A Turn-On Fluorescence Sensor Based on Nitrogen-Doped Carbon Dots and Cu2+ for Sensitively and Selectively Sensing Glyphosate.

Glyphosate has excellent herbicidal activity, and its extensive use may induce residue in the environment and enter into humans living through the food chain, causing negative impact. Here, water-soluble 1.55 nm size nitrogen-doped carbon quantum dots (NCDs) with strong blue fluorescence were synthesized using sodium citrate and adenine. The maximum excitation and emission wavelengths of NCDs were 380 nm and 440 nm, respectively. The above synthesized NCDs were first used for the construction of a fluorescence sensor for glyphosate detection. It was found that Cu2+ could quench the fluorescence of NCDs effectively through the photoinduced electron transfer (PET) process, which was confirmed using fluorescence lifetime measurements. Additionally, the fluorescence was restored with the addition of glyphosate. Hence, a sensitive turn-on fluorescence sensor based on NCDs/Cu2+ for glyphosate analysis was developed. The LODs of glyphosate for water and rice samples were recorded as 0.021 µg/mL and 0.049 µg/mL, respectively. The sensor was applied successfully for ultrasensitive and selective detection of glyphosate in environmental water and rice samples with satisfied recoveries from 82.1% to 113.0% using a simple sample pretreatment technique. The proposed strategy can provide a significant potential for monitoring glyphosate residue in water and agricultural product samples.

The metabolism and dissipation behavior of tolfenpyrad in tea: A comprehensive risk assessment from field to cup.

The metabolites of pesticides usually require rational risk assessment. In the present study, the metabolites of tolfenpyrad (TFP) in tea plants were identified using UPLC-QToF/MS analysis, and the transfer of TFP and its metabolites from tea bushes to consumption was studied for a comprehensive risk assessment. Four metabolites, PT-CA, PT-OH, OH-T-CA, and CA-T-CA, were identified, and PT-CA and PT-OH were detected along with dissipation of the parent TFP under field conditions. During processing, 3.11-50.00 % of TFP was further eliminated. Both PT-CA and PT-OH presented a downward trend (7.97-57.89 %) during green tea processing but an upward trend (34.48-124.17 %) during black tea manufacturing. The leaching rate (LR) of PT-CA (63.04-101.03 %) from dry tea to infusion was much higher than that of TFP (3.06-6.14 %). As PT-OH was no longer detected in tea infusions after 1 d of TFP application, TFP and PT-CA were taken into account in the comprehensive risk assessment. The risk quotient (RQ) assessment indicated a negligible health risk, but PT-CA posed a greater potential risk than TFP to tea consumers. Therefore, this study provides guidance for rational TFP application and suggests the sum of TFP and PT-CA residues as the maximum residual limit (MRL) in tea.

Concentrations, generation and risk characterization of phthalimide in tea-derived from folpet or not?

The fungicide folpet is rapidly degraded into phthalimide (PI) during both thermal processing and analytical procedures in sample preparation; thus, its residue definition has been modified into the sum of itself and PI. Tea is one of the world's most popular nonalcoholic beverages, where folpet is not listed as an applicable pesticide. To demonstrate how serious false-positives and overestimation in dietary risk are caused by the application of a new residue definition, the residue pattern of PI in made tea and processed tea leaves, along with its transfer rate during tea brewing and corresponding dietary risk, were investigated in the present study. The results revealed that PI residue in tea ranged from <10 µg/kg to 180 µg/kg with a median value of 10 µg/kg, 7.3 % of which was over the maximum residue limit established by EU (100 µg/kg, expressed as folpet). The PI residue in green tea was obviously higher than that in black, dark and oolong tea. Simulated heating experiments revealed that PI can arise from improper heating of folpet-free fresh tea leaves, and thus green tea bears a higher risk for its manufacturing employing a comparatively higher temperature. The transfer rate of PI during tea brewing was 104 ± 14 %. Nevertheless, the risk of PI through drinking tea was negligible to humans depending on the risk quotient (RQ) value, which was significantly lower than 1.

Uptake, translocation, and metabolism of anthracene in tea plants.

