is based on inhibition of the activity of a ChE by these two families of pesticides, which is dependent on the concentration of pesticides. The proposed assay system is composed of a test strip with an acetylcholinesterase (AChE)-coated membrane and an enzyme substrate solution. The assay protocol involves incubation of the enzyme-coated strip in the pesticide-containing sample solution followed by incubation of the sample-treated strip in a chromogenic enzyme substrate solution. The color intensity is estimated by the naked eye or a reflectometer. Of the membranes tested as the enzyme support, Hybond N⁺ was the most suitable. Among the compounds tested as the enzyme substrate, indophenyl acetate was the best. The detectable concentration range of the dipstick assay for the OP and CM pesticides was 10⁻⁶-10² and 10⁻⁶-10⁰ μg mL⁻¹, respectively. The sensitivity of the dipstick assay to the oxidized form of parathion (paraoxon) was higher than to parathion. The strip showed a large matrix effect with pesticide-spiked lettuce samples, whereas it showed a small matrix effect with pesticide-spiked rice samples.     

Supercritical fluid extraction of carbamate pesticides from soils and cereals

Summary A method for the supercritical fluid extraction of carbamate pesticides (propoxur, aminocarb, carbaryl and methiocarb) from soil and cereal samples using CO₂ is proposed. Extractions were at 378 bar and 54 °C. Analytes were determined in the extracts by HPLC with fluorescence detection after post-column derivatization. Recoveries from spiked soil ranged between 39.6 and 91.7%, depending on analyte and soil components. Lowest recoveries were from sandy soils. Aminocarb could not be recovered from any soil using CO₂. Recovery of aminocarb from diatomaceous earth was improved by adding methanol to the extraction cell prior to SFE, but the effect was not observed in soil samples. Recoveries for propoxur and aminocarb from spiked wheat were about 75%, and only between 30–50% for aminocarb from corn and oats, and carbaryl from wheat. Fat was coextracted using CO₂ and retained in the trap together with the analytes, however, appropriate rinsing solvent allowed on-line clean-up of the extract.     

Simultaneous determination of 64 pesticides in river water by stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry

A method for determining 68 pesticides in river water using stir bar sorptive extraction (SBSE)-thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS) is described. SBSE sampling was optimized for sample solution pH, salting-out and methanol addition. Although salting-out enhanced the ability of the method to extract most of the pesticides with low absolute recoveries, the absolute recoveries of four pesticides were not improved by salting-out. The detection limits of the method for the pesticides ranged from 0.2 to 20 ng/l. Analyte recoveries from a river water sample spiked with standards at 10 and 100 ng/l were 58.5–132.0% (RSD: 1.8–15.8%) and 61.0–121.3% (RSD: 1.4–20.2%), respectively.     

Retention and selectivity properties of carbamate pesticides on novel polar-embedded stationary phases

This study describes the use of stationary phases with polar functionality suitable for the chemical analysis of carbamates pesticides and comparing with conventional alkyl C8 and C18 phases. The emphasis of this study was to compare the selectivity and retention of the pesticides on different stationary phases, bonded onto 1.7 μm partially porous silica particles under isocratic separation condition. Four stationary phases including: phenylaminopropyl (PAP) phase, bidentate propylurea-C18 (BPUC₁₈), C8 and C18, were successfully bonded on the partially porous silica spheres as evidenced by ²⁹Si and ¹³C solid-state NMR analysis. The phenylaminopropyl phase exhibited smaller retentivity and enhanced selectivity compared to the alkyl C8 phase; the analysis time to run separation of the six carbamate pesticides (i.e., methomyl, propoxur, carbofuran, carbaryl, isoprocarb, and promecarb) on the PAP phase was threefold faster than alkyl C8 phase. In a similar manner, the BPUC₁₈ phase shows similar selectivity to that of the PAP phase, but with longer retentivity; although the BPUC₁₈ phase is characterized with a lesser degree of retentivity for the carbamate pesticides than the conventional alkyl C18 phase. We propose that π–π and weak polar interactions between the carbamate pesticides and the PAP phase dominates the separation mechanism and providing a superior selectivity; faster separation time was also achieved as a result of smaller retentivity. Whereas the C8 and C18 bonded phases exhibits only hydrophobic interactions with the pesticides, leading to larger retentivity. The BPUC₁₈ phase is shown to interact via polar–polar interactions in addition to hydrophobic interactions with the pesticides, providing similar selectivity with the PAP phase but with larger retentivity.     

