Search Results (45)

The protection of natural resources, particularly groundwater, is essential for the sustainability of rural environments, especially when urban centers rely on this water for consumption. The objective of this study was to evaluate the occurrence, seasonal distribution, and associated risk of pesticide residues in groundwater in a region of intensive farming in the Duero river basin (Spain). A total of 40 pesticides and 7 degradation products were analyzed at 20 sampling points over four campaigns conducted in 2018. Overall, twenty-one compounds were detected, including three insecticides, three fungicides, ten herbicides, and five degradation products. Concentrations of eight compounds (one fungicide, five herbicides, and two degradation products) exceeded the limits established by the European Union (EU) for drinking water. Herbicides were the most frequently detected pesticides and were present at the highest concentrations (up to 3.416 μg L⁻¹) across all sampling campaigns. Metolachlor, prosulfocarb, metribuzin, and metolachlor degradation products (ethanesulfonic acid (ESA)– and oxanilic acid (OA)–metolachlor) were detected in concentrations over 1.0 µg L⁻¹. The sum of Toxic Units (∑Tu_i) showed that none of samples posed a high risk. None of compounds presented a high risk for the three aquatic organismstested; only prosulfocarb for algae and Daphnia magna; pendimethalin for algae and fish; and metribuzin, chlorotoluron, and desethyl-terbuthylazine (DETbz) for algae posed high risks. Full article

Ultrasound-assisted microextraction (UAME) has emerged as a powerful and sustainable technique for food chemical contaminant analysis, offering a rapid, efficient, and environmentally friendly alternative to conventional extraction methods. This review provides a comprehensive overview of recent advancements in the application of UAME for the determination of various food chemical contaminants, including pesticide residues, potentially toxic elements, mycotoxins, veterinary drugs, and other chemical contaminants. The fundamental principles of ultrasound-assisted extraction are discussed, with an emphasis on the mechanisms of acoustic cavitation and mass transfer enhancement that enable improved analyte recovery from complex food matrices. Key factors influencing extraction efficiency (solvent selection, ultrasonic frequency and power, extraction time, and sample characteristics) were critically analyzed. Additionally, the integration of UAME with modern analytical platforms, such as LC-MS, GC-MS, and ICP-MS, was explored, highlighting its compatibility with high-throughput and multiresidue detection. Compared with traditional techniques, UAME offers significant benefits, including reduced solvent consumption, shorter extraction times, and improved analytical performance. This review also addresses current limitations and future perspectives, particularly regarding standardization, automation, and application in routine food safety monitoring. Overall, UAME represents a promising direction for more sustainable and efficient food chemical contaminant analysis, aligning with the growing demand for green analytical chemistry approaches. Full article

Fruits and vegetables are crucial components of a healthy diet, which are susceptible to pests. Therefore, the application of pesticides is a basic manner of crop chemical protection. The aim of this study was a comprehensive analysis of pesticide occurrence in 1114 samples of fruits and vegetables. A unified multi-analytical protocol was used composed of primary–secondary amine/graphitized carbon black/magnesium sulfate to purify samples with diversified profile of interfering substances. Moreover, the obtained analytical data were used to evaluate the critical acute health risk in subpopulations of children and adults within European limits criteria. Out of 550 pesticides analyzed, 38 and 69 compounds were noted in 58.6% of fruits and 44.2% of vegetables, respectively. Acetamiprid (14.1% of all detections) and captan (11.3%) occurred the most frequently in fruits, while pendimethalin (10.6%) and azoxystrobin (8.6%) occurred the most frequently in vegetables. A total of 28% of vegetable and 43% of fruit samples were multiresidues with up to 13 pesticides in dill, reaching a final concentration of 0.562 mg kg⁻¹. Maximum residue level (MRL) was exceeded in 7.9% of fruits and 7.3% of vegetables, up to 7900% MRL for chlorpyrifos in dill (0.79 mg kg⁻¹). Notably, 8 out of 38 pesticides found in fruits (21%; 1.2% for carbendazim) and 24 out of 69 compounds in vegetables (35%, 7.4% for chlorpyrifos) were not approved in the EU. Concentrations of pesticides exceeding MRL were used to assess acute health risk for children and adults. Moreover, the incidence of acute health risk was proved for children consuming parsnip with linuron (156%). In other cases, it was below 100%, indicating that Polish food is safe. The work provides reliable and representative scientific data on the contamination of fruits and vegetables with pesticides. It highlights the importance of legislative changes to avoid the occurrence of not approved pesticides in the EU, increasing food and health safety. Full article

