Removal of aflatoxin B(1) in edible plant oils by oscillating treatment with alkaline electrolysed water.

Alkaline electrolysed water (AlEW) with different pHs was produced by an electrolysed water generator through adjusting the electric current and voltage. The produced AlEW had a pH above 10, and a low oxidation-reduction potential (ORP) of less than -560 mV. In the current study, the effectiveness of AlEW on decontamination of aflatoxin B1 (AFB1) in various edible plant oils was investigated. The character of AlEW, oil type and the volume of AlEW were major factors which could influence the AFB1 elimination effectiveness. AlEW with pH 12.2 had the greater potential to remove AFB1. When 10 ml AlEW with pH 12.2 were added to 5 g peanut oil or olive oil (fortified level at 40 µg kg(-1)), followed by oscillation for 5 min at 20 °C, the removal rate of AFB1 could reach nearly 100%. The volume of AlEW needed to completely remove the AFB1 varied with the pH of AlEW and with the oil type. The degradation products of AFB1 were also investigated.

Detection of caffeine in tea, instant coffee, green tea beverage, and soft drink by direct analysis in real time (DART) source coupled to single-quadrupole mass spectrometry.

Ambient ionization direct analysis in real time (DART) coupled to single-quadrupole MS (DART-MS) was evaluated for rapid detection of caffeine in commercial samples without chromatographic separation or sample preparation. Four commercial samples were examined: tea, instant coffee, green tea beverage, and soft drink. The response-related parameters were optimized for the DART temperature and MS fragmentor. Under optimal conditions, the molecular ion (M+H)+ was the major ion for identification of caffeine. The results showed that DART-MS is a promising tool for the quick analysis of important marker molecules in commercial samples. Furthermore, this system has demonstrated significant potential for high sample throughput and real-time analysis.

Dissipation and residue behavior of mepiquat on wheat and potato field application.

A modified LC-MS method for the analysis of mepiquat residue in wheat, potato, and soil was developed and validated. A hydrophilic interaction liquid chromatographic column has been successfully used to retain and separate the mepiquat. Mepiquat residue dynamics and final residues in supervised field trials at Good Agricultural Practice (GAP) conditions in wheat, potato, and soil were studied. The limits of quantification for mepiquat in all samples were all 0.007 mg kg(-1), which were lower than their maximum residue limits. At fortification levels of 0.04, 0.2, and 2 mg kg(-1) in all samples, recoveries ranged from 77.5 to 116.4% with relative standard deviations of 0.4-7.9% (n = 5). The dissipation half-lives (T 1/2) of mepiquat in soil (wheat), wheat plants, soil (potato), and potato plants were 4.5-6.3, 3.0-5.6, 2.2-4.6, and 2.4-3.2 days, respectively. The final residues of mepiquat were below 0.153 mg kg(-1) in soil (wheat), 0.052-1.900 mg kg(-1) in wheat, below 0.072 mg kg(-1) in soil (potato), and below 1.173 mg kg(-1) in potato at harvest time. Moreover, pesticide risk assessment for all the detected residues was conducted. A maximum 0.0012% of acceptable daily intake (150 mg kg(-1)) for national estimated daily intake indicated low dietary risk of these products.

Spinach or amaranth contains highest residue of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin on six leaf vegetables upon open field application.

To select representative leaf vegetables which may contain the highest residue, field experiments of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin on six crops including pakchoi, rape, crown daisy, amaranth, spinach, and lettuce were designed and conducted. In this study, a high-performance liquid chromatograph and electrospray ionization tandem mass spectrometer with multiple reaction monitoring was used to simultaneously determine metalaxyl and fluazifop-P-butyl residue in various samples, and a gas chromatograph with electron capture detector was used to detect chlorpyrifos and lambda-cyhalothrin. The limits of quantification (LOQ) of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin were in the range of 0.001-0.01 mg kg(-1) for all samples, and the average recoveries of all pesticides ranged from 67.6 to 119.1% at spiked levels of 0.01-0.1 mg kg(-1). In supervised field trials, the half-lives of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin were in the range of 1.11-3.79 days, 1.11-2.27 days, 1.13-5.17 days, and 1.77-6.24 days. It was also found that all pesticide residues in spinach and/or amaranth were higher than others after application. It is recommended that spinach or amaranth can be selected as a representative crop of leaf vegetables in studying systemic fungicide, insecticides, and herbicides with similarity as metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin.

A rapid determination method for ethylenethiourea in potato and cucumber by modified QuEChERS - high performance liquid chromatography-tandem mass spectrometry.

