Hongping Chen

Transfer rates of 19 typical pesticides and the relationship with their physicochemical property.

Determining the transfer rate of pesticides during tea brewing is important to identify the potential exposure risks from pesticide residues in tea. In this study, the transfer rates of 19 typical pesticides from tea to brewing were investigated using gas chromatography tandem mass and ultraperformance liquid chromatography tandem mass. The leaching rates of five pesticides (isocarbophos, triazophos, fenvalerate, buprofezin, and pyridaben) during tea brewing were first reported. The pesticides exhibited different transfer rates; however, this result was not related to residual concentrations and tea types. Pesticides with low octanol-water partition coefficients (Logkow) and high water solubility demonstrated high transfer rates. The transfer rates of pesticides with water solubility > 29 mg L(-1) (or <15 mg L(-1)) were >25% (or <10%), and those of pesticides with LogKow < 1.52 (or >2.48) were >65% (or <35%). This result indicates that water solubility at approximately 20 mg L(-1) and LogKow at approximately 2.0 could be the demarcation lines of transfer rate. The results of this study can be used as a guide in the application of pesticides to tea trees and establishment of maximum residue limits of pesticides in tea to reduce pesticide exposure in humans.

Determination of 16 phthalate esters in tea samples using a modified QuEChERS sample preparation method combined with GC-MS/MS

A modified QuEChERS method for the determination of 16 phthalate esters (PAEs) in tea samples using GC-MS/MS was developed and validated. The kinds and amounts of adsorbents were optimised, and the crude extracts were purified using primary secondary amine (PSA), graphitised carbon black (GCB) and anhydrous magnesium sulphate (MgSO4). Compared with extraction without matrix hydration, the addition of water could achieve higher extraction efficiency. The recoveries for PAEs obtained against matrix-matched standards at spiking levels of 50, 200 and 500 μg kg–1 ranged from 84.7% to 112.7% with relative standard deviations below 20% (n = 6) for all cases. Limits of detection (0.6–36.0 μg kg–1) and quantitation (2.0–120.0 μg kg–1) were achieved using the proposed method for all PAEs. A total of 105 tea samples were found to be contaminated with PAEs. Graphical Abstract

Dissipation Pattern, Processing Factors, and Safety Evaluation for Dimethoate and Its Metabolite (Omethoate) in Tea (Camellia Sinensis).

Residue levels of dimethoate and its oxon metabolite (omethoate) during tea planting, manufacturing, and brewing were investigated using a modified QuEChERS sample preparation and gas chromatography. Dissipation of dimethoate and its metabolite in tea plantation followed the first-order kinetic with a half-life of 1.08–1.27 d. Tea manufacturing has positive effects on dimethoate dissipation. Processing factors of dimethoate are in the range of 2.11–2.41 and 1.41–1.70 during green tea and black tea manufacturing, respectively. Omethoate underwent generation as well as dissipation during tea manufacturing. Sum of dimethoate and omethoate led to a large portion of 80.5–84.9% transferring into tea infusion. Results of safety evaluation indicated that omethoate could bring higher human health risk than dimethoate due to its higher hazard quotient by drinking tea. These results would provide information for the establishment of maximum residue limit and instruction for the application of dimethoate formulation on tea crop.

Mass Spectral Fragmentation Pathways of Phthalate Esters by Gas Chromatography–Tandem Mass Spectrometry

Gas chromatography–tandem mass spectrometry was applied to study the mass spectral fragmentation of phthalate esters. The base peaks of phthalate esters with alkyl side chains (except dimethyl phthalate) were m/z 149, indicating that their fragmentation pathways were similar. The base peaks of benzyl butyl phthalate and dibutoxyethyl phthalate were also at m/z 149. Because of the presence of benzyl groups and butoxy groups in the side chains, their mass spectral fragmentation pathways were different from those of phthalate esters with alkyl side chains. The base peaks of dimethyl phthalate and diphenyl phthalate were m/z 163 and m/z 225, respectively, which corresponded to the fragments produced by α-cleavage of their molecular ion peaks. The base peaks of dimethoxyethyl phthalate and diethoxyethyl phthalate were m/z 59 and m/z 72, respectively, which corresponded to fragments produced by McLafferty rearrangement of their molecular ions. The fragmentation pathways provide fundamental information for the determination of phthalate esters and their metabolites.