The origin of 9, 10-anthraquinone (AQ) contamination in tea remains unclear at present. The objective of this study was to test the hypothesis that AQ could be produced from the precursor anthracene in tea plantations. To test this hypothesis, the uptake, translocation, and transformation of anthracene in tea (Camellia sinensis) seedlings using hydroponic experimentation was investigated. Anthracene concentrations in tea tissues rose with increased anthracene exposure, which in the roots were significantly (p < 0.05) higher than those in aboveground parts at the end of the exposure. These results indicated that anthracene tended to be adsorbed into tea seedling via the roots and accumulated largely within roots. The three main pathways of anthracene degradation in tea seedlings were suggested: oxygen was incorporated in the 9th and 10th positions of anthracene resulting in AQ (I) and anthrone (II), and naphthalene was formed by ring fission of anthracene via methylanthracene (III). The principal anthracene metabolites were AQ and anthrone. The concentrations of AQ, like anthrone, were markedly elevated in the roots than those in stems throughout the entire exposure period. Moreover, the translocation factors for anthracene and its primary metabolites AQ and anthrone from roots to stems were persistently lower than 0.1, demonstrating a poor translocation from roots to the aboveground regions. However, tea seedlings could take anthracene up from water and translocate it to the leaves. It was a possible risk for AQ contamination in tea leaves continuously exposed to anthracene for long periods of time because tea plants were perennial crops.

Uptake, Accumulation, Translocation, and Subcellular Distribution of Perchlorate in Tea (Camellia sinensis L.) Plants.

Perchlorate, emerging pollution with thyroid toxicity, has a high detection rate in fresh tea leaves. What needs attention is that the uptake characteristic is insufficiently understood. Herein, the uptake, accumulation, and translocation of perchlorate in a tea plant-hydroponic solution system were investigated, of which the mechanism was further lucubrated by subcellular distribution. The perchlorate concentration in tea tissues is ramped up along with the increase in the exposure level and time. The bioaccumulation factor of tea tissues followed the rank: mature leaves > tender leaves > roots. After the seedlings have been transplanted to a perchlorate-free solution, the perchlorate in mature leaves is reduced significantly, accompanied by a progressive increase in perchlorate in new shoots and solutions. The cell-soluble fractions are the major reservoir of perchlorate both for roots (>59%) and leaves (>76%), which precisely explained the translocation within the tea plant-hydroponic solution system. These results not only illuminate the uptake characteristic in tea plants but also improve the understanding of the behavior of perchlorate in higher plants.

Residue analysis and dietary exposure risk assessment of acibenzolar-S-methyl and its metabolite acibenzolar acid in potato, garlic, cabbage, grape and tomato.

Acibenzolar-S-methyl (ASM) is one of the most effective plant resistance activators and protects against a broad spectrum of fungal, bacterial and viral pathogens. A rapid, efficient and high-throughput analysis method for ASM and its metabolite acibenzolar acid in fruits and vegetables was developed using potato, garlic, cabbage, grape and tomato as representative commodities by modified QuEChERS and UPLC-MS/MS. The modified procedure showed satisfying recoveries (70-108%) fortified in the range of 0.01-1 mg/kg with relative standard deviations (RSDs) lower than 17.7%. With the established analytical method, the dietary risk of ASM in fruits and vegetables from Chinese markets were further monitored using risk quotient (RQ) method. The RQ value based on ASM residue in China are far less than 1, elucidating that the potential health risk induced by ASM ingestion for Chinese population is not significant. Comparing the residue and risk assessment results of ASM in agricultural products in China to those in Codex, the maximum residue limits (MRLs) for ASM on garlic, cabbage and tomato established by CAC (Codex Alimentarius Commission) can be safely adopted in China, whereas the MRLs on potato and grape in China should be proposed as 0.01 mg/kg.

The degradation and metabolism of chlorfluazuron and flonicamid in tea: A risk assessment from tea garden to cup.

