Removal of imidacloprid and acetamiprid from tea infusions by microfiltration membrane

Removal of imidacloprid and acetamiprid in tea infusions by microfiltration membrane using dead‐end model was investigated in the present study. The results showed that microfiltration significantly promoted the removal of both pesticides (P < 0.05) in tea infusions. Furthermore, the extent of removal was strongly influenced by the pore size of membrane, operational pressure and the concentrations of tea infusions. The initial concentration of imidacloprid and acetamiprid showed no significant effect on their removal rates. The maximum removal rates were 79.7% for imidacloprid and 81.9% acetamiprid. The changes in major chemical components of tea infusions after microfiltration were evaluated. The results indicated that microfiltration caused no considerable changes in total polyphenols and total free amino acids, and small but statistically significant losses (6.3–18.0%) of eight catechins and three methylxanthines when filtration volume reached to 200 mL. The present study validated the application of microfiltration as a potentially feasible and promising method for the removal of imidacloprid and acetamiprid residues from tea infusions.     

Detection of aflatoxins in tea samples based on a class‐specific monoclonal antibody

An enzyme‐linked immunosorbent assay (ELISA) using a monoclonal antibody was established to detect aflatoxin B₁ (AFB₁) in tea. The antibody was prepared from a hybridoma derived by fusing Sp2/0‐Ag14 myeloma cells and immunised spleen B cells. The effects from pH, ionic strength, and organic solvents on immunoassay were optimised and the 50% inhibition (IC₅₀) value was 0.057 ± 0.007 ng mL^?1. Spiked black and green tea samples at 10, 20 and 50 ng g^?1 levels of AFB₁ were detected with this proposed ELISA. The recoveries for black tea samples ranged from 68.5% to 117.7% and 73.5 to 114.3% for green tea samples. This immunoassay showed no cross‐reactions with other mycotoxin family but good recognition with related aflatoxins. These results indicate that the ELISA assay could be used as a screening method for aflatoxin detection in tea samples.     

Liquid chromatography–electrospray ionization–tandem mass spectrometry method for determination of twenty multi-class pesticide residues in cashew

This paper describes an analytical methodology employing the extraction QuEChERS (Quick, Easy, Cheap, Effective, Robust and Safe) method and liquid chromatography coupled to mass spectrometry using electrospray ionization source (LC–ESI–MS/MS). The methodology was validated for the determination of twenty multiclass pesticides in cashew. It was evaluated for selectivity, linearity, limits of detection (LOD) and quantification (LOQ), matrix effect, as well as the precision and accuracy in terms of percentage of recovery. Analyses were performed by selected reaction monitoring (SRM) using two transitions (precursor ion → ion product). All pesticides studied showed good linearity with correlation coefficient greater than 0.99. LODs and LOQs ranged from 0.10 to 0.25 ng g⁻¹ and 0.30 to 0.75 ng g⁻¹, respectively. Due to the complexity of the sample, study the effect matrix was performed. Cashew apples samples spiked (5, 50 and 100 ng g⁻¹) showed recovery results ranging from 66 to 119 g/100 g, and RSD ≤ 12%, which is in accordance with standard recommended by Brazilian rules (ABNT NBR 14029/2005), except simazine. The validated method was applied to commercial samples obtained in Fortaleza-CE, Brazil, but no contamination of pesticides residues was observed.     

