Biodegradation of imidacloprid in sandy loam soil by Bacillus aerophilus

A study of the biodegradation of imidacloprid in soil was carried out under laboratory conditions. Sandy soil samples were fortified with imidacloprid at 50, 100 and 150 mg kg^?1 along with 45 x 10⁷ colony forming units (cfus) of Bacillus aerophilus and the samples were compared with unamended soil. The samples were extracted with acetonitrile, cleaned up by treatment with primary secondary amine sorbent and graphitised carbon black. The residues of imidacloprid and its metabolites were analysed by high performance liquid chromatography. The parent compound, imidacloprid, was found to be more persistent in both the treatments. Among metabolites, the highest values were obtained for urea and olefin while 5-hydroxy, 6-chloronicotinic acid (6-CNA), nitrosimine and nitroguanidine (NTG) were also observed in all the treatments in amended soil. In case of unamended (control) soil, 6-CNA was found to be the most persistent metabolite followed by olefin, urea, 5-hydroxy, nitrosimine and NTG metabolites. Total imidacloprid residues for control soil samples followed first-order kinetics at 50 and 150 mg kg^?1 but in case of control imidacloprid fortified at 100 mg kg^?1, the total residues of imidacloprid and its metabolites followed pseudo-first-order kinetics. The respective half-life value for 50 mg kg^?1 was 25.08 days and 30.10 days for both 100 and 150 mg kg^?1. However, total imidacloprid residues followed pseudo-first-order kinetics for its applications at 50, 100 and 150 mg kg^?1 in sandy loam soil amended with B. aerophilus. The half-life values for 50, 100 and 150 mg kg^?1 were worked out to be 14.33, 15.05 and 18.81 days, respectively. With the use of B. aerophilus, the reduction percentage of initial applied dose imidacloprid in sandy loam soil was found to be higher in all the three doses as compared to that of the control samples.     

A liquid chromatography–tandem mass spectrometry method to simultaneously determinate dichlorvos and phoxim in tobacco

A simple pretreatment method with liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed and validated to simultaneously determine dichlorvos and phoxim in tobacco and soil matrices. Satisfactory linearity (R² ≥ 0.9991) of the method was obtained for both analytes. The limits of detection and limits of quantification for dichlorvos and phoxim in three matrices were 0.0015–0.006 and 0.005–0.02 mg/kg, respectively. Average recoveries were 78.24–92.21% for dichlorvos and 76.62–100.51% for phoxim in soil, green tobacco leaves and cured tobacco leaves. The intra‐ and inter‐day relative standard deviations were <6%. The established method was successfully applied for the residual analysis of dichlorvos and phoxim in real soil and tobacco samples. The results indicated that the established method could be used to detect trace amounts of dichlorvos and phoxim in tobacco. The data could also help the Chinese government establish maximum residue limits of dichlorvos and phoxim on tobacco and establish proper and safe use of dichlorvos and phoxim on tobacco plants in China.     

Analysis of imidacloprid and pyrimethanil in shallot (Allium ascalonicum) grown under greenhouse conditions using tandem mass spectrometry: establishment of pre‐harvest residue limits

In this study, the original Quick, Easy, Cheap, Effective, Rugged and Safe method was used for the extraction of imidacloprid and pyrimethanil followed by a rapid clean‐up through dispersive solid‐phase extraction technique with primary secondary amine sorbent and magnesium sulfate in shallot. Residues were analyzed using LC‐tandem mass spectrometry in positive‐ion electrospray ionization mode. The limits of detection and quantification were estimated to be 0.006 and 0.02 mg/kg, respectively. The samples were fortified at two different concentration levels (0.2 and 1.0 mg/kg), and the recoveries ranged between 79.7 and 83.9% with relative standard deviation values < 6%. The method was successfully applied for the establishment of the pre‐harvest residue limits (PHRL). The rate of disappearance of imidacloprid and pyrimethanil on shallot was described with first‐order kinetics (imidacloprid, y² = 0.9670; pyrimethanil, y² = 0.9841), with half‐lives of 2.87 and 2.08 days, respectively. Based on the dissipation patterns of the pesticide residues, the PHRL was recommended at 7.86 mg/kg for 14 days (PHRL₁₄) and 1.98 mg/kg for 7 days (PHRL₇) before harvest for imidacloprid, and 21.64 mg/kg for 7 days (PHRL₇) and 9.28 mg/kg for 4 days (PHRL₄) before harvest for pyrimethanil in shallot. Copyright © 2012 John Wiley & Sons, Ltd.     

