Fate of imidacloprid and acetamiprid residues during black tea manufacture and transfer into tea infusion

The objective of this paper is to investigate the loss/stability of neonicotinoids (imidacloprid and acetamiprid) residues during the manufacture of black tea and to study the transfer of these pesticides from made tea to its infusion. For orthodox black tea, the manufacturing process involves leaf harvesting (plucking two leaves and a bud), withering, rolling, fermentation (oxidation), and drying. Initial withering and final drying resulted in the loss of pesticide residues, but no significant reduction in residue levels resulted from the rolling and fermentation steps. The drying process resulted in a residue transfer of 64–70% and 69–74% of the initial level, whereas the brewing process resulted in a residue transfer of 37–39% and 45–49% of imidacloprid and acetamiprid, respectively, from dried tea into the infusion. The decrease in acetamiprid levels during drying was also significant (8–13%), whereas the total loss during the manufacturing process ranged from 26 to 31%. Further, brewing for longer periods (an extended brewing time) resulted in higher transfer (up to 44% for imidacloprid and 53% for acetamiprid) of pesticides to tea infusion. Further, the extent of pesticide leaching depends on its water solubility, partition coefficient, and the brewing time.     

Persistence of acetamiprid in tea and its transfer from made tea to infusion

Acetamiprid, a new-generation, highly active neonicotinoid insecticide has been used to control mites and insect pests. In the present study, the disappearance trend of acetamiprid residue in tea under field conditions was studied at two dosages for two seasons (dry and wet), and transfer of residues from made tea to infusion was also determined. Acetamiprid dissipation rate was found to be faster in the wet season. Half-life of acetamprid was found to be 1.82–2.33 days in green tea shoots and 1.84–2.25 days in made tea for both dry and wet seasons. The percent transfer of acetamiprid residues from made tea to infusion was 36.84–50.00%; however, 31.11–44.40% of the residues remained stuck to the spent leaves during both the dry and wet seasons. On the basis of transfer of residues from made tea to infusion, a waiting period of 15 days for tea plucking after pesticide application at recommended dose may be suggested.     

固相萃取-高效液相色谱-串联质谱法测定茶叶中啶虫脒、吡虫啉和氟虫腈残留量

目的建立茶叶中吡虫啉、啶虫脒和氟虫腈三种农药残留的固相萃取-高效液相色谱-串联质谱测定方法。方法样品用水浸泡,乙腈提取,经石墨化碳-氨基复合固相萃取小柱净化,采用Agilent Eclipse AAA色谱柱分离,以0.1%乙酸水溶液和乙腈为流动相梯度洗脱,正、负离子切换扫描,多反应监测(MRM)模式检测,外标法定量。结果在3个添加水平下,吡虫啉、啶虫脒和氟虫腈的平均回收率分别为78.8%~91.5%,81.3%~92.8%,和72.8%~90.0%;相对标准偏差分别为2.6%~10.6%,3.7%~6.6%和3.6%~7.4%。啶虫脒、吡虫啉和氟虫腈的检出限均为0.5μg/kg,定量限为2μg/kg。结论建立的方法简便、快速,灵敏度高,可满足出口茶叶中吡虫啉、啶虫脒和氟虫腈残留同时检测的要求。     

Residues and contaminants in tea and tea infusions: a review

Consumers are very aware of contaminants that could pose potential health hazards. Most people drink tea as an infusion (adding hot water); however, in some countries, including India, China and Egypt, tea is drunk as a decoction (tea and water are boiled together). An infusion usually brings the soluble ingredients into solution, whereas a decoction brings all soluble and non-soluble constituents together. Therefore, a cup of tea may contain various kinds of contaminants. This review focuses on green and black tea because they are most commonly consumed. The target was to examine the transfer rate of contaminants – pesticides, environmental pollutants, mycotoxins, microorganisms, toxic heavy metals, radioactive isotopes (radionuclides) and plant growth regulators – from tea to infusion/brewing, factors contributing to the transfer potential and contaminants degradation, and residues in or on the spent leaves. It is concluded that most contaminants leaching into tea infusion are not detected or are detected at a level lower than the regulatory limits. However, the traditional practice of over-boiling tea leaves should be discouraged as there may be a chance for more transfer of contaminants from the tea to the brew.     

