Multi-residue determination of organophosphorus and organochlorine pesticides in environmental samples using solid-phase extraction with cigarette filter followed by gas chromatography-mass spectrometry

A solid‐phase extraction (SPE) method was developed to extract 14 pesticides simultaneously from environment samples using cigarette filter as the sorbent before gas chromatography‐mass spectrometry (GC‐MS) analysis. Parameters influencing the extraction efficiency, such as the sample loading flow rate, eluent and elution volume, were optimized. The optimum sample loading rate was 3 mL/min, and the retained compounds were eluted with 6 mL of eluent at 1 mL/min under vacuum. Good linearity was obtained for all the 14 pesticides (r²>0.99) from 0.1 to 20 μg/L for water and from 2 to 400 μg/kg for soil samples. The detection limits (signal‐to‐noise=3) of the proposed method ranged from 0.01 to 0.20 μg/L for water samples and from 0.42 to 6.95 μg/kg for soil samples. The developed method was successfully applied for determination of the analytes in real environmental samples, and the mean recoveries ranged from 76.4 to 103.7% for water samples and from 79.9 to 105.3% for soil samples with the precisions (relative standard deviation) between 2.0 and 13.6%.     

Application of pneumatic nebulization single‐drop microextraction for the determination of organophosphorous pesticides by gas chromatography–mass spectrometry

Organophosphorous pesticides (OPPs) including dichlorvos, diazinon, malathion, phenamiphos and chlorpyrifos, in water samples were extracted by pneumatic nebulization single‐drop microextraction (PN‐SDME) and then determined by gas chromatography–mass spectrometry (GC‐MS). Experimental parameters affecting the performances of PN‐SDME, such as flow rate of carrier gas, extraction time and microdrop volume, were examined and optimized. The limits of detection for the analytes were in the range of 0.0014–0.0019 μg/mL. The linear range was 0.0050–0.50 μg/mL, except dichlorvos (0.0070–0.50 μg/mL). Water samples were analyzed and the recoveries of the analytes in the spiked water samples were from 75.2 to 105.3%. The relative standard deviations were lower than 12.7%.     

Development of a procedure for the multiresidue analysis of pesticides in vineyard soils and its application to real samples

A procedure for multiresidue analysis was developed for the extraction and determination of 17 pesticides, including herbicides, fungicides, and insecticides, as well as certain degradation products, in vineyard soils from La Rioja region (Spain). Different solvents and mixtures were tested in spiked pesticide‐free soils, and pesticides were comparatively evaluated by gas chromatography with mass spectrometry and liquid chromatography with mass spectrometry. Recoveries >70%, with relative standard deviations <9%, were obtained when a mixture of methanol/acetone or a mixture of methanol/CaCl₂ 0.01 M for the most polar compounds was selected as the extraction solvent. Method validation was accomplished with acceptable linearity (r² ≥ 0.987) within the concentration range of 0.005–1 μg/mL corresponding to 1.667–333.4 μg/kg and 0.835–167.1 μg/kg for liquid chromatography with mass spectrometry and gas chromatography with mass spectrometry, respectively, and detection limits <0.4 μg/kg for the compounds were studied. The extraction method was applied to 17 real vineyard soil samples, and terbuthylazine and its metabolite desethylterbuthylazine were the most ubiquitous compounds, as they were detected in the 100% of the soils analyzed. The presence of fungicides was also high, and the presence of insecticides was lower than other pesticides. The results confirm the usefulness of the optimized procedure for monitoring residues in vineyard soils.     

Development of a single‐run analytical method for the detection of ten multiclass emerging contaminants in agricultural soil using an acetate‐buffered QuEChERS method coupled with LC–MS/MS

