Multiresidue Method Research Articles

Presença de pesticidas organoclorados selecionados (OCPs) em sedimentos e biota do Rio Satluj, Paquistão: primeiro relatório

In the developed countries, the use of OCPs (organochlorine pesticides) has been banned. However, in South Asia several of them are still in use. In Pakistan and India a constant addition of OCPs into the atmosphere has been indicated by various researchers. In this study levels of selected organochlorine pesticide residues were assessed in sediment and biota collected from four (4) water reservoirs (3 Barrages & 1 Siphon) on the River Satluj Pakistan, along 231 miles (372 km) of River stretch which was further divided into 12 sampling sites. It was aimed to find out the levels of organochlorine pesticide (OCPs) residues in sediments and from selected fish species (Labeo rohita, Wallagu attu, Cyprinus carpio) of the River Satluj Pakistan. The Organochlorine residues (seven pesticides) present in samples of sediments and biota were investigated through multi residue method, using Gas Chromatograph (GC-ECD).In the current study, the concentration of DDT, was investigated in Wallago attu (0.786-3.987 ppb), Labeo rohita (0.779-4.355 ppb) and Cyprinus carpio (1.234-5.654 ppb). DDE was also found in Cyprinus carpio (1.244-6.322 ppb), Wallag attu (0.877-4.221 ppb) and Labeo rohita (2.112-5.897 ppb). Aldrin was not observed in Labeo rohita and Wallago attu. Currently, lindane and DDE was found predominately high in the sediments of study area at SZ-4 (Panjnad Barrage) ranging (2.238-8.226 ppb) and (4.234-6.876 ppb), respectively. Heaptachlor was found only at SZ-4 (Panjnad Barrage) from the sediments with concentration ranging (0.032-234 ppb). In short all other residues investigated were found below the MCL (maximum concentration level) in all the compartments of the study area set by various agencies like WHO/FAO- Codex Alimenterious.

Risco determinístico e probabilístico no consumo de morangos com resíduos de agrotóxicos

ABSTRACT: Repeated presence of strawberries amongst produce with pesticide residues results in questionings related to the risks involved by its consumption. Deterministic and probabilistic risk assessment methods might be used depending on the available data. In the present study, both methods were used to estimate risks of pesticide intake by strawberry consumption. Strawberry samples along two years were analyzed via the multiresidue method. Results of active ingredients (a.i.) concentrations were organized and used for calculations for intake estimates. On the deterministic method, intake was calculated based on the data of a.i. concentration and consumption data coming from an online questionnaire and body weight between 5 and 70 kg. On the probabilistic method, the concentrations of a.i. and body weight of 60 kg were evaluated in two scenarios: a) consumption data from an online questionnaire or b) consumption data retrieved from Family Budget Survey of the Brazilian Institute of Geography and Statistics. In the 62 strawberry samples, 38 a.i. were quantified and in 25 samples the residue analyses were considered satisfactory and 37 had an unsatisfactory outcome. In the deterministic approach, 23% of the a.i. had a calculated intake higher than the acceptable daily intake (ADI) and risk concentrated in body weights between 5 and 30 kg. The risk is low when considering a body weight of 60 kg. All a.i. tested in the first scenario of the probabilistic method pointed towards some possibility of intake being higher than the ADI. In the second scenario, only the a.i. procymidone exceeded the ADI.

