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Biosolids are rich in organic matter and other nutrients that contribute to environmental and agricultural sustainability by improving soil textural and biological properties and enhancing plant growth when applied to agricultural crops. Land application of biosolids encourages resource recovery and circumvents drawbacks associated with landfilling or incineration. However, biosolids contain numerous chemicals at trace levels, and quantitative analysis of such mixtures in this complex matrix is crucial for understanding and managing application risks. There are currently few analytical methods available that are capable of extracting and quantifying a large range of the emerging contaminants found in biosolids. In this study, a simplified, rapid, and robust method of analysis was developed and validated for a high-priority organic contaminant mixture of 44 endocrine disrupting compounds known to occur in biosolids. Analytes consisted of chemicals from many classes with a wide range of physiochemical properties (e.g., log Kow values from -1.4 to 8.9). The biosolids extraction and cleanup protocol was validated for 42 of the targeted compounds. The UPLC-MS2 parameters were validated for all 44 organic contaminants targeted for study. From the two batches of biosolids tested using this analytical method, most of the targeted contaminants (86%) were detected with 100% frequency at concentrations ranging from 0.036 to 10,226 μg/kg dw. Performance results highlighted that internal standards alone could not negate biosolids matrix effects; thus, internal standards and the standard addition method were used for residue quantification. This was the first study to detect and quantify 6PPD-q in biosolids, and the first to quantify lidocaine and 11 other chemicals in biosolids using a single analytical method. This method may be expanded for analysis of additional chemicals in biosolids and comparable matrices.

This study aims to apply multivariate analysis algorithms for modeling the same spectra, for simultaneous determination of pymetrozine and carbendazim residues in apple. To mitigate the impact of competitive adsorption, SERS spectra are obtained from mixed solutions of pymetrozine and carbendazim at varying concentration ratios, which are then utilized for modeling. Results suggest that the PLSR model based on full-band SNV processed spectra shows the best performance for predicting pymetrozine and carbendazim contents, with R2 p of 0.9751 and 0.9779, RMSEP of 0.0492 and 0.5531 mg/L, RPD of 6.4297 and 6.8246, respectively. This model yielded R2 p of 0.9644 and 0.9671, RMSEP of 0.0747 and 0.8247 mg/L, RPD of 5.3857 and 5.6066 for pymetrozine and carbendazim in apple, respectively. The findings suggest that the proposed approach is suitable for simultaneous detection of pymetrozine and carbendazim in apples, offering a novel avenue for monitoring food safety.

In this paper, a solid phase extraction procedure was developed for the simultaneous extraction of 22 multiclass high-risk pesticides, containing a variety of chemical groups (organophosphate, neonicotinoid, sulfonylurea, strobilurin, triazole, triazine, and acetanilide), from surface water samples. The target analytes extracted on the HLB SPE cartridge, and then eluted with acetonitrile with 5% (v/v) formic acid. The final sample solution was analysed by high-performance liquid chromatography-tandem quadrupole mass spectrometry (HPLC–MS/MS) system. Under optimum conditions, good linearity was obtained for the target pesticides with correlation coefficient greater than 0.99. The limit of quantitation (LOQ) for the 22 pesticides was 0.1 ng/mL. The absolute recoveries of the pesticides from spiked water samples ranged from 70.0% to 121.5%. Relative standard deviations (RSD) for five replicate determinations were below 14.7%. The proposed method has been successfully applied to detect the presence of multiclass pesticides in environmental water samples. [ABSTRACT FROM AUTHOR]

Pesticides and polychlorinated biphenyls (PCBs) are persistent environmental pollutants. When entering the food chain, they can represent a public health problem due to their negative effects on health. In this study, concentrations of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), pyrethroids, carbamates, and PCBs—a total 73 compounds—were determined in a total of 2268 samples of fat tissues (beef, pork, sheep, goat, poultry, game, horse, rabbit) and processed fat, meat, and processed meat products collected in Croatia during an 8-year period. In fatty tissues, 787 results exceeded the limits of quantification (LOQ): 16 OCPs, eight OPPs, six pyrethroids, one carbamate, and seven PCBs. The most positive results in fat samples were found for OCPs, with a frequency of quantification in the range of 57.5–87.5%. Hexachlorobenzene (HCB) and dichlorodiphenyldichloroethylene (DDE) were quantified in the highest percentages, in the ranges of 5.5–66.7% and 5.4–55.8%. Concentrations above the MRL values were determined for chlorpyrifos in pork fat and for resmethrin in six fat samples and one pâté. In 984 samples of meat and meat products, only 62 results exceeded the LOQ values. The highest frequency of quantification was determined for OCPs (25 samples), of which 40% were DDT isomers (60% DDE). Frequency quantifications of PCBs in fat samples were between 7.23 and 36.7%. An evaluation of the health risk assessment showed that the consumption of fat, meat, and meat products does not pose a threat to consumer health, since all EDI values were well below the respective toxicological reference values. [ABSTRACT FROM AUTHOR]

Antimicrobial drugs and coccidiostat compounds are commonly used in poultry farming. These compounds are subsequently excreted and released into the environment via broiler litter (BL) and can re-enter the food chain as fertilizer or animal feed. Such residue in animal feed can encourage the appearance of antibiotic-resistant bacteria as well as toxicity. Most analytical methods used to identify and quantitate these drug residues are traditional, and are specific to some antimicrobials and present limitations in assessing complex matrixes like BL. The aim of this study was to develop a multi-residue analytic method for assessing 30 antimicrobial drugs and coccidiostats associated with BL. We investigated the presence and the effects of biotic stack treatment on the degradation of drug residue in BL. Liquid-liquid extraction (LLE) and solid phase extraction (SPE) were replaced by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) clean-up steps and detected by liquid chromatography mass spectrometry (LC/MS/MS). Results show that a wide spectrum of residues were detected from 0.4 to 8.9 mg kg−1. Following lab-scale stacking treatment, tilmicosin and eight coccidiostats persisted in BL (26–100%). This research supports the need for better understanding, regulation, and management of the use of BL that might carry a high risk of residue drugs. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Antimicrobial drugs and coccidiostat compounds are commonly used in poultry farming. These compounds are subsequently excreted and released into the environment via broiler litter (BL) and can re-enter the food chain as fertilizer or animal feed. Such residue in animal feed can encourage the appearance of antibiotic-resistant bacteria as well as toxicity. Most analytical methods used to identify and quantitate these drug residues are traditional, and are specific to some antimicrobials and present limitations in assessing complex matrixes like BL. The aim of this study was to develop a multi-residue analytic method for assessing 30 antimicrobial drugs and coccidiostats associated with BL. We investigated the presence and the effects of biotic stack treatment on the degradation of drug residue in BL. Liquid-liquid extraction (LLE) and solid phase extraction (SPE) were replaced by Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) clean-up steps and detected by liquid chromatography mass spectrometry (LC/MS/MS). Results show that a wide spectrum of residues were detected from 0.4 to 8.9 mg kg−1. Following lab-scale stacking treatment, tilmicosin and eight coccidiostats persisted in BL (26–100%). This research supports the need for better understanding, regulation, and management of the use of BL that might carry a high risk of residue drugs.