A rapid and sensitive analytical method for the determination of ethylenethiourea (ETU) in potatoes and cucumbers is developed. This method employs modified QuEChERS followed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis. ETU was extracted by alkaline acetonitrile (containing 1%NH(3).H(2)0), separated on a ZIC-pHILIC column, confirmed by multiple reaction monitoring (MRM) mode with electrospray ionisation source. This modified procedure showed satisfactory recovery (90.6-103.5%) fortified at the range of 0.005-0.05 mg kg(-1) with relative standard deviation (RSD)<7%. The limits of detection (LOD) and the limits of quantification (LOQ) were 0.002 mg kg(-1) and 0.005 mg kg(-1), respectively. Matrix effect and HILIC retention mechanism were also evaluated. The method was finally applied to detect ETU in potato and cucumber samples collected at harvest period. Residues of ETU were detected in four cucumber samples with the level lower than LOQ.

Uniconazole residue and decline in wheat and soil under field application.

Uniconazole residue dynamics and final residues in supervised field trials at GAP conditions were studied. The residue levels and dissipation rate of uniconazole was detected by LC-MS. At fortification levels of 0.04, 0.2 and 2 mg kg(-1), recoveries ranged from 78.7 % to 100.9 % with RSDs of 0.1 %-4.6 % (n = 5). The dissipation experiments showed the half-lives (T1/2) of uniconazole in soil and wheat plants were 2.9-3.3 and 3.8-4.4 days, respectively. At pre-harvest intervals (PHI) of 45 and 60 days, uniconazole residue were no detectable or below the limit of quantification (LOQ) in soil, wheat plants and wheat.

Spinach or amaranth may represent highest residue of thiophanate-methyl with open field application on six leaf vegetables.

To select representative crop among leaf vegetables which may contain the highest residue after fungicide uses, open field applications with thiophanate-methyl on six crops including pakchoi, rape, crown daisy, amaranth, spinach and lettuce were designed and conducted. In this study, a high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry with selected reaction monitoring was used to simultaneously determine thiophanate methyl and its metabolite carbendazim residue in various samples. The limit of quantification for thiophanate methyl and carbendazim were established in the range of 0.005-0.01 mg kg(-1) for all samples. It was shown that recoveries ranged from 67.8 % to 102.3 % for thiophanate methyl, and 72.0 %-112.6 % for carbendazim at spiked levels of 0.01-0.1 mg kg(-1). It's found that thiophanate methyl converts to carbendazim very quickly. In supervised field trials, the half-lives of thiophanate methyl in six leaf vegetables were in the range of 1.26-2.65 days, and the half-lives of carbendazim were in the range of 2.53-4.28 days. It was also found that thiophanate methyl residue in spinach and amaranth was higher than others after application. It's recommended that spinach or amaranth can be selected as representative crop in leaf vegetables in study of systemic fungicides with similarity as thiophanate methyl.

Development of a method for the analysis of four plant growth regulators (PGRs) residues in soybean sprouts and mung bean sprouts by liquid chromatography-tandem mass spectrometry.

A method has been developed for the simultaneous determination of four plant growth regulators (PGRs) residues in soybean sprouts and mung bean sprouts. The sample preparation procedure was based on a QuEChERS method. The method showed excellent linearity (r(2) ≥ 0.9985) and precision (RSDs ≤ 13.0%). Average recoveries of four PGRs ranged between 74.9% and 106.3% at spiking levels 0.05, 0.5 and 1 mg kg(-1). The LODs and LOQs were in the ranges of 0.27-9.3 µg kg(-1) and 0.90-31 µg kg(-1), respectively. The procedure was applied to 18 bean sprout samples, and benzyladenine was found in some of the analyzed samples.

Direct analysis in real time mass spectrometry for the rapid identification of four highly hazardous pesticides in agrochemicals.

RATIONALE: Direct analysis in real time (DART) is a new ion source technique, which is conducted in the open air under ambient conditions, applied to the rapid and direct analysis of any material (gases, liquids, and solids) with minimal or no sample preparation. In order to take advantage of the capacity of DART mass spectrometry for the real-time analysis of hazardous ingredients in commercial agrochemicals, a pilot study of rapid qualitative determination of hazardous pesticides was performed. METHODS: Highly hazardous pesticides were identified by DART ionization coupled to a single-quadrupole mass spectrometer (DART-MS). Acetonitrile was chosen for dissolving samples prior to the analysis. Samples were analyzed by this technique in as little as 5 s. RESULTS: Phorate, carbofuran, ethoprophos and fipronil were be detected directly from commercial agrochemicals. The ionization-related parameters (DART temperature, grid voltage and MS fragment) of these compounds were optimized to obtain highly response. Isotope patterns were taken into consideration for qualitative identification. Relative standard deviations (RSDs, n = 5) of 2.3-15.0% were obtained by measuring the relative abundance of selected isotopes. CONCLUSIONS: This study showed that DART-MS technology was able to qualitatively determine the existence of highly hazardous pesticides in commercial pesticide formulations. It is suggested that this technology should be applied for routine monitoring in the market.

