Selenium foliar application contributes to decrease ratio of water-soluble fluoride and improve physio-biochemical components in tea leaves.

The tea plant accumulates elevated levels of fluoride (F) from environmental sources. Drinking tea containing high F levels poses a potential threat to human health. Selenium (Se) was applied by foliar spray to investigate its effects on F accumulation and physiology in tea plant. Foliar application of different forms of Se, i.e., Na2SeO3, Kappa-selenocarrageenan, Selenomethionine and Nanoselenium, reduced F content in tea leaves by 10.17 %-44.28 %, 16.12 %-35.41 %, 22.19 %-45.99 % and 22.24 %-43.82 %, respectively. Foliar spraying Se could increase F accumulation in pectin through increasing pectin content and pectin demethylesterification to bind more F in the cell wall, which decreased the proportion of water-soluble fluoride in tea leaves. Application of Se significantly decreased the contents of chromium (39.6 %-72.0 %), cadmium (48.3 %-84.4 %), lead (2.2 %-44.4 %) and copper (14.1 %-44.6 %) in tea leaves. Foliar spraying various forms of Se dramatically increased the Se content and was efficiently transformed into organic Se accounting for more than 80 % in tea leaves. All Se compounds increased peroxidase activity by 3.3 %-35.5 % and catalase activity by 2.6 %-99.4 %, reduced malondialdehyde content by 5.6 %-37.1 %, and increased the contents of chlorophyll by 0.65 %-31.8 %, carotenoids by 0.24 %-27.1 %, total catechins by 1.6 %-21.0 %, EGCG by 4.4 %-17.6 % and caffeine by 9.1 %-28.6 %. These results indicated that Se application could be served as a potential efficient and safe strategy diminishing the concentration of F in tea leaves.

The beneficial or detrimental fluoride to gut microbiota depends on its dosages.

Fluoride, widely presented in drinking water and tea, may be detrimental or beneficial to the human health, depending on its dosages ingested. However, the relationship of different dosages of fluoride and gut microbiota is still unclear. In this work, the fermentation model using fecal samples provided by four volunteers was used to evaluate the effects of different dosages of fluoride (1, 2, 10 and 15 mg/L) on the gut microbiota in vitro. The result showed low dosages of fluoride (1 and 2 mg/L) had limited effect on the structure and functional Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway of gut microbiota. Furthermore, the low dosage of fluoride could promote the growth of beneficial gut microbiota, including Faecalibacterium and Lactobacillus. Whereas, the high dosage of fluoride (10 and 15 mg/L) significantly changed the composition and functional KEGG pathway of gut microbiota. Moreover, the high dosage of fluoride could also reduce the beneficial gut microbiota, including Faecalibacterium and Phascolarctobacterium, and increase the harmful bacterium including Proteobacteria and Enterobacteriaceae. Both low and high dosages of fluoride showed limited effect on the productions of short-chain fatty acids (SCFAs). Thus, the beneficial or detrimental fluoride to gut microbiota depends on its dosages. The fluoride is expected to serve as a food additive in suitable dosage to improve human health through modulation of the gut microbiota. Moreover, more attention should be paid to toxicity of fluoride with high dosage to gut microbiota.

Fluoride absorption, transportation and tolerance mechanism in Camellia sinensis, and its bioavailability and health risk assessment: a systematic review.

Tea is the one of the most popular non-alcoholic caffeinated beverages in the world. Tea is produced from the tea plant (Camellia sinensis (L.) O. Kuntze), which is known to accumulate fluoride. This article systematically analyzes the literature concerning fluoride absorption, transportation and fluoride tolerance mechanisms in tea plants. Fluoride bioavailability and exposure levels in tea infusions are also reviewed. The circulation of fluoride within the tea plantation ecosystems is in a positive equilibrium, with greater amounts of fluoride introduced to tea orchards than removed. Water extractable fluoride and magnesium chloride (MgCl2 ) extractable fluoride in plantation soil are the main sources of absorption by tea plant root via active trans-membrane transport and anion channels. Most fluoride is readily transported through the xylem as F- /F-Al complexes to leaf cell walls and vacuole. The findings indicate that tea plants employ cell wall accumulation, vacuole compartmentalization, and F-Al complexes to co-detoxify fluoride and aluminum, a possible tolerance mechanism through which tea tolerates higher levels of fluoride than most plants. Furthermore, dietary and endogenous factors influence fluoride bioavailability and should be considered when exposure levels of fluoride in commercially available dried tea leaves are interpreted. The relevant current challenges and future perspectives are also discussed. © 2020 Society of Chemical Industry.

