Trace organic contaminants in lake waters: Occurrence and environmental risk assessment at the national scale in Canada.

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.

Distribution of Pesticides and Polychlorinated Biphenyls in Food of Animal Origin in Croatia.

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.

A Multi-Residue Analytical Method for Assessing the Effects of Stacking Treatment on Antimicrobial and Coccidiostat Degradation in Broiler Litter.

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.

A high-throughput analytical method for complex contaminant mixtures in biosolids.

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.

Optimization and validation of an extraction method for the analysis of multi-class emerging contaminants in soil and sediment.

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.

A one-step solid-phase extraction with UHPLC-MS/MS for fast and accurate determination of multi-class veterinary drugs in animal muscles.

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.

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

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

Critical Evaluation of Two Qualitative Analytical Approaches for Multiclass Determination of Veterinary Drugs in Bovine Muscle Using UHPLC-Q-Orbitrap: The Wind of Change in Brazilian Monitoring.

Food safety is recognized as a main requirement for consumers, food industries, and official laboratories. Here, we present the optimization and screening qualitative validation of two multianalyte methods in bovine muscle tissues by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry with an Orbitrap-type analyzer, operated with a heated ionization source in positive and negative mode. This aims for not only the simultaneous detection of veterinary drugs regulated in Brazil but also the prospection of antimicrobials not yet monitored. Two different sample preparation procedures were applied: method A-generic solid-liquid extraction with 0.1% formic acid (v/v) in an aqueous solution of EDTA 0.1% (w/v)-acetonitrile-methanol (1:1:1, v/v/v), followed by an additional ultrasound-assisted extraction and method B-QuEChERS. In both procedures, selectivity showed satisfactory conformity. From a detection capability (CCß) equivalent to ½ the maximum residue limit, >34% of the analyte resulted in a false positive rate of <5%, preponderant by the QuEChERS method, which exhibited a higher yield of the sample. The results showed the potential application of both procedures in the routine analysis of foods by official laboratories, enabling the expansion of this methodological portfolio as well as its analytical scopes, thus optimizing the control of residues of veterinary drugs in the country.

Pesticide residues in agricultural soils in light of their on-farm application history.

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.

Ultra-high performance liquid chromatography and gas chromatography coupled to tandem mass spectrometry for the analysis of 32 pyrethroid pesticides in fruits and vegetables: A comparative study.

In this study, multi-residue analysis methods for 32 pyrethroids in fruit and vegetable samples were established in both GC-MS/MS and UHPLC-MS/MS. The parameters that affecting the ionization efficiencies of pyrethroids in UHPLC-ESI-MS/MS, including ion source temperature, in-source fragmentation, and mobile phase conditions were thoroughly investigated to guarantee better performance. These two techniques were comprehensively compared in terms of recovery, LOQ, linearity, and matrix effects. In general, UHPLC-MS/MS was found suitable for more pesticides than GC-MS/MS. Lower LOQs were obtained for most of the selected pyrethroids in UHPLC-MS/MS. Similar results were obtained in terms of recoveries and RSDs for the validated pesticides in fortification experiments. A total of 136 real samples were analyzed by both techniques, obtaining similar results. The results suggest that UHPLC-MS/MS offers a suitable alternative to GC-MS/MS in the routine analysis of pyrethroids in fruits and vegetables.

Target and suspect screening of pesticide residues in soil samples from peach orchards using liquid chromatography quadrupole time-of-flight mass spectrometry.

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.

Dual-template hydrophilic imprinted resin as an adsorbent for highly selective simultaneous extraction and determination of multiple trace plant growth regulators in red wine samples.

In recent years, numerous plant growth regulators have been found in foods and have a toxicity to human health, so its simultaneous multiple monitoring is urgently. For the first time, a rapid, accurate, and high-selective method was established to extract and determine multiple plant growth regulators simultaneously in red wines using a new dual-template hydrophilic molecularly imprinted resin (DHMIR) as an adsorbent of pipette tip solid-phase extraction coupled with HPLC. The as-prepared DHMIR combined the advantages of the hydrophilicity of hydrophilic resin and multi-imprinted recognition of dual-template molecular imprinting, overcoming the poor imprinted recognition ability of traditional imprinting materials in water and low extraction efficiency to multiple targets. Under the optimized conditions, the proposed method exhibited high sensitivity (2.29-3.94 ng mL-1) and recoveries (80.9-109.0 %) using only 15 mg DHMIR. This study provides an effective strategy for rapid, accurate, low-cost, and high-selective determination of the multiple analytes in food samples.

Development of a polyurethane-coated thin film solid phase microextraction device for multi-residue monitoring of pesticides in fruit and tea beverages.

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.

Simultaneous multi-residue analytical method for anesthetics and sedatives in seafood samples by LC-ESI/MSMS.

A simultaneous multi-residue analytical method for 27 regulated and unregulated anesthetics and sedatives in seafood using liquid chromatography/tandem mass spectrometry with electrospray ionization (LC-ESI/MSMS) was developed and tested on flatfish, eels, and shrimp. To optimize the efficiency of the method, extraction and clean-up procedures with various solvents and sorbents were tested. The most efficient pretreatment methods were extraction using acetonitrile (ACN) only (for flatfish and eel) and 0.1 % ammonium acetate in ACN (for shrimp). Validation was performed under the guidelines of CODEX Alimentarius (CAC/GL-71) and the Korean National Institute of Food and Drug Safety Evaluation (NIFDS). The limit of detection (LOD), limit of quantification (LOQ), accuracy, and precision for all compounds ranged from 0.0002 to 0.002 mg/kg, 0.0005-0.005 mg/kg, 64.7-112.5 %, and 1.0-8.6 %, respectively. The coefficient of determination (linearity, R2) was over 0.98. Therefore, the method meets the requirements of both the domestic and international guidelines.