同时脱除吡虫啉和啶虫脒农残的虚拟模板表面分子印迹的制备和应用

以吡虫啉和啶虫脒的结构类似物烟酰胺作为虚拟模板分子、α-甲基丙烯酸(α-methyl acrylic acid,MAA)作为功能单体、乙二醇二甲基丙烯酸酯(ethyleneglycol dimethacrylate,EDGMA)作为交联剂,采用表面分子印迹技术(MIT)制备了虚拟模板表面分子印迹聚合物(dummy template surface molelecularly imprinted polymers,DMIP)。在单因素实验的基础上采用响应面优化法对DMIP的制备方法进行优化,利用扫描电子显微镜对优化后的DMIP形态结构进行表征,考察了DMIP对于吡虫啉和啶虫脒的吸附性能。结果表明,DMIP对吡虫啉和啶虫脒具有较高的吸附容量和选择性,对吡虫啉和啶虫脒的最大吸附量分别为41.73和21.95 mg/g。将DMIP作为柱填充材料从茶多酚中脱除吡虫啉和啶虫脒,去除率分别达到96.2%和95.6%。所得DMIP对茶多酚等天然植物提取物生产过程中吡虫啉和啶虫脒的去除具有良好的应用前景。     

Irreversible sediment formation in green tea infusions

The formation of irreversible tea sediment (IRS) and its chemical components in green tea infusions were investigated. The results showed that the amounts of IRS in the green tea infusions from various tea cultivars ranged from 0.10 to 1.47 mg/mL. The amount of IRS was influenced remarkably by the chemical components in the green tea infusion. Principal component analysis and regression analysis indicated that gallated catechins, Mn, Ca, caffeine, Na, and (-)-gallocatechin gallate (GCG) were the principal components. IRS (mg/mL) = -4.226 + 0.275 gallated catechins + 79.551 Na + 7.321 Mn + 21.055 Ca + 0.513 caffeine - 0.129 GCG (R2 = 0.697). The contents of the main chemical components in the reversible tea sediment (RTS) and IRS were markedly different, especially the minerals. Large amount of minerals participated in the formation of irreversible green tea sediment. The amount of IRS increased with the extraction temperature.     

结冷胶发酵液微滤除菌工艺

采用有机微滤膜对结冷胶发酵液进行过滤除菌实验。考察了不同膜材料的过滤性能,以及结冷胶浓度、温度、压力等操作参数对除菌效果的影响。将结冷胶发酵液脱酰基处理后稀释成浓度为3 g/L的料液,再将酸碱度调至pH10,在0.1 MPa、65℃下用孔径为0.45μm的聚醚砜膜过滤,菌体去除率和结冷胶回收率分别为97%和84%。滤膜污染后采用0.75%HCl和1%NaOH交替清洗,可使膜通量得到较好地恢复。     

陶瓷膜微滤技术在牛乳除菌中的应用

对陶瓷梯度膜用于牛乳微滤除菌的效果及其可行参数进行了研究.结果表明,0.8与1.2 μm孔径梯度膜对细菌高效截流,截留率达到了99.5%以上.0.8μm孔径梯度膜在温度为50℃、浓缩20倍的条件下,蛋白截流率为10%,膜通量为300L/(m2·h).     

Tracking residual organochlorine pesticides (OCPs) in green,herbal, and black tea leaves and infusions of commercially available tea products marketed in Poland

The content of residual organochlorine pesticides (OCPs) was examined in green, herbal, and black tea leaves as well as in their infusions prepared from tea products marketed in the main supermarkets in Poland. It was found that the detected mean levels of organochlorine residues in tea leaves ranged from ?1 dry weight. Among hexachlorocyclohexane isomers, γ-HCH in green tea occurred in the highest concentrations. Among dichlorodiphenyltrichloroethane (DDT) metabolites the highest level of p,p′DDT (1.96 ng g^?1 dw) was in green tea samples. The transfer of OCPs from tea leaves to brew was investigated. The present study revealed that during the infusion process, a significant percentage of the residues, particularly pesticides with high water solubility, were transferred to the infusions. The obtained results show that the percentage transfer of each pesticides from tea to the tea infusions ranged from 6.74% (heptachlor) to 86.6% (endrin). The detected residues were below current MRLs for these pesticides.     

