Search Results (73)

Natamycin is widely used in other countries for the postharvest treatment of agricultural commodities to prevent fungal growth. However, since no MRL has been set in Korea, natamycin residues are regulated under the Positive List System (PLS) with a uniform limit of 0.01 mg/kg, requiring the development of highly sensitive and reliable analytical methods. In this study, a QuEChERS-based analytical method was developed and validated for the quantification of natamycin in five agricultural commodities—soybean, mandarin, hulled rice, green pepper, and potato—using liquid chromatography–tandem mass spectrometry (LC-MS/MS). Extraction using methanol with 3 g of MgSO₄ resulted in high recoveries without crystallization, and clean-up with MgSO₄ and C18 effectively reduced matrix interferences blow <50%. Natamycin was detected in all five matrices at 6.8 min without any interfering peaks. The MLOQ was determined at 0.01 mg/kg for all five matrices. The mean recoveries (82.2–115.4%) and %CV values (1.1–4.6%) values were within the acceptance criteria defined by the CODEX guidelines. Matrix effects were classified as “soft” for mandarin (|ME| < 20%) and “medium” for soybean, hulled rice, green pepper, and potato (20% ≤ |ME| < 50%). The analytical method for natamycin was validated as suitable for regulatory safety monitoring under the Korean PLS. Full article

The increasing use of reclaimed wastewater in agriculture raises growing concerns about the accumulation of priority organic micropollutants in edible crops. In this study, we developed and validated a novel QuEChERS–SPME–GC/MS method for the simultaneous determination of 15 polycyclic aromatic hydrocarbons (PAHs), 3 nitro-PAHs, and 14 polychlorinated biphenyls congeners in Eruca vesicaria (rocket) leaves. The method was optimized to address the matrix complexity of leafy vegetables and included a two-step dispersive solid-phase extraction (d-SPE) cleanup and aqueous dilution prior to SPME. Validation showed excellent performance, with MDLs between 0.1 and 6.7 µg/kg, recoveries generally between 70 and 120%, and precision (RSD%) below 20%. The greenness of the protocol was assessed using the AGREE metric, yielding a score of 0.60. Application to rocket samples irrigated with treated wastewater revealed no significant accumulation of target pollutants compared to commercial samples. All PCB and N-PAH congeners were below detection limits, and PAH concentrations were low and mostly limited to lighter compounds. Human health risk assessment based on toxic equivalent concentrations confirmed that estimated cancer risk (CR) values 10⁻⁹–10⁻⁸ were well below accepted safety thresholds. These findings support the safe use of reclaimed water for leafy crop irrigation under proper treatment conditions and highlight the suitability of the method for trace-level food safety monitoring. Full article

Glyphosate (GLYP) is an effective and low-cost broad-spectrum herbicide. However, this herbicide and its primary degradation product, aminomethylphosphonic acid (AMPA), have been linked with adverse human health effects. The global use of glyphosate has significantly increased in recent years, resulting in more direct and indirect human exposure. In this context, GLYP and AMPA are often detected in fresh and processed foods for adults and infants, as well as in drinking water worldwide. Diverse extraction and quantification methods for GLYP and AMPA from foods have been developed. Solid-phase extraction and QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) are the most frequently employed cleanup strategies, while LC-MS/MS is one of the most sensitive and selective techniques for detecting GLYP and AMPA in food products. Although most studies show that GLYP and AMPA concentrations in foods remain within established maximum residue limits, occasionally they exceed legal limits. Thus, the widespread presence of GLYP and AMPA in foodstuffs is a public concern that may lead to consumers exceeding the acceptable daily intake due to prolonged dietary exposure, even if levels remain within thresholds. Therefore, this review explores the different approaches and techniques used in the extraction, detection, and quantification of GLYP and AMPA in foods. Full article

The global increase in chicken meat production and consumption has heightened concerns regarding the safety of chicken meat and its derived products. This study aimed to investigate the presence of Penicillium and Aspergillus mycotoxins in 50 samples of chicken breast muscle and liver collected from the Croatian market. Eight mycotoxins commonly produced by Aspergillus and Penicillium species were analyzed: aflatoxins B₁ (AFB₁), G₁ (AFG₁), B₂ (AFB₂), and G₂ (AFG₂); sterigmatocystin (STC); ochratoxin A (OTA); cyclopiazonic acid (CPA); and citrinin (CIT). Mycotoxin concentrations were determined using liquid chromatography–tandem mass spectrometry (LC-MS/MS) following sample cleanup with immunoaffinity columns while a QuEChERS-based method was applied for CPA. Mycotoxin occurrence was higher in liver samples, indicating the liver as primary site of mycotoxin accumulation compared to muscle tissue, where only CPA was detected. CPA was present in 20% of all samples, with the highest concentration (6.50 µg/kg) found in breast muscle, detected for the first time in fresh meat. AFB₁ and OTA were each detected in 10% of samples, and CIT was found in 4%—all exclusively in liver tissue. Notably, 4 out of the 17 contaminated samples contained more than one mycotoxin. Although the detected concentrations can be considered too low to pose an immediate health risk, the contamination rate suggests further research into these mycotoxins in chicken and other poultry species is needed. Full article

