Neonicotinoids (NEOs), used as insecticides against aphids, whiteflies, lepidopterans, and beetles, have numerous detrimental impacts on human health, including chronic illnesses, cancer, infertility, and birth anomalies. Monitoring the residues in food products is necessary to guarantee public health and ecological balance. The present work validated a new method to measure seven neonicotinoid insecticides (acetamiprid ACT, clothianidin CLT, dinotefuran DNT, imidacloprid IMD, nitenpyram NTP, thiacloprid TCP, and thiamethoxan THT) in wheat. The analytical procedure was based on simple and fast wheat sample cleanup using solid-phase extraction (SPE) to remove interferents and enrich the NEOs, alongside the NEOs\' separation and quantification by reverse-phase chromatography coupled with a diode array detector (DAD). The validation process was validated using the accuracy profile strategy, a straightforward decision tool based on the measure of the total error (bias plus standard deviation) of the method. Our results proved that, in the future, at least 95% of the results obtained with the proposed method would fall within the ±15% acceptance limits. The test\'s cost-effectiveness, rapidity, and simplicity suggest its use for determining the levels of acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam in routine analyses of wheat.

Pesticides are vital in meeting the challenge of feeding the rapidly increasing world population. However, it is crucial that they are used in a way that does not compromise the safety of humans or the environment. Non-dietary worker risk assessments consider the amount of residue which can be transferred from plant foliage to the skin or clothes, known as dislodgeable foliar residues (DFRs). DFR data scarcity due to the costly and seasonal characteristics of DFR studies is an obstacle to the extrapolation of DFR data to different crops/leaves. This paper validates a new proof-of-concept technique to investigate factors that may affect DFR (leaf texture) using the fungicide difenoconazole EC 10% as an example on various leaves (i.e., French bean, soybean, tomato, oilseed rape, and wheat). DFR was the lowest in the case of oilseed rape (31.0 ± 3.4%) and the highest in French beans (82.0 ± 2.9%). This significant difference in DFR in the findings of this study sheds light on the importance of the leaf surface as a major factor affecting DFR and supports the application of the laboratory method for more extensive data generation. More data generation would enable the extrapolation saving money and resources.

In this study, risk estimation based on sampling and subsampling uncertainty was performed for pesticide analysis in homogeneous spice products such as paprika. The results of the subsampling were also used to estimate the minimum weight necessary in subsampling to minimize overall uncertainty. The results show that subsampling has more uncertainty than sampling in the product due to high homogeneity in the manufacturer\'s batch. On the other hand, results using the Monte Carlo (MC) simulation on the size of the subsample indicate that uncertainty is lower for weights between 20 and 30 g and increases for sample sizes of 100 g. A sample size of 30 g was used for saffron, and the values simulated with the MC method were confirmed.

Over the last decade, the consumption of tea and herbal tea has gained more and more popularity across the globe, but the potential presence of chemical contaminants (e.g. pesticides, trace elements, synthetic drugs) may raise health concerns. This study analysed selected teas available in Belgian retail stores and performed a risk assessment for these samples. No chemical adulteration could be detected in dry tea material. More than 38% of the dry leaves samples contained at least one pesticide exceeding the maximal residue level (MRL) set by the EU. However, further risk assessment, based on the values of pesticide residues and the toxic trace elements encountered in the brew, demonstrate that the consumption of these teas will not give rise to health concerns. Nonetheless, attention should be given to the leaching potential of nickel from teas and the presence of arsenic in brews from algae containing teas.

Robots replacing humans as the executioners is crucial work for intelligent multi-pesticide residue analysis to maximize reproducibility and throughput while minimizing the expertise required to perform the entire process. Traditional analysis methods are predicated on manual execution, so we configured our robot experimenter, automated the analytical workflow, and achieved the goal of robotics execution. Our robot experimenter with an X-Y-Z axis robotic arm was interfaced with seven modules and ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) for automated standard solution preparation, sample pre-treatment, and UPLC-MS/MS detection. An algorithm was established to make the prepared matrix-matched standard solutions meet the monitoring requirements. The strategy was demonstrated and validated for the detection of 325 pesticides in 4 typical food matrices, suggesting that the developed method is applicable for the analysis of pesticide residues in vegetables and tea as part of regulatory monitoring programs and other purposes.