Analysis of Enestroburin Residues in Wheat and Soil by Solid Phase Extraction and High-Performance Liquid Chromatography

A method was developed for the determination of enestroburin residues in wheat grain, wheat straw, and soil by solid-phase extraction (SPE) and HPLC-UV. The analytes were extracted with acetonitrile, cleaned up by PestiCarb/NH₂ cartridges and determined by HPLC with UV detector. This method is characterized by recovery >88.0%, precision (RSD) <7.8% and sensitivity of 0.005 mg/kg, in agreement with directives for method validation in residue analysis. The proposed method was successfully employed for the determination of enestroburin residue levels and its dissipation rates in a field trial in Beijing, China. Dissipation study shows that the half life of enestroburin in wheat straw was 5.35–5.81 days and in soil was 6.13–6.75 days. When enestroburin was applied according to the recommended dose and doubled dose, the final residue in wheat grain was both lower than 0.2 mg/kg. A harvest interval should be more than 7 d, and a dosage of 100–200 g (a.i.)/ha was suggested and considered as safe to human beings and animals.     

Differential-pulse polarographic determination of the insecticide imidacloprid in commercial formulations

The reduction reaction of imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] at a mercury electrode shows two well-defined waves in the range of pH 2.0–11.0. The characteristics of the electrode processes were examined. The analyte captures four electrons in the first step and two in the second to give the hydroxylamine and amine derivatives, respectively. A differential-pulse polarographic method for the determination of imidacloprid based on the first reduction peak of this compound is presented. Britton-Robinson buffer was used as a supporting electrolyte and optimum pH value was found to be pH 8.O. The applicable concentration range was from 10 to 200 ng/ml, with a relative standard deviation of 1.5% (for a level of 80 ng/ml) and a detection limit of 3 ng/ml. The method has been satisfactorily applied to the determination of imidacloprid in commercial formulations.     

Simultaneous determination of pinoxaden,cloquintocet-mexyl,clodinafop-propargyl ester and its major metabolite in barley products and soil using QuEChERS modified with multi-walled carbon nanotubes coupled with LC–MS/MS

Herein, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method with multi-walled carbon nanotube (MWCNT) as a dispersive solid-phase extraction was developed for simultaneous determination of pinoxaden (PXD), cloquintocet-mexyl (CLM), clodinafop-propargyl ester (CPE) and its major metabolite (clodinafop, CP) in barley grass powder, barley grain, and soil using liquid chromatography–tandem mass spectrometry (LC–MS/MS). We found that MWCNT as an absorbent could improve the recoveries of the tested analytes, particularly CP, in complex matrices. Under the optimum conditions, the established MWCNT-modified QuEChERS coupled with LC–MS/MS method exhibited excellent linearity (R²) of ≥0.9912, low limits of detection (LODs) and quantification (LOQs) of 0.02–0.07 and 0.29–1.26 μg kg⁻¹, and acceptable recoveries of 80–130% with intra- and inter-day relative standard deviations (RSDs) < 10.5%. No strong matrix effect (ME) has been observed on the respective samples. The method was successfully applied to monitor the tested analytes in the representative field incurred samples. Conclusively, the proposed method is sensitive and reliable and could be used to monitor the residues of PDX, CLM, CPE, and CP in complicated agro-products and soil matrices.     