Washing fresh tea leaves before picking decreases pesticide residues in tea.

BACKGROUND: The use of pesticides during tea plant cultivation helps agricultural production and prevents and controls pests, diseases and weeds. It is of the utmost importance to balance pesticide application with tea quality, safety and consumer health. The uptake of pesticides into plants may lead to the presence of residues that are hazardous to human health, especially for some foliar-applied insecticides. The movability or penetration behavior of a pesticide remains unknown after it has been sprayed on a tea leaf. RESULTS: Two organophosphate (acephate, trichlorfon) and three neonicotinoid pesticides (imidacloprid, thiamethoxam and acetamiprid) were confirmed with respect to their removal from the treated fresh leaves of tea saplings via washing in a phytotron. Four of the targets have little penetrative ability into tea leaves, mainly existing (> 92%) on the tea leaf surface, except for trichlorfon (> 70%), for 30 days. With higher vapor pressures, trichlorfon and acetamiprid had relatively higher penetration ratios of 8.63-29.60% and 0.28-8.03% respectively. Two organophosphate insecticides were found to degrade more quickly, with lower final amounts of residues on and in the whole leaf compared to the neonicotinoid pesticides. In a field test, these residues could be reduced by 45-72% after a pre-harvest interval of 3 days, and by 16-89% after 7 days, when the fresh tea shoots were sprayed with 2 or 4 L m-2 water. CONCLUSION: Pesticides with different structures have different penetration abilities on the tea leaf surface, and some pesticides in commercial tea can be reduced by spraying with water before fresh leaves are picked. © 2020 Society of Chemical Industry.

Evaluation of the feasibility of short-term electrodialysis for separating naturally occurring fluoride from instant brick tea infusion.

BACKGROUND: Removing excessive naturally occurring fluoride from tea and/or infusions is difficult because the process has low efficiency and causes secondary pollution. In this study, a novel electrodialysis (ED) technology was developed. We examined the effect of crucial parameters (electrolyte concentration, operation voltage, ED duration and initial concentration of the tea infusion) on defluoridation performance using a highly efficient ion-exchange membrane with five-compartment cells. RESULTS: The most effective ED system results were obtained at an electrolyte concentration of 10 g kg-1 and operating voltage of 20 V. Moreover, the fluoride removal capacity (10.70-66.93%) was highly dependent on the ED duration (1-15 min) and initial concentration of the tea infusion (0.5-10 g kg-1 ). The longer the ED duration and the lower the initial concentration, the higher was the defluoridation performance. During ED, limited loss of the main inclusions (total polyphenols, catechins, caffeine and selected ions) was observed. Furthermore, the D201 anion resin-filled ED stack (0.5-5 g) and improvement of concentrate compartment electrolyte (≥5 times the dilute compartment electrolyte) in the ED system enhanced the defluoridation rate significantly. CONCLUSION: ED is a potentially effective method that can be used for defluoridation in the deep processing of tea products. © 2019 Society of Chemical Industry.

Positron-emitting tracer imaging of fluoride transport and distribution in tea plant.

BACKGROUND: Tea (Camellia sinensis (L.) O. Kuntze) is a hyper-accumulator of fluoride (F). To understand F uptake and distribution in living plants, we visually evaluated the real-time transport of F absorbed by roots and leaves using a positron-emitting (18 F) fluoride tracer and a positron-emitting tracer imaging system. RESULTS: F arrived at an aerial plant part about 1.5 h after absorption by roots, suggesting that tea roots had a retention effect on F, and then was transported upward mainly via the xylem and little via the phloem along the tea stem, but no F was observed in the leaves within the initial 8 h. F absorbed via a cut petiole (leaf 4) was mainly transported downward along the stem within the initial 2 h. Although F was first detected in the top and ipsilateral leaves, it was not detected in tea roots by the end of the monitoring. During the monitoring time, F principally accumulated in the node. CONCLUSION: F uptake by the petiole of excised leaf and root system was realized in different ways. The nodes indicated that they may play pivotal roles in the transport of F in tea plants. © 2020 Society of Chemical Industry.

