Fengzu Zhang

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.

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.

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.

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 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.

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.

Removal of aflatoxin B1 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.

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.

Residue Dynamics Studies of Aluminum Phosphide and Magnesium Phosphide in Stored Rice Utilizing a Sulfuric Acid-Toluene Extraction Coupled with Gas Chromatography Analysis

ABSTRACT A method for determination of aluminum phosphide and magnesium phosphide residues in rice was developed and validated. This work, through good laboratory practices, demonstrated aluminum and magnesium phosphide residue dynamics in stored rice. Rice samples were treated with sulfuric acid, which hydrolyzed phosphides to phosphine (PH3), which was simultaneously trapped in toluene. The organic layer was filtered and then analyzed by gas chromatography with a flame photometric detector. The PH3 calibration curves showed a strong linear relationship in the range of 0.012–1.2 mg/L, with a correlation coefficient of 0.999. The limit of detection of this method was 0.004 mg/kg. The average recoveries from samples fortified with aluminum phosphide and magnesium phosphide ranged from 76.8 to 106.5% with relative standard deviations below 10.2% (n = 5). PH3 was applied separately to rice samples to study dissipation dynamics at application dosages of 9.0 and 12 g/m3, respectively. The results showed half-l...