Multi-residue analysis of eight veterinary drugs in buffalo milk using liquid chromatography-tandem mass spectrometry†

Context There are still comparatively few methods for the detection of drug residues in buffalo milk. Aims This study aims to develop a method for the detection of drug residues in buffalo milk. Methods In this study, we developed an analytical method for veterinary drug residues in buffalo milk using liquid chromatography–tandem mass spectrometry. The multi-residue method was established for the simultaneous identification and quantitation of eight common veterinary drugs, including metronidazole, salbutamol, atropine, trimethoprim, hydrocortisone, kitasamycin, roxithromycin and tylosin. Key results The sample processing method for buffalo milk was compared and optimised. The precision, recovery and matrix effects of the method were validated. The precision and accuracy of all analytes ranged from 1.81% to 12.35% and 1.25% to 14.57%, respectively. The average recovery percentages varied between 93.59% and 114.57%, and the average matrix effect ranged from 87.12% to 103.76%. All eight analytes in buffalo milk exhibited stability under different treatment conditions. Conclusions The developed method was successfully applied to laboratory analysis and routine sample analysis. The method was demonstrated to be rapid, sensitive and reliable for the rapid monitoring of veterinary drug residues in buffalo milk. Implications The findings of this study contribute to the risk assessment of veterinary drug residues for preventing the human consumption of contaminated buffalo milk and its derivatives.

Simple multi-residue analysis of persistent organic pollutants and molecular tracers in atmospheric samples

We present a simple, selective and sensitive analytical method to quantitatively determine a wide range of halogenated persistent organic pollutants and molecular tracers in atmospheric samples. Identification and quantification was carried out by high-resolution gas chromatography, hyphenated with low-resolution mass spectrometry operating in electron impact (EI) and electron capture negative ionization (ECNI) mode. Optimization on a number of instrumental parameters was conducted to obtain ultra-trace detection limits, in the range of few fg/m3 for organohalogen compounds. Repeatability and reproducibility of the method was thoroughly evaluated. The analysis was validated with standard reference materials and successfully applied to actual atmospheric samples. The proposed multi-residue method provides a precise, affordable and practical procedure of sample analysis for environmental research laboratories with conventional instrumentation on a routine basis.•A simple combination of alumina, florisil and silica gel adsorbents was applied to sufficiently isolate polychlorinated biphenyls, organochlorine pesticides, polycyclic aromatic hydrocarbons, long chain n-alkanes, hopanes and steranes.•Full elution was achieved in two successive fractions, using small volumes of n-hexane and n-hexane/dichloromethane to recover all target substances.•To maximize analytical response, optimization was applied for three operating parameters in ECNI mode: i) ion source temperature; ii) emission current; and iii) electron energy.

A Rapid Determination of 30 Prohibited Pesticide Residues in Lycii Fructus by UPLC-MS/MS

Prohibited pesticide residues have become one of the main factors affecting the quality and safety of Lycii Fructus, However, rarely studies focus on the rapid determination of these residues. Here, a total of 30 kinds of prohibited pesticide residues were determined by ultra-performance liquid chromatography tandem triple quadrupole mass spectrometry (UPLC-MS/MS) in five different process ways. Pretreatment methods, chromatographic separation and detection conditions in mass spectrometry were all optimized accordingly. Among the five different pretreatment methods, the first and third solid phase extraction failed to provide high recoveries of sulfosulfuron compounds (both lower than 60%). Recovery of chlorphenamidine by the Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) was lower than 60%, which did not meet the requirements of trace determination. The concentrations of 30 prohibited pesticides residues treated by straightforward and solid phase extraction showed good linearity in their corresponding ranges, with correlation coefficients over 0.99. The average recoveries of straightforward ranged from 78.13% to 110.9%, while RSD ranged from 1.3% to 16.9%, albeit poor purification was observed. The recovery yield from solid phase extraction was between 67.75% and 103.08% with RSD value from 0.8% to 14.0%, which met the requirements of trace determination, this method has good precision and stability. These results could be employed to other Traditional Chinese Medicines (TCMs) in detecting prohibited pesticide residues.

A robust multi-residue method for the monitoring of 25 endocrine disruptors at ultra-trace levels in surface waters by SPE-LC-MS/MS.