Pesticides and polychlorinated biphenyls (PCBs) are persistent environmental pollutants. When entering the food chain, they can represent a public health problem due to their negative effects on health. In this study, concentrations of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), pyrethroids, carbamates, and PCBs—a total 73 compounds—were determined in a total of 2268 samples of fat tissues (beef, pork, sheep, goat, poultry, game, horse, rabbit) and processed fat, meat, and processed meat products collected in Croatia during an 8-year period. In fatty tissues, 787 results exceeded the limits of quantification (LOQ): 16 OCPs, eight OPPs, six pyrethroids, one carbamate, and seven PCBs. The most positive results in fat samples were found for OCPs, with a frequency of quantification in the range of 57.5–87.5%. Hexachlorobenzene (HCB) and dichlorodiphenyldichloroethylene (DDE) were quantified in the highest percentages, in the ranges of 5.5–66.7% and 5.4–55.8%. Concentrations above the MRL values were determined for chlorpyrifos in pork fat and for resmethrin in six fat samples and one pâté. In 984 samples of meat and meat products, only 62 results exceeded the LOQ values. The highest frequency of quantification was determined for OCPs (25 samples), of which 40% were DDT isomers (60% DDE). Frequency quantifications of PCBs in fat samples were between 7.23 and 36.7%. An evaluation of the health risk assessment showed that the consumption of fat, meat, and meat products does not pose a threat to consumer health, since all EDI values were well below the respective toxicological reference values.

Pesticides are a class of compounds that are used to protect agricultural products. However, the uncontrolled use of these chemicals increases the risks associated with their overdosing and rises a significant concern about their effect on human health and the ecosystem. Albeit many concerns about their effects, the use of pesticides is inevitable due to the incline in population growth and the presence of limited food resources. As a result, regulatory control of the use of chemicals is critical and the development of methods that provide a reliable determination of pesticide residues in fruits and vegetables is of great importance.In the present study, a new method based on thin film microextraction was developed for the extraction of pesticides from fruit matrices prior to their gas chromatography-mass spectrometric (GC–MS) determination. As a first step, the thin film extractive devices were prepared by immobilization of hydrophilic-lipophilic balanced (HLB) particles on the surface of carbon mesh. The samplers were optimized in terms of extraction and desorption conditions first in PBS and then in apple juice. The final method was also validated in apple juice samples. Analytical figures of merits of the final method showed acceptable precision for intra- and inter-day reproducibility with ≤20% relative standard deviation (RSD%) and accuracy of ≤15% relative error (RE%), except for trifluralin at 300.0 ng mL−1 level. The limits of quantitation (LOQ) for the selected pesticides were found between 1.0 and 5.0 ng mL−1 . The samplers developed in this study were also successfully tested in preliminary investigations for the extraction of the pesticides from the surface of fruits and vegetables using agarose gel as a model matrix with the primary aim of showing the step towards the sampling directly on the field.

Agricultural soil contamination by pesticide residues has become a serious issue of increasing concern due to their high persistence and toxicity to non-target species. However, as the world’s largest peach producer, national scale surveys on pesticide residues in peach orchard soils are scarce in China. In this study, a target and suspect screening method covering over 200 pesticides commonly used in peach orchards was developed using ultra-high performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry in MSE. An identification strategy using different data processing parameters was developed to identify the pesticide occurrence in soil. The method was applied to soil samples from typical peach orchards in 12 regions across China. The present work also discusses in detail the frequency of occurrence, concentration of pesticides, spatial distribution of multiresidues, and relationship between pesticide occurrence and soil properties. In the tested soil samples, 21 herbicides (level 1), 31 fungicides (level 2a), 24 insecticides (level 2a), and 3 growth regulators (level 2a) were identified. The total concentrations of quantifiable herbicides in the soil samples ranged from 1.05 to 327 ng/g. Only in 5.4% of the soil samples, no pesticide residues were present. By contrast, more than 86% of the total contained multiple residues. This study represents the first large-scale survey of pesticides in soil from peach orchards and provides comprehensive and accurate information on the pesticide residue status for risk assessment.

A novel solid‐phase microextraction device coated with an efficient and cheap thin film of polyurethane was developed for trace determination of 13 widely used pesticides in fruit and tea beverages. A round‐shaped polyurethane film covering the bottom of a glass vial was fabricated as the sorbent to exhibit a superior capacity for preconcentrating target compounds and reducing matrix interferences. After optimization of the key parameters including the film type, extraction time, solution pH, ionic strength, desorption solvent, and conditions, this device allowed an efficient adsorption‐desorption cycle for the pesticides accomplished in one vial. Coupled with gas chromatography‐electron capture detection, the polyurethane‐coated thin film microextraction method was successfully established and applied for the analysis of real fruit and tea drinks, showing low limits of detection (0.001–0.015 μg/L), wide linear ranges (1.0–500.0 μg/L, r2 > 0.9931), good relative recoveries (77.2%–106.3%) and negligible matrix effects (86.1%–107.5%) for the target pesticides. The proposed approach revealed strong potential of extending its application by flexibly modifying the type or size of the coating film. This study provides insights into the enrichment of contaminants from complex samples using inexpensive and reusable microextraction devices that can limit the environmental and health impact of the sample preparation protocol. [ABSTRACT FROM AUTHOR]

Liquid chromatography-high resolution mass spectrometry (LC-HRMS) is considered an unavoidable extension of low-resolution LC-MS/MS that stretches the capabilities of multi-residue analysis of chemical contaminants in food. However, LC-HRMS acquisitions generate a massive amount of information available for data processing with supplier software that still miss critical calculation features and adapted reporting tools. Consequently, routine laboratories are still reluctant to switch from LC-MS/MS to LC-HRMS, the latter is still perceived as a cumbersome and demanding technology. In that context, we propose a four-step LC-HRMS workflow to speed-up data processing in situations of multi-residue multi-matrix analysis with the goal to maximize the time spent on data interpretation rather than on data formatting. The first three steps of the workflow imply specific settings on the Orbitrap HRMS associated software (TraceFinderTM) while the fourth step is the novelty i.e. a newly coded R-script capable to translate a raw export file into a comprehensive.xlsx report file in a few seconds. As recommended by various international guidelines and in some official methods, standard addition-based applications are fully embedded in this reporting tool whilst still being the main bottleneck of supplier's software. The reporting tool also allows appropriate data formatting, filtering, and color-coding options to provide a clear picture of compounds being detected or not, and those requiring specific attention due to unmet quality control criteria as required by European legislation (European Commission SANTE 11312/2021). It is hoped that additional functionalities compatible with R scripts will be soon fully embedded in the supplier's software for easier data interpretation and reporting. [ABSTRACT FROM AUTHOR]

In this study, a multi-residue analysis was developed for 32 compounds, including pesticides and metabolites, in five meat products using gas chromatography-tandem mass spectrometry (GC-MS/MS). The validation of the developed analytical method was also evaluated in accordance with Codex Alimentarius guidelines. Aminopropyl (NH2), C18, and florisil solid phase extraction (SPE) cartridges were used to evaluate and optimize the cleanup procedure of the tested samples prior to GC-MS/MS analysis. Based on the analytical performance, the C18 SPE cartridge was deemed to be the most suitable among the examined SPE cartridges. The optimized method demonstrated that 29 out of 32 tested compounds acquired good linearity (R2 ≥ 0.99), and 25 tested compounds displayed the method limit of quantification (MLOQ) ≤ 0.01 mg/kg. Out of the 32 tested compounds, only 21 compounds met the acceptable analytical criteria for the lard and tallow samples, compared to 27 compounds in the beef, pork, and chicken samples that falls within the acceptable standards for recovery (70–120%) and analytical precision (relative standard deviation RSD ≤ 20%). The average matrix effect was widely varied (20.1–64.8%) in the studied meat samples that were affected by either ion enhancement or suppression. In particular, in the lard sample, 13 compounds showed poor recovery and analytical precision due to ion suppression. Thus, the matrix effect (ME) was considered a critical factor during multi-residue pesticide analysis in different meat products. In conclusion, this developed analytical method can be used as a routine monitoring system for residual pesticide analysis in livestock products with acceptable analytical standards. Further meticulous analytical studies should be optimized and validated for multi-residue pesticide analysis in diversified meat products. [ABSTRACT FROM AUTHOR]

