Simple and sensitive determination of sulfites in Chinese herbal teas by ultrahigh-performance liquid chromatography tandem mass spectrometry.

Sulfites are used widely in food and beverage production to prevent browning or oxidation. However, the overingestion of sulfites is harmful to human health and may cause medical complications. Chinese herbal teas have been widely consumed for centuries. However, sulfite levels in Chinese herbal teas are rarely investigated and reported. Here, we present a simple, sensitive, and quantitative method to determine sulfites in Chinese herbal teas using ultrahigh-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) coupled with dispersive solid phase extraction. The method utilized a SeQuant ZIC-HILIC column for separation, and the optimal gradient eluents consisted of acetonitrile and aqueous solution with 0.1% acetic acid and 10 mM ammonium acetate. Porous chitosan/partially reduced graphene oxide/diatomite (CS/prGO/DM) composites were used as efficient dispersive solid phase extraction adsorbents for sample preparation. Several parameters were investigated during the extraction process, including sample-to-extraction solvent volume ratios, the extraction procedure and dosage of the adsorbent. Under the optimum conditions, the developed method gave a good determination coefficient (r2 > 0.99), low detection limits (0.51-12.1 µg kg-1) and high recoveries in the range of 83.8-102.7% at different spiked levels. The method has the great advantages of being time saving, good reproducibility and much lower detection limits when compared to titration methods. The method was further applied to analyze real herbal tea samples collected from the local market, demonstrating that our developed method is robust and useful for determining sulfites in practical application.

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.

Residue pattern of polycyclic aromatic hydrocarbons during green tea manufacturing and their transfer rates during tea brewing.

Residues of polycyclic aromatic hydrocarbons (PAHs) in green tea and tea infusion were determined using gas chromatography-tandem mass spectrometry to study their dissipation pattern during green tea processing and infusion. Concentration and evaporation of PAHs during tea processing were the key factors affecting PAH residue content in product intermediates and in green tea. PAH residues in tea leaves increased by 2.4-3.1 times during the manufacture of green tea using the electric heating model. After correction to dry weight, PAH residue concentrations decreased by 33.5-48.4% during green tea processing because of PAH evaporation. Moreover, spreading and drying reduced PAH concentrations. The transfer rates of PAH residues from green tea to infusion varied from 4.6% to 7.2%, and PAH leaching was higher in the first infusion than in the second infusion. These results are useful for assessing exposure to PAHs from green tea and in formulating controls for the maximum residue level of PAHs in green tea.

Profiling elements in Puerh tea from Yunnan province, China.

Puerh tea, as the most representative Chinese dark tea, has attracted global interest in recent years. Profiling the levels of metal elements in Puerh tea is very important since its presence is related to human health. In this study, 41 elements in 98 Puerh tea samples from Yunnan province, China including Puerh raw tea and Puerh ripe tea were evaluated by microwave digestion combined with inductively coupled plasma mass spectrometry . The content of toxic elements, essential elements and rare earth elements of Puerh tea from different regions was discussed in detail. The concentrations of Ba, Cr, As, Pb, Bi, Fe, Zn, V, Mn, Be, Ag and Tl showed significant differences (p < 0.05) by ANOVA analysis. Principal component analysis and linear discriminant analysis were used to describe the relationship of Puerh tea from different regions. This study provided a comprehensive database for Puerh tea quality control and intake risk assessment.

Occurrence and Residue Pattern of Phthalate Esters in Fresh Tea Leaves and during Tea Manufacturing and Brewing.

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 ∑5PAEs during green tea manufacturing ranged from 61 to 63% and were significantly influenced by the drying process. The transfer rates of PAEs-D4 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 Kow 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.

Solid-phase purification and extraction for the determination of trace neonicotinoid pesticides in tea infusion.

An analytical protocol that includes solid-phase purification and extraction is successfully developed for the determination of trace neonicotinoid pesticides in tea infusion. The method consists of a purification on amino-functionalized mesoporous silica SBA-15 followed by a solid-phase extraction based on graphene oxide before ultra high performance liquid chromatography with tandem mass spectrometry analysis. Parameters that significantly affected the extraction of the neonicotinoids onto graphene oxide, such as the amount of adsorbent, extraction time, pH, elution solvent, etc. were optimized. The amino-functionalized mesoporous silica SBA-15 has been proved to be an efficient adsorbent for removal of polyphenols especially catechins from tea infusion. Graphene oxide exhibits a very rapid adsorption rate (within 10 min) and high adsorption capacities for neonicotinoids at low initial concentration (0.01-0.5 mg/L). The analysis method gave a good determination coefficient (r(2) > 0.99) for each pesticide and high recoveries in the range of 72.2-95.0%. Powder X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and UV-vis spectroscopy were utilized to identify the structure and morphology of graphene oxide. The adsorption driving force of neonicotinoids on graphene oxide mainly depends on π-π electron donor-acceptor interaction and electrostatic interaction.

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.