Multimycotoxin Determination in Tunisian Farm Animal Feed

Mycotoxins presence was evaluated in animal feed marketed in Tunisia for the first time ever. A QuEChERS method was performed to analyze the natural copresence of 22 mycotoxins (enniatins, beauvericin, ochratoxin A, aflatoxins, alternariol monomethyl ether, alternariol, tentoxin, zearalenone, deoxynivalenol, 3‐acetyldeoxynivalenol, 15‐acetyldeoxynivalenol, nivalenol, neosolaniol, diacetoxyscirpenol, T‐2 toxin, and HT‐2 toxin) in 122 Tunisian marketed feed samples, intended for poultry (n = 43), cattle (n = 35), rabbit (n = 12), sheep (n = 16), and horse (n = 16). Analytes detection and quantification were done using both liquid chromatography and gas chromatography coupled to tandem mass spectrometry. The analytical method showed good linearity (R > 0.996) and sensitivity, the limits of quantification ranged from 0.1 ng/g (enniatin A1) to 225 ng/g (3‐acetyldeoxynivalenol). Eighty‐five percent of the analyzed samples were positive. Poultry (n = 43) and rabbit (n = 12) feed samples were the most contaminated. Enniatin B was the most prevalent mycotoxin with values ranged between 0.5 ng/g for horse feed and 40 ng/g for poultry feed, followed by deoxynivalenol detected from 16 ng/g in cattle feed to 250 ng/g in poultry feed. None exceeded the limits set by EU recommendations for animal feed. Mycotoxins co‐occurrence was observed at most by five different mycotoxins (26%) and up to eight mycotoxins was recorded in 5% of samples. Furthermore, a relatively high copresence rate of different fusariotoxins was registered. Even if no toxicological concern was clearly revealed, the contamination is a real fact and will probably present influence on meat production and on food safety.     

Quantitative analysis of acrylamide in tea by liquid chromatography coupled with electrospray ionization tandem mass spectrometry

An effective sample preparation procedure was optimized and a liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed for the quantitative analysis of acrylamide in tea. [¹³C₃]-acrylamide was used as internal standard. Acrylamide was extracted at 25 °C for 20 min by 10 ml water followed by 10 ml acetonitrile, and then 4 g of magnesium sulfate and 0.5 g of sodium chloride were added to the above mixture under stirring thoroughly. In order to increase the response of acrylamide, 9 ml acetonitrile layer was taken and concentrated to 0.5 ml. Solid-phase extraction with an Oasis MCX cartridge was carried out for clean-up. The limit of detection (LOD) and limit of quantification (LOQ) were 1 and 5 ng/ml, respectively. The recovery efficiency of the extraction procedure ranged between 74% and 79%. The levels of acrylamide in 30 tea samples were less than 100 ng/g. Black, oolong, white and yellow tea samples had quite low acrylamide contents (<20 ng/g). Higher acrylamide levels occurred in baked, roasted, and one sun-dried green tea samples (46–94 ng/g).     

Comparison of extraction and isolation efficiency of catechins and caffeine from green tea leaves using different solvent systems

Catechins from green tea (Camellia sinensis L.) have received considerable attention due to their beneficial effects on human health, such as antioxidant and anticancer activities. Optimisation of extraction conditions of the catechins from green tea leaves was performed using different solvents (ethanol or distilled water), different extraction methods (ultrasound‐assisted, room temperature or reflux extractions) and various extraction times (0.5–24 h). The optimal extraction conditions were determined using 40% ethanol with ultrasound‐assisted extraction method for 2 h at 40 °C. In addition, two isolation methods for the recovery of catechins from green tea extracts were compared using different solvent combinations (chloroform/ethyl acetate versus ethyl acetate/dichloromethane). The results showed that the ethyl acetate/dichloromethane system could achieve much higher content of catechins than the other isolation approaches, indicating the method that extract catechins first with organic solvent such as ethyl acetate before removing caffeine is much effective than removing caffeine first when organic solvents are used for the recovery of catechins without caffeine from green tea extracts.     

Sample preparation optimization for the simultaneous determination of mycotoxins in cereals

