The bitter side of teas: Pesticide residues and their impact on human health.

Tea (Camellia sinensis) is one of the most widely consumed non-alcoholic beverages globally, known for its rich composition of bioactive compounds that offer various health benefits to humans. However, the cultivation of tea plants often faces challenges due to their high vulnerability to pests and diseases, resulting in the heavy use of pesticides. Consequently, pesticide residues can be transferred to tea leaves, compromising their quality and safety and potentially posing risks to human health, including hormonal and reproductive disorders and cancer development. In light of these concerns, this review aims to: (I) present the maximum limits of pesticide residues established by different international regulatory agencies; (II) explore the characteristics of pesticides commonly employed in tea cultivation, encompassing aspects such as digestion, bioaccessibility, and the behavior of pesticide transfer; and (III) discuss the effectiveness of detection and removal methods for pesticides, the impacts of pesticides on both tea plants and human health and investigate emerging alternatives to replace these substances. By addressing these critical aspects, this review provides valuable insights into the management of pesticide residues in tea production, with the goal of ensuring the production of safe, high-quality tea while minimizing adverse effects on human health.

Evaluation of a septumless mini-cartridge for automated solid-phase extraction cleanup in gas chromatographic analysis of >250 pesticides and environmental contaminants in fatty and nonfatty foods.

The QuEChERSER mega-method has recently been introduced to quantify and identify a wide range of chemical residues (pesticides, veterinary drugs, environmental contaminants, among others) in nearly all types of foods. The approach calls for taking a small amount of the initial extract to cover analytes amenable to liquid chromatography, and the remainder is salted out for analysis by gas chromatography (GC), both with mass spectrometry (MS) based detection. In the case of GC-MS(/MS), the extract undergoes automated robotic mini-cartridge solid-phase extraction (SPE) cleanup in a technique known as µSPE or instrument-top sample preparation (ITSP). In 2022, a septumless mini-cartridge for µSPE was introduced to improve upon the ITSP design. The new design houses a bed of 20 mg anhydrous MgSO4, 12 mg each of C18 and primary secondary amine sorbents, and 1 mg of graphitized carbon black, the latter substituting for CarbonX used in the ITSP product. The septumless µSPE mini-cartridge employs a different gripping mechanism with the syringe needle that allows leak-free operation at higher flow rates (e.g. 10 µL/s), whereas the ITSP design is limited to 2 µL/s. Based on cleanup and analyte elution profiles, the extract load volume and flow rate was increased in µSPE for QuEChERSER from 300 µL at 2 µL/s to 500 µL at 5 µL/s, which improved accuracy of results, sped the cleanup step, and obviated the need for micro-vial inserts in the receiving vials. The new design also reduced both the amount and consistency of dead (void) volumes in the mini-cartridges from 83 ± 14 µL to 52 ± 7 µL for 200-600 µL load volumes. Normalization of peak areas to internal standards led to recoveries between 80 and 120% with typical RSDs <5% in low-pressure GC-MS/MS of 227-242 out of 252 pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons in hemp powder, spinach, whole milk, egg, avocado, and lamb meat.

Pesticide residues in milk and dairy products: An overview of processing degradation and trends in mitigating approaches.

Milk and dairy products present considerable socioeconomic importance but are also a regular pesticide residue contamination source, which is considered a worldwide public health concern and a major international trade issue. Thus, a literature review was conducted to assess pesticide residue levels in milk and dairy products, as well as the residue degradation capacity during its processing. Organochlorine, organophosphate, synthetic pyrethroid and/or triazine were found in fluid milk, powder products, yogurts, cheese, butter, and sour cream. Thermal processing reduced most residue levels, although some treatments increased total hexachlorocyclohexane and its isomers (α-, γ-, δ-, and ß-). Emerging non-thermal treatments presented promising results, but some by-products had higher toxicity than their precursors. Biodegradation by lactic acid bacteria were effective during yogurt and cheese fermentation. However, ß-hexachlorocyclohexane level seems to increase in yogurts containing Lactobacillus acidophilus and Bifidobacterium animalis subsp. lactis, while increase or maintenance of pesticide residue concentration was observed during coagulation and cheese maturation. Deep research is needed to understand the isomerization and degradation mechanisms after thermal, non-thermal, and fermentation processing. Emerging heat technology can be an excellent topic to be investigated for pesticide residues degradation in the future. These mitigation approaches can be a feasible future alternative to milk and dairy production.

