Automated micro-solid-phase extraction clean-up and gas chromatography-tandem mass spectrometry analysis of pesticides in foods extracted with ethyl acetate.

Generic extraction methods for the multi-compound pesticide analysis of food have found their solid place in laboratories. Ethyl acetate and acetonitrile extraction methods have been developed as fast and easy to handle standard multi-compound methods, both feature benefits and limitations. The direct injection to gas chromatography can be impaired by a high burden of coextracted matrix, resulting in deterioration of the chromatographic system and matrix effects, requiring frequent maintenance. Therefore, common clean-up methods, such as dispersive solid-phase extraction, freeze-out of fats, or gel permeation chromatography, have been applied in clean-up. Automated clean-up using micro-solid-phase extraction (µSPE) is a recent development with several demonstrated advantages when employed in the analysis of pesticides and other contaminants in foods extracted with acetonitrile, but it has not yet been evaluated in this application using ethyl acetate for extraction. In this study, an automated procedure using µSPE cartridges was developed and established on an x,y,z robotic sampler for the raw extract clean-up and preparation of diluted samples for injection on a GC-MS/MS system. Validation experiments for 212 pesticides, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons in lettuce, avocado, raspberry, paprika, egg, and liver extracts were performed using µSPE with MgSO4, PSA, C18, and CarbonX. The performance in routine operation is briefly discussed.

A study of the pesticide residues in rapeseeds in China: Levels, distribution and health risk assessment.

The aim of this survey was to evaluate the residue levels, distribution and exposure risk of the 38 most commonly used pesticides in rapeseed samples collected from the main production areas in China over a two-year period. The sampling area covered 12 provinces, including Guizhou, Shaanxi, Yunnan, Hunan, Jiangxi, Sichuan, Chongqing, Anhui, Henan, Hubei, Zhejiang, and Jiangsu provinces. The pesticide residues were determined using a QuEChERS (Quick Easy Cheap Effective Rugged and Safe) method coupled with gas chromatography-tandem mass spectrometry and liquid chromatography-tandem mass spectrometry. 8.4% of the rapeseed samples contained pesticides with a residue level ranging from 0.001 to 0.634 mg/kg. The detected analytes were imidacloprid, quizalofop-P-ethyl, thiamethoxam, paclobutrazol, prochloraz, tebuconazole, difenoconazole, s-metolachlor, carbofuran, and carbendazim. The concentrations of four analytes, including thiamethoxam, difenoconazole, carbendazim and prochloraz, exceeded the maximum residue level set by the Chinese government for rapeseed, with exceedance rates of 0.1%, 0.1%, 0.1%, and 1.1%, respectively. Based on the index of quality for residues (IqR) values, 91.6% of the total rapeseed samples had an IqR category of Excellent (IqR = 0). Only 1.5% of the tested samples were of inadequate quality. Furthermore, the assessment of chronic and acute exposure, as well as health risks associated with pesticide residues in rapeseed, was conducted for different age groups within the Chinese population, including adults (6-14 years), children (15-49 years), and the elderly (50-74 years). The results of this assessment indicated that pesticide residues in rapeseed cultivated in China are not expected to be of short- or long-term risks to the Chinese customers.

Pesticide residues in European sediments: A significant concern for the aquatic systems?