A QuEChERS-HPLC-MS/MS Method with Matrix Matching Calibration Strategy for Determination of Imidacloprid and Its Metabolites in Procambarus clarkii (Crayfish) Tissues

We developed a method for determination of imidacloprid and its metabolites 5-hydroxy imidacloprid, olefin imidacloprid, imidacloprid urea and 6-chloronicotinic acid in Procambarus clarkii (crayfish) tissues using quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography-triple quadrupole mass spectrometry. Samples (plasma, cephalothorax, hepatopancrea, gill, intestine, and muscle) were extracted with acetonitrile containing 0.1% acetic acid and cleaned up using a neutral alumina column containing a primary secondary amine. The prepared samples were separated using reverse phase chromatography and scanned in the positive and negative ion multiple reaction-monitoring modes. Under the optimum experimental conditions, spiked recoveries for these compounds in P. clarkii samples ranged from 80.6 to 112.7% with relative standard deviations of 4.2 to 12.6%. The limits of detection were 0.02–0.5 μg·L⁻¹, the limits of quantification were 0.05–2.0 μg·L⁻¹ and the method of quantification was 0.05–2.0 μg·kg⁻¹. The method is rapid, simple, sensitive and suitable for rapid determination and analysis of imidacloprid and its metabolites in P. clarkii tissues.     

Solidification of floating organic droplet microextraction for determination of seven insecticides in fruit juice,vegetables and agricultural runoff using gas chromatography with flame ionization and mass spectrometry detection

Liquid microextraction employing solidification of the floating organic droplet, with vortexing and heating to optimize extraction efficiency, was developed for the determination of seven insecticides in fruit juice, vegetables, and agricultural runoff water. The extracts were analyzed by gas chromatography with both flame ionization and mass spectrometry detection for the determination of chlorpyrifos, prothiofos, profenofos, ethion, λ‐cyhalothrin, permethrin, and cypermethrin, respectively. Using 20 μL of 1‐undecanol in 10 mL of aqueous solution containing 1% w/v sodium chloride provided preconcentration factor of 500. The enrichment factor of the analytes was in the range of 355 to 509 with extraction recovery >71%. The linearity ranges were 4–200 μg/kg for gas chromatography with flame ionization detection and 1–100 μg/kg for gas chromatography with mass spectrometry, with limits of detection ranging from 0.04 to 1.2 μg/kg, which are lower than the international maximum residue limits for vegetables and fruit juice. Intra‐day and inter‐day precisions are less than 5.4 and 7.0% relative standard deviation, respectively. The method was successfully applied to the determination of the seven insecticides in samples of vegetables, fruit juice and agricultural runoff, with recoveries ranging from 61.7 to 120.8%. The extraction method is simple, efficient and environmentally friendly.     

Development of extraction procedures for the determination of imidacloprid: application to residue analysis and dynamics of two formulations in Chinese cabbage

This study was undertaken to investigate whether an additional column clean-up procedure can affect the accuracy of an analytical method developed for the determination of imidacloprid residues in Chinese cabbage. Thereafter, the residue levels and the degradation rates of imidacloprid were investigated in experimental Chinese cabbage plots after treatment with two different commercial formulations: emulsifiable concentrate (EC) and wettable powder (WP). The analyte was determined using high-performance liquid chromatography-ultraviolet detection (HPLC-UVD) and confirmed by high-performance liquid chromatography-mass spectrometry (HPLC-MS) in the select ion-monitoring mode. The mean recoveries ranged from 75.34 to 98.00% and 96.95 to 100.97%, with relative standard deviations of 0.86-4.14 and 1.22-3.52%, in samples treated with and without additional column clean-up procedures, respectively. The minimum detectable amount of imidacloprid was 4 ng, while the limits of detection and quantitation were 0.2 and 0.5 ppm, respectively. The degradation of pesticide was monitored throughout a period of 13 days under greenhouse conditions. Although the behaviors of the EC and WP formulations appear to be similar, the absolute residue levels obtained with EC and WP treatments differed slightly. When imidacloprid formulations were applied (as foliar treatments) according to the recommended rate, the final residues (13 days post-treatment) in Chinese cabbage were much lower than the maximum residue limit (MRL = 3.5 ppm) established by the Korean Food and Drug Administration. Taken together, our study suggests that the analysis of imidacloprid can be performed without an additional column clean-up procedure, and the decline curve and the residue levels in Chinese cabbage could change if the same active ingredient is used in different formulations.     

