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Pyrrolizidine alkaloids (PAs) and their N-oxide (PANOs), as emerging environmental pollutants and chemical hazards in food, have become the focus of global attention. PAs/PANOs enter crops from soil and reach edible parts, but knowledge about their uptake and transport behavior in crops is currently limited. In this study, we chose tea (Camellia sinensis L.) as a representative crop and Sp/SpNO as typical PAs/PANOs to analyze their root uptake and transport mechanism. Tea roots efficiently absorbed Sp/SpNO, utilizing both passive and active transmembrane pathways. Sp predominantly concentrated in roots and SpNO efficiently translocated to above-ground parts. The prevalence of SpNO in cell-soluble fractions facilitated its translocation from roots to stems and leaves. In soil experiment, tea plants exhibited weaker capabilities for the uptake and transport of Sp/SpNO compared to hydroponic conditions, likely due to the swift degradation of these compounds in the soil. Moreover, a noteworthy interconversion between Sp and SpNO in tea plants indicated a preference for reducing SpNO to Sp. These findings represent a significant stride in understanding the accumulation and movement mechanisms of Sp/SpNO in tea plants. The insights garnered from this study are pivotal for evaluating the associated risks of PAs/PANOs and formulating effective control strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Applying selenium (Se) fertilizer is the only way to alleviate soil Se deficiency. Although effects of nanoselenium foliar application on plant growth and stress resistance have been extensively investigated, soil application of nanoselenium on soil microorganisms and their relationship with crop quality and soil health remains unclear. In this study, a steady-state homogeneous nanoparticle of epigallocatechin gallate Se (ESe) was synthesized, and a pot experiment was conducted applying ESe at five concentrations (0, 1, 10, 50, and 100 mg kg -1 ) to the tea planattion soil. The study revealed a significant increase in Se concentration in soil and tea with ESe application and identified 2.43-7.8 mg kg -1 as the safe and optimal range for soil application. Specifically, the moderate dose of ESe improved the tea quality [reduced tea polyphenols (TP), increased free amino acids (AA), and reduced TP/AA] and soil quality index (SQI). Besides, in marure tea leaves, antioxidant enzyme activities [promote catalase (CAT) superoxide dismutase (SOD), and peroxidase (POD)] increased, while level of oxidative stress [malondialdehyde (MDA), hydrogen peroxide (H 2 O 2 ) and superoxide anion (O 2 - )] decreased with ESe application. The 16S rRNA of the soil bacteria showed that ESe application significantly changed the community structure of soil bacteria but did not alter the diversity of the bacteria and the abundance of dominant taxa (phylum and genus levels). Statistical analysis of the taxonomic and functional profiles (STAMP) detected 21 differential taxa (genus level), mainly low-abundance ones, under the ESe application. Linear regression and random forest (RF) modeling revealed that the low-abundance bacterial taxa were significantly correlated with SQI (R 2  = 0.28, p < 0.01) and tea quality (R 2  = 0.23-0.37, p < 0.01). Thus, the study's findings suggest that ESe application affects soil and tea quality by modulating the low-abundance taxa in soil. The study also highlights the crucial role of low-abundance bacterial taxa of the rhizosphere in regulating soil functions under the ESe application., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The processing techniques, geographical origins, and harvesting seasons have a significant impact on tea compound accumulation, leading to different flavor characteristics and consumer preferences for tea. Herein, six categories of tea involving 1329 samples revealed the distribution characteristics via compound accumulation, as well as the impact of production regions and harvesting seasons on flavor chemicals. With the increasing fermentation degree, the average content of tea polyphenols, catechins, and theanine in dark tea decreased by 57.78%, 94.64%, and 98.57% compared to green tea, respectively. The compounds in tea fluctuate with the geographical origins and seasons, with theanine and free amino acids being more accumulated in the Jiangnan tea region in spring tea, while total polyphenols and catechins were more abundant in Southwest China's tea region in summer and autumn tea. This study comprehensively understands the accumulation characteristics of tea compounds corresponding to processing techniques and the geographical origins of Chinese tea., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Camellia sinensis (L.) is a perennial evergreen woody plant with the potential for