The efficiency of three extraction solvents and three clean-up procedures was compared for simultaneous extraction and purification of aflatoxins (AFB1, AFB2, AFG1 and AFG2), ochratoxin A (OTA), and zearalenone (ZEA) from spiked cereal samples. The best recovery rates for all mycotoxins were achieved using methanol: water (80:20) as the extraction solvent and AOZ multi-functional immunoaffinity column (IAC), as clean up method with recovery values of 61–89%, while that of Oasis HLB and MycoSep 226 were 37–67% and 44–78%, respectively. Then, five variables in the IAC clean-up conditions, including primary conditioning with phosphate buffer saline (PBS) (0–10 mL) (X1), extract load up volume (10–20 mL) (X2), washing volume with PBS (10–20 mL) (X3), and eluting solution volumes with methanol (1–3 mL) (X4) and acetic acid (0–1.5 mL) (X5), were optimized for the specific purification and enrichment of the mycotoxins. Results showed that primary conditioning and PBS washing did not have a significant effect on the recovery responses of mycotoxins. Optimized conditions were selected as 0, 15, 10, 1.3, and 1.5 mL for X1–X5, respectively. The recovery rates of AFB1, AFB2, AFG1, AFG2, OTA and ZEA were within 93–104% in spiked rice, under optimal conditions. LOD and LOQ were 0.0125 and 0.05 ng/g for AFB1 and AFG1, 0.0037 and 0.015 ng/g for AFB2 and AFG2, 0.05 and 0.2 ng/g for OTA, and 0.5 and 2 ng/g for ZEA, respectively. Extraction of spiked cereal samples with methanol: water (80:20) and clean up using AOZ IAC column in optimal condition provided recovery range of 77–104% for all targeted mycotoxins.     

Analysis of tea catechins in vegetable oils by high‐performance liquid chromatography combined with liquid–liquid extraction

In this study, a method was developed for the determination of various tea catechins in vegetable oils. Firstly, vegetable oils including tea seed oil, sunflower seed oil and soya bean oil were extracted by methanol/water (40:60, v/v), and then, a high‐performance liquid chromatography (HPLC) method was developed for the simultaneous determination of GA, caffeine, EGC, EGCG, EC, ECG, GC, GCG, C and CG. For the compounds detected in tested vegetable oils, LODs were in the range of 0.05–1.65 ng, both intraday and interday relative standard deviations (RSDs) were <5.0%, and the recovery rates were in the range of 96.2–100.5% with RSD <3.7%. The results showed in vegetable oils which declared to had added tea catechins in, the concentrations of tea catechins were less than that showed in package label, and the content of EGCG was the highest in all samples. Therefore, the advancement made in our study will facilitate studies of tea catechins in oil industry.     

Polycyclic aromatic hydrocarbons (PAH) in various types of tea

For the analysis of the 16 PAH (EFSA-PAH), which are classified as priority for different food groups by the Scientific Committee on Food (SCF) and the Joint FAO/WHO Experts Committee on Food Additives (JECFA) in tea, a sensitive analytical Fast-GC/HRMS method was used. The sample preparation included accelerated solvent extraction (ASE) and the highly automated clean up steps, gel permeation chromatography and solid phase extraction. The analytical parameters, limit of detection (0.01–0.02 μg/kg) and limit of quantification (0.03–0.06 μg/kg), were determined. The repeatability (RSD, n = 3) of different PAH in fruit tea ranged from 0.1 to 11%. It was observed that the total contents of the 16 PAH in tea samples ranged from 14 to 2,662 μg/kg. The analysed tea samples showed an increasing presence of PAH in the following order: herbal and fruit tea (n = 7) < black tea (n = 11) < green tea (n = 11) < white tea (n = 3) < mate-tea (n = 8). The correlation coefficient (R) between BaP and the sum of the 16 EFSA-PAH was established considering the contamination amount in all the 40 tea samples analysed.     

Direct Determination of Molybdenum in Milk and Infant Food Samples Using Slurry Sampling and Graphite Furnace Atomic Absorption Spectrometry

A fast and efficient method to determine molybdenum, Mo, in milk and other infant food by atomic absorption spectrometry with electrothermal atomization employing slurry sampling was developed. Slurries were prepared in ultrapure water with 5 to 20 min of sonication in concentrations of 10% w/v. The injection of 5.0 μL of a 0.1% (v/v) cetyl trimethyl ammonium chloride solution before the temperature program reduced the effect of build-up of carbonaceous residues within the atomizer. Europium (chemical modifier) and niobium (permanent modifier) were chosen for use from several potential modifiers. The parameters of merit were obtained in the optimized conditions T _a  =  2,700 oC, T _p  = 2,000 oC, tp = 20 s, and Eu 5.0 μg + permanent Nb 500.0 μg. These parameters were linear working range up to 100.0 μg/L, limit of detection (1.1 ± 0.1) μg/L, aqueous calibration, and standard addition curves with r ² > 0.9900 and relative standard deviation of 0.6% to 8.7%. The accuracy was evaluated by recovery tests and by certified material analysis; the agreement among these numbers validated the method. The powdered sample concentrations were between 39 and 1,570 μg/kg.     