The presence of pesticide residues in waterbed sediments poses a significant concern for aquatic ecosystems' health. This study examined pesticide contamination in sediments of 38 water bodies, embedded in agricultural-dominated regions, across eight European countries. Three indicators were targeted: occurrence, type, and concentrations of multiple pesticide residues in sediments. 196 pesticide residues (including degradation products) were tested in the sediment samples. The analytical results showed that only one sample was 'pesticide-free', three samples contained a single pesticide residue, and the remaining 34 samples contained mixtures of residues. Overall, 99 different residues were found in the sediments, with a maximum of 48 in a single sample. Twenty-seven out of the 99 detected residues were not approved for agricultural use at the time of sampling. The numbers of detected residues and pesticide levels varied among countries. AMPA, glyphosate and DDTs were the most common residues in sediment samples with frequencies of 76, 61, and 52%, respectively. The sediments from the Czech Republic had the highest pesticide concentrations, with total pesticide concentrations ranging between 600 and 1200 µg kg-1. The lowest total pesticide concentrations were found in Slovenia, Switzerland, Croatia, and Denmark, ranging between 80 and 120 µg kg-1. Sediments presented a mix of non-persistent and persistent compounds. Twelve of the detected pesticides are very persistent/stable in sediments, raising concerns about the long-term impacts of pesticides. Our study on the distribution of pesticide residues in European sediments provides valuable insights into the extent of pesticide contamination and possible risks of pesticides to water bodies' health. It also underlines the need for monitoring, research, and policy efforts to mitigate the impacts of pesticides, and to evaluate potential risks of re-use of dredged sediments.

Detection of 11 carbamate pesticide residues in raw and pasteurized camel milk samples using liquid chromatography tandem mass spectrometry: Method development, method validation, and health risk assessment.

This study aimed to use ultra-high-performance liquid chromatography coupled to a triple-quadrupole mass spectrometer to detect 11 carbamate pesticide residues in raw and pasteurized camel milk samples collected from the United Arab Emirates. A method was developed and validated by evaluating limits of detection, limits of quantitation, linearity, extraction recovery, repeatability, intermediate precision, and matrix effect. Due to the high protein and fat content in camel milk, a sample preparation step was necessary to avoid potential interference during analysis. For this purpose, 5 different liquid-liquid extraction techniques were evaluated to determine their efficiency in extracting carbamate pesticides from camel milk. The established method demonstrated high accuracy and precision. The matrix effect for all carbamate pesticides was observed to fall within the soft range, indicating its negligible effect. Remarkably, detection limits for all carbamates were as low as 0.01 µg/kg. Additionally, the coefficients of determination were >0.998, demonstrating excellent linearity. A total of 17 camel milk samples were analyzed, and only one sample was found to be free from any carbamate residues. The remaining 16 samples contained at least one carbamate residue, yet all detected concentrations were below the recommended maximum residue limits set by Codex Alimentarius and the European Union pesticide databases. Nonetheless, it is worth noting that the detected levels of ethiofencarb in 3 samples were close to the borderline of the maximum residue limit. To assess the health risk for consumers of camel milk, the hazard index values of carbofuran, carbaryl, and propoxur were calculated. The hazard index values for these 3 carbamate pesticides were all below 1, indicating that camel milk consumers are not at risk from these residues.

Low-dose thiram exposure elicits dysregulation of the gut microbial ecology in broiler chickens.

Thiram, a typical fungicide pesticide, is widely used in agricultural production. The presence of thiram residues is not only due to over-utilization, but is also primarily attributed to long-term accumulation. However, there is a paucity of information regarding the impact of prolonged utilization of thiram at low doses on the gut microbiota, particularly with respect to gut fungi. Our objective is to explore the effect of thiram on broilers from the perspective of gut microbiota, which includes both bacteria and fungi. We developed a long-term low-dose thiram model to simulate thiram residue and employed 16 S rRNA and ITS gene sequencing to investigate the diversity and profile of gut microbiota between group CC (normal diet) and TC (normal diet supplemented with 5 mg/kg thiram). The results revealed that low doses of thiram had a detrimental effect on broiler's growth performance, resulting in an approximate reduction of 669.33 g in their final body weight at day 45. Our findings indicated that low-dose thiram had a negative impact on the gut bacterial composition, leading to a notable reduction in the abundance of Merdibacter, Paenibacillus, Macrococcus, Fournierella, and Anaeroplasma (p < 0.05) compared to the CC group. Conversely, the relative level of Myroides was significantly increased (p < 0.05) in response to thiram exposure. In gut fungi, thiram significantly enhanced the diversity and richness of gut fungal populations (p < 0.05), as evidenced by the notable increase in alpha indices, i.e. ACE (CC: 346.49 ± 117.27 vs TC: 787.27 ± 379.14, p < 0.05), Chao 1 (CC: 317.63 ± 69.13 vs TC: 504.85 ± 104.50, p < 0.05), Shannon (CC: 1.28 ± 1.19 vs TC: 5.39 ± 2.66, p < 0.05), Simpson (CC: 0.21 ± 0.21 vs TC: 0.78 ± 0.34, p < 0.05). Furthermore, the abundance of Ascomycota, Kickxellomycota, and Glomeromycota were significantly increased (p < 0.05) by exposure to thiram, conversely, the level of Basidiomycota was decreased (p < 0.05) in the TC group compared to the CC group. Overall, this study demonstrated that low doses of thiram induced significant changes in the composition and abundance of gut microbiota in broilers, with more pronounced changes observed in the gut fungal community as compared to the gut bacterial community. Importantly, our findings further emphasize the potential risks associated with low dose thiram exposure and have revealed a novel discovery indicating that significant alterations in gut fungi may serve as the crucial factor contributing to the detrimental effects exerted by thiram residues.

