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Pyrrolizidine alkaloids (PAs) and pyrrolizidine alkaloid N-oxides (PANOs) are toxic secondary metabolites in plants, and one kind of main exogenous pollutants of tea. Herein, the dissipation pattern and conversion behavior of PAs/PANOs were investigated during tea manufacturing and brewing using ultra high-performance liquid chromatography tandem mass spectrometry. Compared with PAs (processing factor (PF) = 0.73-1.15), PANOs had higher degradation rates (PF = 0.21-0.56) during tea manufacturing, and drying played the most important role in PANOs degradation. Moreover, PANOs were firstly discovered to be converted to corresponding PAs especially in the time-consuming (spreading of green tea manufacturing and withering of black tea manufacturing) and high-temperature tea processing (drying). Moreover, higher transfer rates of PANOs (≥75.84%) than that of PAs (≤56.53%) were observed during tea brewing. Due to higher toxicity of PAs than PANOs, these results are conducive to risk assessment and pollution control of PAs/PANOs in tea.

Gibberellic acid (GA3) is widely applied in agriculture and food worldwide. Profiling the degradation products and their formation pattern under stress are helpful for deeply understanding GA3 regulating plant physiology and GA3 safety in agricultural crops. This study firstly investigated the degradation behavior of GA3. Different stress factors such as light, pH and temperatures were investigated through photolysis and hydrolysis experiments. Five degradation products were identified using ultra high-performance liquid chromatography Q-Exactive Orbitrap mass spectrometry (UHPLC Q-Exactive Orbitrap MS). Three degradation products were produced under ultraviolet photolysis conditions. Two isomers (iso-GA3 and gibberellenic acid) were formed under alkaline conditions. In order to characterize each degradation product, complete mass fragmentation pathways of all analytes were initially established. These results could provide a practical reference for the safety of agricultural products and the guidance for scientific application of GA3 and proposed storage conditions of GA3.

Pyrethroid pesticides are widely used on tea plants, and their residues of high frequency and concentration have received great attention. Until recently, the residues of typical metabolites of pyrethroid pesticides in tea were unknown. Herein, a modified &ldquo, quick, easy, cheap, effective, rugged and safe&rdquo, (QuEChERS) method for the determination of three typical metabolites of pyrethroid pesticides in tea, using ultra performance liquid chromatography tandem mass spectrometry, was developed. The mixture of florisil, octadecylsilane, and graphite carbon black was employed as modified QuEChERS adsorbents. A Kinetex C18 column achieved good separation and chromatographic peaks of all analytes. The calibration curves of 3-phenoxybenzoic acid (3-PBA) and 4-fluoro-3-phenoxybenzoic acid (4-F-3-PBA) were linear in the range of 0.1&ndash, 50 ng mL&minus, 1 (determination coefficient R2 higher than 0.999), and that of cis-3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylic acid (TFA) was in the range of 1&ndash, 100 ng mL&minus, 1 (R2 higher than 0.998). The method was validated and recoveries ranged from 83.0% to 117.3%. Intra- and inter-day precisions were lower than or equal to 13.2%. The limits of quantification of 3-PBA, 4-F-3-PBA, and TFA were 5, 2, and 10 &mu, g kg&minus, 1, respectively. A total of 22 tea samples were monitored using this method, and 3-PBA and TFA were found in two green tea samples.