Degradation and metabolism of chlorfluazuron and flonicamid from tea garden to cup were simultaneously investigated by a modified QuEChERS method coupled with UPLC-MS/MS quantification. The dissipation half-lives of chlorfluazuron, flonicamid, and total flonicamid (the sum of flonicamid and its metabolites TFNG, TFNA, and TFNA-AM) in fresh tea leaves during tea growth were 6.0 d, 4.8 d, and 8.1 d, respectively. TFNG and TFNA were generated during tea growth. After tea processing, the residues of chlorfluazuron, flonicamid, and its metabolites in black tea were higher than those in green tea. The average processing factors of chlorfluazuron, flonicamid, and total flonicamid in black tea were 2.54, 3.02, and 2.87, respectively, while in green tea they were 2.40, 2.93, and 2.79, respectively. TFNG, TFNA, and TFNA-AM were formed rapidly during the drying step. Considering the influence of water content at various processing steps, the average loss rates of chlorfluazuron, flonicamid, and total flonicamid residue from fresh tea leaves to black tea were 16.7%, 33.8%, and 20.7%, respectively, and 29.6%, 14.0% and 18.2%, respectively, in the case of green tea. The highest leaching rates of chlorfluazuron, flonicamid, and total flonicamid during tea brewing were 6.8%, 97.0%, and 97.4%, respectively, in black tea infusion, and 6.0%, 98.9%, and 98.6%, respectively, in green tea infusion. The metabolites, especially TFNG, had a higher leaching rate during tea brewing. The migration of chlorfluazuron from fresh leaves to tea infusion was low, and the migration of flonicamid was high. The RQc and RQa of chlorfluazuron and total flonicamid were less than 1. This result indicates that the potential dietary intake risk of chlorfluazuron from tea is negligible. However, the risk of total flonicamid intake is three times higher than that of chlorfluazuron. There is a potential risk of intake of flonicamid and its metabolites in tea for human consumption.

Residue reduction and risk evaluation of chlorfenapyr residue in tea planting, tea processing, and tea brewing.

The chlorfenapyr residues in the entire tea chain, i.e., in tea planting, tea processing, and tea brewing, were systematically investigated. The degradation rate constants of chlorfenapyr in the tea plants ranged from 0.2460 to 0.2870 with the half-life of 2.4-3.0 days, and 87.5-89.9% of the chlorfenapyr in tea shoots dissipated in the interval of 7 days. In the processing process of both black tea and green tea, the chlorfenapyr residue decreased by 59.1-67.6% compared with the residue in tea shoots due to high vapor pressure (1.2 × 10-2 mPa 25 °C), and drying was the key step that dissipated the chlorfenapyr. A low leaching efficiency of 2.2-3.4% from tea leaves to tea infusion, resulted in low water solubility (0.14 mg L-1 25 °C), indicated that >90% of the residual chlorfenapyr was eliminated before the intake of tea infusion. On the basis of these results, an extremely large proportion of the chlorfenapyr deposited on tea shoots was degraded during tea planting, tea processing, and tea brewing, and the health risk was reduced primarily in the first and the last step rather than during tea processing. The remaining 0.2% chlorfenapyr sprayed on the tea shoots represents a negligible health risk based on the RQ assessment. The pesticides with high vapor pressure and low water solubility were more recommended in tea garden for pest control.

Residue dissipation and dietary exposure risk assessment of methoxyfenozide in cauliflower and tea via modified QuEChERS using UPLC/MS/MS.

BACKGROUND: Methoxyfenozide possesses efficacy against a variety of lepidopteron pests, including the major pests in cauliflower and tea, so it is of great importance to generalize the practical use of methoxyfenozide in the field. RESULTS: An efficient method was developed and validated in both vegetable matrix and extract-rich matrix (cauliflower and tea) using modified QuEChERS combined with UPLC/MS/MS analysis. The recoveries in cauliflower, made tea and tea shoots ranged from 94.5 to 108.0%, from 85.0 to 91.6% and from 77.3 to 82.0% respectively, with relative standard deviations (RSDs) below 17.3% in all cases. The field results showed that methoxyfenozide dissipated in cauliflower with half-life (t1/2 ) at 2.5-3.5 days and in tea with t1/2 at 1.2 days. Combining the above experimental data and statistical food intake values, the risk quotient (RQ) values were significantly lower than 1. CONCLUSION: The quantification method of methoxyfenozide in cauliflower or tea has not been established until this study. The dissipation and dietary exposure risk assessment of methoxyfenozide in cauliflower and tea were investigated in the field. Methoxyfenozide dissipated rapidly in cauliflower despite different climates, and it dissipated faster in tea. The dietary risk of methoxyfenozide through cauliflower or tea was negligible to humans. This study not only provides guidance for the safe use of methoxyfenozide but also serves as a reference for the establishment of maximum residue limits (MRLs) in China. © 2019 Society of Chemical Industry.