Enantioselective Dissipation of Acephate and Its Metabolite, Methamidophos, during Tea Cultivation, Manufacturing, and Infusion

The enantioselective dissipation of acephate and its metabolite, methamidophos, was investigated during tea cultivation, manufacturing, and infusion, using QuEChERS sample preparation technique and gas chromatography coupled with a BGB-176 chiral column. Results showed that (+)-acephate and (-)-acephate dissipated following first-order kinetics in fresh tea leaves with half-lives of 1.8 and 1.9 days, respectively. Acephate was degraded into a more toxic metabolite, methamidophos. Preferential dissipation and translocation of (+)-acephate may exist in tea shoots, and (-)-methamidophos was degraded more rapidly than (+)-methamidophos. During tea manufacturing, drying and spreading (or withering) played important roles in the dissipation of acephate enantiomers. The enantiometic fractions of acephate changed from 0.495-0.496 to 0.479-0.486 (P ≤ 0.0081), whereas those of methamidophos changed from 0.576-0.630 to 0.568-0.645 (P ≤ 0.0366 except for green tea manufacturing on day 1), from fresh tea leaves to made tea. In addition, high transfer rates (>80%) and significant enantioselectivity (P ≤ 0.0042) of both acephate and its metabolite occurred during tea brewing.

Simultaneous Determination of Thiophanate-Methyl and Its Metabolite Carbendazim in Tea Using Isotope Dilution Ultra Performance Liquid Chromatography–Tandem Mass Spectrometry

A rapid method has been developed for the determination of thiophanate methyl and its metabolite carbendazim in tea samples using ultra-high-performance liquid chromatography tandem mass. Dispersive solid-phase extraction was optimized and employed as a sample preparation technique without concentration and solvent exchange. Degradation of thiophanate methyl and its isotope were observed and they declined at the similar rate during sample preparation. The results showed that calibration by isotope internal standards was reliable to correct the degradation. With the extraction solvent at pH range of 2.3-10.3, difference for thiophanate methyl degradation was not much significant due to the buffer action of tea matrix solution. Matrix effects were dependent on the nature of the analytes and tea categories, but calibrated effectively by isotope internal standards. Recoveries ranged 97.2-110.6%, and relative standard deviations were <25.0%. The limit of quantification was both 0.010 mg kg(-1) for thiophanate methyl and carbendazim. The developed method was utilized to measure concentrations of thiophanate methyl and carbendazim in tea samples from seven provinces of China, as well as to investigate the degradation of thiophanate methyl in tea crop.

Occurrence and risk assessment of organophosphorus pesticide residues in Chinese tea

ABSTRACT Tea is the second widely consumed beverage next to water. Tea drinking is one of the important pathways for human exposure of organonphosphorus pesticide. Consequently, incidence of organonphosphorus pesticide residues and risk assessment should be clear. In this study, the level of organonphosphorus pesticide residues in 810 Chinese teas manufactured between 2010–2013 was investigated using gas chromatography coupled with tandem mass spectrometry and a flame photometric detector. Incidence of organonphosphorus pesticide residues occurred with a frequency of 29% and the average concentration of 93 μg kg−1. The residue levels varied from tea types, sale spots, and production area. Chlorpyrifos, isocarbophos, and triazophos were the only three organonphosphorus pesticides with detectable residues, and the detectable rates were 13.0%, 13.6%, and 17.4%, respectively. The corresponding average daily intake of chlorpyrifos, isocarbophos, and triazophos by tea drinking was 0.000083 μg kg−1 bw day−1, 0.0036 μg kg−1 bw day−1, and 0.0022 μg kg−1 bw day−1. These results showed that the total hazard quotient of organonphosphorus pesticide pesticides from tea drinking was less than 0.02 and that the tea-drinking originated organonphosphorus pesticide exposure had a little adverse health effect for human being.