High-Throughput Mega-Method for the Analysis of Pesticides, Veterinary Drugs, and Environmental Contaminants by Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry and Robotic Mini-Solid-Phase Extraction Cleanup + Low-Pressure Gas Chromatography-Tandem Mass Spectrometry, Part 1: Beef.

In this work, a new mega-method of sample preparation called "QuEChERSER" (more than QuEChERS) is being presented for the first time. Fast, efficient, and cost-effective analysis of chemical contaminants in meat is useful for international trade, domestic monitoring, risk assessment, and other purposes. The goal of this study was to develop and validate a simple high-throughput mega-method for residual analysis of 161 pesticides, 63 veterinary drugs, 24 metabolites, and 14 legacy environmental contaminants (polychlorinated biphenyls) in bovine muscle for implementation in routine laboratory analyses. Sample preparation of 2 g test portions entailed QuEChERS-based extraction with 10 mL of 4:1 (v/v) acetonitrile/water, and then 204 µL was taken, diluted, and ultracentrifuged prior to analysis of veterinary drugs and pesticides by ultra-high-performance liquid chromatography-tandem mass spectrometry. The remaining extract was salted out with 4:1 (w/w) anhydrous MgSO4/NaCl, and 1 mL was transferred to an autosampler vial for automated mini-cartridge solid-phase extraction (Instrument Top Sample Preparation) cleanup with immediate injection using fast low-pressure gas chromatography-tandem mass spectrometry analysis. The automated cleanup and both instruments were all operated in parallel in 13-15 min cycle times per sample. Method validation according to United States Department of Agriculture requirements demonstrated that 221 (85%) of the 259 analytes gave average recovery between 70 and 120% and interday relative standard deviation of ≤25%. Analysis of a certified reference material for veterinary drugs in freeze-dried bovine muscle was also very accurate, further demonstrating that the QuEChERSER mega-method can be implemented to save time, labor, and resources compared to current practices to use multiple methods to cover the same analytical scope.

Persistence of indoor permethrin and estimation of dermal and non-dietary exposure.

Pesticides applied indoors may persist longer than they would in outdoor environments, making people more vulnerable to the risk of exposure. Permethrin is a pyrethroid insecticide used in agricultural, residential, and public health sites, and is commonly detected in indoor environments. The objectives of this study were to evaluate the persistence of permethrin indoors and to estimate the levels of possible dermal and non-dietary exposure to this insecticide. Permethrin was applied on aluminum foil and kept in a glass chamber and a test house for 112 days; its concentration was measured at application and after 28, 56, and 112 days. Permethrin persisted for the entire 112 days in concentrations equal to a maximum of 89.6% of the initial concentration. We observed low levels of human dermal and non-dietary exposure to permethrin.

High-throughput analysis of pesticides in minor tropical fruits from Colombia.

In this work, a method has been applied and validated for the determination of a group of 35 multiclass pesticides in the minor tropical fruits rose apple/pomarrosa (Syzygium malaccense), starfruit/carambola (Averrhoa carambola), yoyomo (Spondias purpurea) and papayuela (Vasconcellea pubescens) cultivated and exported in Colombia. The AOAC 2007.1 QuEChERS method, that uses an acetic acid/acetate buffer, was applied together with gas chromatography coupled to a triple quadrupole mass spectrometer. The method was validated in terms of calibration, recovery at three levels of concentration and matrix effects (MEs). A mixture of analyte protectants was also used. A good linearity was obtained in all cases, while the study of the ME revealed the need of developing matrix-matched calibration for many pesticides. Recovery values were in the range 70-120% with relative standard deviation values less than 20% for most of the pesticides studied. The lowest calibration level was 5 µg/kg. Several samples of each type were analysed.

National short-term dietary exposure assessment of a selected group of pesticides in Argentina.