To detect two types of β2-agonist residues at the same time, we coupled two haptens of clenbuterol (CLE) and ractopamine (RAC) to the same carrier protein through diazotization to prepare dimeric artificial antigen, and a fluorescent lateral flow immunoassay method based on europium nanoparticles (EuNP-FLFIA) was established by combining polyclonal antibodies with europium nanoparticles to form probes. Under optimized conditions, the EuNP-FLFIA could simultaneously detect eight aniline-type and one phenol-type β2-agonists, and the limits of detection (LOD) were 0.11–0.19 ng/mL and 0.12 ng/mL, respectively. The recovery rate of this method was 84.00–114.00%. This method was verified by liquid chromatography–tandem mass spectrometry (LC-MS/MS), and the test results were consistent (R2 > 0.98). Therefore, the method established in this study could be used as a high-throughput screening for the efficient and sensitive detection of β2-agonists in food. [ABSTRACT FROM AUTHOR]

In this study, a multi-residue analysis was developed for 32 compounds, including pesticides and metabolites, in five meat products using gas chromatography-tandem mass spectrometry (GC-MS/MS). The validation of the developed analytical method was also evaluated in accordance with Codex Alimentarius guidelines. Aminopropyl (NH2), C18, and florisil solid phase extraction (SPE) cartridges were used to evaluate and optimize the cleanup procedure of the tested samples prior to GC-MS/MS analysis. Based on the analytical performance, the C18 SPE cartridge was deemed to be the most suitable among the examined SPE cartridges. The optimized method demonstrated that 29 out of 32 tested compounds acquired good linearity (R2 ≥ 0.99), and 25 tested compounds displayed the method limit of quantification (MLOQ) ≤ 0.01 mg/kg. Out of the 32 tested compounds, only 21 compounds met the acceptable analytical criteria for the lard and tallow samples, compared to 27 compounds in the beef, pork, and chicken samples that falls within the acceptable standards for recovery (70–120%) and analytical precision (relative standard deviation RSD ≤ 20%). The average matrix effect was widely varied (20.1–64.8%) in the studied meat samples that were affected by either ion enhancement or suppression. In particular, in the lard sample, 13 compounds showed poor recovery and analytical precision due to ion suppression. Thus, the matrix effect (ME) was considered a critical factor during multi-residue pesticide analysis in different meat products. In conclusion, this developed analytical method can be used as a routine monitoring system for residual pesticide analysis in livestock products with acceptable analytical standards. Further meticulous analytical studies should be optimized and validated for multi-residue pesticide analysis in diversified meat products.

Numerous contaminants are produced and used daily, a significant fraction ultimately finding their way into natural waters. However, data on their distribution in lakes is lacking. To address this gap, the presence of 54 trace organic contaminants (TrOCs), representative of various human activities, was investigated in the surface water of 290 lakes across Canada. These lakes ranged from remote to highly impacted by human activities. In 88% of the sampled lakes, contaminants were detected, with up to 28 detections in a single lake. The compounds most frequently encountered were atrazine, cotinine, and deethylatrazine, each of which was present in more than a third of the lakes. The range of detected concentrations was from 0.23 ng/L to about 2200 ng/L for individual compounds, while the maximum cumulative concentration exceeded 8100 ng/L in a single lake. A risk assessment based on effect concentrations for three aquatic species (Pimephales promelas , Daphnia magna , and Tetrahymena pyriformis) was conducted, revealing that 6% of lakes exhibited a high potential risk for at least one species. In 59% of lakes, some contaminants with potential sub-lethal effects were detected, with the detection of up to 17 TrOCs with potential impacts. The results of this work provide the first reference point for monitoring the evolution of contamination in Canadian lakes by TrOCs. They demonstrate that a high proportion of the sampled lakes bear an environmentally relevant anthropogenic chemical footprint. [Display omitted] • Mixtures of trace organic contaminants are omnipresent in lake water across Canada. • 8 out of the 12 quantified pesticides exceeded acceptable water quality thresholds. • 6% of the sampled lakes exhibited potential risk of toxicity for aquatic organisms. • Sub-lethal effects can be expected from detected contaminants in 59% of lakes. • The results provide insights to improve water protection and conservation efforts. [ABSTRACT FROM AUTHOR]

Biosolids are rich in organic matter and other nutrients that contribute to environmental and agricultural sustainability by improving soil textural and biological properties and enhancing plant growth when applied to agricultural crops. Land application of biosolids encourages resource recovery and circumvents drawbacks associated with landfilling or incineration. However, biosolids contain numerous chemicals at trace levels, and quantitative analysis of such mixtures in this complex matrix is crucial for understanding and managing application risks. There are currently few analytical methods available that are capable of extracting and quantifying a large range of the emerging contaminants found in biosolids. In this study, a simplified, rapid, and robust method of analysis was developed and validated for a high-priority organic contaminant mixture of 44 endocrine disrupting compounds known to occur in biosolids. Analytes consisted of chemicals from many classes with a wide range of physiochemical properties (e.g., log K ow values from −1.4 to 8.9). The biosolids extraction and cleanup protocol was validated for 42 of the targeted compounds. The UPLC-MS2 parameters were validated for all 44 organic contaminants targeted for study. From the two batches of biosolids tested using this analytical method, most of the targeted contaminants (86%) were detected with 100% frequency at concentrations ranging from 0.036 to 10,226 μg/kg dw. Performance results highlighted that internal standards alone could not negate biosolids matrix effects; thus, internal standards and the standard addition method were used for residue quantification. This was the first study to detect and quantify 6PPD-q in biosolids, and the first to quantify lidocaine and 11 other chemicals in biosolids using a single analytical method. This method may be expanded for analysis of additional chemicals in biosolids and comparable matrices. [Display omitted] • An analytical method was validated for a complex mixture of chemicals in biosolids. • Internal standards could not be used to fully negate biosolids matrix effects. • Of the analytes, 86% were detected at concentrations from 0.036 to 10,226 μg/kg dw. • This was the first study to detect and quantify 6PPD-q and lidocaine in biosolids. • This was the first study to quantify 11 other chemicals in biosolids using a single method. [ABSTRACT FROM AUTHOR]

To detect two types of β2-agonist residues at the same time, we coupled two haptens of clenbuterol (CLE) and ractopamine (RAC) to the same carrier protein through diazotization to prepare dimeric artificial antigen, and a fluorescent lateral flow immunoassay method based on europium nanoparticles (EuNP-FLFIA) was established by combining polyclonal antibodies with europium nanoparticles to form probes. Under optimized conditions, the EuNP-FLFIA could simultaneously detect eight aniline-type and one phenol-type β2-agonists, and the limits of detection (LOD) were 0.11–0.19 ng/mL and 0.12 ng/mL, respectively. The recovery rate of this method was 84.00–114.00%. This method was verified by liquid chromatography–tandem mass spectrometry (LC-MS/MS), and the test results were consistent (R2 > 0.98). Therefore, the method established in this study could be used as a high-throughput screening for the efficient and sensitive detection of β2-agonists in food.