This study was undertaken to develop and validate a single multiresidue method for the monitoring of ten multiclass emerging contaminants, viz. ceftiofur, clopidol, florfenicol, monensin, salinomycin, sulfamethazine, sulfathiazole, sulfamethoxazole, tiamulin, and tylosin in agricultural soil. Samples were extracted using an acetate‐buffered, modified quick, easy, cheap, effective, rugged, and safe method followed by liquid chromatography with tandem mass spectrometric analysis in positive ion mode. Separation on an Eclipse Plus C₁₈ column was conducted in gradient elution mode using a mobile phase of methanol (A) and distilled water (B), each containing 0.1% formic acid and 5 mM ammonium formate. The linearity of the matrix‐matched calibrations, expressed as determination coefficients, was good, with R ² ≥ 0.9908. The limits of quantification were in the range 0.05–10 μg/kg. Blank soil samples spiked with 4 × and 20 × the limit of quantification provided recovery rates of 60.2–120.3% (except sulfamethoxazole spiked at 4 × the limit of quantification, which gave 131.9%) with a relative standard deviation < 13% (except clopidol spiked at 20 × the limit of quantification, which gave 25.2%). This method was successfully applied to the monitoring of 51 field‐incurred agricultural loamy‐sand soil samples collected from 17 provincial areas throughout the Korean Peninsula. The detected and quantified drugs were clopidol (≤ 4.8 μg/kg), sulfathiazole (≤ 7.7 μg/kg), sulfamethazine (≤ 6.6 μg/kg), tiamulin (≤ 10.0 μg/kg), and tylosin (≤ 5.3 μg/kg). The developed method is simple and versatile, and can be used to monitor various classes of veterinary drugs in soil.     

Pesticides and degradation products in groundwaters from a vineyard region: Optimization of a multiresidue method based on SPE and GC‐MS

A reliable multiresidue method based on solid phase extraction was developed using GC–MS to determine and quantify 34 pesticides, including herbicides, fungicides, insecticides, and some of their degradation products, in groundwater in a vineyard region of La Rioja (northern Spain). Different parameters were optimized and good recoveries (65–108% range) and precisions (12–19% range) were achieved with spiked water samples for a concentration of 0.1 μg/L. The experimental results showed an excellent linearity (r² > 0.99) over the 0.1–1.5 μg/L range. The detection limits of the proposed method were 1–37 ng/L for most of the compounds studied. The methodology has been successfully applied to the analysis of groundwater samples from vineyard areas in La Rioja and the presence of pesticides, especially fungicides and herbicides, at several concentration levels was revealed. Terbuthylazine, its metabolite desethyl‐terbuthylazine, and fluometuron were the pesticides most frequently detected in higher concentrations. Overall and taking into consideration the European Union maximum residue limit of pesticides in groundwater, 16 of the 34 compounds included in this study were detected in concentrations over that limit in at least one of the samples analyzed.     

Multiresidue analysis of 36 pesticides in soil using a modified quick,easy, cheap,effective, rugged,and safe method by liquid chromatography with tandem quadruple linear ion trap mass spectrometry

A new method for simultaneous determination of 36 pesticides, including 15 organophosphorus, six carbamate, and some other pesticides in soil was developed by liquid chromatography with tandem quadruple linear ion trap mass spectrometry. The extraction and clean‐up steps were optimized based on the quick, easy, cheap, effective, rugged, and safe method. The data were acquired in multiple reaction monitoring mode combined with enhanced product ion to increase confidence of the analytical results. Validation experiments were performed in soil samples. The average recoveries of pesticides at four spiking levels (1, 5, 50, and 100 μg/kg) ranged from 63 to 126% with relative standard deviation below 20%. The limits of detection of pesticides were 0.04–0.8 μg/kg, and the limits of quantification were 0.1–2.6 μg/kg. The correlation coefficients (r²) were higher than 0.990 in the linearity range of 0.5–200 μg/L for most of the pesticides. The method allowed for the analysis of the target pesticides in the lower μg/kg concentration range. The optimized method was then applied to the test of real soil samples obtained from several areas in China, confirming the feasibility of the method.     

Development and validation of a multiresidue method for determination of 37 pesticides in soil using GC-NPD

In this study, a multiresidue analytical method for the detection of 37 pesticides in a soil matrix was developed and validated. The soil sample was fortified with a known quantity of pesticides at two different concentration levels (0.1 and 0.01 µg/g) and the analytes were extracted via a liquid–solid extraction method. The pesticides were separated on an HP5 capillary column and were analyzed with a gas chromatograph coupled to a nitrogen–phosphorous detector (GC‐NPD). Method validation was accomplished with good linearity (r² = 0.994–0.999) within a considerable range of concentrations. Satisfactory recoveries (70.5–110.4%) were obtained with 32 pesticides at both spiking concentration levels, whereas five pesticides—dimepiperate, buprofezin, prometryn, pirimicarb, and fludioxonil—were recovered at relatively low levels (43.6–61.8%). The applicability of the method was demonstrated by analyzing field samples collected from 24 different sites around Yeongsan and Sumjin rivers in the Republic of Korea. No residues of the selected pesticides were detected in any of the samples. The developed method could be employed as a simple and cost‐effective method for the routine detection and analysis of 37 pesticides in soil samples. Copyright © 2010 John Wiley & Sons, Ltd.     