The QuEChERS method was adjusted to determine bifenthrin residues in grapes and grape leaves. Extraction and cleanup procedures were optimized to decrease co-extracted materials and enhance the detection of bifenthrin. The method was validated per the European Union (EU) Guidelines criteria. Accuracy ranged from 98.8% to 93.5% for grapes and grape leaves, respectively. Precision values were 5.5 and 6.4 (RSDr) and 7.4 and 6.7 (RSD_R) for grapes and grape leaves, respectively. LOQs (the lowest spiking level) were 2 and 20 µg/kg for grapes and grape leaves, respectively. Linearity as determination coefficient (R²) values were 0.9997 and 0.9964 for grapes and grape leaves, respectively, in a matrix over 1–100 µg/L range of analyte concentration. This was very close to the value in the pure solvent (0.9999), showing the efficiency of the cleanup in removing the co-extracted and co-injected materials; the matrix effect was close to zero in both sample matrices. Dissipation of bifenthrin was studied in a supervised trial conducted in a grapevine field during the summer of 2023 at the recommended dose and double the dose. Dissipation factor k values were 0.1549 and 0.1672 (recommended dose) and 0.235 and 0.208 (double dose) for grapes and grape leaves, respectively. Pre-harvest interval (PHI) was calculated for the Maximum Residue Limit (MRL) values of the EU database. Residues of bifenthrin were removed effectively from grapes using simple washing with tap water in a laboratory study. Residues reached the MRL level of 0.3 mg/kg in both washing treatments, running or soaking in tap water treatments for 5 min. Removal from leaves did not decrease residue levels to the MRL in grape leaves. Full article

Nitro-substituted neonicotinoid insecticides have been widely used until recently to control a range of important agricultural pests. Growing concerns about thiamethoxam’s toxicity to pollinators have led to its use being restricted or to it even being banned in some countries. Nevertheless, in Asia, Africa, Southeast Europe, and South America thiamethoxam is still used. Although thiamethoxam has been intensively studied all over the world, its dissipation dynamics have not been studied in depth. The subject of the present study was to (1) develop and validate a QuEChERS/LC-MS/MS protocol for the determination of thiamethoxam and its main metabolite clothianidin in samples of young oilseed rape plants with high chlorophyll content, and (2) make a comparison of the degradation behaviors of thiamethoxam and clothianidin in two crops of winter oilseed rape, cultivated on soils with different pH. For determination of thiamethoxam and clothianidin in plant material with high chlorophyll content, a QuEChERS/LC–MS/MS protocol enabling the detection of low levels of compound concentrations was developed. The proposed clean-up protocol provided recoveries within the range of 92–98% for the compounds under analysis. Precision, calculated as relative standard deviation, was below 20%. Satisfactory linearity of the method was obtained in the concentration range under analysis (0.001–1.0 mg kg⁻¹). Differences in degradation of both insecticides, depending on the physico-chemical properties of the soil, were observed. Thiamethoxam and clothianidin residues disappeared in plants very quickly, and they were not detected below the limit of quantitation in oilseed rape at the flowering stage. Full article

A facile procedure for extracting and determining seven neonicotinoids was developed. Water was the only extraction solvent without phase separation and cleanup steps. The method was validated according to European Union standards, and the values obtained were compared with the criteria. The accuracy values were between 99.8% (thiamethoxam) and 106.8% (clothianidin) at the spiking levels of 0.01, 0.1, and 1 mg/kg in the tested matrices. The precision as pooled RSD values was ≤6.1% (intra-day) and ≤6.9% (inter-day). The limit of quantification was set and tested at 0.01 mg/kg. The matrix effect was evaluated, and all matrices had a suppressive effect. The matrix of the cucumber was the most effective, with −20.9% for dinotefuran and an average of −9.8% for all compounds, while the tomato matrix had the slightest effect. Real marketed samples were analyzed using the developed and QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) methods; the results were not significantly different. A supervised field trial was conducted in the open field to study the dissipation patterns of imidacloprid and dinotefuran in tomatoes. The dissipation of both compounds followed first-order kinetics. The half-life (T_½) values were 3.4 and 2.5 days, with dissipation rates k of 0.2013 and 0.2781 days, respectively. Following the EU-MRL database, the calculated pre-harvest interval (PHI) values were 7 and 14 days for imidacloprid and dinotefuran, respectively, and 3 days for both compounds following Codex Alimentarius regulations. The risk of imidacloprid and dinotefuran residues was estimated from chronic and acute perspectives. The risk factors of dinotefuran were lower than those of imidacloprid. Nonetheless, the highest expected residues of both compounds were below the tolerance limits. Full article