This study aimed to perform an in-depth investigation of olive oil mill wastewater (OOMW). Two OOMW samples (OOMW-A and OOMW-B) from conventionally farmed olives were collected from two different olive oil mills in Palermo province (Italy). Multiresidual analysis indicated that both OOMW samples were unsuitable for food production due to pesticide residues. Specifically, OOMW-A contained 4 active compounds totaling 5.7 μg/L, while OOMW-B had 16 analytes with a total content of 65.8 μg/L. However, polyphenol analysis in the OOMW revealed 23 compounds with high concentrations of hydroxytyrosol, secoiridoid derivatives, phenolic acids, flavones, and total polyphenol content ranging from 377.5 μg/mL (for OOMW-B) to 391.8 μg/mL (for OOMW-A). The microbiological analysis of OOMW samples revealed only detectable viable bacteria (10² CFU/mL) of the lactic acid bacteria (LAB) group. Two distinct LAB strains, Lactiplantibacillus plantarum OMW1 and Leuconostoc mesenteroides OMW23, were identified. These strains demonstrated notable acidification capabilities and produced antibacterial compounds. In conclusion, despite the high polyphenolic content and microbiological suitability of OOMW, the presence of micro-contaminants hinders their use in food production. Thus, further studies are underway to investigate OOMW from organically farmed olives for bakery product functionalization, employing the two selected LAB strains resistant to olive polyphenols as leavening agents. Full article

Honey, a natural food with a rich history, is produced by honeybees and other species of bees from nectar, other plant fluids, and honeydew of sap-sucking insects. During foraging, these bees may be exposed to plant protection products (PPPs), metals, and metalloids, potentially leading to residues in honey and hive products that could have a negative impact on human safety. Recognizing the lack of an appropriate methodology for pesticide contamination of honey and other hive products, this research aims to support the need for studies on residues in pollen and bee products for human consumption to establish safe maximum residue levels (MRLs) for consumers. A UHPLC-MS/MS residues method and a modified QuEChERS extraction were applied to simultaneously determine 237 pesticide residues in honey and pollen. The study in North Sardinia analyzed honey and pollen samples from six areas for pesticide residues and verified 27 heavy metals and metalloid residues using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The data obtained showed residues at levels close to the LOQ of the method, cycloate in a few samples of pollen, and dichlorvos, zoxamide, cycloate, and chlorantraniliprole in honey samples. All samples showed the absence of heavy metal contamination. Overall, no risk to human health was identified. The results of this study confirm that honey and pollen may be a good bioindicator of environmental contamination of a wide area surrounding honeybee hives. Full article

A robust analytical method was developed for the simultaneous detection of 504 pesticide multiresidues in various crops using ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UHPLC-QTOF). The method integrates both MS¹ and MS² levels through sequential window acquisition of all theoretical mass spectra (SWATH) analysis, allowing for accurate mass measurements and the construction of a spectral library to enhance pesticide residue identification. An evaluation of the method was carried out according to international standards, including the FAO guidelines and SANTE/11312/2021. Validation across five representative crops—potato, cabbage, mandarin, brown rice, and soybean—demonstrated exceptional sensitivity, with over 80% of the analytes detected at trace levels (≤2.5 μg/kg). Moreover, an impressive 96.8% to 98.8% of the compounds demonstrated LOQs of ≤10 μg/kg. Most compounds exhibited excellent linearity (r² ≥ 0.980) and satisfactory recovery rates at spiking levels of 0.01 and 0.1 mg/kg. Among 42 crop samples analyzed, pesticides were detected in 1 cabbage, 3 mandarin, and 6 rice samples, with a mass accuracy within ±5 ppm and a Fit score ≥ 70.8, confirming the method’s practical applicability and reliability. The detected residues ranged from 12.3 to 339.3 μg/kg, all below the established maximum residue limits (MRLs). This comprehensive approach offers an efficient, reliable, and scalable solution for pesticide multiresidue monitoring, supporting food safety programs and regulatory compliance. Full article