Simultaneous determination of three organophosphorus pesticides in different food commodities by gas chromatography with mass spectrometry

A sensitive and selective gas chromatography with mass spectrometry method was developed for the simultaneous determination of three organophosphorus pesticides, namely, chlorpyrifos, malathion, and diazinon in three different food commodities (milk, apples, and drinking water) employing solid‐phase extraction for sample pretreatment. Pesticide extraction from different sample matrices was carried out on Chromabond C₁₈ cartridges using 3.0 mL of methanol and 3.0 mL of a mixture of dichloromethane/acetonitrile (1:1 v/v) as the eluting solvent. Analysis was carried out by gas chromatography coupled with mass spectrometry using selected‐ion monitoring mode. Good linear relationships were obtained in the range of 0.1–50 μg/L for chlorpyrifos, and 0.05–50 μg/L for both malathion and diazinon pesticides. Good repeatability and recoveries were obtained in the range of 78.54–86.73% for three pesticides under the optimized experimental conditions. The limit of detection ranged from 0.02 to 0.03 μg/L, and the limit of quantification ranged from 0.05 to 0.1 μg/L for all three pesticides. Finally, the developed method was successfully applied for the determination of three targeted pesticides in milk, apples, and drinking water samples each in triplicate. No pesticide was found in apple and milk samples, but chlorpyrifos was found in one drinking water sample below the quantification level.     

Determination of trace organophosphorus pesticides in water samples with TiO2 nanotubes cartridge prior to GC‐flame photometric detection

This article described a new method for the sensitive determination of organophosphorus pesticides in water samples using SPE in combination with GC‐flame photometric detection. In the procedure of method development, TiO₂ nanotubes were used as SPE adsorbents for the enrichment of organophosphorus pesticides from water samples. Several factors, such as eluent and its volume, sample pH, sample volume, sample flow rate, and concentration of humic acid, were optimized. Under the optimal conditions, the proposed method had good linear ranges as 0.1–40 μg/L for each of them, LOD of 0.11, 0.014, and 0.0025 μg/L, and LOQs of 0.37, 0.047, and 0.0083 μg/L for chlorpyrifos, phorate, and methyl parathion, respectively. The proposed method was validated with real environmental water samples and the spiked recoveries were over the range of 86.5–115.1%. All these results indicated that TiO₂ nanotubes, as a new SPE adsorbent, would be used widespread for the preconcentraiton and determination of environmental pollutants in the future.     

Simultaneous determination of thiamethoxam,clothianidin, and metazachlor residues in soil by ultrahigh performance liquid chromatography coupled to quadrupole time‐of‐flight mass spectrometry

A rapid pioneering method has been developed to simultaneously determine residues of three pesticides (thiamethoxam, clothianidin, and metazachlor) in soil by ultrahigh performance liquid chromatography coupled to a mass spectrometry detector (quadrupole time‐of‐flight). An efficient extraction procedure (90–105% average analyte recoveries) has also been proposed, involving solid–liquid extraction by a mixture of water and methanol (60:40, v/v), centrifugation, and concentration. A chromatographic analysis of the compounds was achieved in 5.5 min by means of a core–shell technology based column (Kinetex^® EVO C₁₈, 50 × 2.1 mm, 1.7 μm, 100 Å). The mobile phase (0.3 mL/min, gradient elution mode) consisted of 0.1% v/v formic acid in water and 0.1% v/v formic acid in acetonitrile. The method was fully validated in terms of selectivity, detection and quantification limits, matrix effect, linearity, trueness, and precision. Low limits of detection and quantification were obtained, ranging from 0.2 to 3.0 μg/kg, which are similar to those published in previous studies, while the absence of a significant matrix effect allowed quantification of the pesticides with standard calibration curves. The proposed method was applied for an analysis of pesticides in several soil samples from experimental fields dedicated to oilseed rape cultivars.     