Index design and safety evaluation of pesticides application based on a fuzzy AHP model for beverage crops: tea as a case study.

BACKGROUND: A fuzzy analytic hierarchy process (AHP) is shown to be an effective methodology for multiple criteria decision-making from various heterogeneous data. Despite application of AHP to some decision-making problems in agriculture, research on AHP utilization for screening the safe use of pesticides for tea plantations based upon multiple criteria has not been reported. The overall safety chain from tea plantation to tea manufacture to tea cup after pesticides had been sprayed on a tea plantation was considered and the AHP network was constructed at two levels with two categories, tea-related parameters and pesticide toxicity. Seven criteria were selected as safety indexes, half-lives of pesticides on the tea plant (T1/2 ), water solubility (Ws), vapor pressure (Vp), acceptable daily intake (ADI), acute oral lethal dose of pesticides to rat (LD50 ), and ecotoxicity of pesticides including LD50 to bees and LD50 to aquatic organisms. RESULTS: According to the AHP, water solubility was the most important factor in the evaluation pesticide safety for use on a tea plantation, followed by the half-lives of the pesticides on the tea plant and the acceptable daily intake. Combined with the scale of seven criteria and relative weight (W), 48 pesticides with an overall score (S) < 25 could be regarded as relatively safe compounds when applied in tea plantations. CONCLUSION: An AHP approach was suggested to evaluate the safe use of pesticides on tea plantations. This study provides a new idea for the evaluation of safety in beverage crops. © 2019 Society of Chemical Industry.

Dissipation and Risk Assessment of Multiresidual Fungicides in Grapes under Field Conditions.

Grapes are among the most popular fruits globally, and various fungicides are widely applied to grape crops. As such, the presence of multiple fungicide residues and dietary risks in grapes has become the focus of significant attention. In this study, an easy-to-implement and sensitive UPLC-MS/MS approach was developed to simultaneously determine pyraclostrobin, dimethomorph, cymoxanil, cyazofamid and its metabolite CCIM in grapes via QuEChERS. This approach achieved 78.1-106.0% recovery and a 0.01 mg kg-1 limit of quantitation (LOQ). Field trials revealed that these compounds had degradation half-lives ranging from 0.9 to 13.3 days. And their terminal residues ranging from < LOQ to 1.36 mg kg-1 were below the official maximum residue limit (MRL) in China. The short-term risk for each tested fungicide was below 54%. The long-term risk of individual chemicals ranged from 0.0086% to 3.1%, and their cumulative risk was 4.4%. Results indicated that the dietary risk of these fungicides in grapes was minor.

Application and enantioselective residue determination of chiral pesticide penconazole in grape, tea, aquatic vegetables and soil by ultra performance liquid chromatography-tandem mass spectrometry.

Penconazole is a typical triazole fungicide with wide use on fruits, vegetables, and tea plants to control powdery mildew. In the present study, an efficient graphite carbon black solid phase extraction (GCB-SPE) purification combined with chiral ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed for determination of penconazole enantiomers in different complex matrices, including grape, tea, soil, lotus root, lotus leaf, lotus seed and hulls. The method was then applied to investigate the enantioselective dissipation of penconazole enantiomers in a real field experiment of grape and soil. As a result, a satisfactory separation of penconazole enantiomers on a chiral Lux Cellulose-2 column (150 mm × 2 mm i.d., 3 µm) was obtained with 0.1% formic acid in methanol and 10 mmol L-1 ammonium acetate in water (75/25, v/v) as mobile phase at 0.25 mL min-1. The enantiomer (+)-penconazole was firstly eluted, and (-)-penconazole was then eluted. The method showed reliable performances in linearity, recovery and precision, the recoveries of (+)-penconazole and (-)-penconazole in all of six matrices were between 70.5% and 121.0% with the relative standard deviations (RSDs) ranging from 0.8% to 23.6% at the low, medium and high spiked levels. The limits of quantitation (LOQs) of this method were lower than 0.0025 mg kg-1 in grape, soil and lotus root, 0.005 mg kg-1 in lotus leaf, lotus seed meat and lotus seed shell, and 0.0125 mg kg-1 in tea. Results of field trials indicated that (-)-penconazole degraded faster than its (+)-isomer in grape. While only a moderate stereoselectivity was observed in soil, with (-)-penconazole preferential degraded. The proposed method could be used to investigate enantioselective environmental behavior of penconazole enantiomers in complex matrices. And results in this study could provide useful information on realistic risk assessment of penconazole in grape.