MOF-derived multi-"hotspot" 3D Au/MOF-808 (Zr) nanostructures as SERS substrates for the ultrasensitive determination of thiram.

A convenient self-assembly method is proposed for synthesis of 3D Au/MOF-808 (Zr) composite nanostructures with a cerium metal-organic framework loaded with gold nanoparticles. We combine adsorption properties of MOF materials with surface plasmon resonance of noble metals to construct hotspot-dense 3D Au/MOF-808 (Zr) SERS substrates, by using a two-step method of solvothermal and reduction reactions. The results show that optimal SERS substrates are obtained from a volume ratio of gold nanoparticles to MOF-808 (Zr) solution of 4:1 and a self-assembly time of 2 h. Rhodamine 6G (R6G) is used as a molecular probe to characterize and analyze SERS properties of substrates of 3D Au/MOF-808 (Zr) prepared under the optimal process conditions, where the substrates are capable to detect R6G concentrations down to 10-10 M with a relative standard deviation of 8.81%. Finally, we applied the SERS substrates of 3D Au/MOF-808 (Zr) to the detection of pesticide thiram, and establish a quantitative determination method. 3D Au/MOF-808 (Zr) provides a sensitive detection of thiram in lake water by SERS with a detection limit of 1.49 × 10-9 M. Application tests show that a SERS enhancement factor of the MOF-based SERS substrates for the detection of thiram can be significantly increased to 5.91 × 105. Thus, the above results indicate that such substrate has high sensitivity, good adsorption, homogeneity, and reproducibility, which can be extended for sensitive detection of pesticide residues in food and environment.

Africanized honey bee colonies in Costa Rica: first evidence of its management, brood nest structure and factors associated with varroa mite infestation.

Management, brood nest structure and factors associated with varroa mite infestation were studied in 60 apiaries of Africanized honey bees in the northwest region of the Central Valley of Costa Rica. Apiaries were monitored two times. The first monitoring was taken forward during the rainy season between May and November 2019. The second monitoring during the dry season between February and March 2020. Information about the beekeepers, apiaries and management was collected through a survey. Amount of open and capped brood, honey and pollen were measured in the field. The infestation rate of varroa (IRV) was quantified using standard laboratory methods. A determination of multi-residue pesticides in bee bread was made through GC-MS/MS and LC-MS/MS techniques. According to the results, most of the beekeepers produce honey (96.7%), participate in training activities (82.2%), and change the bee queens annually (70%). The first monitoring was characterized by a lower amount of capped brood and honey reserves compared to the second one. IRV was significantly higher in the first monitoring (6.0 ± 0.4) in comparison with the second one (3.0 ± 0.3) (U Mann-Whitney p < 0.001). The maximum value for the first monitoring exceeds 40%, while this value was close to 25% in the second monitoring. Mite infestation exposed significant differences in relation to the variables associated to the beekeeper's management, i.e., change of bee queen (p = 0.002) or when beekeepers monitor varroa mites (p = 0.004). Additionally, the IRV had inverse correlations (p < 0.01) with the number of comb sides with capped brood (Spearman's rho coefficient = - 0.190), and honey reserves (Spearman's rho coefficient = - 0.168). Furthermore, 23 of 60 bee bread samples presented one to five pesticide residues, being the most frequent antifungal agrochemicals.