Estrogenic endocrine disruptors are one of the biggest ecotoxicological threats in water that pose a significant ecological burden and health-risk for humans due to their high biological activity and proven additive effects. Therefore, we have developed and validated the most comprehensive and ultra-sensitive analytical method published to date, for reliable quantification of 25 high-risk endocrine disruptors at their ecologically relevant concentrations: naturally excreted hormones (estradiol, estrone, estriol, testosterone, corticosterone, and progesterone), synthetic hormones used for contraception and menopausal symptoms (ethinylestradiol, drospirenone, chlormadinone acetate, norgestrel, gestodene, tibolone, norethindrone, dienogest, and cyproterone) and bisphenols (BPS, BPA, BPF, BPE, BPAF, BPB, BPC, and BPZ). It is based on a solid-phase extraction of water samples, followed by a robust dansyl chloride derivatization with detection by liquid chromatography-tandem mass spectrometry with a single sample preparation and two analytical methods using the same analytical column and mobile phases. The achieved limits of quantitation are in the sub-ng L-1 range, and detection limits as low as 0.02 ng L-1, meeting the newest proposal for environmental quality standards (EQS) by the EU water framework directive for estradiol and ethinylestradiol. The method was extensively validated and applied to seven representative Slovenian water samples, where we detected 21 out of 25 analytes; 13 were quantified in at least one sample. Estrone and progesterone were quantified in all samples, reaching levels up to 50 ng L-1; ethinylestradiol was higher than the current EQS (0.035 ng L-1) in three samples, and estradiol was above its EQS (0.4 ng L-1) in one sample, proving the method's applicability and the necessity for monitoring these pollutants.

Multiresidue chromatographic method for the determination of antibiotic residues in honey by high-performance liquid chromatography with DAD detection

Clandestinely, consumers may be exposed to antibiotic (ATB) residues in honey, which could pose a health concern. For the first time, the simultaneous determination of Florfenicol (FF), Penicillin G (PG), and Tetracycline is described in this paper. The multiresidual method was developed and optimized using high-performance liquid chromatography (HPLC) coupled to a diode array detector (DAD). These ATBs were separated on a C18 analytical column after a cleanup process followed by solid-phase extraction (SPE). For the first time, the chromatographic conditions were perfected. After the method validation process, the method was used to assess ATB residues in four Lebanese honey samples. ATBs were separated in less than 15 min with an isocratic elution using a mixture of 80 % potassium dihydrogen phosphate aqueous solution, and 20 % acetonitrile. The UV detection was performed at 350 nm for TC, 224 nm for FF, and 230 nm for PG. The proposed method was linear (R2 ≥ 0.996) within the concentration ranges of 0.7-17.5 mg.Kg 1 for the three compounds. Both intra- and inter-day precision, expressed as RSD, were ≤15 %. The method was subsequently successfully applied to analyze examined ATB residues in honey samples collected from Lebanese beekeeping. The method described could be a valuable tool to conduct a comprehensive survey of honey samples produced in Lebanon, especially in the lack of serious national oversight.

Monitoring and Exposure Assessment of Fosetyl Aluminium and Other Highly Polar Pesticide Residues in Sweet Cherry.

Cherries are popular fruits due to their health benefits, organoleptic quality, and attractive appearance. Since highly polar pesticides are of low mass and amphoteric character, and are not amenable to traditional multi-residue extraction methods, they are more commonly not included in the pesticide monitoring program. This study aims to determine twelve highly polar pesticide residues in cherry samples intended for export from Turkey. A total of 16,022 cherry samples from 2018-2020 harvests in four production areas of Turkey were analyzed using a modification of the Quick Polar Pesticides method and liquid chromatography-tandem mass spectrometry. The method was validated at two fortification levels (0.01 and 0.05 mg kg-1), and good recoveries (87.4-111.4%) and relative standard deviations (<6%) were achieved for all analytes. The limits of quantification were in the range of 1.08-2.55 μg kg-1. Overall, 28.4% of the analyzed cherry samples were detected with phosphonic acid, calculated as fosetyl aluminium (fosetyl-Al) in amounts up to 77.7 mg kg-1. For 2304 samples (14.4%), the residues exceeded the European Union maximum residue level of 2 mg kg-1. There is no reason to be concerned about long-term exposure to phosphonic acid/fosetyl-Al, and the other highly polar pesticides through the consumption of sweet cherry.