An evaluation of acute dietary exposure to pesticide residues, applying deterministic and stochastic methods, was performed for a selected group of pesticides in two representative age groups from Argentina. Thus, 28 active ingredients (a.i.) and 75 food items were evaluated for the group of 2-5-year-old children, while 9 a.i. and 59 food items were considered for the 10-49-year-old women group. A deterministic assessment was conducting following the Food and Agriculture Organization (FAO) and World Health Organization (WHO) procedure but using the national maximum residue limits (MRLs) as pesticide residue concentration data, while in the stochastic approach, a theoretical distribution modeled with the available information was used. Food consumption data were obtained from the 2004-2005 comprehensive national nutrition and health survey. The risk was estimated by comparing the short-term dietary exposure with the acute reference dose (ARfD) values for each pesticide-food combination evaluated. In the deterministic assessment, 173 (39.1%) and 40 (31.3%) combinations exceeded the ARfD thresholds for the 2-5-year-old children and 10-49-year-old women groups, respectively. This conservative study generated relevant information as a first stage of acute dietary risk assessment in Argentina.

Pirimiphos-methyl residues in corn and popcorn grains and some of their processed products and the insecticide action on the control of Sitophilus zeamais Mots. (Coleoptera: Curculionidae) / Resíduos de pirimifós-metil em milho, milho pipoca, em alguns de seus produtos derivados e ação no controle de Sitophilus zeamais Mots. (Coleoptera: Curculionidae)

The degradation/persistence of residues of the organophosphorus insecticide pirimiphos-methyl was determined in corn and popcorn grains and in some of their processed products such as grain, bran, hominy and corn flour from corn and prepared popcorn and grain from popcorn. The action of the insecticide on the control of the corn weevil, Sitophilus zeamais Mots., was also evaluated. The grains were treated with the concentration of 12 mg.kg-1 (ppm) a.i. pirimiphos-methyl for the control of the weevils. Samples were taken at zero, 15, 30, 60, 120 and 240 days after treatment. Quantitative measurements were made by gas chromatography, by using a flame photometric detector. For pirimiphos-methyl residual action studies, samples of both types of grain were taken at 15, 30 days after treatment and subsequently at monthly intervals up to one year. Treated and non-treated (control) grains were infested with weevil adults. Mortality was checked 15 days after exposure. Pirimiphos-methyl residues were not persistent in either types of grains or their processed products. Residues dropped 5- 8-fold in corn bran and popcorn. They were stable in hominy and corn flour, but the concentration levels were low. Higher residues in corn bran than in grain are related to the higher oil content in that processed product. The insecticide remained effective against the pest over the entire period of observation (1 year) for both types of grains.

Foi avaliada a degradação/persistência dos resíduos do inseticida organofosforado pirimifós-metil em grãos e produtos derivados de milho (farelo, canjica e farinha de milho) e de milho pipoca (pipoca), bem como a ação residual do inseticida no controle do gorgulho do milho, Sitophilus zeamais Mots. Os grãos foram tratados com a concentração de 12 mg.kg-1 (ppm) de ingrediente ativo para controle do gorgulho. As amostras foram tomadas logo após o tratamento e também aos 15, 30, 60, 120 e 240 dias após o tratamento. A determinação quantitativa foi feita por cromatografia em fase gasosa, usando-se um detector fotométrico de chama. Para os estudos sobre a ação residual de pirimifós-metil, amostras de ambos os tipos de grãos foram tomadas aos 15 e 30 dias após o tratamento e subseqüentemente a intervalos mensais pelo período de um ano. Grãos tratados e não-tratados (testemunha) foram infestados com adultos do gorgulho. A mortalidade foi avaliada 15 dias após a exposição. Os resíduos de pirimifós-metil não foram persistentes em ambos os tipos de grãos nem nos seus produtos derivados. Os resíduos decresceram 5-8 vezes no farelo de milho e na pipoca. Na canjica e na farinha de milho eles foram estáveis, porém os níveis foram baixos. Resíduos maiores no farelo do que nos grãos estão relacionados com o maior teor de óleo no produto processado. O inseticida manteve-se eficiente contra a praga por todo período de observação (1 ano) para os dois tipos de grãos.