The concentration of pesticides in onion samples from Iran: a non-carcinogenic health risk assessment.

Pesticide residues were extracted using the QuEChERS method, followed by detection by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The non-carcinogenic health risk in adult and child consumers was calculated by target hazard quotient (THQ) and total target hazard quotient (TTHQ) in the Monte Carlo Simulation (MCS) method. The rank order of pesticides detected by UHPLC-MS/MS based on median concentration in onion was tebuconazole (0.004551 mg/kg) > imidacloprid (0.00233 mg/kg) > boscalid (0.00211 mg/kg) > diazinon (0.00079 mg/kg) > thiabendazole (0.00075 mg/kg) > acetamiprid (0.00052 mg/kg) > thiophanate-methyl (0.00052 mg/kg) > dichlorvos (0.000349 mg/kg) > fenitrothion (0.000132 mg/kg) > penconazole (0.00005 mg/kg). The median of TTHQ in adults and children's consumers were 4.00E-3 and 2.00E-2, respectively. TTHQ in adults and children's consumers was lower than 1 value. Hence, consumers were in the acceptable range (TTHQ <1). Consequently, onion consumption cannot endanger consumers' health status due to the pesticide residues.

Concentration and non-dietary human health risk assessment of pesticide residues in soil of farms in Golestan province, Iran.

Detection of pesticide residues in soil samples was conducted using UHPLC-MS/MS. Non-dietary health risk assessment was conducted using calculate chronic daily intake (CDI) from ingestion, inhalation and dermal contact pathways and following non-carcinogenic and carcinogenic risks in the adults and adolescent. The rank order of pesticide in soil based on their concentration was malathion (0.082 mg kg-1)> cyproconazole (0.019 mg kg-1)> propargite (0.018 mg kg-1)> butachlor (0.016 mg kg-1) > chlorpyrifos (0.0067 mg kg-1)> diazinon (0.0014 mg kg-1)> imidacloprid (0.0007 mg kg-1). Hazard index (HI) values obtained of exposure to pesticides in soil in adults and adolescent were 0.0012 and 0.0035, respectively. Hence, exposed population are at the acceptable range of non-carcinogenic risk (HI < 1). Cancer risk (CR) values due to propargite in soil via ingestion pathway in adults and adolescent were 2.03E-09 and 2.08E-09, respectively; therefore, carcinogenic risk due to the exposure to pesticide contaminated soil was safe range (CR < 1E-06).

Dissipation kinetics and the evaluation of dietary risks associated with deltamethrin, ethion, fenazaquin, and fenpropathrin on bell pepper (Solanum annuum L.).

Bell peppers, a globally significant crop, face infestations from various pests. In a study, bell peppers were treated with deltamethrin, ethion, fenazaquin, and fenpropathrin at recommended and double the doses, repeated twice with a 10-day interval. The QuEChERS method underwent validation for linearity, matrix match, accuracy, and precision in bell pepper matrices for residue analysis. The limit of detection for the tested pesticides on bell peppers was 0.01 mg/L, with a quantification limit of 0.05 mg/L. Recovery studies showed a range of 94.80% to 102.80%. Initial deposits of deltamethrin, ethion, fenazaquin, and fenpropathrin on bell peppers at recommended doses were 0.371, 1.237, 0.617, and 0.640 mg/L, respectively, and at double doses were 0.712, 1.945, 1.221, and 1.189 mg/L, respectively. Safe waiting periods of 10, 11, 10, and 8 days were suggested for deltamethrin, ethion, fenazaquin, and fenpropathrin, respectively. The corresponding half-lives for the pesticides were 1.96, 1.79, 2.06, and 1.69 days, all following first-order dissipation kinetics. Dietary risk assessment indicated Hazard Quotients (HQ) below 1 and Theoretical Maximum Daily Intake (TMDI) below Acceptable Daily Intake (ADI) and Maximum Permissible Intake (MPI) levels. Therefore, at their recommended doses, the pesticides were deemed safe for bell pepper cultivation.