Synthesis of core‐shell magnetic molecularly imprinted polymer for the selective determination of imidacloprid in apple samples

This work demonstrates the synthesis and characterization of core‐shell magnetic molecularly imprinted polymers based on surface imprinting using methacryloyl chloride as a functional monomer for the selective extraction of imidacloprid (template) from apple fruit. The characterization analysis results ensured the successful synthesis of the magnetic molecularly imprinted polymers owing to their heterogeneous structure and good magnetic properties. An isothermal binding test was assessed with a pseudo‐second‐order kinetic model, and the kinetic results fit well to the Freundlich isothermal model. The polymers exhibited an adsorption capacity of 5.75 mg/g for the target analyte with a good selective extraction ability. In addition, the polymers can be reused several times without significant performance loss. The molecularly imprinted polymers showed good performance in the analysis of spiked apple sample with a linear range of 0.05–1.0 mg/L, a limit of detection of 0.048 mg/L and a limit of quantification of 0.146 mg/L (S/N = 3/10). The recoveries of the samples were 77.66–96.57% and their respective relative standard deviations were 3.36–0.45%. All the results indicated that the proposed method provided good selective extraction, as qualifying the analytical standards.     

Dispersive solid‐phase extraction followed by vortex‐assisted dispersive liquid–liquid microextraction based on the solidification of a floating organic droplet for the determination of benzoylurea insecticides in soil and sewage sludge

A novel dispersive solid‐phase extraction combined with vortex‐assisted dispersive liquid–liquid microextraction based on solidification of floating organic droplet was developed for the determination of eight benzoylurea insecticides in soil and sewage sludge samples before high‐performance liquid chromatography with ultraviolet detection. The analytes were first extracted from the soil and sludge samples into acetone under optimized pretreatment conditions. Clean‐up of the extract was conducted by dispersive solid‐phase extraction using activated carbon as the sorbent. The vortex‐assisted dispersive liquid–liquid microextraction based on solidification of floating organic droplet procedure was performed by using 1‐undecanol with lower density than water as the extraction solvent, and the acetone contained in the solution also acted as dispersive solvent. Under the optimum conditions, the linearity of the method was in the range 2–500 ng/g with correlation coefficients (r) of 0.9993–0.9999. The limits of detection were in the range of 0.08–0.56 ng/g. The relative standard deviations varied from 2.16 to 6.26% (n = 5). The enrichment factors ranged from 104 to 118. The extraction recoveries ranged from 81.05 to 97.82% for all of the analytes. The good performance has demonstrated that the proposed methodology has a strong potential for application in the multiresidue analysis of complex matrices.     

Development and validation of a multiresidue method for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection

A multiresidue method has been developed and validated for the simultaneous determination of organophosphorus insecticides and their toxic metabolites in sugarcane juice and refined sugar by gas chromatography with flame photometric detection. Limits of quantification of the method varied between 0.007 and 0.01 μg/g. Ethyl acetate based extraction followed by dispersive solid‐phase extraction cleanup with primary secondary amine yielded internationally acceptable recoveries of acephate, chlorpyrifos, dichlorvos, monocrotophos, malathion, malaoxon, phorate, phorate‐sulfoxide, phorate‐oxon, phorate‐sulfone, and quinalphos from selected matrices. The recoveries of target analytes from cane juice were 75.55 ± 0.5–102.57 ± 4.2, 77.45 ± 4.7–103.33 ± 3.3, and 80.55 ± 6.6–105.82 ± 9.8% at 0.01, 0.02, and 0.1 μg/g levels of fortification, respectively. The recoveries from cane sugar were 73.24 ± 3.5–104.47 ± 1.9, 75.23 ± 1.5–116.10 ± 3.7, and 70.75 ± 5.7–110.15 ± 2.7%, respectively at 0.01, 0.02, and 0.1 μg/g levels of fortification. Matrix effect and measurement uncertainty were within the permissible limit (less than 20%) as prescribed for pesticide residue analysis.     