Dissipation of imidacloprid in Orthodox tea and its transfer from made tea to infusion

Imidacloprid is a systemic insecticide used widely in controlling mites, mealy bugs and other related pests in fruits, vegetables and tea. The dissipation behaviour of imidacloprid residues in green tea shoots, made tea and its transfer potential from made tea to infusion in hot water was studied. Analysis in tea matrices of imidacloprid was carried out using high-performance liquid chromatography with diode array detection. Under field conditions, imidacloprid dissipation rate was found to be faster in the wet season than the dry season. Half lives in green shoots were in the range 1.14–1.23 and 1.03–1.09 days, and 1.14–1.25, 1.04–1.07 days in made tea, for the dry and wet season, respectively. The percent transfer of imidacloprid residue from made tea to infusion was in the range of 29.2–42.0% during the dry and wet season; however, 38.2% and 57.9% of the residues remained stuck to the spent leaves during the dry and wet seasons, respectively. On the basis of transfer of residues from made tea to hot water infusion, a waiting period of 7 days after pesticide application at a recommended dose for tea plucking is suggested.     

Efficient removal of spores from skim milk using cold microfiltration: Spore size and surface property considerations

Bacterial spores present in milk can cause quality and shelf-life issues for dairy products. The objectives of this study were to evaluate the effectiveness of microfiltration (MF) in removing Bacillus licheniformis and Geobacillus sp. spores from skim milk using membranes with pore sizes of 1.4 and 1.2 µm, and to investigate the role of spore surface properties in MF removal. Cell sizes were determined by scanning electron microscopy, surface charge by zeta potential analysis, and surface hydrophobicity by contact angle measurements. Commercially pasteurized skim milk was inoculated with a spore suspension at about 10⁶ cfu/mL, and then processed by MF using ceramic membranes at 6°C, a cross-flow velocity of 4.1 m/s, and transmembrane pressure of 69 to 74 kPa. Total aerobic plate and spore counts in the milk were determined before and after MF. All processing runs and surface and product analyses were conducted in triplicate, and data were analyzed statistically. For the same strain, spores were shorter and wider than vegetative cells, averaging 1.37 to 1.59 µm in length and 0.64 to 0.81 µm in width. Reduction of B. licheniformis spores significantly increased with a reduction in MF pore size, from 2.17 log for 1.4-µm pore size, to 4.57 log for 1.2-µm pore size. Both pore sizes resulted in almost complete removal of Geobacillus sp. spores. All spores and the ceramic membrane had a negative surface charge at milk pH, indicating an electrostatic repulsion between them. Bacillus licheniformis spores were hydrophilic, whereas Geobacillus sp. spores were hydrophobic. Consequently, Geobacillus sp. spores had a tendency to cluster in skim milk, preventing their passage even through the 1.4-µm MF membrane, whereas some B. licheniformis spores could still pass through a 1.2-µm membrane. This study demonstrates that efficient removal of spores from skim milk by cold MF may require a smaller membrane pore size than required for removal of vegetative cells of the same species, and that cell surface properties may interfere with the outcome of filtration as would be anticipated based on size alone.     

陶瓷膜微滤制备食用级浓缩磷脂的研究

用无机陶瓷膜微滤饲料级大豆磷脂-正己烷混合溶液制备出了杂质含量少、透明程度高的食用级浓缩磷脂。研究了膜孔径、压力、料溶比、温度与膜通量的关系以及不同膜孔径、溶料比、温度对磷脂丙酮不溶物含量、正己烷不溶物含量的影响。实验表明,在40℃,0.20MPa压力下,饲料级浓缩磷脂与正己烷质量比为1∶3的混合溶液用1.2μm孔径陶瓷膜微滤,初始膜通量为110L/(m2·h),微滤后产品中丙酮不溶物含量和正己烷不溶物含量分别为60.20%和0.0082%,符合食用级浓缩磷脂的要求。     

Total content and speciation of aluminium in tea leaves and tea infusions

A total of 29 tea samples of different origin, 13 green tea samples, 13 black tea samples, two semi-fermented and one white tea, imported to the Czech Republic, were collected and analysed for total content of aluminium (Al) in tea leaves and tea infusions, as well as for Al compounds in these infusions. The total content of metals in tea leaves differs according to the type of tea (green or black) and is probably influenced by many factors, e.g., soil properties. The HPLC/IC speciation of Al in tea infusions was performed for all samples. The addition of Al³⁺ to the tea infusion proved that Al³⁺, Al(Y)²⁺ and Al(X)¹⁺ species can be determined in tea infusions. Increased extraction time did not show any affect on Al speciation, neither did the addition of sugar. After the addition of lemon juice, the speciation changed in one sample of black tea and five samples of green tea. These findings suggest that lemon juice as an additive can significantly influence Al speciation in tea infusions.     