Insecticidal Activity and Insecticidal Mechanism of Total Saponins from Camellia oleifera.

Chemical pesticides are commonly used during the cultivation of agricultural products to control pests and diseases. Excessive use of traditional pesticides can cause environmental and human health risks. There are ongoing searches for new plant-derived pesticides to reduce the use of chemical pesticides. In this study, tea saponin extracts of different purities were extracted from Camellia oleifera seeds using AB-8 macroporous resin and gradient elution with ethanol. The insecticidal effects of the tea saponin extracts were evaluated by contact toxicity tests and stomach toxicity tests using the lepidopteran pest of tea plantation, Ectropis obliqua. The total saponins extracted using 70% ethanol showed strong contact toxicity (LC50 = 8.459 mg/L) and stomach toxicity (LC50 = 22.395 mg/L). In-depth mechanistic studies demonstrated that tea saponins can disrupt the waxy layer of the epidermis, causing serious loss of water, and can penetrate the inside of the intestine of E. obliqua. After consumption of the tea saponins, the intestinal villi were shortened and the cavities of the intestinal wall were disrupted, which resulted in larval death. This study highlights the potential of tea saponins as a natural, plant-derived pesticide for the management of plant pests.

Using stable isotope signatures to delineate the geographic point-of-origin of Keemun black tea.

BACKGROUND: Confirmation of food labeling that claims production in a small geographic region is critical to traceability, quality control and brand protection. In the current study, isotope ratio mass spectrometry (IRMS) was used to generate profiles of δ13 C and δ15 N to determine if the stable isotope signatures of Keemun black tea differ within the three counties that claim production. Other factors (cultivar type, leaf maturity and manufacturing process) were considered for their potential effects. RESULTS: Both cultivar type and leaf maturity have remarkable impact on the δ15 N values of tea leaves, and that the cultivar influenced the δ13 C values. Keemun black tea from Qimen county could be easily discriminated from samples from Dongzhi and Guichi counties based on δ15 N signatures. The k-NN model was cross-validated with an accuracy of 91.6%. Environmental factors and/or genotype seem to be the major reasons for δ15 N differences in Keemun black tea from the selected regions. CONCLUSION: This article provides a potential effective method to delineate the geographic point-of-origin of Keemun black tea based on δ15 N signatures. © 2018 Society of Chemical Industry.

Highly selective defluoridation of brick tea infusion by tea waste supported aluminum oxides.

BACKGROUND: Brick tea usually contains very high fluoride, which may affect human health. Biosorbents have received much attention for selective removal of fluoride because of low cost, environmental friendliness, and relative safeness. RESULTS: In the present study, a highly selective fluoride tea waste based biosorbent, namely, aluminum (Al) oxide decorated tea waste (Tea-Al), was successfully prepared. The Tea-Al biosorbent was characterized by energy-dispersive spectrometry, Fourier transform infrared spectroscopy, powder X-ray diffraction and X-ray photoelectron spectroscopic analysis. The Tea-Al sample exhibited remarkably selective adsorption for fluoride (52.90%), but a weaker adsorption for other major constituents of brick tea infusion, such as catechins, polyphenols and caffeine, under the same conditions. Fluoride adsorption by Tea-Al for different times obeyed the surface reaction and adsorption isotherms fit the Freundlich model. In addition, the fluoride adsorption mechanism appeared to be an ion exchange between hydroxyl and fluoride ions. CONCLUSION: Results from this study demonstrated that Tea-Al is a promising biosorbent useful for the removal of fluoride in brick tea infusion. © 2016 Society of Chemical Industry.

Critical factors determining fluoride concentration in tea leaves produced from Anhui province, China.