environmental pollution due to its unique growth environment and extended growth cycle. Pollution sources and pathways for tea plants encompass various factors, including atmospheric deposition, agricultural inputs of chemical fertilizers and pesticide, uptake from soil, and sewage irrigation. During the cultivation phase, Camellia sinensis (L.) can absorb organic pollutants through its roots and leaves. This review provides an overview of the uptake and translocation mechanisms involving the absorption of polycyclic aromatic hydrocarbons (PAHs), pesticides, anthraquinone (AQ), perchlorate, and other organic pollutants by tea plant roots. Additionally, we summarize how fresh tea leaves can be impacted by spraying pesticide and atmospheric sedimentation. In conclusion, this review highlights current research progress in understanding the pollution risks associated with Camellia sinensis (L.) and its products, emphasizing the need for further investigation and providing insights into potential future directions for research in this field., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are phytotoxins produced by various plant species and have been emerged as environmental pollutants. The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots. This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics. Sorption amounts for seneciphylline (Sp) and seneciphylline-N-oxide (SpNO) in three acidic soils ranged from 2.9 to 5.9 µg/g and 1.7 to 2.8 µg/g, respectively. Desorption percentages for Sp and SpNO were from 22.2% to 30.5% and 36.1% to 43.9%. In the mixed PAs/PANOs systems, stronger sorption of PAs over PANOs was occurred in tested soils. Additionally, the Freundlich models more precisely described the sorption/desorption isotherms. Cation exchange capacity, sand content and total nitrogen were identified as major influencing factors by linear regression models. Overall, the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity. PANOs were more likely to migrate within soils and be absorbed by tea plants. It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Phenolamides (PAs) are important secondary metabolites present in plants with multiple bioactivities. This study aims to comprehensively identify and characterize PAs in tea (Camellia sinensis) flowers using ultra-high-performance liquid chromatography/Q-Exactive orbitrap mass spectrometry based on a lab-developed in-silico accurate-mass database. The PAs found in tea flowers were conjugates of Z/E-hydroxycinnamic acids (p-coumaric, caffeic and ferulic acids) with polyamines (putrescine, spermidine and agmatine). The positional and Z/E isomers were distinguished through characteristic MS 2 fragmentation rules and chromatographic retention behavior summarized from some synthetic PAs. 21 types of PAs consisting of over 80 isomers were identified, and the majority of them were found in tea flowers for the first time. Among 12 tea flower varieties studied, they all possessed tris-(p-coumaroyl)-spermidine with the highest relative content, and C. sinensis 'Huangjinya' had the highest total relative contents of PAs. This study shows the richness and structural diversity of PAs in tea flowers., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Background: Chlorpyrifos (CPF) is a broad-spectrum organophosphorus pesticide widely used to control tea geometrid (Ectropis oblique) and tea green leafhoppers (Empoasca pirisuga Matsumura) in tea trees. The major metabolite of CPF in water, plants, and animals is 3,5,6-trichloro-2-pyridinol, which is more toxic than CPF. However, the dissipation pattern of CPF in tea is unknown., Results: An optimized QuEChERS sample preparation method combined with ultra-performance liquid chromatography-tandem mass spectrometry was applied to determine the residues of chlorpyrifos and its metabolite in tea during tea planting and green tea processing. During tea planting, the sum of chlorpyrifos and its metabolite dissipated rapidly with a half-life of 1.93 days for tea shoots. The residues of chlorpyrifos and its metabolite in made green tea were 96.89 and 35.88 μg kg -1 on the seventh day. The values for processing factors of chlorpyrifos and its metabolite were all less than 1, showing that each green tea manufacturing step was responsible for the reduction. The transfer rates of chlorpyrifos and its metabolite from made green tea to its infusion were 0.68-4.62% and 62.93-71.79%, respectively., Conclusion: The risk of chlorpyrifos was negligible to human health based on the hazard quotient, which was 7.4%. This study provides information relevant to the reasonable application of chlorpyrifos in tea planting and is potentially helpful for tea exporting and importing countries to establish harmonized maximum residue limits. © 2020 Society of Chemical Industry., (© 2020 Society of Chemical Industry.)