An amphiphilic block copolymer consisting of poly(N-acryloyl-glucosamine) (PAGA) and poly(tert-butyl methacrylate) (PtBMA) was designed and grafted on magnetic multi-walled carbon nanotubes (Fe3O4MWCNTs). The resultant Fe3O4MWCNTs@copolymer was proposed as QuEChERS adsorbent for determination of 15 mycotoxins and 25 pesticides in grains via liquid chromatography tandem mass spectrometry. The adsorbent was characterized by a transmission electron microscope, scanning electron microscope, elemental analysis, and other techniques. The common matrix interferences were efficiently removed by the proposed adsorbent, such as pigment, fatty acids, and the saccharide. PAGA segment played an important role in removing the hydrophilic interferences through hydrogen bonding due to the high density of hydroxyl groups. PtBMA segment removed the fatty residues through its strong hydrophobic carbon moiety. In comparison with the commercially available QuEChERS adsorbents, the proposed adsorbent had higher adsorption capacities towards the typical matrix interferences. To achieve satisfactory recoveries of analytes, various parameters in the QuEChERS procedure were comprehensively investigated. Under the optimal conditions, 95.0% of the analytes showed satisfactory recoveries in the range 70.0–120% as well as negligible matrix effects. The limits of detection (LOD) were in the range 0.00015–1.3 μg kg−1. Compared with previously reported QuEChERS methods, the proposed method had improved sensitivity and benefited from low matrix effects. The recoveries of analytes in various grains were in the range 60.8–108% with relative standard deviations (RSD) less than 13%. Moreover, the Fe3O4MWCNTs@copolymer exhibited good synthetic reproducibility and rapid magnetic separation (less than 10 s). The research provides a versatile platform to develop multi-functional QuEChERS adsorbents based on the amphiphilic block copolymer. [ABSTRACT FROM AUTHOR]

According to EU guidance SANCO/7525/VI/95 Rev. 10.3, residue data extrapolation from a surrogate major crop to a minor crop can be used for setting maximum residue levels (MRLs) with a reduced number of residue trials and representative selected pesticides. In this work, a QuEChERS method (citrate-buffered version and PSA with MgSO4 clean-up) and LC-ESI-MS/MS for the determination of boscalid, pyraclostrobin, fludioxonil, fluopyram and tebuconazole in persimmon was developed and validated according to EU Commission guidelines and afterwards used for the determination of residues in four field trials. Residue levels at harvest for each pesticide ranged between 0.347 and 0.028 mg/kg. After comparing EFSA residue data on apples, as the surrogate major crop, and conducting a consumer risk assessment, a proposal of residue data extrapolation to set MRLs in persimmons was performed. The results showed that pesticide residues in persimmons at harvest were consistently lower than residues in apples when substances were applied according to the same critical GAP. MRLs were set at 0.5 mg/kg for fludioxonil, 0.6 mg/kg for boscalid, 0.3 mg/kg for tebuconazole, 0.4 mg/kg for fluopyran and 0.3 mg/kg for pyraclostrobin. The ratio of the MRLs for apple/persimmon varied between 2.5 for boscalid and 1.25 for fluopyram, suggesting that residue extrapolation can be feasible, promoting the process of pesticide registration for minor crops and the settlement of MRL.

A method was developed for the simultaneous detecting of 70 banned and commonly used pesticide residues in S. miltiorrhiza via gas chromatography-tandem mass spectrometry (GC-MS/MS) by optimizing the sample pretreatment and chromatographic analysis conditions. 44 samples of S. miltiorrhiza from different cities in Sichuan Province were tested by this method. The samples were extracted by aqueous acetonitrile, salted out by QuEChERS extract package (containing anhydrous magnesium sulfate and anhydrous sodium acetate), the extract solution was concentrated and added internal standard triphenyl phosphate, and detected by GC-MS/MS with multiple reaction monitoring (MRM) mode. The results showed that all the 70 pesticides had good linearity within the range of 1-100 μg/L, with the correlation coefficients (r) higher than 0.998 5. More than 87.1% of the tested pesticides had recovery rates between 70% and 120%, and the RSDs were less than 15% at three spiked levels (5×LOD、10×LOD and 20×LOD). The limits of quantitation of this method ranges from 0.01 to 0.03 mg/kg. In 44 batches of samples, 1-5 kinds of pesticides were detected in 22 samples, including dicofol, which was banned by China. This simple, sensitive and accurate method is suitable for the fast screening and detection of pesticide residues in S. miltiorrhiza Bge.. The test results can be applied as a reference for the cultivation and circulation supervision of S. miltiorrhiza from Sichuan Province. [ABSTRACT FROM AUTHOR]

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Due to the growing number of analysed pesticide residues, analytical strategies have evolved for the data processing of 100s of pesticides in a single analysis. We present herein a LC-MS/MS method based on triple quadrupole technology capable of detecting concentrations at 5 ng/g and confirming 381 pesticides in a single injection. Confirmatory analysis is performed using data-dependent acquisition that compares full MS/MS spectra of candidates to a fast library interrogation within the same injection. A comparison on more than 200 samples of fruits and vegetables (representing principal types: normal, pigmented, and fatty) with pre-existing workflow based on single MRM analysis per compound was performed to validate this approach. A fast turnaround time was demonstrated due to more-unambiguous identification suppressing the need for reinjection to confirm candidates. The automated library searching and confirmation only of putative hits also allowed focusing on the manual verification and validation steps just for putative candidates which hence also increased overall throughput and results quality. Superior robustness of the method due partially to a reduced volume injected was also one of the key points achieved using this methodology. An interesting feature is also the capability to enrich the library and the number of pesticides screened with ease. [ABSTRACT FROM AUTHOR]

[Display omitted] • A robust method is proposed for determination of multi-class veterinary drugs in animal muscles. • High recovery, simple operation and effective cleanup were achieved in this method. • Application to several animal muscle samples analysis demonstrate its practicality. Excessive use of veterinary drugs in livestock growth poses a threat to food safety. It is, however, challenging to quantify these multi-class veterinary drugs within animal muscles, because of their varied physicochemical properties. In this work, we presented a simple, efficient and sensitive method for the simultaneous determination of multi-class veterinary drugs with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The method involves a highly efficient extraction using a EDTA (pH 7)-ACN (30:70, v/v) solvent system, followed by a one-step solid-phase extraction cleanup approach with PRiME HLB sorbent (Reversed-phase N -vinylpyrrolidone and divinylbenzene copolymer). For all the analytes, over a wide range of polarity, satisfactory recoveries were obtained between 70% and 120%, with relative standard deviations <15%. Excellent sensitivities were achieved with the limits of quantification ranging from 0.2 μg/kg to 3.0 μg/kg. This developed method provides a new targeted strategy for the analysis of multi-class veterinary drugs in muscle matrices. [ABSTRACT FROM AUTHOR]

Honeybees closely rely on insect-pollinated plants for their survival. Each forager bee displays a tendency of loyalty toward specific plant species during the many daily foraging flights. Due to the ease of collection, pollen loads have been extensively used as a proxy for detection of pesticide residues. Pollen is the main protein food source for colonies, and its contamination has also been addressed as a reason for the colony losses phenomenon. As honeybees fly over a variable but wide range territory, they might collect pollen from both agricultural, urban and wild environments, also displaying considerable preferences in botanical sources between colonies of the same apiary. It is thus difficult to address the source of the pesticide contamination, when pollen is analyzed as a whole. In the current study, a practical and reliable approach has been proposed to narrow down the source of contamination. Pollen loads have been collected from colonies placed in eight locations over large apple orchard extensions in Trentino-South Tyrol region (Italy), during and 2 weeks after apple blossom. The pollen loads have been separated by the color due to the predominant plant species. On each color group, palynology and multi-residual chemical analyses have been performed in parallel. The pollen hazard quotient (PHQ) was used to estimate the risk to honeybees of each color group and of the total collected pollen. Apple and dandelion pollen were the main portions of the first collection, while a greater variety emerged after the apple blossom. Dandelion was always present in the samples. The frequency and the amount of pesticide residues differed according to the collection periods, the locations and the pollen color groups. The amount of insecticide residues increased after the apple blossom, while no difference between the period was found on fungicide residues. The PHQ values were higher after the blossom due to the insecticide contribution, with highest values of 160,000 and 150,000. The variations within samples did not allow to identify a unique source of contamination, whereas it seems that the pollen from plants outside the agricultural areas has as much residues as the pollen from apple orchards. [ABSTRACT FROM AUTHOR]