Monitoring and risk assessment of 74 pesticide residues in Pu-erh tea produced in Yunnan, China

A number of 100 Pu-erh tea samples from the 2013 harvest in Yunnan Province (China) were analysed for 74 pesticides. A total of 11 pesticides were detected. At least one pesticide was detected in 56% of the samples. None of these samples contained the 74 monitored pesticides at concentrations above the Chinese maximum residual levels. Imidacloprid, bifenthrin and acetamiprid were most frequently found, with percentages of 53%, 46% and 31%, respectively. These were also the top three pesticides with maximum concentrations of 140, 246 and 672 μg kg−1, respectively. Residual levels of the monitored pesticides showed no significant correlation with the production time or area of Pu-erh tea. Whereas a high incidence of pesticide residues was detected in Pu-erh tea, the contamination levels observed do not pose any serious health risks.

Degradation of the Neonicotinoid Pesticides in the Atmospheric Pressure Ionization Source

AbstractDuring the analysis of neonicotinoid pesticide standards (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) by mass spectrometry, the degradation of these pesticides (M-C=N-R is degraded into M-C=O, M is the skeleton moiety, and R is NO2 or CN) was observed in the atmospheric pressure ionization interfaces (ESI and APCI). In APCI, the degradation of all the five neonicotinoid pesticides studied took place, and the primary mechanism was in-source ion/molecule reaction, in which a molecule of water (confirmed by use of H218O) attacked the carbon of the imine group accompanying with loss of NH2R (R=NO2, CN). For the nitroguanidine neonicotinoid pesticides (R=NO2, including thiamethoxam, clothianidin, and imidacloprid), higher auxiliary gas heater temperature also contributed to their degradation in APCI due to in-source pyrolysis. The degradation of the five neonicotinoid pesticides studied in ESI was not significant. In ESI, only the nitroguanidine neonicotinoid pesticides could generate the degradation products through in-source fragmentation mechanism. The degradation of cyanoamidine neonicotinoid pesticides (R=CN, including acetamiprid and thiacloprid) in ESI was not observed. The degradation of neonicotinoid pesticides in the ion source of mass spectrometer renders some adverse consequences, such as difficulty interpreting the full-scan mass spectrum, reducing the sensitivity and accuracy of quantitative analysis, and misleading whether these pesticides have degraded in the real samples. Therefore, a clear understanding of these unusual degradation reactions should facilitate the analysis of neonicotinoid pesticides by atmospheric pressure ionization mass spectrometry. Graphical Abstract

Facile synthesis of amine-functional reduced graphene oxides as modified quick, easy, cheap, effective, rugged and safe adsorbent for multi-pesticide residues analysis of tea

Amine-functional reduced graphene oxide (amine-rGO) with different carbon chain length amino groups were successfully synthesized. The graphene oxides (GO) reduction as well as amino grafting were achieved simultaneously in one step via a facile solvothermal synthetic strategy. The obtained materials were characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectrometry and X-ray photoelectron spectroscopy to confirm the modification of GO with different amino groups. The adsorption performance of catechins and caffeine from tea acetonitrile extracts on different amine functional rGO samples were evaluated. It was found that tributylamine-functional rGO (tri-BuA-rGO) exhibited the highest adsorption ability for catechins and caffeine compared to GO and other amino group functional rGO samples. It was worth to note that the adsorption capacity of catechins on tri-BuA-rGO was 11 times higher than that of GO (203.7mgg-1 vs 18.7mgg-1). Electrostatic interaction, π-π interaction and surface hydrophilic-hydrophobic properties of tri-BuA-rGO played important roles in the adsorption of catechins as well as caffeine. The gravimetric analysis confirmed that the tri-BuA-rGO achieved the highest efficient cleanup preformance compared with traditional dispersive solid phase extraction (dSPE) adsorbents like primary-secondary amine (PSA), graphitized carbon black (GCB) or C18. A multi-pesticides analysis method based on tri-BuA-rGO is validated on 33 representative pesticides in tea using gas chromatography coupled to tandem mass spectrometry or high-performance liquid chromatography coupled with tandem mass spectrometry. The analysis method gave a high coefficient of determination (r2>0.99) for each pesticide and satisfactory recoveries in a range of 72.1-120.5%. Our study demonstrated that amine functional rGO as a new type of QuEChERS adsorbent is expected to be widely applied for analysis of pesticides at trace levels.