Hyphenated liquid electrode glow discharge-dielectric barrier discharge molecular emission spectrometry for determination of dithiocarbamates.

A hyphenated liquid electrode glow discharge (LEGD)-dielectric barrier discharge (DBD) molecular emission spectrometer was constructed and used as a novel liquid chromatography (LC) detector for dithiocarbamates (DTC) determination. The LEGD was used as an acidolysis reactor for the in-situ transformation of DTCs into CS2 with high efficiencies of 74.11-97.98%. The DBD was used to excite CS2 gas to generate a specific molecular emission at 257.94 nm. The linear correlation coefficient of the method was > 0.99 from 1 to 200 µg mL-1. The detection limits ranged from 0.1 to 0.3 µg mL-1 with 76-119% recovery and relative standard deviations of 0.2-8.5%. Moreover, the hyphenated microplasma spectrometer achieved low power consumption, low temperature, immediate acidolysis, and high transformational efficiency, and can detect each DTC when combined with LC.

Simultaneous Determination of Eight Pesticide Residues in Cowpeas by GC-ECD.

A sensitive and effective method, using gas chromatography (GC) and an electron capture detector (ECD), for the simultaneous quantitative determination of bifenthrin, chlorothalonil, cyfluthrin, cypermethrin, difenoconazole, fenvalerate, procymidone and pyridaben residues in cowpea was developed and validated. The method involved extracting with acetonitrile, purification with a graphitized carbon black/amino solid phase extraction cartridge, and then determining by GC-ECD. Recovery studies were carried out at three spiked levels (0.01, 0.1 and 0.5 mg/kg). The average recoveries at the three spiked levels ranged from 76.6 to 107.0% with relative standard deviations in the range of 1.2-5.6% for all analytes. The quantification limit was 0.01 mg/kg for each pesticide and was less than or equal to the relevant MRLs set by China, the Codex Alimentarius or the European Union. The developed analyzing method was convenient, time and cost saving, environment-friendly and readily available than the traditional methods.

Monitoring and exposure assessment of pesticide residues in cowpea (Vigna unguiculata L. Walp) from five provinces of southern China.

Residues of 14 pesticides were determined in 150 cowpea samples collected in five southern Chinese provinces in 2013 and 2014.70% samples were detected one or more residues. 61.3% samples were illegal mainly because of detection of unauthorized pesticides. 14.0% samples contained more than three pesticides. Deterministic and probabilistic methods were used to assess the chronic and acute risk of pesticides in cowpea to eight subgroups of people. Deterministic assessment showed that the estimated short-term intakes (ESTIs) of carbofuran were 1199.4%-2621.9% of the acute reference doses (ARfD) while the rates were 985.9%-4114.7% using probabilistic assessment. Probabilistic assessment showed 4.2%-7.8% subjects may suffer from unacceptable acute risk from carbofuran contaminated cowpeas from the five provinces (especially children). But undue concern is not necessary, because all the estimations are based on conservative assumption.

Acute Toxicity and Genotoxicity of Carbendazim, Main Impurities and Metabolite to Earthworms (Eisenia foetida).

The acute toxicity and genotoxicity of carbendazim, two impurities (3-amino-2-hydroxyphenazine and 2,3-diaminophenazine) and one metabolite (2-aminobenzimidazole) to Eisenia foetida were assessed using artificial soil test and comet assay respectively. Acute toxicity results showed carbendazim was moderately toxic to the earthworms with 14 day-LC50 of 8.6 mg/kg dry soil while 3-amino-2-hydroxyphenazine, 2,3-diaminophenazine, and 2-aminobenzimidazole were of low toxicity with 14 day-LC50 values of 19.0, 14.9, and 27.7 mg/kg dry soil respectively (nominal concentration). The olive tail moment and percentage of DNA in the tail were used as genotoxicity indices, and carbendazim could significantly induce DNA damage to the earthworm coelomocytes with obviously positive dose- and duration-response relationships while the other three substances showed similar (p = 0.05) genotoxicity results to the negative controls in all of the tests.