Pesticide Residues and Heavy Metals in Vineyard Soils of the Karst and Istria

Pesticide residues and heavy metal concentrations were determined in two depths (0–20 and 20–40 cm) of Chromic Cambisol in 69 vineyards in the Slovenian winegrowing region of the Karst. Similarly, pesticide residues and heavy metal concentrations were also determined in two depths of Calcaric Cambisol in 11 vineyards in the other Slovenian and Croatian winegrowing regions of Istria. The topsoil (0–20 cm) was analysed for the presence of 176 different pesticidal active substances using two multiresidue analytical methods: (a) gas chromatography coupled with mass spectrometry (GC/MS) and (b) liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). Seven active substances (five fungicides and two insecticides) were detected in the soil samples. Their concentrations were compared with the maximum concentrations observed in the vineyards of the winegrowing regions of France, Italy, and Spain. In addition to pesticides, the soil samples were analysed for the presence of nine heavy metals commonly detected in vineyard soils. The concentrations of arsenic, cadmium, cobalt, chromium, copper, molybdenum, nickel, lead, and zinc were below the critical thresholds set by Slovenian legislation, with the exception of one soil sample in which the Cu concentration exceeded the critical threshold. Compared with the maximum concentrations measured in other vineyard soils in Spain, Italy, and France, the heavy metal concentrations in the vineyard soils of Karst and Istria were lower. Both the heavy metal concentrations and the residual concentrations of pesticidal active substances in the vineyard soils of the Karst and Istria regions were significantly lower than the concentrations that are occasionally discussed in the literature.

A short review of extraction methods associated with chromatographic analysis for the control of pesticide residues in processed fruit juices

In recent years, the number of publications related to the control of pesticides in food has been increasing, due to the risks associated with the intensive use of pesticides and the requirements of the legislations. This study aims to carry out a bibliographic review of research involving sample preparation and analysis of pesticides in processed foods of plant origin using efficient and modern methodologies for identifying and quantifying pesticide residues. This paper describes the studies related to food security and quality of processed products using chromatographic analysis related to Mass Spectrometry, modern multiresidue methods and the investigation of toxic residues in fruit juices. This study may assist the scientific community on the main advances in techniques for controlling the levels of residues in juices. The data emphasizes the importance of continuous monitoring of the processed product chain and seeks to encourage an increase in the scope of legislations.

Establishment of an LC-MS/MS Method for the Determination of 45 Pesticide Residues in Fruits and Vegetables from Fujian, China.

Pesticide residues in food have become an important factor seriously threatening human health. Therefore, this study was conducted to determine the pesticide residues in fruits and vegetables commonly found in Fujian, China, with the aim of constructing a simple and rapid method for pesticide residue monitoring. We collected 5607 samples from local markets and analyzed them for the presence of 45 pesticide residues. A fast, easy, inexpensive, effective, robust, and safe (QuEChERS) multi-residue extraction method followed by liquid chromatography equipped with triple-quadrupole mass spectrometry (LC-MS/MS) was successfully established. This 12-min-long analytical method detects and quantifies pesticide residues with acceptable validation performance parameters in terms of sensitivity, selectivity, linearity, the limit of quantification, accuracy, and precision. The linear range of the calibration curves ranged from 5 to 200 mg/L, the limits of detection for all pesticides ranged from 0.02 to 1.90 μg/kg, and the limits of quantification for the pesticides were 10 μg/kg. The recovery rates for the three levels of fortification ranged from 72.0% to 118.0%, with precision values (expressed as RSD%) less than 20% for all of the investigated analytes. The results showed that 726 (12.95%) samples were contaminated with pesticide residues, 94 (1.68%) samples exceeded the maximum residue limit (MRL) of the national standard (GB 2763-2021, China), 632 (11.23%) samples were contaminated with residues below the MRL, and 4881 (87.05%) samples were pesticide residue-free. In addition, the highest number of multiple pesticide residues was observed in bananas and peppers, which were contaminated with acetamiprid, imidacloprid, pyraclostrobin, and thiacloprid.