This study investigated the fluoride present in tea plants (Camellia sinensis (L.) O. Kuntze) and its relationship to soils, varieties, seasons and tea leaf maturity. The study also explored how different manufacturing processes affect the leaching of fluoride into tea beverages. The fluoride concentration in the tea leaves was significantly correlate to the concentration of water-soluble fluoride in the soil. Different tea varieties accumulated different levels of fluoride, with varieties, Anji baicha having the highest and Nongkang zao having the lowest fluoride concentration. In eight different varieties of tea plant harvested over three tea seasons, fluoride concentration were highest in the summer and lowest in the spring in china. The fluoride concentration in tea leaves was directly related to the maturity of the tea leaves at harvest. Importantly, the tea manufacturing process did not introduced fluoride contamination. The leaching of fluoride was 6.8% and 14.1% higher in black and white tea, respectively, than in fresh tea leaves. The manufacturing step most affecting the leaching of fluoride into tea beverage was withering used in white, black and oolong tea rather than rolling or fermentation. The exposure and associated health risks for fluoride concentration in infusions of 115 commercially available teas from Chinese tea markets was determined. The fluoride concentration ranged from 5.0 to 306.0mgkg(-1), with an average of 81.7mgkg(-1). The hazard quotient (HQ) of these teas indicated that there was no risk of fluorosis from drinking tea, based on statistical analysis by Monte Carlo simulation.

Zirconium­cerium modified polyvinyl alcohol/NaCMC biocomposite film: Synthesis of films through high-speed shear assisted technique and removal fluoride from water.

A new zirconium and cerium-modified polyvinyl alcohol (PVA) sodium carboxymethyl cellulose (NaCMC) film (PVA/CMC-Zr-Ce) was synthesized thru a high-speed shear-assisted method and its adsorption for the removal of fluoride was studied, in which the NaCMC provided -COONa for ion exchange between Na and Zr-Ce, thus the loading amount of Zr-Ce on films was accordingly increased. The morphology and structure of PVA/CMC-Zr-Ce were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Besides, the mechanical properties, water contact angle, and swelling ratio of film were also evaluated. The addition of high-speed shear improved the dispersion of the emulsion system, and PVA/CMC-Zr-Ce film with good adsorption performance and film stability was prepared. While, it was found that the adsorption capacity could reach 67.25 mg/g and equilibrium time could reach 20 min. The adsorption mechanism of PVA/CMC-Zr-Ce revealed that ion exchange between hydroxide and fluoride, electrostatic interactions and complexation were the dominating influencing factors. Based on these findings, it can be concluded that PVA/CMC-Zr-Ce film- synthesized with high-speed shear assistance technique is a promising adsorbent for fluoride removal from water.

Alleviation of fluoride-induced colitis by tea polysaccharides: Insights into the role of Limosilactobacillus vaginalis and butyric acid.

Endemic fluorosis has gained increasing attention as a public health concern, and the escalating risk of colitis resulting from excessive fluoride intake calls for effective mitigation strategies. This study aimed to investigate the potential mechanisms underlying the alleviation of fluoride-induced colitis by Tea polysaccharides (TPS). Under conditions of excessive fluoride intake, significant changes were observed in the gut microbiota of rats, leading to aggravated colitis. However, the intervention of TPS exerted a notable alleviating effect on colitis symptoms. Antibiotic intervention and fecal microbiota transplantation (FMT) experiments provided evidence that TPS-mediated relief of fluoride-induced colitis is mediated through its effects on the gut microbiota. Furthermore, TPS supplementation was found to modulate the structure of gut microbiota, enhance the relative abundance of Limosilactobacillus vaginalis in the gut microbiota, and promote the expression of short-chain fatty acid (SCFAs) receptors in colonic tissue. Notably, L. vaginalis played a significant role in alleviating fluoride-induced colitis and facilitating the absorption of butyric acid in the rat colon. Subsequent butyric acid intervention experiments confirmed its remarkable alleviating effect on fluoride-induced colitis. Overall, these findings provide a potential preventive strategy for fluoride-induced colitis by TPS intervention, which is mediated by L. vaginalis and butyric acid.