Residues, dissipation, and risk assessment of spinosad in cowpea under open field conditions.

The dissipation and residues of an eco-friendly bio-pesticide, spinosad, in cowpea under field conditions were studied using ultra-performance liquid chromatography with tandem mass spectrometry (UPLC-MSMS) after Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) extraction. The method exhibited good linearity with respect to spinosyn A and spinosyn D in solvent or blank cowpea matrix with correlation coefficients>0.99. Additionally, matrix effects were not significant in the range 0.987-1.014, and the average recoveries at three concentration levels were 75.1-91.1 and 79.4-90.5% for spinosyn A and spinosyn D, respectively. The intra- and inter-day relative standard deviations were 2.5-9.3 and 7.8-9.8% for spinosyn A, respectively, and 4.1-7.9 and 6.6-8.3% for spinosyn D, respectively. The limits of detection (LODs) and limits of quantification (LOQs) were 0.005 and 0.01 mg kg(-1), respectively, for spinosyn A, and 0.002 and 0.005 mg kg(-1), respectively, for spinosyn D. The dissipation of spinosad (sum of spinosyn A and spinosyn D) fitted well to first-order kinetics with half-lives of 0.9-1.5 days. The highest residue (HR) at pre-harvest interval (PHI) of 12 h was 0.321 mg kg(-1). Compared with the maximum residue limit (MRL) set by Codex, a PHI of at least 24 h was recommended. The estimated daily chronic intake of spinosad from cowpea was less than 0.14% of the acceptable daily intake (ADI). Therefore, the risk of consuming cowpea sprayed with spinosad under recommended field conditions was considered acceptable for the Chinese population.

Effect of Chinese traditional cooking on eight pesticides residue during cowpea processing.

Thermal processing can concentrate residues or convert residues to more toxic metabolites in food. Chinese traditional cooking pays more attention to thermal processing and more vegetables were eaten after thermal processing. In this study, the effect of Chinese traditional cooking (washing, blanching, stir-frying, frying and combined operations) on eight pesticides residues (pyridaben, procymidone, chlorothalonil, difenoconazole, α-cypermethrin, bifenthrin, S-fenvalerate and λ-cyhalothrin) in cowpea which was one of the most important legume crops in China was examined. Result showed washing and blanching could reduce residues with low Kow while stir-frying and frying were more effective to residues with high Kow; stir-frying and frying could concentrate residues with low Kow; the residue levels in oil increased following increasing frying time and frequency especially the residues with high Kow; one metabolite studied in this paper was not detected. Blanching (5 min) followed by stir-frying (3 min) was the most effective combined operation.

Dissipation and residues of difenoconazole and azoxystrobin in bananas and soil in two agro-climatic zones of China.

Residues of a fungicide suspension (12 % difenoconazole, 18 % azoxystrobin) in bananas and soil were studied under tropical and subtropical monsoon climates, in Hainan and Yunnan provinces, respectively. The half-lives in bananas were shorter in Hainan (difenoconazole: 8.4-10.7 days; azoxystrobin: 7.8-8.4 days) than Yunnan (difenoconazole: 11.3-13.0 days; azoxystrobin: 10.4-11.6 days), possibly because of the higher temperatures and solar radiation levels in Hainan. The half-lives in soil were shorter in Yunnan (difenoconazole: 15.5-16.7; azoxystrobin: 11.9-13.9 days) than Hainan (difenoconazole: 23.1-23.2 days; azoxystrobin: 16.0-16.1 days), possibly because the organic carbon content was higher and rainfall lower in Yunnan than Hainan. Their physico-chemical properties suggest difenoconazole and azoxystrobin should be stable in bananas and soil, but both decreased to safe concentrations by the minimum harvest time after spraying the mixture at the recommended dosage and 1.5 times that dosage, through physical, chemical, and biological processes.