Pesticide contamination pattern from Morocco, insights into the surveillance situation and health risk assessment: a review.

The widespread application of pesticides in Morocco's agriculture renders their monitoring in food and environmental samples very necessary. Recent years have witnessed a growing interest in reporting studies related to the monitoring of pesticide residues in food, water, groundwater, and soil as well as their quantitative health risk assessment. Most published studies have been done by university researchers. However, the lack of research reproducibility remains a problem that considerably limits the possibility of exploiting data from the literature. Our study involves an extensive literature review utilizing search engines with keywords like "pesticide residues," "monitoring," "vegetables and fruits," "water and soil," "risk assessment," and "Morocco" from 2009 to 2023. Analysis of pesticide residues in foodstuffs and environmental samples highlights concerns over compliance with EU regulations, the health risks associated with pesticide exposure, and the necessity for comprehensive monitoring and risk assessment strategies. This paper could help influence policies to develop a strategy and action plan for the sound management of pesticides, including measures to reduce their use, raise awareness, and monitor compliance. Also, this paper could be useful for scientists interested in understanding the current situation and challenges regarding pesticide residues in Morocco, as well as countries with which commercial links exist.

Pesticide application behavior in green tea cultivation and risk assessment of tea products: a case study of Rizhao green tea.

Previous research on pesticides in green tea mainly focused on detection technology but lacked insights into pesticide use during cultivation. To address this gap, a survey was conducted among Rizhao green tea farmers. The survey results showed that most tea farmers were approximately 60 years old and managed small, scattered tea gardens (< 0.067 ha). Notably, tea farmers who had received agricultural training executed more standardized pesticide application practices. Matrine and thiazinone are the most used pesticides. A total of 16 types of pesticides were detected in the tested green tea samples, with 65% of the samples containing residues of at least one pesticide. Notably, higher levels of residues were observed for bifenthrin, cyfluthrin, and acetamiprid. The presence of pesticide residues varied significantly between seasons and regions. The risk assessment results indicated that the hazard quotient (HQ) values for all 16 pesticides detected in green tea were < 1, suggesting that these residue levels do not pose a significant public health concern.

A potential toxicological risk assessment of heavy metals and pesticides in irrigated rice cultivars near industrial areas of Dhaka, Bangladesh.

Rice intake represents a significant pathway through which humans accumulate heavy metals. This study presents a comprehensive analysis of heavy metal and pesticide contamination in rice cultivars irrigated with industrial wastewater near Dhaka, Bangladesh, a region heavily influenced by industrial activities. This study employed a unique methodology that not only quantified the concentrations of heavy metals and pesticide residues in rice grains but also extended to evaluating the physicochemical properties of rice stems, husks, soil, and irrigation water. The findings revealed alarmingly high levels of heavy metals such as lead, cadmium, chromium, nickel, and mercury in the soil and irrigation water, with concentrations in some cases exceeding the World Health Organization safety thresholds by 2 to 15 times. Notably, the rice grains also exhibited significant contamination, including substantial amounts of diazinon and fenitrothion pesticides, exceeding the established safety limits. The study employed hazard quotients (HQs) and cancer risk (CR) assessments to evaluate the potential health risks associated with the consumption of contaminated rice. The results indicated HQ values were greater than 1 for rice grains across the sampled fields, suggesting a considerable non-carcinogenic health risk, particularly from lead exposure, which was found at levels twice the standard limit in all the sampling fields. Moreover, the CR values for As, Pb, Cd, Co, and Mn highlighted a significant carcinogenic risk in several instances.