Analysis of highly polar pesticides in foods by LC-MS/MS.

Highly polar pesticides (HPP) are a group of pesticides that are characterize as low Log Kow. Many high-throughput multi-residue analysis methods based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the simultaneous determination of such polar pesticides have been proposed. In this article, we summarize the various sample preparation methods including quick polar pesticides (QuPPe), dispersive solid phase extraction (dSPE), solid phase extraction (SPE) and QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe), especially for QuPPe, which are mainly used for the determination of HPP in foods. In addition, we summarize LC-based separation methodologies that are currently used for the analysis of HPP in foods, including reversed-phase chromatography (RPC), hydrophilic interaction liquid chromatography (HILIC), ion chromatography (IC) and mixed-mode chromatography (MMC). Finally, the current mass spectrometry-based methodologies for the analysis of HPP are summarized with a specific focus on MS configurations and acquisition modes.

Development of QuEChERS-based multiresidue analytical methods to determine pesticides in corn, grapes and alfalfa

Analytical methods based on QuEChERS and liquid chromatography-tandem mass spectrometry were developed for the determination of 42 polar and semi-polar pesticides in three representative vegetable matrices, viz. corn, grapes and alfalfa. A 26-2 fractional factorial experimental design was used to cost-effectively optimize the extraction procedure. The optimal analytical approaches were validated in terms of linearity, sensitivity, trueness, and precision. Most of the target pesticides showed a relative recovery of 70–120 %. Moreover, limits of detection (between 0.01 ng/g and 20 ng/g) were below the maximum residue levels set for the target analytes in nearly all cases. Analysis of real samples showed the presence of five pesticides in grapes and alfalfa at concentrations between the method LOQs and 40 ng/g. To the authors’ knowledge, these methods are the first ever described for the determination of 6, 13 and 24 of the 42 target pesticides measured in corn, grapes and alfalfa, respectively.

Validation of a Multi-Residue Analysis Method for 287 Pesticides in Citrus Fruits Mandarin Orange and Grapefruit Using Liquid Chromatography-Tandem Mass Spectrometry.

Since the introduction of the positive list system (PLS) for agricultural products in the Republic of Korea, the demand for a quick, easy multi-residue analysis method increased continuously. Herein, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique combined with liquid chromatography−tandem mass spectrometry was employed to optimize a method for the multi-residue analysis of 287 pesticide residues in mandarin orange and grapefruit. Method validation was conducted in terms of selectivity, limit of quantitation (LOQ), linearity, accuracy, precision, and matrix effect. All the compounds at low spiking levels (1, 2.5, 5, or 10 mg/kg) could be quantified at LOQs lower than 0.01 mg/kg (PLS level). The linearity of the matrix-matched calibration curve for each compound is in the range 0.5−50 μg/L, and its coefficient of determination (R2) is >0.990. Satisfactory recovery values of 70−120% with a relative standard deviation of ≤20% are obtained for all compounds in the mandarin orange and grapefruit samples. A negligible matrix effect (−20−20%) is observed for more than 94.8% and 85.4% of the pesticides in mandarin orange and grapefruit, respectively. Therefore, this analytical method can contribute to pesticide residue analyses of citrus fruits for routine laboratory testing.