Simultaneous determination of saflufenacil and its two metabolites in soil samples by ultra‐performance liquid chromatography with tandem mass spectrometry

Saflufenacil is a new protoporphyrinogen‐IX‐oxidase inhibitor herbicide. When used, it can enter the soil and has a high risk to reach and contaminate groundwater and aquatic systems. A rapid and sensitive method of ultra‐performance LC with MS/MS was developed for the simultaneous determination of saflufenacil and its two metabolites in soil samples. A modified quick, easy, cheap, effective, rugged, and safe method was applied as the pretreatment procedure. The method was validated by five types of soil samples collected from several regions of China, which all showed good linearity (R² ≥ 0.9914) and precision (RSD ≤ 26.2%). The average recoveries of the three analytes ranged between 74.1 and 118.9% at spiking levels of 3–300 μg/kg. The method limits of detection (S/N 3:1) and method limits of quantification (S/N 10:1) achieved are in the ranges of 0.25–2.75 and 0.83–9.16 μg/kg, respectively. This indicated that the developed ultra‐performance LC with MS/MS method is a promising analytical tool for monitoring the environmental risks posed by saflufenacil.     

Residual levels and dietary risk assessment of bifenthrin and dinotefuran and its major metabolites in open wheat field conditions

To evaluate the residual levels of bifenthrin and dinotefuran, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) and high-performance liquid chromatography–tandem mass spectrometry method for simultaneous detection of bifenthrin and dinotefuran and its major metabolites in wheat was developed and validated. Dietary risk assessments were further performed based on the relevant residual data from 12 wheat fields, toxicology data and dietary patterns. In wheat grain and straw, the recoveries of all analytes ranged from 77 to 102% with the relative standard deviation <9.7% and the limit of quantitation 0.05 mg kg⁻¹. The highest terminal residue of bifenthrin in wheat grain was 0.069 mg kg⁻¹ and dinotefuran was 0.34 mg kg⁻¹. Residual concentrations of bifenthrin and dinotefuran decreased to <0.05 and 0.15 mg kg⁻¹ at 21 days (pre-harvest interval), respectively. The chronic risk quotient ranged from 6.4 to 62.7% and the acute risk quotient varied from 0.38 to 17.73%. The chronic and acute dietary risks caused by the terminal residues of the two insecticides were negligible for Chinese populations. The recommended pre-harvest interval was proposed to ensure safe wheat consumption. These data could provide a scientific reference to establish the Chinese maximum residue limit of dinotefuran in wheat.     

Development of validated LC-MS/MS method for imidacloprid and acetamiprid in parsley and rocket and evaluation of their dissipation dynamics

Fast and efficient method based on quick, easy, cheap, effective, rugged and safe followed by liquid chromatography–tandem mass spectrometry for acetamiprid and imidacloprid residues determination in parsley and rocket was developed and validated. Linearity (R²) ranged from 0.996 to 0.999. Accuracy ranged from 95.9 to 99.1%. Precision was <11%. Limit of quantification was 2.8–10.3?µg/kg. Matrix effect was evaluated. Dissipation of acetamiprid and imidacloprid in parsley and rocket was investigated under open field conditions. The dissipation behavior of both compounds followed first-order kinetics. Half-lives (t_1/2) were 2.68 and 4.24 days with dissipation rate (k) values of 0.25 and 0.165 days^?1 for acetamiprid; 0.24 (in parsley) and 0.25 (in rocket) days^?1 with k values of 0.636 (in parsley) and 0.718 (in rocket) days for imidacloprid. Preharvest interval values were 5.53 and 1.42 days for acetamiprid; 2.5 and 0.49 days for imidacloprid in parsley and rocket, respectively. Residues of both compounds were searched in real samples. None of the real samples violated maximum residues limits of the European Commission regulations.     

Residual level of dimethachlon in rice‐paddy field system and cooked rice determined by gas chromatography with electron capture detector

In this study, a modified quick, easy, cheap, effective, rugged and safe method coupled with gas chromatography with electron capture detection was established to determine dimethachlon residues in paddy soil, rice husk, rice straw, brown rice and cooked rice. The limits of quantification of dimethachlon were 0.01 mg/kg for paddy soil, brown rice and cooked rice and 0.02 mg/kg for rice straw and rice husk. The mean recoveries were in the range 78.59–104.7% with relative standard deviation values of <10% for dimethachlon in the five matrices. For field experiments, the final residues of dimethachlon in paddy soil were < 0.05 mg/kg and were < 1.21 mg/kg in rice straw from six sites. The final residues of dimethachlon in the brown rice at 21, 28 and 35 days after spraying from six sites were 0.08–7.58 mg/kg, and 0.16–30.1 mg/kg in rice husk. Our six test sites covered the main rice–producing areas of China. The routine rice cooking process of a Chinese family could apparently increase the removal of dimethachlon in rice compared with brown rice, and the reduction ratios were > 96%.     