Analytical method for 44 pesticide residues in spinach using multi‐plug‐filtration cleanup based on multiwalled carbon nanotubes with liquid chromatography and tandem mass spectrometry detection

Spinach is one of the most commonly planted vegetables worldwide. A high chlorophyll content makes spinach a complicated matrix in pesticide residue analysis. In this study, a rapid clean‐up method was developed for the analysis of pesticide multi‐residues in spinach followed by liquid chromatography with tandem mass spectrometry. A modified QuEChERS method with multiwalled carbon nanotubes and carbon material was adopted in the multi‐Plug Filtration Cleanup procedure. This method was validated for 44 representative pesticides spiked at two concentration levels of 10 and 100 μg/kg. The pesticides of different physicochemical properties were registered on spinach in China. The recoveries were between 76 and 114% for major pesticides with relative standard deviations of less than 15%, except for quizalofop‐P‐ethyl, pyrimethanil, and carbendazim. Matrix‐matched calibration curves were performed with the coefficients of determination higher than 0.995 for the studied pesticides for concentration levels of 10–500 μg/kg. The limits of quantitation ranged from 2 to 10 μg/kg. The developed method was successfully applied to determine pesticide residues in Chinese market spinach samples.     

Fast ultrasound‐assisted extraction followed by capillary gas chromatography combined with nitrogen–phosphorous selective detector for the trace determination of tebuconazole in garlic,soil and water samples

A fast and an efficient ultrasound‐assisted extraction technique using a lower density extraction solvent than water was developed for the trace‐level determination of tebuconazole in garlic, soil and water samples followed by capillary gas chromatography combined with nitrogen–phosphorous selective detector (GC–NPD). In this approach, ultrasound radiation was applied to accelerate the emulsification of the ethyl acetate in aqueous samples to enhance the extraction efficiency of tebuconazole without requiring extra partitioning or cleaning, and the use of capillary GC–NPD was a more sensitive detection technique for organonitrogen pesticides. The experimental results indicate an excellent linear relationship between peak area and concentration obtained in the range 1–50 μg/kg or μg/L. The limit of detection (S/N, 3 ± 0.5) and limit of quantification (S/N, 7.5 ± 2.5) were obtained in the range 0.2–3 and 1–10 μg/kg or μg/L. Good spiked recoveries were achieved from ranges 95.55–101.26%, 96.28–99.33% and 95.04–105.15% in garlic, Nanivaliyal soil and Par River water, respectively, at levels 5 and 20 μg/kg or μg/L, and the method precision (% RSD) was ≤5%. Our results demonstrate that the proposed technique is a viable alternative for the determination of tebuconazole in complex samples.     

Simultaneous determination of anthracyclines and taxanes in human serum using online sample extraction coupled to high performance liquid chromatography with UV detection

An online SPE‐LC method that can determine both anthracyclines and taxanes simultaneously in human serum samples is reported. The entire method of extraction, separation and UV detection was achieved online by column switching between an SPE column (Biotrap 500 (20×4 mm)) and an analytical column (Zorbax XDB C18, 150×4.6 mm, 5 μm) with a 23 min total cycle time. The method is linear (r²>0.998) over the range of 0.5–25 μg/mL. The analytes of interest are retained on the SPE column with good recovery (84–117%), while proteins and other serum components elute to waste. This online clean‐up is much faster (150 s) and less manual than traditional off‐line extraction methods. Using 0.1 mL spiked serum samples, the LOQ was 0.5 μg/mL. Intra‐ and inter‐day precision were acceptable (≤15% RSD) at and above the LOQ. The method was applied to the analysis of serum samples from patients undergoing chemotherapy with these agents.     