As a widely used plant growth regulator, the gibberellic acid (GA 3 ) residue in tea has potential risk for human health. Herein, the degradation of GA 3 and its conversion into main metabolites were investigated during tea planting, manufacturing, and brewing using ultrahigh-performance liquid chromatography tandem mass spectrometry. The metabolite iso-GA 3 was first discovered during the tea production chain and identified using Q-Exactive Orbitrap mass spectrometry. GA 3 dissipated following first-order kinetics in tea shoots with half-lives ranging from 2.46 to 2.74 days. It was degraded into iso-GA 3 in tea shoots, which had a longer residual period than GA 3 . Meanwhile, external application of GA 3 could increase the proportion of growth-promoting endogenous phytohormones and lead to rapid growth of tea plants. During tea manufacturing, iso-GA 3 was quickly and massively converted from GA 3 . Fixing (heat at 220-230 °C) played an important role in the dissipation of GA 3 and iso-GA 3 during green tea manufacturing, but there were high residues of iso-GA 3 in black tea. High transfer rates (77.3 to 94.5%) of GA 3 and iso-GA 3 were observed during tea brewing. These results could provide a practical reference for food safety in tea and other agricultural products and the guidance for scientific application of GA 3 in tea planting.

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 (R 2 ) > 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This study aimed to determine the residues of fipronil, metabolites, and enantiomers in tea (Camellia sinensis) during tea planting and green tea manufacture. An AD-RH chiral column was used to separate the fipronil enantiomers. During tea planting, the half-lives of the sum of fipronil and metabolites were similar to those of fipronil, which were 2.37 and 3.88 days for tea shoots and mature leaves, respectively. The residues of fipronil and its metabolites increased 2.3-3.6-fold during green tea manufacture. The values for the processing factors of fipronil and metabolites ranged from 1.0 to 2.1. A slightly significant enantioselectivity of (R)- and (S)-fipronil was observed during tea planting and green tea manufacturing. The residue pattern indicated that fipronil should not be applied in tea gardens due to its long persistence. The maximum residual limits of fipronil and metabolites at 2 μg kg -1 were considered optimal.

The residues of 16 phthalate esters (PAEs) in fresh tea leaves and made tea were determined via gas chromatography-tandem mass spectrometry to study their distribution and degradation characteristics during tea planting and processing. Five PAEs were detected in all fresh tea leaves, and higher concentrations were detected in mature leaves. The distribution of PAEs in fresh tea leaves ranged from 69.7 to 2244.0 μg/kg. The degradative percentages of ∑ 5 PAEs during green tea manufacturing ranged from 61 to 63% and were significantly influenced by the drying process. The transfer rates of PAEs-D 4 ranged from 5.2 to 100.6%. PAEs with a high water solubility showed the highest transfer coefficient in the range of 91.8-100.6%, whereas PAEs with a high log K ow showed a low leaching efficiency below 11.9%. These results benefit the risk evaluation and establishment of a maximum residue limit for PAEs in tea.

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.

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.

The residues of gibberellic acid (GA(3)) in tea shoots, made tea, and tea infusion were determined by ultra-performance liquid chromatography tandem mass (UPLC-MS/MS) to study its degradation pattern during tea planting, processing, and brewing. The dissipation rate of GA(3) was described using first-order kinetics. Its half-life ranged from 1.67 to 2.01 days in tea shoots. Degradation and concentration during green tea processing had equally important functions on GA(3) residues in product intermediates and made tea. Except for water content, little GA(3) residue difference was found in tea shoots and made tea. GA(3) dissipated rapidly in the baking stage during processing. The transfer coefficient of GA(3) residues from made tea to infusion was from 26.23% to 54.55%. GA(3) extraction efficiency varied with different infusion times and concentrations of GA(3) in made tea. This research revealed that GA(3) may be safe when applied in tea gardens at suitable doses and picking intervals., (Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.)