Pesticides are used to increase crop yields and preserve quality by protecting crops against pests; however, their overuse can adversely affect human health and the environment. Herein, we report the development of a multi-pesticide screening method using optimized QuEChERS coupled with liquid chromatography/quadrupole time-of-flight (QTOF) mass spectrometry for the analysis of 13 pesticides in wheat flour. Mass accuracies with errors of less than 2.4 ppm were obtained for all analysed pesticides, and the method provided satisfactory recovery and linearity. Repeatabilities of 0.3–12.7% and reproducibilities of 2.5–15.2% were observed in full-scan TOF mode. The performance of the developed full-scan TOF method was compared to that obtained in high-resolution multiple reaction monitoring (MRM-HR) mode. The limits of quantification for the full-scan TOF and MRM-HR modes ranged from 2 to 10, and 3 to 9 μg kg−1, respectively. The two quantification methods exhibited high sensitivities (limit of detections: 1–3 μg kg−1 in full-scan TOF, and 1–3 μg kg−1 for MRM-HR mode). No pesticide residues were detected when the developed method was applied to 22 real wheat flour samples. [ABSTRACT FROM AUTHOR]

The release of pharmacologically active compounds (PhACs) into aquatic ecosystems poses an environmental risk resulting in a chronic exposure of non-target organisms. A great variety of PhACs, of generally low concentrations, and the complicated sample preparation, makes circumstantial the accurate detection and quantification. Additionally, there is little information published about the spatiotemporal variation of the PhAC load in a larger catchment area utilised for touristic purposes. In addition to the natural biotic and abiotic changes, the seasonal variation of tourism also has a dramatic impact on water quality and the natural ecosystem in larger catchment areas. Therefore, our aim was to develop a reliable solid-phase extraction (SPE)-supercritical fluid chromatography tandem mass spectrometry (SFC-MS/MS) method for simultaneous multi-residue analysis of drugs to reveal the spatiotemporal changes in the PhAC contaminations in the waters of an important touristic region, the catchment area of the largest shallow lake in Central Europe, Lake Balaton (Hungary). The environmental application of the developed method revealed 69 out of the traced 134 chemical compounds, including 15 PhACs, which were detected from natural waters for the first time. Wastewater treatment plant (WWTP) loads have a major role in the PhAC contamination of the studied area; at the same time, the mass tourism-induced PhAC contamination was also detectable. Furthermore, the impact of tourism was indicated by elevated concentrations of recreational substances (e.g., caffeine and illicit drugs) in the touristic season affecting the water quality of this important summer holiday destination. Unlabelled Image • The SPE SFC-MS/MS method offers multi-residue analysis from surface water sample. • Investigation of spatiotemporal variation of the PhAC load in a large catchment area • Effect of mass tourism is detectable in the seasonal changes of drug contamination. • The wetlands can play a significant role in reducing PhACs concentrations. [ABSTRACT FROM AUTHOR]

A rapid extraction and cleanup method using selective fabric phase sorptive extraction combined with gas chromatography and mass spectrometry has been developed and validated for the determination of broad polarity spectrum emerging pollutants, ethyl paraben, butyl paraben, diethyl phthalate, dibutyl phthalate, lidocaine, prilocaine, triclosan, and bisphenol A in various aqueous samples. Some important parameters of fabric phase sorptive extraction such as extraction time, matrix pH, stirring speed, type and volume of desorption solvent were investigated and optimized. Calibration curves were obtained in the concentration range 0.05–500 ng/mL. Under the optimum conditions, the limits of detection were in the range 0.009 –0.021 ng/mL. This method was validated by analyzing the compounds in spiked aqueous samples at different levels with recoveries of 93 to 99% and relative standard deviations of <6%. The developed method was applied for the determination of the emerging contaminants in tap water, municipal water, ground water, sewage water, and sludge water samples. The results demonstrate that fabric phase sorptive extraction has great potential in the preconcentration of trace analytes in complex matrix. [ABSTRACT FROM AUTHOR]

In this study, we developed a novel analysis method based on liquid chromatography/ tandem mass spectrometry (LCeMS/MS) to allow the simultaneous identification of 20 coccidiostats in eight matrix categories, including the muscles of chicken, swine, cow, and fish as well as chicken eggs, bovine milk, and porcine viscera. In the pretreatment procedure, acetonitrile/methanol (95:5, v/v) containing 1% formic acid, 5 g of sodium acetate, and 6.0 g of anhydrous magnesium sulfate was used for extraction, followed by a clean-up procedure using n-hexane saturated with ACN to facilitate the elimination of analytes from high lipid samples. Chromatographic separations were achieved using a Poroshell 120SB C18 column and operated with a gradient mobile phase system consisting of methanol (with 0.1% formic acid) and 5 mM ammonium formate, and the MS detection was monitored simultaneously. The method was validated in accordance with the Guidelines for the Validation of Food Chemical Methods by the Taiwan Food and Drug Administration. The limit of quantitation among 8 matrices were 0.5-2 ng g-1. The proposed method proved highly effective in detecting the presence of targeted veterinary drugs, providing a high degree of precision and accuracy over a broad range of matrices. [ABSTRACT FROM AUTHOR]

The current model of pigs and poultry production has increased stocking density and reduced downtime between lots. This scenario may favour a rise of infection and disease risk in animals. To avoid this problem, routine use of drugs has been made, intensifying the possibility of residues in animal products and antimicrobial resistance. The aim of this study was to measure carry-over and contaminants of veterinary drugs included in the feed production lines for poultry and pigs. Samples were taken from 25 production lines. LC-MS/MS was used for simultaneous analysis of 62 active ingredients. In the medicated feed, 80.4% of the samples had a concentration of active ingredients different from the stated doses. In 70% of the feed samples, there was heterogeneity in the mixture of active ingredients. In subsequent feeds, carry-over was greater than 1% of the stated dose in 63% of cases. Of the 25 analysed lines, only one showed no contamination with other active ingredients. No correlations were found between the nutritional composition of the feed and carry-over. The present study demonstrated that the current production model allows the occurrence of unwanted drugs in feed-in doses that can contaminate animal products and can select antimicrobial-resistant bacteria. [ABSTRACT FROM AUTHOR]

A fast and sensitive method for the determination of a structurally and physico-chemically diverse group of contaminants of emerging concern (CEC) based on large-volume direct injection liquid chromatography-tandem mass spectrometry was developed. The method can be used to determine 20 CECs belonging to different pollutant families (pharmaceuticals, personal care products, and pesticides) in river water at nanogram per liter. A single analytical run is required and the positive and negative ionization modes can be used simultaneously. Because of the large-volume injections of samples and the high sensitivity of the current mass spectrometers, the method has no need of a preconcentration step. The analytes are quantitated with matrix-matched calibration curves. The estimated limits of detection were in the range 0.1–5 ng L−1. The accuracy of the method was in the range 86–114%, and the precision, expressed as a relative standard deviation (RSD %), was below 18% for all the analytes (n = 5, at 5, 10, and 25 ng L−1). The method was applied to water samples taken from different points along the lower course of the Ebro River, Spain. A total of 12 out of the 20 target analytes were detected, and the ones at higher concentrations were caffeine and the pharmaceuticals paracetamol and ibuprofen (184.8 ng L−1, 63.3 ng L−1, and 23.3 ng L−1, respectively). [ABSTRACT FROM AUTHOR]