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.

Matrix effects (MEs) can heavily affect the accuracy and reproducibility of a pesticide residue analysis method, especially in complex matrices such as herbs. Therefore, it is of great importance to assess MEs of pesticides in herbal matrices. In this research, the MEs of 28 pesticides and their metabolites in five types of herbs representing different medicinal parts were evaluated by UHPLC-MS/MS analysis after QuEChERs pretreatment. Suppression MEs were found for most organophosphorus and carbamate pesticides while enhancement MEs were observed for sulfonylurea. Besides, stronger inhibition effects were observed for early or late elution pesticides and in matrices of Lonicerae japonicae flos and Perillae folium. Some pesticides were observed with enhancement MEs in Astragali radix. These results indicated that MEs were mainly affected by the retention time of the analytes, the ionization mode of the precursor ions, the overall structure of the compounds, and the chemical composition of the matrices.

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.

Dithiocarbamates constitute an important class of broad-spectrum antifungal compounds used extensively in agriculture, including in the cultivation of spices. Maximum residue limits for these compounds have been enforced by several importing countries in international food trade. Validation of analytical methods for dithiocarbamates in spices have not been reported previously. A quick and sensitive method for estimation of total dithiocarbamates as carbon disulphide (CS2) using GC-MS in two major spices, viz. small cardamom (Elettaria cardamomom) and black pepper (Piper nigrum) was optimized and validated. Dithiocarbamate residues in these spice matrices were extracted and subjected to acid hydrolysis followed by reduction to CS2, which was then quantitatively absorbed into isooctane and analysed using GC-MS, employing selected ion monitoring and post-run mid-column backflush technique. For fortification levels from 0.1 to 1.0 mg kg- 1, recoveries obtained ranged from 75 to 98% in cardamom and 76-98% in black pepper, with intra-day precision (RSDr) < 12% and inter-day precision (RSDR) < 15% in all cases. Limit of Quantification of 0.05 mg kg- 1 was achieved in both spices. It was found that there was negligible interference in quantitative accuracy due to essential oils present in the two spices studied. Matrix effect was seen to be suppressive in the two spices studied, and sufficiently low to exclude the use of matrix-matched calibration in routine quantitative analysis. The optimized analytical method was found to be suitable for evaluation of compliance of real samples against the Codex maximum residue limits for cardamom and black pepper. Safety evaluation for human consumption, based on the incidence of Dithiocarbamate residues, was performed in real samples of cardamom and black pepper. This method offers the possibility of extending applicability to other spices also.
UNASSIGNED: The online version contains supplementary material available at 10.1007/s13197-022-05462-9.

The aim of this study was to develop a method for the determination of glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and glufosinate ammonium residues in beebread samples, which could then be used to assess bees\' exposure to their residues. The complexity of beebread\'s matrix, combined with the specific properties of glyphosate itself, required careful selection and optimization of each analysis step. The use of molecularly imprinted solid-phase extraction (MIP-SPE) by AFFINIMIP glyphosate as an initial clean-up step significantly eliminated matrix components and ensured an efficient derivatization step. Colorless beebread extracts were derivatized by the addition of 9-fluorenylmethyl chloroformate (FMOC-Cl). After derivatization, in order to remove FMOC-OH and residual borate buffer, a solid-phase extraction (SPE) clean-up step using Oasis HLB was carried out. Instrumental analysis was performed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The method was validated according to the SANTE/11312/2021 guideline at concentrations of 5, 10, and 100 µg/kg, and satisfactory recovery (trueness) values (76-111%) and precision (RSDr) ≤ 18% were obtained. The limit of quantification (LOQ) was 5 µg/kg for AMPA and glufosinate ammonium and 10 µg/kg for glyphosate. The method was positively verified by the international proficiency test. Analysis of beebread samples showed the method\'s usefulness in practice. The developed method could be a reliable tool for the assessment of beebread\'s contamination with residues of glyphosate, its metabolite AMPA, and glufosinate ammonium.