Monitoring and risk assessment of pesticide residues in yuza fruits (Citrus junos Sieb. ex Tanaka) and yuza tea samples produced in Korea

The objective of this study was to establish an analytical method to measure pesticides used to cultivate yuza (Citrus junos Sieb. ex Tanaka) and to analyze pesticide residue levels of yuza and yuza tea samples. Risk assessments were also performed by calculating estimated daily intake (EDI) and acceptable daily intake (ADI). An excellent linear correlation was achieved with coefficient correlation values of 0.9750–0.9999. Percent recoveries were 80.4–109.9% for most pesticides with a <6.9% relative standard deviation (RSD). The limits of quantification for the method were 0.10–0.67 μg/ml. The RSD of intra-day and inter-day variability was <15.3%. Seven pesticides in yuza (n = 80) and yuza tea (n = 75) were analyzed with the optimized analytical method. Acequinocyl, spirodiclofen and carbendazim were detected in yuza samples in the concentration range of 0.07–0.15 μg/g, 0.11–1.89 μg/g, and 0.03–5.15 μg /g, respectively, whereas chlorpyrifos, prothiofos, phosalone, and deltamethrin were not detected in yuza or yuza tea. The concentrations of acequinocyl, spirodiclofen and carbendazim ranged from 0.18–1.05 μg/g, 0.13–0.29 μg/g, and 0.17–2.36 μg/g, respectively, in yuza tea samples. The percent ratios of EDI to ADI for acequinocyl, spirodiclofen, and carbendazim were 24.6%, 22.7%, and 58.5%, respectively.     

Application of dispersive liquid–liquid microextraction for the determination of selected organochlorine pesticides in honey by gas chromatography–mass spectrometry

Dispersive liquid–liquid microextraction (DLLME) is a rapid and easy technique that consumes minute amounts of organic solvents. In this work, we present chemometric study on optimization of DLLME parameters for the extraction of aldrin, endrin, lindane, α-endosulfan, 4,4′-DDT and its metabolites from honey matrix. Method quantification limits (MQLs) vary between 0.3 ng/g for 2,4′-DDE and 4,4′-DDE to 13.2 ng/g for α-endosulfan and enable determination at levels below EU-established Maximum Residue Limits. The developed method is linear (R ² > 0.994) in the investigated range (MQL—100 ng/g), with preconcentration factors of 13.2–30.5 and good repeatability (CV ≤ 17%). A comparison with other available methods reported in the last decade is provided. The method has been applied to 19 real samples from Poland, and the results show that organochlorine pesticides (OCPs) are present in analysed honeys at levels not posing threat to human health (below 14 ng/g for sum of 4,4′-DDT and metabolites and below 5 ng/g for aldrin, endrin and lindane). To the best of our knowledge, this is the first reported application of DLLME for the determination of OCPs in honey.     

Simultaneous Determination of Caffeine and Aspartame in Diet Supplements and Non-Alcoholic Beverages Using Liquid-Chromatography Coupled to Corona CAD and UV-DAD Detectors

A method for the simultaneous determination of caffeine and aspartame in various diet supplements and non-alcoholic beverages is presented. The analytes were analysed by high-performance liquid chromatography coupled to a charged aerosol detector (Corona CAD) and ultraviolet-diode array detector (UV-DAD) simultaneously connected in series. The method was validated using a Thermo Hypersil Gold-C18 column packed with 5 μm shell particles (150 × 4.6 mm) and acetonitrile–water (15/85% v/v) mobile phase at a flow rate of 1.00 mL/min. The elaborated method was validated for linearity, precision and accuracy. The rapid HPLC–CAD–UV-DAD technique is suitable for quantifying caffeine and aspartame in the range of 0.25–75 μg/mL in diet supplements and non-alcoholic beverages. The limit of detection for caffeine and aspartame was 62 and 43 ng/mL for Corona CAD and 31 and 30 ng/mL for UV-DAD detector, respectively. Each analyte calibration curve had a correlation coefficient of at least 0.999 and was linear in the defined range. The accuracies of CAD and UV-DAD detection were all acceptable, with the mean value of 100% for aspartame and 98.3% for caffeine. Precision values ranged from 0.09% to 1.12%. The work has demonstrated that charged aerosol detector can be successfully used in a rapid screening technique for biologically active substances in non-alcoholic beverages and diet supplements.     