Abstract Owing to the ease and effectiveness of removing suspended substances (SSs), filtration has become a universal pretreatment step during water sample preparation. However, it can lead to the underestimation of contaminants if the targets easily associate with the SSs or filters. For the first time, this study comprehensively assessed issues related to filtration for the accurate quantification of 35 typical pharmaceuticals, including 28 antibiotics and seven non-steroidal anti-inflammatory drugs (NSAIDs), in water samples by comparing the effects of different filter materials, preservatives, and water matrices on the recoveries. The results showed that some sulfonamides and NSAIDs had an affinity for nylon filters, whereas trimethoprim and macrolides were easily retained on mixed cellulose ester filters. The use of glass fiber filter (0.7 μm) resulted in improved recovery of all the targets. Acidification promoted the adsorption of fluoroquinolones, tylosin, and roxithromycin on SSs, whereas 5% methanol resulted in desorption of macrolides from the SSs and other pharmaceuticals (sulfadiazine, trimethoprim, etc.) from the solid-phase extraction cartridges. Without additional detection of targets adsorbed on the SSs and filters, the addition of appropriate surrogates prior to filtration can help correct the loss. Graphical abstract Unlabelled Image Highlights • Issues relating to filtration for accurate detection of 35 drugs are first studied. • NSAIDs and macrolides readily interact with nylon and cellulose filters, respectively. • Fluoroquinolones, tylosin, and roxithromycin are affected by acidification. • Surrogates are recommended to be used before filtration in surface water analysis. [ABSTRACT FROM AUTHOR]

A method for the simultaneous determination of 30 pesticides residues in soil was developed and validated. Among the studied agrochemicals, there are herbicides (auxines, sulfonylureas, fops, imidazolinones), fungicides (azoles) and insecticides (organophosphorus) widely used in extensive agricultural activities in Uruguay. Five methods with different extraction times, type and amount of solvent, as well as the possibility of a clean-up step were compared in terms of percentage of recovery and repeatability. The final method was based on the extraction of the pesticides' residues from soil using two successive solvent extraction steps. First, the soil was extracted with methanol in an orbital shaker for 4 h. Secondly, the solid residue was re-extracted overnight with ultrapure water. The methanolic extract was concentrated under vacuum, whereas the aqueous solution was passed through an OASIS HLB® cartridge, eluted with an appropriate solvent and concentrated under nitrogen stream. Both extracts were finally combined and analysed by LC-QQQ-MS/MS using the Document SANTE/11,945/2015 criteria. Recovery percentages at 1 and 10 μg kg−1 for the studied compounds were in the range 70106% with relative standard deviations below 19 %. The quantification was performed using matrix-matched calibration curves as some compounds presented very strong signal suppression. Residuals of the matrix-matched calibration curves were below 20% for all the validated analytes. The quantification limit was1 μg kg−1. The method also allows the screening of 11 pesticides in soil. Sixty-five real samples collected from regions where the use of pesticides is intensive were analysed. Quinclorac, tebuconazole, penoxsulam and clomazone were the most frequently pesticides detected. [ABSTRACT FROM AUTHOR]

• The method is based on QuEChERS extraction which is cost-effective and simple. • QuEChERS extraction was successfully validated for the quantification of 90 CECs. • Targeted CECs include plasticizers, pharmaceuticals, PFASs, pesticides. • Good recoveries, good reproducibility and low limit of quantification were obtained. • The method has been applied successfully to several real samples. Analytical methods for the determination of multi-class emerging contaminants are limited for soil and sediment while they are essential to provide a more complete picture of their distribution in the environment and to understand their fate in different environmental compartments. In this paper, we present the development and optimization of an analytical strategy that combines reliable extraction, purification and the analysis using ultra-pressure liquid chromatography triple quadrupole mass spectrometry (UPLC-MS/MS) of 90 emerging organic contaminants including pesticides, pharmaceuticals and personal care products, flame retardants, per- and polyfluoroalkyl substances (PFASs) and plasticizers in soil and sediment. To extract a wide range of chemicals, the extraction strategy is based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach. A number of different options were investigated (buffer, acidification, addition of EDTA, different types and combinations of dispersive SPE etc.) and the effectiveness of the chemical extraction procedure and the clean-up was assessed for two matrices: soil (organic matter content of 9%) and sediment (organic matter content of 1.9%). The method was fully validated for both matrices, in terms of accuracy, linearity, repeatability (intra-day), reproducibility (inter-day), method limits of detection and quantification (LODs and MLOQs, respectively). The final performance showed good accuracy and precision (mean recoveries were between 70 and 120% with relative standard deviations (RSD) less than 20% in most cases), low matrix effects, good linearity for the matrix-matched calibration curve (R2≥0.991) and MLOQs ranged from 0.25 and 10 µg/kg. To demonstrate the applicability and suitability of the validated method, soil and sediment samples from Vietnam, France, Sweden and Mexico were analyzed. The results showed that of the 90 target compounds, a total of 33 were quantified in the sediment and soil samples analyzed. In addition to multi-target analysis, this strategy could be suitable for non-target screening, to provide a more comprehensive view of the contaminants present in the samples. [ABSTRACT FROM AUTHOR]

[Display omitted] • A simple and rapid HPLC method was developed for the determination of ML residues in cow, sheep and goat milk. • Five compounds were separated using an analytical C18 column following a modified QuEChERS extraction method. • The method was validated according to European Commission Decision 2002/657/EC. • The developed method was successfully applied to real milk samples. Anthelmintic macrocyclic lactones (MLs) [ivermectin (IVM), abamectin (ABA), doramectin (DRM), eprinomectin (EPR) and moxidectin (MXD)] are used worldwide for the treatment of parasitic infections in large and small ruminants because of their low mammalian toxicity and higher efficacy against internal and external parasites at low dose levels. A rapid, simple and sensitive HPLC and a modified QuEChERS extraction method were developed and validated for the analysis of five anthelmintic MLs residues in cow, sheep and goat milk. The analytes were extracted from milk samples by acetonitrile deproteinization, followed by the addition of sodium sulphate and sodium chloride to generate a phase partition. HPLC separation was conducted at 50⁰C using a C18 analytical column (Zorbax, Eclipse Plus, 250 mm × 4,6 mm, 5µ). The mobile phase consisted of a mixture of acetonitrile: methanol: water (58:38:4, v/v/v), delivered by an isocratic program at the flow rate of 1.3 ml/min. The elution of five analytes was completed within 11 min. The fluorescence detector (FLD) was set at an excitation wavelength of 375 nm and an emission wavelength of 470 nm. Recoveries ranged between 78.44% and 92.66%. The quantification limits (LOQ) of anthelmintic MLs in the milk samples from 3 different ruminant species ranged between 2.01 and 3.10 ng/g. The developed method was validated in accordance with the criteria of Commission Decision 2002/657/EC. Linearity, decision limit, detection and quantification limits, recovery, accuracy, precision, sensitivity and selectivity were determined, and satisfactory results were obtained. This developed and validated method is rapid, simple, sensitive and environmentally friendly, and can be used for multiple residue analyses of anthelmintic MLs in cow, sheep and goat milk for human consumption. The quantification limits for all drugs were below the maximum residue limits (MRLs), making the method appropriate for routine testing. Finally, the application of this method was assessed using real samples of cow, sheep and goat milk. The presence of MLs was confirmed in 8 out of 70 tested milk samples, which shows the method can be successfully used to determine the residue of anthelmintic MLs in three types of milk. [ABSTRACT FROM AUTHOR]