9,10-Anthraquinone deposit in tea plantation might be one of the reasons for contamination in tea.

9,10-Anthraquinone (AQ) was a new contaminant, with unknown sources, occurred globally in tea. European Union (EU) fixed the maximum residue limit (MRL) of 0.02mg/kg. The pollution source of AQ in tea was traced from the view of AQ deposit on tea crop by simulation. The possible contamination pathway and main factors to decrease AQ were explored in tea cultivation- tea manufacture- tea infusion, on the basis of AQ analytical methods by using solvent extraction and gas chromatography-tandem mass spectrometry (GC-MS/MS) quantification. 58.8-84.6% of AQ degraded in tea processing, and drying played a key role to reduce the AQ contamination. Certain concentration of AQ deposited on tea shoots could resulted in AQ beyond the MRL of 0.02mg/kg in tea. AQ leaching into tea brew (about 10%) could lead to the possible health risk. AQ deposit on tea crop during the tea cultivation might cause the AQ contamination in tea.

Dissipation, transfer and safety evaluation of emamectin benzoate in tea.

The dissipation and residue of emamectin benzoate in tea leaves and the residue transfer from tea leaves to tea brew were investigated by modified QuEChERS (quick, easy, cheap, effective, rugged and safe) combined with ultra performance liquid chromatography tandem mass (UPLC-MS/MS). The average recoveries ranged 85.3-101.3% with relative standard deviation (RSD) less than 15%. The limits of quantification (LOQ) were 0.005mgkg(-1) in tea leaves and 0.0004mgL(-1) in brew. Emamectin benzoate dissipated rapidly in tea with half-life (t1/2) of 1.0-1.3days. The terminal residues of emamectin benzoate were less than 0.062mgkg(-1). The leaching rate of emamectin benzoate from freshly-made tea to brew was <5%. The risk of emamectin benzoate at the recommended dosage was negligible to humans depending on risk quotient (RQ) value, that was lower than 1 significantly. This study could provide guidance for the safe use of emamectin benzoate and serve as a reference for the establishment of maximum residue limits (MRLs) in China.

Simultaneous and enantioselective determination of cis-epoxiconazole and indoxacarb residues in various teas, tea infusion and soil samples by chiral high performance liquid chromatography coupled with tandem quadrupole-time-of-flight mass spectrometry.

A novel and sensitive method for simultaneous enantiomeric analysis of two pesticides-cis-epoxiconazole and indoxacarb-in various teas, black tea infusion, and soil samples has been developed. The samples were initially subjected to acetonitrile extraction followed by cleanup using lab-made florisil/graphitized carbon black mixed solid phase extraction (SPE) column (for the different teas and soil samples) and a BondElut C18-SPE column (for the black tea infusion samples). Separation of the analytes was performed on a chiral stationary phase using high performance liquid chromatography (HPLC) under a reversed-phase isocratic elution mode followed by tandem quadrupole time-of-flight mass spectrometry (Q-TOF/MS) detection. The mobile phase components, mobile phase ratios, flow rates, column temperatures, and MS parameters were all optimized to reach high sensitivity and selectivity, good peak shape, and satisfactory resolution. The performance of the method was evaluated based on the sensitivity, linearity, accuracy, precision, and matrix effects. Under optimal conditions, for the various teas (green tea, black tea, and puer tea), fresh tea leaf, soil and black tea infusion samples spiked at low, medium, and high levels, the mean recoveries for the four enantiomers ranged from 61.0% to 129.7% with most relative standard deviations (RSDs) being 17.1% or below. Good linearity can be achieved with regression coefficients (R) of 0.9915 or above for all target enantiomers, and matrix-matched calibration concentration ranging from 5.0 to 1000µg/L. The limits of detection (LODs) for all four target enantiomers were 1.4µg/kg or below in the different teas and soil samples and 0.05µg/kg or below in the black tea infusion, whereas the limits of quantification (LOQs) for those did not exceed 5.0µg/kg and 0.2µg/L, respectively. The proposed method is convenient and reliable and has been applied to real tea samples screening. It has also been extended for studies on the degradation kinetics and environmental behaviors in the field trials, providing additional information for reliable risk assessment of these chiral pesticides.