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. Full article

The misuse of growth-promoting drugs such as beta-2 agonists and steroids is a known problem in farming and sports competitions. Prior to the analysis of biological samples via liquid chromatography (LC)–mass spectrometry (MS) or gas chromatography (GC)–MS, sufficient sample preparation is required to reliably identify or determine the residues of drugs. In practice, broad screening methods are often used to save time and analyze as many compounds as possible. This review was conceptualized to analyze the literature from 2018 until October 2023 for sample preparation procedures applied to animal specimens before LC- or GC-MS analysis. The animals were either used in farming or sports. In the present review, solid phase extraction (SPE) was observed as the dominant sample clean-up technique for beta-2 agonists and steroids, followed by protein precipitation. For the extraction of beta-2 agonists, mixed-mode cation exchanger-based SPE phases were preferably applied, while for the steroids, various types of SPE materials were reported. Furthermore, dispersive SPE-based QuEChERs were utilized. Combinatory use of SPE and liquid–liquid extraction (LLE) was observed to cover further drug classes in addition to beta-2 agonists in broader screening methods. Full article

In recent years, recurrent droughts have weakened stone pine (Pinus pinea) forests and facilitated the emergence of harmful pests and diseases, including the Leptoglossus occidentalis. The production of stone pine nuts has declined over the past five years. To control this hemipteran pest, a synthetic pyrethroid insecticide called deltamethrin is being tested. However, it is necessary to estimate the residue left by these treatments in forest stands. Therefore, a fast and robust analytical procedure was developed based on QuEChERS clean-up extraction, followed by gas chromatography coupled with an electron capture detector. This optimized method can detect residual concentrations of deltamethrin in pine nuts and pine needles up to 0.1 and 6 μg kg⁻¹, respectively, with a limit of quantification of 0.4 and 20 μg kg⁻¹. Great recoveries (between 84 and 102%) were obtained for both matrices, and no matrix effect was observed. The results showed that two weeks after spraying, the deltamethrin content in the needles of stone pines decreased by up to 75%, and after nine months, its presence was like that of nontreated trees. Full article

Chlorothalonil is an organochlorine fungicide that blocks the respiratory process of cells and persists in agricultural products because it is used extensively to prevent fungal diseases. An analytical method of chlorothalonil using the modified QuEChERS method and gas chromatography– mass spectrometry (GC-MS/MS) was developed to analyze the residue in agricultural commodities distributed in Republic of Korea. Acetonitrile, including acetic acid and formic acid, was used to compare the extraction efficiency. The extraction and purification processes were established by comparing three versions of the QuEChERS method and various dispersive solid-phase extraction (d-SPE) combinations. Ultimately, 1% formic acid in acetonitrile with QuEChERS original salts and d-SPE (PSA, C₁₈) were selected for the extraction and clean-up procedures for method validation and establishment. Five agricultural commodities, viz., brown rice, mandarin, soybean, pepper, and potato, were examined to validate the established method, which displayed excellent linearity, with a coefficient of determination of R² = 0.9939–0.997 in the calibration curve range of 0.002–0.1 mg/kg. The limits of detection (LOD) and quantification (LOQ) were calculated to be 0.003 mg/kg and 0.01, respectively, for the method. The LOQ value satisfied the suitable level for the Positive List System (PLS). The mean recovery of chlorothalonil was 79.3–104.1%, and the coefficient of variation was <17.9% for intra- and inter-day precision at 0.01, 0.1, and 0.5 mg/kg. The matrix effects in the five commodities were confirmed by the ion suppression effects, except for brown rice, in which a medium enhancement effect was observed at 21.4%. Chlorothalonil was detected in eight apples, one watermelon, and one cucumber. Ultimately, chlorothalonil was detected in ten agricultural products. Thus, this analytical method could be used for the routine detection of chlorothalonil in agricultural products, and the data may be used to inform and improve current food policies. Full article