Biochemical Response of the Endogeic Earthworm (Balanteodrilus extremus) Exposed to Tropical Soils.

This work evaluated the biochemical responses of the endogeic earthworm Balanteodrilus extremus exposed for 14 and 48 days (d) to soils collected from two tropical agricultural systems: maize-sorghum (MS) and soybean-sorghum (SS). A soil without agricultural management (WAM) and the use of pesticides was selected as a reference. The presence of organochlorine (OC) and organophosphate (OP) pesticide residues was quantified in MS and SS soils. Biomarkers of detoxification [glutathione S transferase (GST)], neurotoxicity [acetylcholinesterase (AChE)] and oxidative stress [superoxide dismutase (SOD), catalase (CAT) and lipoperoxidation (LPO)] were evaluated in B. extremus. The concentration of OP pesticide residues was higher in SS than in MS. Activity of AChE in B. extremus exposed to SS soil for 14 d was significantly more inhibited (78%) than in MS soil (68%). B. extremus has been shown to be a good bioindicator of contaminated soils in tropical regions.

[Review and prospects of pesticide use and residues in cultivation of medicinal and food homologous substances].

As people's living standards and awareness of health care are increasing in recent years, the demand for the medicinal and food homologous substances is rising. Promoting the healthy development of this industry to meet people's growing demand and popularizing the TCM concept of preventive treatment of diseases are essential for building a healthy China. The abuse of pesticides by some growers in the one-sided pursuit of economic benefits causes serious pesticide residue, which affects the safety and effectiveness of the medicinal and food homologous substances. Since pesticide residues has received increasing attention, the reasonable control of pesticide residues becomes an important part of the research on these herbs, which, however, is rarely studied. This paper reviewed the publications involving pesticide residues in the cultivation of medicinal and food homologous substances that were published in the last two decades, and put forward the problems faced by the cultivation. According to the current situation of this industry, this paper proposed the management suggestions for the control of pesticide residues in the cultivation. This review will provide the government with data and references for formulating relevant policies and standards to promote the high-quality development of the industry of medicinal and food homologous substances and guarantee the development of TCM and the building of a healthy China.

Determination of pesticide residues in oat flour using low-temperature partition extraction and GC-MS analysis.

A simple method based on solid-liquid extraction with a low-temperature partition (SLE/LTP) and analysis by gas chromatography coupled to mass spectrometry (GC-MS) was optimized and validated for determining residues of the pesticides triadimenol, flutriafol, λ-cyhalothrin, difenoconazole, and azoxystrobin in oat flour. A factorial design was employed to optimize the technique and establish the best conditions for the simultaneous extraction of the analytes. Acetonitrile-sample extraction and its 4 h freezing made it possible to recover the pesticides and clean the extracts in a single step. The limit of detection ranged from 1.72 to 12.9 µg kg-1, and the limit of quantification from 5.73 to 43.0 µg kg-1. These values are below the maximum residue limit (MRL) permitted by National legislation. The recovery percentage fell between 91.7 and 108%, with coefficients of variation under 12%. The validated method was applied to oat flour samples randomly acquired from the local market of Viçosa (Minas Gerais, Brazil) and no residues were detected. The SLE/LTP-GC-MS method proved simple, efficient, selective, and sensitive for determining pesticide residues from oat flour samples, offering a more simplified approach compared to techniques described in the literature. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-024-06006-z.

Recent progress in organic-inorganic hybrid materials as absorbents in sample pretreatment for pesticide detection.