High-throughput analytical techniques for multiresidue, multiclass determination of 653 pesticides and chemical pollutants in tea--Part III: Evaluation of the cleanup efficiency of an SPE cartridge newly developed for multiresidues in tea.

A comparative study was conducted over three stages on the cleanup efficiency of SPE cartridge Cleanert TPT, newly developed for multigroups of pesticide residues in tea. In Stage I, different SPE cartridges C18, graphite carbon black (GCB), primary secondary amine (PSA), and amino (NH2) were purchased and combined into 12 different sequences. Through the comparative test on cleanup efficiency of 84 representative pesticides in tea, Envi-Carb GCB + PSA with a good cleanup effect was selected. In Stage II, GC/MS test results from the comparative study of the extraction efficiency of 201 pesticides spiked into green tea and Woolong tea with Cleanert TPT and Envi-Carb + PSA SPE showed that average recoveries fell within 70-110% and RSD <20% for 193 and 184 pesticides, respectively, for green tea, accounting for 96.0 and 91.0% of the total number, respectively. GC/MS/MS test results also found 193 and 184 pesticides, respectively, meeting the recovery and RSD conditions, accounting for 96.0 and 91.5%, respectively, of the total number. For Woolong tea samples, GC/MS results showed that with Cleanert TPT and Envi-Carb + PSA SPE for cleanup, there were 192 and 177 pesticides, respectively, meeting the conditions, accounting for 95.5 and 88.1% of the total number, respectively. GC/MS/MS results demonstrated that there were 195 and 184 pesticides, respectively, meeting the conditions, accounting for 97.0 and 91.5% of the total number, respectively. It was seen that Cleanert TPT was superior to Envi-Carb + PSA in cleanup efficiency, whether for green or Woolong tea samples, or GC/MS or GC/MS/MS determination. In Stage III, 61104 results of the average content value of pesticides and RSD (two teas xtwo Youden pair concentrations x two kinds of SPE cartridges x two instruments x 19 tests x 201 pesticides) were derived from the 19 times stability tests over 3 months by paralleling three samples every 5 days via two instruments with two kinds of SPE cartridges for cleanup, respectively, against Youden Pair samples of the 201 incurred pesticides from green and Woolong teas. The statistical analysis found that detected values from the target pesticides of the incurred Youden pair samples showed no marked differences with cleanup by either Cleanert TPT or Envi-Carb + PSA, whether for green or Woolong tea, or G/IMS or G/IM/IMS. The test results using the two aforementioned kinds of SPE cleanup for above 93% pesticides had a tolerance less than 15%, which testifies that both cartridge cleanups met the requirement for pesticide residue analysis.

[Determination of 92 pesticide residues in tea by gas chromatography with solid-phase extraction].

A multiresidue analytical method was developed for the determination of ninety-two pesticides in tea using solid-phase extraction (SPE) and gas chromatographic determination. Tea samples were extracted with acetonitrile, organophosphorus pesticides were clean-up by an Envi-Carb SPE cartridge, eluted with 10 mL acetonitrile-toluene (3:1, v/v) and determined by gas chromatography-flame photometric detection (GC-FPD); organochlorine pesticides and pyrethroids pesticides were cleaned-up by Envi-Carb + NH2 SPE cartridges, eluted with 5 mL acetonitrile-toluene (3:1, v/v) and determined by gas chromatography-electron capture detection (GC-ECD). The recoveries of those pesticides were ranged from 80.3% to 117.1% by fortification test with the relative standard deviations being from 1.5% to 9.8%. The limits of detection were 0.0025 - 0.10 mg/kg. The proposed method is characterized by simplicity, higher sensitivity and accuracy.