Simple, rapid, efficient and cost-effective UPLC-ESI-MS/MS confirmatory method for the simultaneous determination of 14 coccidiostatic agents (salinomycin, monensin, lasalocid, halofuginone, robenidine, nicarbazin as 4,4′-dinitrocarbanilide, narasin, maduramycin, decoquinate, diclazuril, semduramycin, clopidol, amprolium and toltrazuril as parent drug and as its metabolites toltrazuril sulfone and toltrazuril sulfoxide) in chicken and turkey meat and liver was developed, validated and approved in routine laboratory practice. Main steps of sample preparation are as follows: homogenization, ultrasonication with acetonitrile and buffer solution, centrifugation, extraction by organic solvents mixture containing ethyl acetate and dichloromethane, evaporation and defatting of reconstituted residue by hexane. The technique is capable for multi-analyte determination of coccidiostats with LODs of 1–3 μg kg−1 depending on analyte using matrix-fortified calibrations. Procedure's adequacy was evaluated according to Commission Implementing Regulation (EU) 2021/808. Proposed method's efficiency is provided by the rational selection of extractants and ultracentrifugation at last stage of sample preparation. The developed technique is suitable to be used, when applying external standards and internal standards approaches. Time-consuming and costly procedures with ion suppressive desalting agents or SPE purification, which are common for coccidiostats assay, are not involved in the elaborated method, being method's main benefit comparing with known multi-residue LC-MS/MS techniques for coccidiostats analysis. This method is suitable for the control of safety parameters of poultry meat and liver as well as for establishing withdrawal periods of veterinary drugs based on coccidiostatic agents. • UPLC-MS/MS method is developed for coccidiostats residues assay in meat and liver. • LLE sample preparation protocol fits for 14 coccidiostats simultaneous analysis. • Method's benefit is use of three-component organic solvents mixture instead of SPE. • Validation according to 2021/808/EC confirms method's fitness for purpose. • Method is also suitable for establishing withdrawal periods of veterinary drugs. [ABSTRACT FROM AUTHOR]

The present work aimed at the development of a simple and accurate direct immersion-solidphase microextraction-gas-chromatography-mass spectrometry (DI-SPME-GC-MS) method for simultaneous determination of PAHs, PCBs, and pesticide residues in edible seaweeds. As the target contaminants possess a wide range of physical-chemical properties, multivariate experimental design was used for method optimization. In particular, two different methods were optimized and validated: one that allows for simultaneous determination of all targets, and an ad hoc method for determination of hydrophobic analytes, a class that often poses a challenge for extraction from food matrices. Optimum conditions suitable for simultaneous quantitation of all targeted compounds, namely buffer at pH = 7.0, 20% acetone (v/v), 10% NaCl (w/w), 0.02% NaN 3 , 60 min DI extraction at 55 °C, and 20 min desorption at 270 °C, afforded limits of quantitation (LOQs) in the range of 1–30 μg kg −1 , a wide linear range of 5–2000 μg kg −1 , the attainment of satisfactory determination coefficients (R 2 ˃0.99) with no significant lack of fit (p > 0.05) at the 5% level, and satisfactory accuracy and precision values. By modifying the extraction conditions to favor extraction of the most hydrophobic analytes (e.g. higher amount of organic modifier and pH, and lower salt content) lower LOQs were obtained for these compounds ranging from 0.2 to 13.3 μg kg −1 . The established methods were then used for screening of commercial, edible dry seaweeds, with PCBs (≤16.0 ng g −1 ) and PAHs (≤15.5 ng g −1 ) detected in some samples. This method overcomes most challenges commonly encountered in dry sample analysis applications, and represents the first report of a DI-SPME method employing the matrix-compatible fiber for simultaneous multiclass and multiresidue analysis of seaweeds. [ABSTRACT FROM AUTHOR]

Highlights • A multi-residue LC-TOF-MS method is proposed in muscle tissue of European sea bass. • Confirmation of antibiotics was achieved by the QTOF-MSE approach for the first time. • The new method was fully validated according to 2002/657/EC guideline. Abstract A UPLC-QTOF-MS method for the simultaneous determination of 20 veterinary drug residues and metabolites (tetracyclines, quinolones, sulfonamides and diaminopyrimidines) in edible muscle plus skin tissue of European sea bass (Dicentrarchus Labrax) was developed. For the identification of analytes a positive electrospray ionization quadropole time-of flight mass spectrometer operating in MSE mode (UPLC-QTOF-MSE) was used. MSE mode provides high chromatographic resolution and accurate mass measurements in both MS and MS/MS modes simultaneously in a single run. Separation was achieved on a UPLC BEH C18 (50 mm × 2.1 mm, 1.7 μm) column in a gradient elution program of 10 min. Examined antibiotics were isolated easily after a simple solid-liquid extraction procedure with acidic acetonitrile (0.1% v/v formic acid) and Na 2 EDTA 0.1 M. Recovery rates from muscle plus skin tissue ranged from 93.8% to 107.5% for all targeted compounds. The detection limits and the limits of quantification ranged from 2.22 to 15.00 μg/kg, and from 6.67 to 45.46 μg/kg, respectively. The developed method was validated in terms of selectivity, matrix effect, linearity, accuracy, precision, stability and sensitivity, CCα and CCβ according to European Union Decision 2002/657/EC. The proposed method was applied for the analysis of contaminated fish samples after in feed administration of danofloxacin mesylate. [ABSTRACT FROM AUTHOR]

In this study, trichlorfon and chlorpyrifos conjugated to CdSe/ZnS quantum dots with different emission wavelengths were adopted as labels. A hydrophilic imprinted film synthesized directly on the surface of a 96-well plate was used as the antibody. A direct competitive biomimetic immunoassay method for simultaneous determination of trichlorfon and chlorpyrifos in fruits and vegetables was developed. Under optimal conditions, the limit of detection of this method was 18.0 μg/L for chlorpyrifos (55 mg/kg for sample) and 19.0 μg/L for trichlorfon (45 mg/kg for sample). Orange and carrot samples spiked with chlorpyrifos and trichlorfon were extracted and determined by this method with recoveries ranging from 77.8 to 92.0%. The method was applied for detection of chlorpyrifos and trichlorfon residues in banana and apple samples, and the results correlated well with those obtained using gas chromatography. [ABSTRACT FROM AUTHOR]

A quantitative method using ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was developed for the determination of 60 compounds, belonging to a variety of veterinary drug (VD) classes, in meat. The included analytes belong to the following VD classes: β-agonists, sulfanilamides, quinolones, macrolides, tetracyclines, β-lactams, nitroimidazoles, glucocorticoids, sex hormones, chloromycetins, sedatives, and olaquindox metabolite. The effective PRiME pass-through cleanup procedure was used to ensure high extraction efficiency and good sample cleanup after a simple liquid extraction of the meat samples with acetonitrile/water. The developed method was validated successfully. Mean recoveries for all analytes ranged from 80 to 116%, with the relative standard deviations (RSDs) ≤ 7.8%. Limits of quantification were in the range 0.05-3.0 μg kg−1 and limits of detection were in the range 0.1-10 μg kg−1. The matrix effect was evaluated for the different meat matrices and was found to be markedly different in different matrices. The validated method was used in a pilot study to analyze real samples of pork, beef, mutton, chicken, and pork liver, lambs’ liver, and chicken liver. Trace amounts of β-agonists, oxytetracycline, quinolones, chloromycetin sulfadimidine, and 3-methyl-quinoxaline-2-carboxylicacid were detected in these samples. In conclusion, this workflow can provide a simpler and more cost-effective alternative to conventional analytical methods and is compatible with processing large sample numbers in a short time period. [ABSTRACT FROM AUTHOR]

Pesticides application is essential in protecting crops and increases their productivity. However, this causes the pesticide residues to contaminate the crops and their surrounding environment that will eventually lead to exposure to human being. There is very little understanding on the human health effects of pesticides, thus many studies are being carried out for this purpose. In conjunction to this, there are various analytical methods on multi-residue pesticides analysis that have been developed over the years in various samples. This review provides an overview of the reported concentration of pesticides, the extraction and determination techniques of pesticides in environmental samples and the potential health effects they imposed on human in Malaysia from 2007 to 2017. [ABSTRACT FROM AUTHOR]