Sample pretreatment is essential for trace analysis of pesticides in complex food and environment matrices. Recently, organic-inorganic hybrid materials have gained increasing attention in pesticide extraction and preconcentration. This review highlighted the common organic-inorganic hybrid materials used as absorbents in sample pretreatment for pesticide detection. Furthermore, the preparation and characterization of organic-inorganic hybrid materials were summarized. To obtain a deep understanding of adsorption toward target analytes, the adsorption mechanism and absorption evaluation were discussed. Finally, the applications of organic-inorganic hybrid materials in sample pretreatment techniques and perspectives in the future are also discussed.

Rapid smartphone-based assays for pesticides inspection in foods: current status, limitations, and future directions.

Smartphone-based assays to inspect pesticides in foods have attracted much attention as such assays can transform tedious laboratory-based assays into real-time, on-site, or even home-based assay and hence overcoming the limitations of conventional assays. Although an array of smartphone-based assays is available, information on the use of these assays for pesticides inspection is scattered. The purposes of this review are therefore to compile, summarize and discuss state-of-the-art as well as advantages and limitations of the relevant technologies. Suggestions are provided for further development of smartphone-based assays for rapid inspection of pesticides in foods. Smartphone-based assays relying on enzyme inhibitions are noted to be nonselective qualitative, capable of reporting results in a quantitative manner only when a sample contains an individual pesticide. Smartphone-based assays relying on chemical reactions also target only individual pesticides. Smartphone-based visible spectroscopy can, on the other hand, inspect individual and multiple pesticides with the aid of appropriate colorimetry-, luminescence-, or fluorescence-based assay. Smartphone-based visible-near infrared and Raman spectroscopies are suitable for simultaneous multiple pesticides inspection. Raman spectroscopy is of particular interest as it can detect pesticides even at lower concentrations. This spectroscopic technique can also serve as a real-time assay with the aid of cloud network computations.

Pesticide residue analysis in different spice samples by automatic µSPE clean-up workflow determination using LC-MS/MS.

Spices such as paprika, curry, turmeric, dry chilli, and black pepper are grown in various geographic locations and widely used by consumers across the world. Pesticides applied during crop production practices could contaminate the produce, affecting the quality and posing a health risk for consumers. The complexity of the spice matrix and the wide range of target pesticides potentially present require special sample extraction and clean-up treatments to overcome matrix interference and ion suppression. In this study, sample extracts from spice matrices (paprika/curry/turmeric/dry chilli/black pepper) were cleaned up by an automated µSPE clean-up method for multi-residue analysis of pesticides using LC-MS/MS. The automated µSPE clean-up method involves pre-filled cartridges containing various sorbent materials suitable for numerous co-extractives and the automated clean-up process was carried out using an autosampler. The regulatory limit for pesticides in spices varies with type, with a low MRL of 0.05 mg kg-1 or higher for 99% of the analytes. At spiking concentrations of 0.05 and 0.1 mg kg-1, good recoveries between 70 and 120% with RSD values below 20% were achieved for more than 98% of the compounds. With automatic clean-up of samples that takes 5 min/sample, 20% increased output per day shows an important advantage achieved compared to manual clean-up.

Metabolism-based category formation for the prioritisation of genotoxicity hazard assessment for plant protection product residues (part 3): Strobilurins.

In dietary risk assessment of plant protection products, residues of active ingredients and their metabolites need to be evaluated for their genotoxic potential. The European Food Safety Authority recommend a tiered approach focussing assessment and testing on classes of similar chemicals. To characterise similarity, in terms of metabolism, a metabolic similarity profiling scheme has been developed from an analysis of 46 chemicals of strobilurin fungicides and their metabolites for which either Ames, chromosomal aberration or micronucleus test results are publicly available. This profiling scheme consists of a set of ten sub-structures, each linked to a key metabolic transformation present in the strobilurin metabolic space. This metabolic similarity profiling scheme was combined with covalent chemistry profiling and physico-chemistry properties to develop chemical categories suitable for chemical prioritisation via read-across. The method is a robust and reproducible approach to such read-across predictions, with the potential to reduce unnecessary testing. The key challenge in the approach was identified as being the need for metabolism data and individual groups of plant protection products as the basis for the development of such profiling schemes.