Pyrrolizidine alkaloids (PAs) and their corresponding N-oxides (PANOs) are natural plant toxins, which are widely distributed in various types of teas. The source of PAs contamination in tea is probably related to weeds in tea gardens. The method of simultaneously detecting PAs/PANOs in teas and weeds has not been reported. A sensitive method was developed for detecting 14 PAs/PANOs simultaneously in teas and weeds using ultra high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Sample preparation was optimized step by step. Sulfuric acid at 0.1 M was used to extract the target compounds. Large capacity PCX column was used to enrich target compounds and remove complex matrices effectively, following by the elution solvent with methanol containing 0.5% NH4OH. The method showed good linearity for all 14 analytes with regression coefficients (R2) > 0.99. Satisfactory recoveries of target compounds spiked at three concentrations (10, 50, 100 μg/kg) ranged from 68.6% to 110.2%, while intra-day and inter-day precision were below 18.5%. Limits of detection (LODs) and limits of quantification (LOQs) of 14 PAs/PANOs in different matrices were in the range of 0.001–0.4 μg/kg and 1–5 μg/kg, respectively. This method was firstly applied to monitor the occurrence of PAs/PANOs in different kinds of teas from China and weed samples collected in the local tea gardens. Seven PAs/PANOs (>LOQs) were detected in 15.32% of tea samples and maximum total PAs/PANOs content was 151.33 μg/kg. Pollution levels and patterns of PAs/PANOs were different significantly in various types of teas. Based on the occurrence of PAs/PANOs in teas and weeds, weeds in tea garden were likely to be the source of PAs/PANOs in teas and the most relevant contaminating species of tea samples could be Crassocephalum crepidioides (Benth.) S. Moore.

Trace plant hormones play an important role in tea growth, development and quick response to biotic and abiotic stresses. However, lack of a sensitive method limits the research on plant hormone regulation for tea quality and yields. Herein, a highly sensitive method was developed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) for profiling and quantification of 13 acidic phytohormones and their analogues, including auxins, abscisic acid and gibberellins in fresh tea leaves. After optimizing the different C18 columns and mobile phase systematically, an Agilent Eclipse Plus C18 column combined with the mobile phase A (acetonitrile) and B (water) was employed. Target acidic phytohormones were extracted using acidified methanol, and tea matrices were cleaned up by dispersive solid phase adsorbents of polyvinylpolypyrrolidone (PVPP) and graphitized carbon black (GCB) followed by polymer-based mixed-mode cation-exchange solid phase extraction. The method showed good linearity for all 13 analytes with regression coefficients (R2) > 0.998. Satisfactory recoveries of 12 analytes spiked with three levels ranged from 71.8% to 109.9%, while intra-day and inter-day precisions were below 20%. Limits of detection (LODs) and limits of quantitation (LODs) for 12 acidic phytohormones were 0.1–4.2 μg kg−1 and 0.3–13.9 μg kg−1, respectively. Finally, this method was firstly employed to analyze 13 analytes in fresh tea leaves (with the treatment of dormancy, light qualities, exogenous hormones and infestation of pests), highlighting its sufficient capability for rapid analysis of multiclass phytohormones in agriculture field.

Cartap applied widely in agricultural crops and tea plants is readily degraded into nereistoxin, resulting in a longer residual period and higher exposure risk to humans. The photolysis kinetics of cartap and nereistoxin in water and tea beverages was firstly investigated to explore the effect and mechanism of pesticide residue removal. Cartap and nereistoxin could be effectively photolyzed by ultraviolet and their photolysis rate increased with light intensity increasing. The photolysis percentage of cartap and nereistoxin in different solutions under ultraviolet irradiation of 200 W mercury lamp reached 81.8%-100.0% within 6 h. Relative to water solution, the water-soluble components in tea had an inhibition effect on the photodegradation of cartap and nereistoxin. This research provided a reference for the development of effective methods for the removal of cartap and its metabolite in water and tea beverages.

There are few studies for risk assessment of cartap and its metabolites, although cartap is easily transformed into metabolites which could induce higher toxicity. This study aimed to investigate the dissipation pattern of cartap and its metabolites during tea planting, manufacturing and brewing for evaluating the safety of cartap pesticide. Cartap metabolites were identified using Q-Exactive Orbitrap mass spectrometry. Half-lives of cartap in fresh tea leaves ranged from 0.49 to 0.59 days. Cartap decreased rapidly with time, and it was degraded into nereistoxin and cartap monothiol during tea production chain. Cartap monothiol residues dissipated rapidly by 98% in three days during tea planting. Nereistoxin had a longer residual period than cartap and it dominated the total residue in made tea after tea manufacturing. Transfer rates of nereistoxin during tea brewing ranged from 78.24% to 121.56%. Therefore, we suggested sum of cartap and nereistoxin residues as maximum residual limits in tea.