气相色谱-串联质谱法测定茶叶茶汤中多种农药残留量

目的采用Qu ECh ERS方法和气相色谱-串联质谱(gas chromatography-tandem mass spectrometry,GC-MS/MS)分析技术,建立茶叶茶汤中65种不同极性农药残留量的快速检测方法。方法利用乙腈(含1%乙酸)提取茶叶茶汤样品,分散固相萃取法净化样品,GC-MS/MS检测采用选择反应监测模式(selective reactions monitoring,SRM),灵敏度最高的离子对用作定量。结果 65种农药在3个浓度添加水平上的加标回收率范围是76%~134.6%,相对标准偏差(RSD,n=6)范围为1.0%~18.41%,茶叶样品定量限是0.15~3.0μg/kg,茶汤样品定量限是0.1~1.5μg/kg。结论该方法灵敏度高,准确性好,快速简便,适用于绿茶、乌龙茶、白茶和红茶中多种农药残留量的检测。     

Determination of essential and non-essential elements in various tea leaves and tea infusions consumed in Turkey

Tea is one of the most popular beverages in the world. Thus, the chemical components in tea are of great interest, especially in relation to health. In this study, 12 tea samples (10 black, 1 white and 1 green) and 5 herbal tea samples were purchased from supermarkets in Izmir, Turkey. Sample preparation has been performed using wet and microwave digestion procedures. The elemental content (Fe, Zn, Cu, Mn, Ni, Na and K) in the digests and infusions has been analysed. Generally, elemental contents in tea leaves were found to be higher than those in tea infusions. The accuracy of the method was checked and confirmed by standard reference material analyses. The comparison of wet and microwave digestion has not shown significantly different results. Therefore, the microwave digestion procedure was preferred because it is less laborious. The elemental intake related to tea consumption has also been studied.     

微滤-超滤组合工艺精制粗茶皂素的研究

针对纯度为70％左右的粗茶皂素体系,采用0．5μm的陶瓷微滤膜与截留相对分子质量为10000的螺旋卷式有机超滤膜（PW4040）组合工艺对粗茶皂素水溶液进行精制。结果表明,此组合工艺可以将粗茶皂素纯度提高到91％左右,皂素产品得率约为66％。根据皂素的性质对膜清洗再生进行了考察,陶瓷膜及超滤膜通量分别恢复到87．6％与93．0％左右。     

微孔滤膜与大孔树脂纯化苦瓜皂苷的工艺研究

研究苦瓜皂苷的纯化工艺,考察微孔滤膜精制、大孔树脂富集纯化苦瓜皂苷的性能和参数,苦瓜浸取液经过微孔滤膜精制,上大孔树脂柱,吸附平衡后将苦瓜皂甙富集于80%乙醇洗脱液中。冷冻干燥乙醇洗脱液所得的产品中苦瓜皂苷含量达79%。     

气相色谱-三重四级杆串联质谱法测定茶叶中 茚虫威、溴虫腈、啶虫脒残留

目的建立应用气相色谱质谱/质谱法(gas chromatography/mass spectrograph/mass spectrograph,GC/MS/MS)同时测定茶叶中茚虫威、溴虫腈和啶虫脒的方法。方法收集吉林省10个市的210份茶叶样品,样品经乙腈提取,氮吹浓缩,固相萃取柱净化,浓缩定容后,采用三重四级杆气质联用仪,MRM测定,对质谱测定的目标离子对进行选择。结果茚虫威、溴虫腈、啶虫脒的质量浓度在0.05~1.0μg/m L范围时,其峰面积与浓度间呈现良好的线性关系,方法的检出限和定量限分别为0.01 mg/kg和0.03 mg/kg,3种农药在3个添加水平下的平均加标回收率为84%~110%,相对标准偏差(relative standard deviation,RSD)≤10.12%。样品中茚虫威的超标率为2.86%,啶虫脒的超标率高达22.86%。结论 GC/MS/MS法的精密度和准确度较好,能够实现茶叶样品中茚虫威、溴虫腈和啶虫脒的同时准确测定。