Vortex‐assisted liquid–liquid microextraction using a low‐toxicity solvent for the determination of five organophosphorus pesticides in water samples by high‐performance liquid chromatography

Vortex‐assisted liquid–liquid microextraction followed by high‐performance liquid chromatography with UV detection was applied to determine Isocarbophos, Parathion‐methyl, Triazophos, Phoxim and Chlorpyrifos‐methyl in water samples. 1‐Bromobutane was used as the extraction solvent, which has a higher density than water and low toxicity. Centrifugation and disperser solvent were not required in this microextraction procedure. The optimum extraction conditions for 15 mL water sample were: pH of the sample solution, 5; volume of the extraction solvent, 80 μL; vortex time, 2 min; salt addition, 0.5 g. Under the optimum conditions, enrichment factors ranging from 196 to 237 and limits of detection below 0.38 μg/L were obtained for the determination of target pesticides in water. Good linearities (r > 0.9992) were obtained within the range of 1–500 μg/L for all the compounds. The relative standard deviations were in the range of 1.62–2.86% and the recoveries of spiked samples ranged from 89.80 to 104.20%. The whole proposed methodology is simple, rapid, sensitive and environmentally friendly for determining traces of organophosphorus pesticides in the water samples.     

Bioanalytical method for the estimation of co‐administered esomeprazole,leflunomide and ibuprofen in human plasma and in pharmaceutical dosage forms using micellar liquid chromatography

The present study represents a connection between basic science and clinical applied science through providing a bioanalytical method for the analysis of certain co‐administered drugs used for the treatment of rheumatoid arthritis. The studied drugs are esomeprazole, leflunomide and ibuprofen. The proposed bioanalytical method is a simple reversed phase high performance liquid chromatographic method using micellar mobile phase. The method is conducted using a Shim‐pack VP‐ODS (150 mm × 4.6 mm ID) stainless steel column at ambient temperature with ultraviolet detection at 285 nm. The micellar mobile phase consisted of 0.1 m sodium dodecyl sulfate, 10% n‐propanol, 0.3% triethylamine in 0.02 m orthophosphoric acid (pH 3.5) and is pumped at a flow rate of 1.0 mL/min. The calibration curve was rectilinear over the concentration range of 0.1–5.0, 0.5–10.0 and 1.0–20.0 μg/mL for esomeprazole, leflunomide and ibuprofen respectively. The proposed method was successfully applied to the analysis of these drugs in dosage forms. The method is extended to the in‐vitro , in‐vivo determination of these drugs in spiked and real human plasma samples.     

Simultaneous extraction and determination of various pesticides in environmental waters

A simple and rapid method was developed for the simultaneous analysis of nine different pesticides in water samples by gas chromatography with mass spectrometry. A number of parameters that may affect the recovery of pesticides, such as the type of solid‐phase extraction cartridge, eluting solvent in single or combination and their volumes, and water pH value were investigated. It showed that three solid‐phase extraction cartridges (Strata‐X, Oasis HLB, and ENVI‐18) produced the greatest recovery while ethyl acetate/dichloromethane/acetone (45:10:45, 12 mL) followed by dichloromethane (6 mL) was efficient in eluting target pesticides from solid‐phase extraction cartridges. Different water pH values (4–9) did not show a significant effect on the pesticides recovery. The optimized method was verified by performing spiking experiments with a series of concentrations (0.002–10 μg/L) in waters, with good linearity, recovery, and reproducibility for most compounds. The limit of detection and limit of quantification of this optimized method were 0.01–2.01 and 0.02–6.71 ng/L, respectively, much lower than the European Union environmental quality standard for the pesticides (0.1 μg/L) in waters. The proposed method was further validated by participation in an interlaboratory trial. It was then subsequently applied to river waters from north‐east Scotland, UK, for the determination of the target pesticides.     

Multiplug filtration clean‐up with multiwalled carbon nanotubes in the analysis of pesticide residues using LC–ESI‐MS/MS

A novel design for a rapid clean‐up method was developed for the analysis of pesticide residues in fruit and vegetables followed by LC–ESI‐MS/MS. The acetonitrile‐based sample extraction technique was used to obtain the extracts, and further clean‐up was carried out by applying the streamlined procedure on a multiplug filtration clean‐up column coupled with a syringe. The sorbent used for clean‐up in this research is multiwalled carbon nanotubes, which was mixed with anhydrous magnesium sulfate to remove water from the extracts. This method was validated on 40 representative pesticides and apple, cabbage, and potato sample matrices spiked at two concentration levels of 10 and 100 μg/kg. It exhibited recoveries between 71 and 117% for most pesticides with RSDs < 15%. Matrix‐matched calibrations were performed with the coefficients of determination >0.995 for most studied pesticides between concentration levels of 10–500 μg/L. The LOQs for 40 pesticides ranged from 2 to 50 μg/kg. The developed method was successfully applied to the determination of pesticide residues in market fruit and vegetable samples.     