Dissipation and residues of emamectin benzoate in cabbage.

Emamectin benzoate residue dynamics and final residues in supervised field trials at GAP conditions were studied. An HPLC-MS analytical method for the determination of emamectin benzoate in cabbage and soil was developed. The recoveries of emamectin benzoate on cabbage and soil were observed from 71% to 102% at fortification levels of 0.01, 0.1 and 1.0 mg/kg. The reported limit of quantification (LOQ) was found to be 0.01 mg/kg. The dissipation experiments showed the half-lives (T(1/2)) of emamectin benzoate was around 1 days. At pre-harvest intervals (PHI) of 7 and 12 days, emamectin benzoate residue was observed to be below the LOQ.

Dispersive cleanup of acetonitrile extracts of tea samples by mixed multiwalled carbon nanotubes, primary secondary amine, and graphitized carbon black sorbents.

A method for analysis of 37 pesticide residues in tea samples was developed and validated and was based on reversed-dispersive solid-phase extraction (r-DSPE) cleanup in acetonitrile solution, followed by liquid chromatography-electrospray tandem mass spectrometry determination. Green tea, oolong tea, and puer tea were selected as matrixes and represent the majority of tea types. Acetonitrile was used as the extraction solvent, with sodium chloride and magnesium sulfate enhancing partitioning of analytes into the organic phase. The extract was then cleaned up by r-DSPE using a mixture of multiwalled carbon nanotubes, primary secondary amine, and graphitized carbon black as sorbents to absorb interferences. Further optimization of sample preparation and determination allowed recoveries of between 70% and 111% for all 37 pesticides with relative standard deviations lower than 14% at two concentration levels of 10 and 100 µg kg(-1). Limits of quantification ranged from 5 to 20 µg kg(-1) for all pesticides. The developed method was successfully applied to the determination of pesticide residues in market tea samples.

Determination of six neonicotinoid insecticides residues in spinach, cucumber, apple and pomelo by QuEChERS method and LC-MS/MS.

A modified QuEChERS and LC-MS/MS method has been developed for the simultaneous determination of residues of six neonicotinoids in various crops, including spinach, cucumber, apple and pomelo. The method showed good linearity (R(2) ≥ 0.9995) and precision (RSD ≤ 14.0%). Average recoveries of the six neonicotinoids ranged between 73.7% and 103.8% at spiking levels 0.005, 0.1 and 1 mg kg(-1). The LODs and LOQs were in the ranges of 0.20-0.85 µg kg(-1) and 0.66-2.84 µg kg(-1), respectively. The method was satisfactorily validated for the analysis of 50 agricultural samples. Imidacloprid and imidaclothiz were detected at concentration levels ranging from 7 to 5.3 µg kg(-1).

Multi-walled carbon nanotubes as alternative reversed-dispersive solid phase extraction materials in pesticide multi-residue analysis with QuEChERS method.

A multi-residue method based on modified QuEChERS sample preparation with multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid phase extraction (r-DSPE) material and gas chromatography-mass spectrometry determination by selected ion monitoring (GC/MS-SIM) mode was validated on 30 representative pesticides residues in vegetables and fruits. The acetonitrile-based QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation technique was used to obtain the extracts, and the further cleanup was carried out by applying r-DSPE. It was found that the amount of MWCNTs influenced the cleanup performance and the recoveries. The optimal amount of 10mg MWCNTs was suitable for cleaning up all selected matrices, as a suitable alternative r-DSPE material to primary secondary amine (PSA). This method was validated on cabbage, spinach, grape and orange spiked at concentration levels of 0.02 and 0.2 mg/kg. The recoveries of 30 pesticides were in the range of 71-110%, with relative standard deviations (RSDs, n=5) lower than 15%. Matrix effects were observed by comparing the slope of matrix-matched standard calibration with that of solvent. Good linearity was achieved at the concentration levels of 0.02-0.5 mg/L. The limits of quantification (LOQs) and the limits of detection (LODs) for 30 pesticides ranged from 0.003 to 0.05 mg/kg and 0.001 to 0.02 mg/kg at the signal-to-noise ratio (S/N) of 10 and 3, respectively. The method was successfully applied to analysis real samples in Beijing. In conclusion, the modified QuEChERS method with MWCNTs cleanup step showed reliable method validation performances and good cleanup effects in this study.