Investigation of preconcentration strategies for the trace analysis of multi-residue pesticides in real samples by capillary electrophoresis

In this work, on-line preconcentration strategies were investigated for the multi-residue analysis of pesticides in drinking water and vegetables using micellar electrokinetic chromatography. Among the on-line strategies, sweeping and stacking with reverse migration of micelles (SRMM), with and without the insertion of a plug of water before sample injection, were contrasted. A new version of SRMM was also introduced. The modification consisted of momentarily applying a positive voltage at the inlet vial right after sample has been injected, increasing the efficiency by which the analytes are captured. Nine pesticides from different classes, carbendazim (benzimidazole), simazine, atrazine, propazine and ametryn (triazine), diuron and linuron (urea), carbaryl and propoxur (carbamate), were baseline separated in less than 6 min with a electrolyte composed of 20 mmol l(-1) phosphate buffer at pH 2.5, containing 25 mmol l(-1) sodium dodecyl sulfate and 10% methanol. Limits of detection (LODs) in the order of 2-46 microg l(-1) for the pesticides under investigation were obtained solely using the on-line strategies. Enrichment factors of 3-18-fold were obtained. These factors were computed as the improvement of the concentration LODs with respect to the reference condition (injection of 10 s at 2.5 kPa pressure). The proposed methodologies were applied to the analysis of pesticides in complex matrices such as carrot extracts where the detection of 2.5 microg l(-1) was illustrated. By combining off-line solid-phase extraction and the proposed on-line strategies, the detection of pesticides in drinking water at the 0.1 microg l(-1) level was conceived.     

Comparison of Different d-SPE Sorbent Performances Based on Quick,Easy, Cheap,Effective, Rugged,and Safe (QuEChERS) Methodology for Multiresidue Pesticide Analyses in Rapeseeds

Pesticide extraction in rapeseed samples remains a great analytical challenge due to the complexity of the matrix, which contains proteins, fatty acids, high amounts of triglycerides and cellulosic fibers. An HPLC-MS/MS method was developed for the quantification of 179 pesticides in rapeseeds. The performances of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method were evaluated using different dispersive solid-phase extraction (d-SPE) sorbents containing common octadecylsilane silica/primary–secondary amine adsorbent (PSA/C18) and new commercialized d-SPE materials dedicated to fatty matrices (Z-Sep, Z-Sep⁺, and EMR-Lipid). The analytical performances of these different sorbents were compared according to the SANTE/12682/2019 document. The best results were obtained using EMR-Lipid in terms of pesticide average recoveries (103 and 70 of the 179 targeted pesticides exhibited recoveries within 70–120% and 30–70%, respectively, with low RSD values). Moreover, the limits of quantification (LOQ) range from 1.72 µg/kg to 6.39 µg/kg for 173 of the pesticides. Only the recovery for tralkoxydim at 10 μg/kg level was not satisfactory (29%). The matrix effect was evaluated and proved to be limited between −50% and 50% for 169 pesticides with this EMR-Lipid and freezing. GC-Orbitrap analyses confirmed the best efficiency of the EMR-Lipid sorbent for the purification of rapeseeds.     

The high throughput analysis of N-methyl carbamate pesticides in wine and juice by electrospray ionization liquid chromatography tandem mass spectrometry with direct sample injection into a short column

We developed a new analysis method for the N-methyl carbamate pesticides in juice and wine. The juice and wine were diluted with ultra pure water, and determined by electrospray ionization tandem mass spectrometry (ESI LC/MS/MS) with direct sample injection into a short column. The new method, including sample preparation and determination, is simple and rapid, and allows simultaneous determination of nine N-methyl carbamate pesticides in juice and wine within analysis time that is much shorter as compared with the traditional method. The average recoveries from juice and wine fortified at the level of 0.1 ppm ranged from 59.6 to 126.7% with the coefficients of variation ranging from 0.4 to 5.1% for intra-day (n = 5 × 3 days) and from 0.5 to 22.6% for inter-day (n = 15). At the fortified level of 0.5 ppm, the recoveries ranged from 69.3 to 127.2% with the coefficients of variation ranging from 0.4 to 6.9% for intra-day (n = 5 × 3 days) and from 0.5 to 22.6% for inter-day (n = 15). The method is considered to be satisfactory for the monitoring of the carbamate pesticides residues in juice and wine, suggesting that the present method is applicable to other pesticide residues in foods.     

A highly sensitive,dual-signal assay based on rhodamine B covered silver nanoparticles for carbamate pesticides

A highly sensitive sensor for determination of carbamate pesticides based rhodamine B (RB) modified silver nanoparticle (RB-AgNPs) was developed. Compared with the classical method, it combined colorimetric with fluorescence for detecting carbamate pesticides in complex solutions. Carbamate pesticides can inhibit the activity of acetylcholinesterase (AChE), thus preventing the generation of thiocholine. On the other hand, thioncholine can transform the yellow RB-AgNPs solutions gray color and unquenches the fluorescence of RB simultaneously. Once the activity of AChE was inhibited by the pesticide, the color of the RB-AgNPs solution remains yellow and the fluorescence of RB molecules remains quenched. Under optimized experimental conditions, carbaryl was detected in a concentration range from 0.1 ng/L to 8.0 ng/L with a detection limit of 0.023 ng/L (it was detected by fluorescence spectra). This simple method is suitable for determination of carbamate pesticides in complex samples, such as tomato, apple and river water.     

Synthesis of Nitrogen-Containing Phenoxyacetic Acid Derivatives

Nitrogen-containing phenoxyacetic acid derivatives were synthesized by reactions of substituted phenoxyacetic acids with amines, urea, and ethyl carbamate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 4, 2005, pp. 557–561.Original Russian Text Copyright © 2005 by Yamansarova, Kukovinets, Zainullin, Galin, Abdullin.