Development and optimization of an ultra-fast microextraction followed by HPLC-UV of tetracycline residues in milk products.

The present study developed a new ultra-fast microextraction (within 8 min) with acetonitrile followed by gradient reversed-phase HPLC-UV method to determinate six tetracyclines simultaneously in various milk products with HPLC analysis time of 9 min. Chromatographic separations were achieved with a phenomenex™ Synergi 4 µm Fusion-RP (150 × 4.60 mm) column at 220 nm, using acetonitrile/KH2PO4 buffer (4 mmol·L-1, pH 2.5) as mobile phase. The HPLC method showed excellent peak resolutions (3.3-8.8) and peak symmetry (0.99-1.11) inspite of short analysis time. The extraction rates from milk products showed consistently very good values over all tetracyclines (milk 80.58 ± 5.39 %, yoghurt 82.61 ± 5.63 %, cream cheese 80.13 ± 6.32 %, buttermilk 81.07 ± 6.49 %, kefir 79.69 ± 6.51 %, skyr 78.12 ± 5.22 %, quark 65.37 ± 4.72 %). The optimized method was found to be specific, reproducible, robust. This study combines for the first time a fast, cheap quantification of six tetracyclines via HPLC-UV with a reliable microextraction applicable to various milk products using only standard laboratory equipment.

Wide-Scope Multi-residue analysis of pesticides in beef by gas chromatography coupled with quadrupole Orbitrap mass spectrometry.

Increasing pesticide contamination in foods of animal origin has made the wide-scope multi-residue analysis of pesticides an international concern. By using 191 pesticides, this study investigates a sensitive and reliable method for multi-residue analysis of pesticides in beef to determine the extent of the application of this method. The QuEChERS method was employed to extract and purify the pesticides as C18 was utilized as the absorbents. Then, the purified pesticides were analysed using gas chromatography - quadrupole orbitrap mass spectrometry (GC-Q-Orbitrap-MS). The validation test results revealed that this method was satisfactorily sensitive since its screening detection limit (SDL) ranged from 0.2 to 100 µg∙kg-1. The recovery tests implemented at three spiking levels, namely 100, 200, and 500 µg∙kg-1, generated the results of 71.95 %-113.97 %, while the intra- and inter-day precisions were 0.27 %-17.94 %, indicating that this method had excellent accuracy and precision.

Optimization of a Multi-Residue Analytical Method during Determination of Pesticides in Meat Products by GC-MS/MS.

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.

Rapid and Reliable Data Treatment for the Control of Food Chemical Contaminants by LC-HRMS.

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.

Simultaneous screening and analysis of 155 veterinary drugs in livestock foods using ultra-high performance liquid chromatography tandem quadrupole linear-ion-trap mass spectrometry.

Veterinary drugs are widely used to improve the health and growth of livestock. The supervision of these residues is necessary to ensure food safety. A high-throughput method based on Oasis PRiME HLB with solid phase extraction for simultaneous qualitative and quantitative analysis of 155 veterinary drugs in livestock foods was developed by the ultra-high performance liquid chromatography tandem quadrupole linear-ion-trap mass spectrometry (UHPLC-QTRAP-MS). The limits of detection and quantification ranged from 0.5 µg/kg to 5 µg/kg and 2 µg/kg to 20 µg/kg, respectively. For over 85% of the analytes, the recoveries were between 60% and 120%. The positive simulated samples perfectly matched with a purity fit value over 70% from the self-built library. The screening results of UHPLC-QTRAP-MS were almost consistent with UHPLC tandem quadrupole-exactive orbitrap mass spectrometry (UHPLC-Q-Exactive Orbitrap/MS). The evaluated UHPLC-QTRAP-MS method was powerful and reliable for the screening and quantification of veterinary drugs in real samples.

Simultaneous analysis of multiple pesticide residues in tobacco by magnetic carbon composite-based QuEChERS method and liquid chromatography coupled to quadrupole time-of-flight mass spectrometry.

Magnetic carbon composite (Fe3O4@C) was synthesized and applied as a reversed-dispersive solid-phase extraction sorbent for the simultaneous analysis of 40 pesticide residues in tobacco by ultrahigh-performance liquid chromatography coupled to quadrupole time-of-fight mass spectrometry. Compared to the traditional QuEChERS method, the optimized Fe3O4@C simplified clean-up process and exhibited better clean-up capability than conventional sorbents. The pesticides were qualitatively identified by accurate mass of protonated molecules, fragment ions, isotopic peak clusters, and retention time, and quantitatively determined by matrix-matched external standard method. Good linearity of the proposed method was obtained with R value greater than 0.997 for all target pesticides at concentration levels of 2-200 µg/L. The limit of detection ranged from 0.14 to 2.67 µg/kg. The recoveries and relative standard deviations of all target pesticides at three spiked concentrations of 20, 50 and 200 µg/kg were in the ranges of 80.8%-113.3% and 0.6%-16.3%, respectively. Compared with the reported methods for the analysis of multiple pesticide residues in tobacco, the proposed method has the advantages of simple to operate, high clean-up ability and less time-consuming in clean-up process.