Leaching of Triazine Pesticides in Loamy Soil and their Determination by Reversed Phase HPLC

Abstract

The separation and identification of triazine pesticides (ametryn, atrazine, cyanazine and simazine) was carried out on Nova Pak C₁₈ column (150 × 3.9mm). The mobile phase used was acetonitrile-water (65:35, v/v) adjusted to pH 4.5 with acetic acid. The flow rate of the mobile phase used was 1.0mL/min. The detection of the pesticides was carried out at 250 nm. The values of the separation factor (α) were in the range of 1.49–5.32 and the values of the resolution factors (R _s) were ranged from 1.18 to 2.99 for the separated pesticides. The developed HPLC method was used to determine the concentrations of the reported pesticides in the loamy soil samples. The recovery of the pesticides from soil samples was found to be about 50%. The relative standard deviation and limit of detection were in the range of 0.01–0.02 and 0.5–1.0 μg/mL respectively.     

Study of immobilized metal affinity chromatography sorbents for the analysis of peptides by on‐line solid‐phase extraction capillary electrophoresis‐mass spectrometry

Several commercial immobilized metal affinity chromatography sorbents were evaluated in this study for the analysis of two small peptide fragments of the amyloid β‐protein (Aβ) (Aβ(1–15) and Aβ(10–20) peptides) by on‐line immobilized metal affinity SPE‐CE (IMA‐SPE‐CE). The performance of a nickel metal ion (Ni(II)) sorbent based on nitrilotriacetic acid as a chelating agent was significantly better than two copper metal ion (Cu(II)) sorbents based on iminodiacetic acid. A BGE of 25 mM phosphate (pH 7.4) and an eluent of 50 mM imidazole (in BGE) yielded a 25‐fold and 5‐fold decrease in the LODs by IMA‐SPE‐CE‐UV for Aβ(1–15) and Aβ(10–20) peptides (0.1 and 0.5 μg/mL, respectively) with regard to CE‐UV (2.5 μg/mL for both peptides). The phosphate BGE was also used in IMA‐SPE‐CE‐MS, but the eluent needed to be substituted by a 0.5% HAc v/v solution. Under optimum preconcentration and detection conditions, reproducibility of peak areas and migration times was acceptable (23.2 and 12.0%RSD, respectively). The method was more sensitive for Aβ(10–20) peptide, which could be detected until 0.25 μg/mL. Linearity for Aβ(10–20) peptide was good in a narrow concentration range (0.25–2.5 μg/mL, R² = 0.93). Lastly, the potential of the optimized Ni(II)‐IMA‐SPE‐CE‐MS method for the analysis of amyloid peptides in biological fluids was evaluated by analyzing spiked plasma and serum samples.     

Multi-residue determination of organochlorine pesticides in vegetables in Kirklareli,Turkey by gas chromatography–mass spectrometry

The aim of this study was to investigate the level of organochlorine pesticides use for treatment of tomatoes, eggplants and cucumbers in Kirklareli, Turkey. Eighteen organochlorine pesticides were identified in vegetable samples using microwave or Soxhlet extraction, and results were obtained by gas chromatography–mass spectrometry. The optimized conditions were 1 mL/min for flow rate in the mobile phase, 1 μL for injection volume and 70 V for fragmentation potential. The analytical parameters show that the microwave oven extraction procedure provided the best results when compared to the Soxhlet extraction procedure. Samples were prepared for analysis with hexane?dichlormethane (1: 1, v/v, 40 mL) using a solid-phase extraction method. The limits of detection and quantitation for the eighteen analytes were between 0.02–0.26 and 0.06–0.87 μg/L, respectively, and the relative standard deviations of the migration time ranged from 2.4 to 8.9%. The recoveries of surrogate spiked in vegetable samples ranged from 70 to 116%, respectively. The obtained concentrations of pesticides in all vegetables studied were proved in the range of ND–123 μg/kg. The organochlorine pesticide sum was below the legal limit, except for Endrin and Methoxychlor, which requires a further elucidation of the organochlorine pesticides pollution sources in the region. These studies on accumulation of organochlorine pesticides were necessary for accomplishing a comprehensive ecological risk assessment.