Simultaneous determination and method validation of clethodim and its metabolites clethodim sulfoxide and clethodim sulfone in tobacco by LC‐MS/MS

A simple method was developed and validated for the simultaneous determination of clethodim, clethodim sulfoxide, and clethodim sulfone in soil and tobacco by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile, and the extracts were purified using octadecyl silane. The proposed method showed satisfactory linearity (R² ≥ 0.9973) for the target compounds. The limits of detection and quantitation of the three analytes in all matrices were 0.024−0.06 and 0.08−0.2 mg/kg, respectively. The recovery was tested in blank soil and tobacco leaf samples and calculated to be 74.8–104.4% with relative standard deviations of 1.9–12.1%. The developed method was successfully applied to the analysis of residues of clethodim, clethodim sulfoxide and clethodim sulfone in real soil and tobacco samples. The results indicated that the developed method can meet the requirements for the analysis of trace amounts of all three analytes in soil and tobacco.     

Simultaneous determination of residues of metalaxyl,cyazofamid and a cyazofamid metabolite in tobacco leaves and soil by liquid chromatography with tandem mass spectrometry

A simple method was developed and validated for the simultaneous determination of metalaxyl, cyazofamid and the cyazofamid metabolite 4‐chloro‐5‐p‐tolylimidazole‐2‐carbonitrile (CCIM) by liquid chromatography with tandem mass spectrometry. The three target compounds were extracted from tobacco and soil with acetonitrile containing 0.1% acetic acid, and the extracts were purified using octadecylsilane. The proposed method showed satisfactory linearity (R² ≥ 0.9985) for the target compounds. The limits of detection for metalaxyl, cyazofamid and CCIM were 0.006, 0.06 and 0.06 mg/kg in soil and green tobacco leaves and 0.03, 0.3 and 0.3 mg/kg in cured tobacco leaves, respectively. The limits of quantification for metalaxyl, cyazofamid and CCIM were 0.02, 0.2 and 0.2 mg/kg in soil and green tobacco leaves and 0.1, 1 and 1 mg/kg in cured tobacco leaves, respectively. The average recoveries from soil and tobacco were 72.91–98.40% for metalaxyl, 76.73–105.80% for cyazofamid and 74.48–106.45% for CCIM. The relative standard deviation range was 1.23–6.99%. The developed method was successfully applied to analysis of residues of metalaxyl, cyazofamid and CCIM in real soil and tobacco samples. The results indicated that the established method could meet the requirement for the analysis of trace amounts of all three analytes in soil and tobacco.     

Reinforced microextraction of polycyclic aromatic hydrocarbons from polluted soil samples using an in‐needle coated fiber with polypyrrole/graphene oxide nanocomposite

The surface of a stainless‐steel wire was platinized using electrophoretic deposition method to create a high‐surface‐area with porous and cohesive substrate. The platinized fiber was coated by the polypyrrole/graphene oxide nanocomposite by electropolymerization and accommodated into a stainless‐steel needle to fabricate an in‐needle coated fiber. The developed setup was coupled to gas chromatography with flame ionization detection and applied to extract and determine polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, fluoranthene, and pyrene) in complicated solid matrices, along with reinforcement of the extraction by cooling the sorbent, using liquid carbon dioxide. To obtain the best extraction efficiency, the important experimental variables including extraction temperature and time, temperature of cooled sorbent, sampling flow rate, and desorption condition were studied. Under the optimal condition, limits of detection for five studied analytes were in the range of 0.2–0.8 pg/g. Linear dynamic ranges for the calibration curves were found to be in the range of 0.001–1000 ng/g. Relative standard deviations obtained for six replicated analyses of 1 ng/g of analytes were 4.9–13.5%. The reinforced in‐needle coated fiber method was successfully applied for the analysis of polycyclic aromatic hydrocarbons in contaminated soil samples.