Development of GC–MS/MS method for environmental monitoring of 49 pesticide residues in food commodities in Al-Rass, Al-Qassim region, Saudi Arabia

The harmful effects of pesticide residues are a threat to our health. Therefore, the current study aimed to validate a simple method for the determination of pesticide residues in commonly consumed fruits and vegetables from Al-Rass, Al-Qassim region, Saudi Arabia. A total of 1430 samples were collected from a local market and then analyzed for monitoring of 49 pesticide residues. A quick, easy, cheap, effective, rugged, and safe (QuEChERS) multi-residue extraction method followed by gas chromatography equipped with triple-quadrupole mass spectrometry (GC–MS/MS) was successfully implemented. This 17-min-run analytical method detects and quantifies pesticide residues with acceptable validation performance parameters in terms of sensitivity, selectivity, linearity, the limit of quantification, accuracy, and precision. The linear range of the calibration curves ranged from 10 to 300 µg/L, all the pesticide LODs ranged from 0.0005 to 0.0024 mg/kg, and the pesticide LOQs ranged from 0.0011 to 0.0047 mg/kg. The recovery values at the three fortification levels ranged from 78 % to 107 %, and the precision values (expressed as RSD%) were less than 20 % for all of the investigated analytes. The results showed that 138 (9.65 %) of the analyzed samples were contaminated with pesticide residues, 40 (2.80 %) of the analyzed samples exceeded the maximum residue limit (MRL) of the European Commission regulations (EC) for pesticides residues, 98 (6.85 %) of the analyzed samples were contaminated with residues below the MRL, and 1292 (90.35 %) of the analyzed samples were pesticide residue-free. Coriander contained the highest percentage (46.88 %) of pesticide residues, particularly tetradifon that representing 18.75 % noncompliance with the MRL, followed by parsley, with 20.59 % pesticide residues (10.29 % non-compliance). Multiple pesticide residues were observed most frequently in tomatoes and dates which were contaminated with buprofezin and ethion respectively.

Comparison of QuEChERS and Liquid–Liquid extraction methods for the simultaneous analysis of pesticide residues using LC-MS/MS

In 2004, the Food Code of Korea adopted a multi-class multi-residue pesticide analysis method, which employed liquid–liquid extraction (LLE) and solid-phase extraction for sample purification. After several modifications, the LLE stage was replaced by the QuEChERS method in October 2021. Thus, in the current study a comparison was carried out between the new QuEChERS method and the conventional LLE method for the simultaneous analysis of multiple pesticide residues. More specifically, 275 pesticide compounds were measured in spinach, rice, and mandarin matrices using LC-MS/MS, and the linearity, LOD, LOQ, recovery, and matrix effect were determined. Following both the QuEChERS and LLE, the matrix-matched calibration curve plotted using the extracts of blank matrix extracts showed that the majority of pesticides exhibited a highly linear relationship, with coefficients of determination >0.99. In addition, the LOD was 0.00003–0.004 mg/kg, and the LOQ was 0.0001–0.01 mg/kg. For the different matrices, the average recovery of the QuEChERS method was 101.3–105.8%, while that of the LLE method was 62.6–85.5%. Due to the fact that the LLE and QuEChERS methods exhibited a tendency of suppression for the various matrices examined, matrix-matched calibration was required during quantification. Indeed, introduction of the QuEChERS method allowed matrix-matched calibration to be conducted during quantification, while the previously employed LLE method did not involve such processes. These changes therefore resulted in a more accurate quantification in addition to a reduced experimental time and cost. • We compared QuEChERS to LLE in multi-residue analysis in foods by LC-MS/MS. • QuEChERS has higher and more uniform recovery rates among matrices than LLE. • Both methods require matrix-matched calibration owing to ion suppression. • QuEChERS and matrix-matched calibration improve quantification accuracy.

Development and validation of multiresidue method for organophosphorus pesticides in lanolin using gas chromatography-tandem mass spectrometry.