Multiresidue analysis of pesticides in tea by supercritical fluid extraction (SFE) and GC-MS

A multiresidue analysis of pesticides in tea using supercritical fluid extraction (SFE) and GC-MS was developed. The preprocessing using SFE shortened the total analysis time. The SFE extract contained less matrices than the extract obtained with organic solvents. However, these matrices disturbed instrumental analysis. So, the extract was cleaned up with ENVI?-Carb/NH2 and InertSep? SI cartridge. A recovery test was carried out for 245 pesticides spiked in samples at the level of 0.1 μg/g. Recovery rates of 178 pesticides ranged from 70 to 120%, the relative standard deviations (RSDs) were less than 15%, and quantitation limits were between 0.01 and 0.05 μg/g. Based on these results, this method is considered to be useful for multiresidue analysis of pesticides in tea samples.     

Determination of Anthraquinone Derivatives in Chang-Qing Tea by Using Cloud-Point Extraction and High-Performance Liquid Chromatography

In this paper, a cloud-point extraction method was developed for the determination of five anthraquinone derivatives in Chang-Qing tea by high-performance liquid chromatography. The optimum conditions for micelle extraction were obtained as follows—15% (w/v) Genapol X-080 as extractant, pH 3.5, liquid/solid ratio 80, and extraction time, 40 min. For cloud point preconcentration, 20% (w/v) NaCl was added, and the solution was incubated at 55 °C for 30 min. The detection limits for the five anthraquinone derivatives were in the range of 0.55–3.30 ng ml⁻¹. Average recoveries for the anthraquinone derivatives at three spiked levels were in the range of 84.3–104.1%. Relative standard deviations for six replicate determinations of Chang-Qing tea sample were below 2.39. The established method has been successfully applied to the determination of anthraquinone derivatives in Chang-Qing tea products from three different manufacturers.     

Applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry to screening for 140 pesticides in agricultural products

The applicability of GC, GC/MS and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to screening for 140 pesticides in agricultural products was examined. Validation of multi-residue screening methods for the determination of 88 pesticides in 12 crops (asparagus, cauliflower, burdock, carrot, broccoli, spinach, matsutake mushroom, orange, soybean, sesame, millet and tea) was done by GC and GC/MS. Of the 88 pesticides, 63 were obtained with recoveries in the range from 50 to 150% at the 0.1 microg/g level in the 12 crops. Applicability of the official methods in Japan to 74 pesticides, including 22 pesticides with low recovery (< 50%) by GC or GC/MS analysis, was also examined by LC/MS/MS. LC/MS/MS acquisition parameters were established for 67 pesticides in positive and negative electrospray ionization (ESI) modes. Of 67 pesticides validated in 7 crops using LC/MS/MS at the 0.1 microg/g level, 44 showed recoveries in the range from 50 to 150%. The occurrence of matrix interference in LC/MS/MS can lead to false-positive detection of MCPA in spinach, cabbage and orange and false-negative detection of four pesticides in orange, spinach, apple and unpolished rice. Good linearity was observed in the studied ranges by GC, GC/MS (r > 0.990) and LC/MS/MS (r > 0.995). Of the total of 140 pesticides validated by GC, GC/MS and LC/MS/MS, 107 were newly recognized as suitable subjects for screening.     