In current study, the effects of Iranian rice cooking method (Kateh) on residue levels of 41 pesticides were investigated. The pesticides were selected according to Iranian National Standards Organization (INSO) regulations and covered 18 permitted and 23 banned pesticides belonging to different chemical classes such as organophosphate, triazole, and carbamate. A 250 g portion of rice sample was soaked in 2.5 L spiked tap water containing studied pesticides at final concentration 2 µg/mL and then, the effects of washing and cooking were investigated. The pesticides were analyzed simultaneously in a single run using positive electrospray ionisation with multiple reaction monitoring (MRM) after extraction with QuEChERS method. The results showed that washing removed different portions of pesticide residues in the range between 12.0-88.1%. Washing effect was not associated with the water solubility of the pesticides but amount of residue binding to rice matrix was a major factor for residue reduction. In Iranian method of rice preparation, cooking process includes boiling and steam cooking. In this study, the amount of the pesticide residues was decreased in the range of 20.7-100%. Under these conditions, volatilization, hydrolysis, and thermal degradation caused the reduction of the pesticide residues. [ABSTRACT FROM AUTHOR]

A multi-residue method was developed for the determination of organophosphorous pesticides and Herbicide by liquid-liquid extraction (LLE) and followed by gas chromatography-nitrogen-phosphorus detector (GC/NPD). The method was evaluated with respect to the limit of detection and quantification, linearity and accuracy (repeatability, reproducibility, recovery). The method is linear over the range 2.5-25 µg L-1 for eleven pesticides and 5-25 µg L-1 for methamidophos. Correlation coefficients were higher or equal to 0.992. The limits of detection (LODs) were between 0.67 and 2.23 µg L-1. The limits of quantification (LOQs) ranged from 2.24 and 7.45 µg L-1. Recoveries of fortified water samples in two different concentration levels with 12 organophosphorous pesticides and herbicide were over 95% in high concentration and 80% in low concentration. For repeatability, relative standard deviation (RSD%) ranged between 2.79 and 10.99%, and for reproducibility (RSD%) ranged between 1.56 and 10.36 %. The developed method is suitable for routine application in water samples in accordance with the validation data and the parameter as the high sample throughput and cost effective. [ABSTRACT FROM AUTHOR]

This study attempts at uniting the analysis of four different classes of contaminants for both liquid and solid tea samples. A total of 32 compounds, classified as pesticides, mycotoxins, process-induced toxicants or packaging contaminants, were carefully chosen for their diversity of structures and physicochemical properties. The proposed method combines a sample treatment strategy coming from metabolomics with liquid chromatography analysis using a silica bonded C18-pentafluorophenyl column coupled to high resolution mass spectrometry. For tea brew, dilute and shoot method provides good quantification (70–120% recoveries and <20% RSD) for more than 80% of compounds. For tea leaves, strong matrix effects are observed, thus, matrix-matched calibration is required to reach good performances, i.e. 63% of compounds quantified and 81% detected at 10 µg/kg. Finally, method performances were evaluated against existing regulations, and it appears that 69% of contaminants are quantified and 91% detected at levels lower than their respective European regulation limits. [ABSTRACT FROM AUTHOR]

An ultrahigh-performance liquid chromatography/hybrid quadrupole time-of-fight mass spectrometry (UPLC/QTOF-MS) method for the simultaneous identification and quantification of 50 multi-class pesticides in minor fruits is reported. The method consists of a sample extraction step, followed by analysis of the pesticides by UPLC/QTOF-MS. Satisfactory chromatographic separation was achieved over a 20 min runtime. The pesticides were identified by the accurate mass measurements of the protonated molecules ([M+H] + ) and their main fragment ions, isotopic pattern analysis and retention time matching. The mass accuracy obtained was below 2 ppm error for all the pesticides analysed. The method was validated by spiking starfruit with the 50 analytes. Satisfactory results regarding sensitivity and linearity were obtained. The method was successfully applied to the analysis of 87 real-world starfruit and Indian jujube samples, demonstrating its applicability for the routine analysis of multiple pesticide residues in minor tropical fruits. [ABSTRACT FROM AUTHOR]

A simple, sensitive and inexpensive LC–MS/MS method was developed and validated for for the simultaneous detection and quantification of (five) neonicotinoid insecticides in sugarcane juice. The juice samples were extracted with acetonitrile and subsequent cleanup was done by dispersive solid-phase extraction (QuEChERS method). The quantification was carried out by liquid chromatography–tandem mass spectrometry with electrospray ionization source (LC-ESI-MS/MS). After the optimization of the extraction parameters, the method was validated by evaluating linearity, limits of detection and quantification, precision (repeatability) and accuracy (recovery). Validation was based on analyses at three fortification levels that showed satisfactory recoveries (62.06–129.93%) and high precision (RSDs between 2.52% and 14.57%). Detection levels for all the five analytes ranged from 0.0007 to 0.002 μg g −1 and quantification level ranged from 0.002 to 0.005 μg g −1 , respectively. [ABSTRACT FROM AUTHOR]

Pesticides are needed to maintain high production in the vineyard area of La Rioja (Spain), and monitoring their spatial distribution is a priority for preserving the quality of natural resources. Accordingly, the purpose of this work was to conduct a study to evaluate the presence and seasonal distribution of herbicide and insecticide residues in ground and surface waters in this region. The monitoring network comprised 12 surface waters and 78 groundwaters, covering the three subareas (63,593 ha) into which the vineyard region is divided. The quality of natural waters was examined through the analysis of twenty-two herbicides, eight of their main degradation products, and eight insecticides. Pesticides were extracted by solid-phase extraction, and analysed by gas chromatography–mass spectrometry or by liquid-chromatography-mass spectrometry. The results reveal the presence of most of the herbicides and insecticides included in the study in one or more of the samples collected during the four campaigns. The herbicide terbuthylazine and its metabolite desethylterbuthylazine were the compounds more frequently detected (present in > 65% of the samples across all the campaigns). Other compounds detected in > 50% of the samples in one sampling campaign were the herbicides fluometuron, metolachlor, alachlor and ethofumesate. Insecticides were present in a small number of samples, with only pirimicarb being detected in > 25% of the samples in March and June campaigns. The results reveal that the sum of compounds detected (mainly herbicides) was higher than 0.5 μg L − 1 in > 50% of the samples, especially in the campaigns with the highest application of these compounds. A possible recovery of the quality of the waters was detected outside the periods of crop cultivation, although more monitoring programmes are needed to confirm this trend with a view to preventing and/or maintaining the sustainability of natural resources. [ABSTRACT FROM AUTHOR]

The application of synthetic pesticides to agricultural fields for the protection of crops leads to the formation of residues in soils. While the short-term behavior of pesticide residues in soils after an application is generally known from laboratory and field studies required for authorization (prospective risk assessments), there is still a lack of in-situ observations that address their long-term fate. Long-term soil monitoring programs, with comprehensive site-specific records of pesticide application data, constitute an invaluable, complementary, retrospective exposure assessment tool to address this gap. Considering the pesticide applications over the past 10–15 years, this study assessed the occurrence of pesticides in agricultural soils of Switzerland and put their presence or absence, as well as their concentrations, in the context of their previous application. The results showed that pesticides could also be detected at sites without a connection to previous applications and that small residual mass fractions of pesticides, even of some non-persistent compounds, were found in soils, years or decades after their last application. This finding points to an environmental issue that may not be adequately captured in prospective risk assessment and calls attention to the need for comprehensive long-term recording and monitoring as a complementary retrospective exposure assessment. [Display omitted] • Soils from 31 agricultural sites were analyzed for 34 pesticides and 7 metabolites. • The presence or absence of pesticides was related to their previous application. • Pesticides were also detected at sites not associated with previous applications. • Some pesticides persisted much longer than predicted from their half-lives. • Residual mass fractions of a few % were found years after the last application. [ABSTRACT FROM AUTHOR]