A multi-residue method was developed to identify and quantify pharmaceutical drug residues in full-fat milk, using a modified QuEChERS extraction procedure and sonication combined with Ultra-High-Performance Liquid Chromatography–High-Resolution Orbitrap Mass Spectrometry (UHPLC-HR-Orbitrap-MS). Sample preparation involves three different QuEChERS extraction procedures and sorbents for the purification step. The optimized modified extraction method, combined with the clean-up approaches using C18 and the EMR-Lipid sorbent, has been validated in terms of linearity, recovery, precision, LOD and LOQ, matrix effects (ME) and expanded uncertainty. The optimized method showed a linearity >0.9903, recoveries within the range 65.1–120.1%, precision (expressed as %RSD) <17.5%, medium (<39.9%) to low (<16.7%) matrix effects and acceptable expanded uncertainty (<33.1%). Finally, the proposed method was applied to representative real samples of milk (by local markets), revealing the existence of one pharmaceutical drug (imidocarb) in one sample. Full article

Mycotoxins, produced by fungi as secondary metabolites, have the potential to induce both short-term and long-term toxic consequences in animals and humans. The present study aimed to determine multi-mycotoxin levels in Algerian workers using urine as the target. A method based on a QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction procedure followed by liquid chromatography–tandem mass spectrometry (LC-MS/MS) was optimized and validated for the determination of eleven mycotoxins in 96 urine samples. Different sorbents were tested to be used in the dispersive solid-phase extraction (d-SPE) cleanup step of QuEChERS. The final method was fit-for-purpose and showed good analytical performance in terms of specificity, linearity, and precision. All samples contained at least two mycotoxins, and toxin-2 (T-2) was the most common, being found in 92.7% of the samples, followed by zearalenone (ZEN) in 90.6% of positive samples, and ochratoxin A (OTA) in 86.4%. T-2 levels ranged from 0.3 μg/L to 36.3 μg/L, while OTA ranged from 0.3 μg/L to 3.5 μg/L, and ZEN ranged from 7.6 μg/L to 126.8 μg/L. This was the first mycotoxin biomonitoring study carried out in the Algerian population. The findings highlight the need for accurate data for better risk assessment and for the development of better regulation to manage mycotoxin contamination in this country. Full article

Oligomers are a particular category of non-intentionally added substances (NIAS) that may be present in food contact materials (FCMs), such as polyethylene terephthalate (PET), and consequently migrate into foods. Here, an ultra-high-pressure liquid chromatography quadruple time-of-flight mass spectrometry (UHPLC-qTOF-MS) method was developed for the analysis of 1st series cyclic PET oligomers in virgin olive oil (VOO) following a QuEChERS clean-up protocol. Oligomer migration was evaluated with two different migration experiments using bottles from virgin and recycled PET: one with VOO samples stored in household conditions for a year and one using the food simulant D2 (95% v/v ethanol in water) at 60 °C for 10 days. Calibration curves were constructed with fortified VOO samples, with the LOQs ranging from 10 to 50 µg L⁻¹ and the recoveries ranging from 86.6 to 113.0%. Results showed no migration of PET oligomers in VOO. However, in the simulated study, significant amounts of all oligomers were detected, with the migration of cyclic PET trimers from recycled bottles being the most abundant. Additional substances were tentatively identified as linear derivatives of PET oligomers. Again, open trimer structures in recycled bottles gave the most significant signals. Full article

In this study a multi-residue determination method for 36 pesticides in dried hops was reported. The sample preparation procedure was based on the acetate buffered QuEChERS method. A few mixtures of dispersive solid phase extraction (dSPE) sorbents consisting PSA, C₁₈, GCB, Z-Sep and Z-Sep+ were investigated to clean-up the supernatant and minimize matrix co-extractives. The degree of clean-up was assessed by gravimetric measurements, which showed the best results for mixtures containing the Z-Sep+ sorbent. This is the first study to apply Z-Sep+ sorbent for hops material and the first to improve the method for pesticide residues determination in hops. Samples were analysed using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and the procedure was validated according to the SANTE/11813/2017 document at four concentration levels: 0.02, 0.05, 0.1 and 1 mg/kg. The limits of quantification (LOQ) were in the range of 0.02–0.1 mg/kg. For all active substances, the trueness (recovery) ranged from 70 to 120% and the precision (RSD_r) value was <20%. Specificity, linearity and matrix effect were also evaluated. The validated method was applied to the analysis of 15 real dried hop samples and the relevant data on detected residues were included. Full article