Dissipation and residue behavior of emamectin benzoate on apple and cabbage field application.

A LC-ESI-MS/MS method with QuEChERS for analysis of emamectin benzoate in cabbage, apple and soil was established. At fortification levels of 0.001, 0.01 and 0.1 mg/kg in cabbage, apple and soil, it was shown that recoveries ranged from 75.9 to 97.0 percent with relative standard deviation (RSD) of 4.4-19.0 percent. The limit of quantification (LOQ) was 0.001 mg/kg for cabbage, apple and soil. The dissipation half-lives of emamectin benzoate in cabbage, apple and soil were 1.34-1.72 day, 2.75-3.09 day and 1.89-4.89 day, respectively. The final residues of emamectin benzoate ranged from 0.001 to 0.052 mg/kg in cabbages, 0.003 to 0.090 mg/kg in apples and 0.001 to 0.089 mg/kg in soils, respectively. Therefore, it would be unlikely to cause health problems if emamectin benzoate was applied according to the use pattern suggested by the manufactures on the label.

Diafenthiuron residue and decline in pakchoi and soil under field application.

A simple analytical method based on QuEChERs was established for diafenthiuron residues in packhoi and soil. The residue levels and diaaipation rates of diafenthiuron in packhoi and soil were detected by HPLC-MS. And ultrasonic extraction was employed in the study to improve extraction effectiveness. At three fortification levels of 0.02, 0.1 and 1 mg/kg in packhoi and soil, recoveries were in the range 74.0 percent-100 percent, with relative standard deviations (RSD) of 6.1-14.8 percent. The limit of quantification (LOQ) of method was 0.02 mg/kg for packhoi and soil. In the supervised field trials, the half-lives of diafenthiuron in packhoi and soil were 1.27 and 5.94 day, respectively. The final residue levels of diafenthiuron could not be detected in soil, while only trace amount of diafenthiuron residues were detected in pakchoi.

Dissipation and residues of monosultap in rice plant and environment.

A modified method for the analysis of monosultap residue in rice plant and environment was developed and validated. Monosultap residue dynamics and final residues in supervised field trials at GAP conditions were studied. At fortification levels of 0.05, 0.5 and 1 mg kg(-1), it was shown that recoveries ranged from 75.0% to 109.2% with RSDs of 1.2-5.1% (n = 5). The dissipation experiments showed the half-lives (T(1/2)) of monosultap in water, soil and rice plants were 1.1-1.9, 1.4-2.1 and 1.3-2.1 days, respectively. At pre-harvest intervals (PHI) of 21 and 30 days, monosultap residue were 0.01-0.06 mg kg(-1) in soil, 0.01-0.19 mg kg(-1) in rice plants, and 0.01-0.09 mg kg(-1) in husked rice.

Residue dynamics of pyraclostrobin in peanut and field soil by QuEChERS and LC-MS/MS.

A modified QuEChERS-LC-MS/MS (acronym of quick, easy, cheap, effective, rugged and safe-liquid chromatography tandem mass spectrometry) method for the analysis of pyraclostrobin residue in peanut and soil was developed and validated. Pyraclostrobin residue dynamics and final residues in supervised field trials at Good Agricultural Practice (GAP) conditions in peanut and soil were studied. The limits of quantitation (LOQs) for pyraclostrobin in soil, plant, shell and peanut samples were 0.00057, 0.00026, 0.003 and 0.0037 mg kg(-1), respectively. At fortification levels of 0.005, 0.05 and 0.5 mg kg(-1) in all samples, it was shown that recoveries ranged from 80.3% to 109.4% with relative standard deviations of 1.1-8.2% (n=5). The dissipation experiments showed the half-lives (T(1/2)) of pyraclostrobin in soil and plants were 13.1-16.5 days and 10.3-11.2 days, respectively. At pre-harvest intervals (PHI) of 14, 21 and 28 days, pyraclostrobin residue were 0.005-0.20 mg kg(-1) in soil, 0.006-0.27 mg kg(-1) in plants, below 0.053 mg kg(-1) in shells and not detectable in peanuts.