Correction: Fang et al. Gandouling Mitigates CuSO4-Induced Heart Injury in Rats. Animals 2022, 12, 2703.

In the original publication [...].

1H NMR-based metabolomics combined with chemometrics to detect edible oil adulteration in huajiao (Zanthoxylum bungeanum Maxim.).

Huajiao is a highly valued spice that is susceptible to fraudulent adulteration, particularly the addition of edible oils to increase weight and improve color. Nuclear magnetic resonance (1H NMR) and chemometrics were used to analyze 120 huajiao samples adulterated with different types and levels of edible oils. Using untargeted data and partial least squares-discriminant analysis (PLS-DA), the discrimination rate between types of adulteration reached 100% accuracy, and the R2 value of the prediction set for the level of adulteration using the targeted analysis dataset combined with PLS-regression methods reached 0.99. Triacylglycerols, major components of edible oils, were identified as a marker of adulteration through the variable importance in projection of the PLS-regression. A quantitative method based on the sn-3 triacylglycerol signal was developed that can achieve a detection limit of 0.11%. Testing of 28 market samples showed adulteration with various edible oils, with adulteration rates ranging from 0.96% to 4.41%.

Zirconium/lanthanum-modified chitosan/polyvinyl alcohol composite adsorbent for rapid removal of fluoride.

A novel and easily separable adsorbent in the shape of a membrane for the rapid removal of fluoride from water was prepared after testing Zr, La and LaZr to modify a chitosan/polyvinyl alcohol composite adsorbent (CS/PVA-Zr, CS/PVA-La, CS/PVA-LA-Zr). The CS/PVA-La-Zr composite adsorbent can remove a large amount of fluoride within 1 min of contact time, and the adsorption equilibrium can be reached within 15 min. The fluoride adsorption behavior of the CS/PVA-La-Zr composite can be described by pseudo-second-order kinetics and Langmuir isotherms models. The morphology and structure of the adsorbents were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The adsorption mechanism was studied using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), and which showed that ion exchange occurred mainly with hydroxide and fluoride ions. This study showed that an easily operable, low-cost and environmentally friendly CS/PVA-La-Zr has the potential to remove fluoride effectively from drinking water in a short time.

Simultaneous Analysis of 53 Pesticides in Safflower (Carthamus tinctorius L.) by Using LC-MS/MS Coupled with a Modified QuEChERS Technique.

OBJECTIVE: An optimized quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique was investigated and compared with the conventional QuEChERS technique for the simultaneous analysis of fifty-three pesticide residues in safflower using ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). METHOD: Graphitic carbon nitride (g-C3N4) consisting of a major amount of carbon and nitrogen with a large surface area was used as a QuEChERS adsorbent instead of graphitized carbon black (GCB) for safflower extraction purification. Validation experiments were performed using spiked pesticide samples, and real samples were analyzed. RESULTS: The linearity of the modified QuEChERS technique was evaluated with high coefficients of determination (R-2) being higher than 0.99. The limits of detection were <10 µg/kg. The spiked recoveries ranged from 70.4% to 97.6% with a relative standard deviation of less than 10.0%. The fifty-three pesticides exhibited negligible matrix effects (<20%). Thiamethoxam, acetamiprid, metolachlor, and difenoconazole were detected in real samples using an established method. CONCLUSION: This work provides a new g-C3N4-based modified QuEChERS technique for multi-pesticide residue analysis in complex food matrices.

Hierarchical camellia-like metal-organic frameworks via a bimetal competitive coordination combined with alkaline-assisted strategy for boosting selective fluoride removal from brick tea.