Evaluation of hot and cold extraction of bioactive compounds in teas

This study evaluated the bioactive compounds of different types of tea by comparing hot and cold infusions. A multivariate data analysis was carried out, where the principal components analysis (PCA) and hierarchical cluster analysis (HCA) were used. Phenolic compounds varied between 267.27–2896.00 mg GAE L^?1 and 215.10–7351.33 mg GAE L^?1 for hot (80 °C) and cold extraction (20–25 °C), respectively. In the case of their antioxidant activity, results with DPPH were 43.10‐73.67% for hot extraction and 46.80‐77.13% for cold extraction. The average values for the ABTS˙⁺ method ranged between 2535.43 and 33 300.17 μmol TE L^?1 and between 1110.34 and 38 300.67 μmol TE L^?1, respectively, for hot and cold extraction. Different compounds were identified by liquid chromatography in the samples evaluated, where caffeine presented the higher concentrations in the teas. Samples of green and black tea (hot extraction) and white tea (cold extraction) showed bacteriostatic activity for S. aureus and E. coli. No extract had any bactericide activity. The current study revealed that cold infusion was more efficient in the extraction of bioactive compounds.     

FTNIR Spectroscopic Method for Determination of Moisture Content in Green Tea Granules

The feasibility of measuring moisture content in green tea by Fourier transform near infrared (FTNIR) spectroscopic technique was investigated. Green tea granules samples with different moisture contents were scanned using FTNIR spectroscopy. The spectra were measured in diffused reflectance mode by keeping 4–5 g samples in small sample bottle. A partial least-square regression model was developed with vector normalization method in the near-infrared region (4,000–12,000 cm⁻¹ or 800–2,500 nm). The developed model was validated using cross-validation technique. Maximum coefficient of determination (r ²) value of 0.997 was obtained for the calibration model developed. The developed method was used further for quantification of moisture content in fresh green tea samples, and the results were compared with other methods like gravimetric method and moisture analyzer. Results indicated that FTNIR spectroscopy could be used for rapid detection of moisture content in green tea granules without destruction of samples. The measurement will take only 5–10 s.     

Melatonin contents in mulberry (Morus spp.) leaves: Effects of sample preparation,cultivar, leaf age and tea processing

The effects of sample preparation, cultivar, leaf age and tea processing on melatonin content of mulberry (Morus spp.) leaves were investigated. Sample preparation using ultrasonic technique in combination with solid phase extraction resulted in high recovery rate (76%), when compared to homogenisation in combination with liquid–liquid extraction procedure (12% recovery rate). The melatonin contents in mulberry leaves harvested from three major cultivars (Buriram 60, Sakonnakhon and Khunphai) grown in Thailand were identified and quantified using high-performance liquid chromatography combined with fluorescence detector. The average melatonin content of the mulberry leaves cv. Buriram 60 (279.6 ng/g dry weight (DW)) was higher than those of cv. Sakonnakhon (100.5 ng/g DW) and cv. Khunphai (40.7 ng/g DW). The melatonin contents of all cultivars tested were highest in the tip of the leaves, followed by that in the young leaves, whereas the lowest was found in the old leaves. The melatonin contents of the two types of tea produced from mulberry leaves cv. Buriram 60 were also determined. Heat treatment during tea processing decreased the melatonin content in mulberry leaves cv. Buriram 60 by approximately 87%, when compared to that of the fresh leaves. However, there were no significant differences between the melatonin contents of the mulberry leaf tea produced with blanching (mulberry green tea) and those produced without blanching (mulberry black tea).     

QuEChERS-UPLC-MS/MS法测定鸡蛋中19种氨基甲酸酯类农药及其代谢物残留量

采用QuEChERS-超高效液相色谱-串联质谱法（UPLC-MS/MS）同时测定鸡蛋中的19种氨基甲酸酯类农药及其代谢物残留量。鸡蛋样品通过乙腈提取,分散固相萃取净化,UPLC-MS/MS测定。19种氨基甲酸酯类农药及其代谢物残留在0.2~50 ng/mL范围内线性良好（R2>0.999）,方法的检出限为1.0~10 μg/kg。在添加水平为10、20、50 μg/kg时,回收率为69.3%~107.6%,相对标准偏差低于9.21%。该方法简单快速,高效准确,回收率高,能够满足鸡蛋中19种氨基甲酸酯类农药及其代谢物残留检测与确证的需要。