Lanolin, also known as wool wax, is derived from sheep and has diverse applications in food, cosmetic, textile and lubricant industries. Owing to its direct contact with human, there is a need of studying pesticide residues as contaminants in lanolin. The present study describes a single novel hyphenated gas chromatography-tandem mass spectrometry (GC-MS/MS) technique for the quantification of 14 organophosphorus (OP) pesticides (tecnazene, propetamphos, diazinon, dichlofenthion, chlorpyrifos methyl, fenchlorphos, malathion, chlorpyrifos, pirimiphos ethyl, bromophos ethyl, tetrachlorvinphos, ethion, phosalone, and coumaphos) in lanolin using electrospray ionization (EI) with multiple reaction monitoring (MRM) acquisition mode. The method is simple in terms of sample preparation steps based on matrix solid-phase dispersion (MSPD). The method was found to be linear over the analytical range of 0.05-2.0μg/g, with acceptable coefficient of determination (r2 ≥0.99) for all the 14 pesticides. The limit of detection (LOD) and limit of quantification (LOQ) of the method were found to be less than 0.05 and 0.1μg/g, respectively, for all the 14 OP pesticide residues. The precision and accuracy of the method were found to be within the acceptable limits, that is, recoveries in the range of 83.5%-104.1% with less than 12.5% of relative standard deviation for all the pesticides. The multiresidue method for estimating pesticide residues employing GC-MS/MS technique will be useful for OP pesticide levels in large number of lanolin samples.

A Multi-Residue Method for the Determination of 77 Pesticides in Red Ginseng Using QuEChERS and Gas Chromatography/Tandem Mass Spectrometry (GC-MS/MS)

A simple, sensitive, and rapid multi-residue analytical method was developed based on gas chromatography-tandem mass spectrometry (GC–MS/MS) and used to determine 77 multiclass pesticides in red ginseng. Samples were extracted and purified via a modified QuEChERS method. The calibration curves were in the range of 5 to 200 ng mL−1. The limits of detection (LODs) of the method were from 0.08 to 4.0 μg kg−1 and limits of quantification (LOQs) were in the range of 0.2–12.0 μg kg−1. The average recoveries of the method ranged from 61% to 133.9% at two spiked levels of 20 and 100 μg kg−1 in red ginseng samples, with relative standard deviations (RSDs) of 0.2% to 14.9%.

Toxic effects of detected pyrethroid pesticides on honeybee (Apis mellifera ligustica Spin and Apis cerana cerana Fabricius)

To obtain the presence of environmental contaminants in honeybee and compare the toxicity of the detected pesticides to Apis mellifera ligustica Spin and Apis cerana cerana Fabricius. In this work, 214 honeybee samples were collected to simultaneous monitoring 66 pesticides between 2016 and 2017 in China. A modified QuEChERS extraction method coupled with multi-residue analytical methods by Ultra-high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and Gas chromatography-mass spectrum (GC–MS). Among, four pyrethroid pesticides were selected to test and compare the acute oral toxicities of two honeybees. And the survival risk of beta-cypermethrin was analyzed to them. Using this method, 21 compounds were detected, including 3 neonicotinoids, 5 pyrethroids, 5 organophosphorus and 8 others. Importantly, detected frequencies of pyrethroid pesticides were accounted for 53.3%. Among, acute toxicity values (LD50) of four pyrethroid pesticides to the A.m. ligustica were higher than of that the A.c. cerana. When they were exposed to the same concentration of beta-cypermethrin (0.2906 mg/L), the survival rate of the A.m. ligustica (40.0%) was higher than the A.c. cerana (18.9%). Our work is valuable to analyze multiple pesticide residues of honeybees and evaluate the survival risk of two honeybee species, which also provides a basis for the risk assessment.

Analysis of 181 Pesticides with Multi-residue Method by LC–MS/MS and GC–MS/MS in Flowers, Leaves and Tree Trunks and the Results of Catalan Production from 2014 to 2021

Analysis of 181 Pesticides with Multi-residue Method by LC–MS/MS and GC–MS/MS in Flowers, Leaves and Tree Trunks and the Results of Catalan Production from 2014 to 2021