Developing an efficient and easy scale-up adsorbent with excellent fluoride adsorption and selectivity from brick tea is urgently desired. However, the separation of fluoride from tea is particularly challenging due to it contains abundant active compounds. Herein, we report ultrahigh fluoride adsorption from brick tea by a hierarchical camellia-like bimetallic metal-organic frameworks (MOFs). The hierarchical camellia-like Ca2Al1Fu is fabricated via a Ca/Al competitive coordination combined with alkaline-assisted strategy to tailor the morphology and porous structure. Subsequently, we systematically explore how the kinetic, thermodynamic, pH, and coexisting ions parameters employed during fluoride adsorption influence the resulting uptake behavior of Ca2Al1Fu. Further, sensory evaluation of the tea after adsorption is explored to determine the optimal dose that makes Ca2Al1Fu as a practical adsorbent for application. Importantly, the fluoride adsorption capacity of optical CaAlFu with mixed CaAl metals molar ratio of 2:1 is 3.15 and 2.11 times higher than that of pristine CaFu and AlFu, respectively. Theoretical results reveal that the boosting selective fluoride removal can be ascribed to the specific interactions between fluoride and CaAl coordinatively unsaturated bimetallic centers. These results present an effective design strategy for the construction of bimetallic MOFs with hierarchically porous structures for broad prospect in adsorption-based applications.

The types of brewing water affect tea infusion flavor by changing the tea mineral dissolution.

The effects of different brewing water samples, including natural drinking water (NDW), pure water (PW), mineral water (MW), distilled water (DW), and tap water (TW) on flavor and quality of green tea infusion were investigated. The results showed the dissolution rate of mineral substances varied greatly depend on the type of water used. Notably, the tea infusion brewed with MW showed the highest taste response and darker but higher brightness in color. Furthermore, the content of volatile compounds was highest in tea infusion brewed with NDW and lowest in tea infusion brewed with MW. The mineral substances content and pH were the main factors affecting volatile compounds in green tea infusion. Thereinto, Ca2+ and Fe3+ remarkably affected the content of alcohols and aldehydes in volatile compounds. These results suggested that water with a neutral pH value and lower mineral substance content is more conducive for brewing green tea.

Aggregating-agent-assisted surface-enhanced Raman spectroscopy-based detection of acrylamide in fried foods: A case study with potato chips.

This study developed a simple, rapid, stable, and reliable technique for acrylamide (AAm) detection through surface-enhanced Raman scattering (SERS) on an AgNPs substrate with an aggregating agent. Specifically, the agglomeration effects of five types of salt solutions (NaCl, KCl, MgCl2, Na2SO4, and MgSO4) were investigated at different concentrations and optimized using an orthogonal experiment. The optimal amounts of the aggregating agent, analytes, and AgNPs were 4, 4, and 12 µL, respectively. A linear relationship (peak area I1449 = 7.4197x + 5984.8, R2 = 0.9971) between the characteristic peak area and AAm concentration was established in the range of 10 to 500 µg/L, and the LOD was 2.5 µg/L. The recoveries and relative standard deviations in the analysis of potato chips samples were 94.67 %-117.50 % and 8.43 %-12.29 %, respectively. The results of the proposed method were consistent with those obtained by LC-MS/MS method. This study demonstrated that SERS has excellent potential for application in the qualitative and quantitative analyses of AAm in fried foods.

Gandouling Mitigates CuSO4-Induced Heart Injury in Rats.

We assessed the protective effects of Gandouling (GDL) on copper sulfate (CuSO4)-induced heart injuries in Sprague−Dawley rats, which were randomly divided into the control, CuSO4, GDL + CuSO4 and penicillamine + CuSO4 groups. The rats received intragastric GDL (400 mg/kg body weight) once per day for 42 consecutive days after 56 days of CuSO4 exposure, and penicillamine was used as a positive control. The levels of plasma inflammatory cytokines (IMA, hFABP, cTn-I and BNP) were determined using the enzyme-linked immunosorbent assay. The histopathological symptoms were evaluated using hematoxylin and eosin staining and transmission electron microscopy. To determine the underlying mechanism, Western blotting was conducted for the detection of the heme oxygenase 1 (HO-1) expression. The results revealed that GDL supplementation alleviated the histopathological symptoms of the rat heart tissue, promoted Cu excretion to attenuate impairment, and significantly decreased inflammatory cytokine levels in the plasma (p < 0.01). In addition, GDL increased the HO-1 expression in the rat hepatic tissue. The protective effect of GDL on the heart was superior to that of penicillamine. Overall, these findings indicate that GDL alleviates hepatic heart injury after a Cu overaccumulation challenge, and GDL supplements can be beneficial for patients with Wilson's disease.