Dispersive solid-phase extraction (dSPE) is a crucial step for multiresidue analysis used to remove matrix components from extracts. This purification prevents contamination of instrumental equipment and improves method selectivity, sensitivity, and reproducibility. Therefore, a clean-up step is recommended, but an over-purified extract can lead to analyte loss due to adsorption to the sorbent. This study provides a systematic comparison of the advantages and disadvantages of the well-established dSPE sorbents PSA, GCB, and C18 and the novel dSPE sorbents chitin, chitosan, multi-walled carbon nanotube (MWCNT), and Z-Sep^® (zirconium-based sorbent). They were tested regarding their clean-up capacity by visual inspection, UV, and GC-MS measurements. The recovery rates of 98 analytes, including pesticides, active pharmaceutical ingredients, and emerging environmental pollutants with a broad range of physicochemical properties, were determined by GC-MS/MS. Experiments were performed with five different matrices, commonly used in food analysis (spinach, orange, avocado, salmon, and bovine liver). Overall, Z-Sep^® was the best sorbent regarding clean-up capacity, reducing matrix components to the greatest extent with a median of 50% in UV and GC-MS measurements, while MWCNTs had the largest impact on analyte recovery, with 14 analytes showing recoveries below 70%. PSA showed the best performance overall. Full article

In this study, we developed and validated a multiresidue analytical method for the simultaneous detection of 24 pesticides in fishery products. Using the EN15662 extraction method and C₁₈ as the adsorbent for purification, the validation results complied with Codex guidelines, achieving recovery rates between 70% and 120% and relative standard deviation values (%RSD) within 20%, indicating excellent performance. The limit of detection ranged from 0.25 to 0.8 ng/kg, and the limit of quantification was between 3 and 10 ng/g, providing sufficient sensitivity to comply with future regulatory standards. The calibration curves for all 24 pesticides exhibited great linearity (R² > 0.98), also satisfying the Codex requirements. The matrix effect was less than 30% for some pesticides—within ±20%—indicating minimal interference from impurities. An analysis of 300 fishery samples from nine regions across South Korea detected lufenuron at 10 ng/g in eels; however, the risk assessment was below 0.19%, posing no significant hazard to public health. This newly developed analytical method proved effective for the multi-analysis of pesticide residues in fishery products, offering rapid and reliable monitoring of the import and export safety of fishery products. Full article

Multi-residue methodologies necessitate a tailored and precise approach across all areas of analysis. Analyte extraction must be closely correlated with the sample matrix to ensure the optimal recovery for the maximal array of analytes, thereby fulfilling all legal requirements concerning analytical determination. Although the QuEChERS method offers undeniable advantages, it proves unsuitable for pesticide residue determination in matrices with high oil contents. A pivotal component of the method involves employing n-hexane as the extraction solvent and utilizing solvent exchange in obtaining the final extract. The analytical method developed by our laboratory, as presented here, enabled the determination of all requisite pesticides in accordance with European Union (EU) Regulation 396/2005. The linearity, limits of detection and quantification, matrix effects, accuracy, and precision of the method were evaluated in line with the aforementioned regulation. Of the analyzed pesticide residues, 273 exhibited expanded uncertainty with an RSDr ≤ 20%, with recoveries falling within the range of 70–120%, meeting all the requirements of document SANTE/11312/2021 V2. For 9 pesticides, the recovery was below 30%, and the precision of the obtained content for 21 compounds surpassed 20%, necessitating the removal of these compounds from the analytical method. Full article

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO₄ and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers. Full article

In this work, a method of simultaneously analyzing pesticide concentration and assessing its risks was developed. Assessments were conducted to evaluate the distribution characteristics and risks to human health of pesticides in shallow groundwater in agricultural areas. We developed multi-residue analytical methods using liquid chromatography (LC-MS/MS) and gas chromatography–tandem mass spectrometry (GC-MS/MS) to analyze 57 pesticides in groundwater. In addition, risk assessments were performed by setting scenarios considering the routes of pesticide infiltration into groundwater. For the simultaneous analysis of 57 pesticides, the liquid–liquid extraction method was applied twice using dichloromethane under acidic and alkaline conditions. The extract was concentrated and analyzed using LC-MS/MS (41 pesticides) and GC-MS/MS (16 pesticides). The precision and accuracy ranges of the analytical methods were 0.1~12.9% (within ±15%) and 80.3~113.6% (within ±20%), respectively. The limit of quantification was found to range from 0.0004 to 0.0677 μg/L. In total, 57 pesticides were monitored in 200 groundwater wells from 2019 to 2020. Twenty-six pesticides, including metolachlor and imidacloprid, were detected, with an average concentration of 0.0008 μg/L in groundwater. The pesticide types and detection levels differed depending on the survey period and surrounding land. When the risks associated with alachlor, metolachlor, and carbofuran were assessed, their health risks when found in groundwater were evaluated to be negligible (non-carcinogenic risk: less than 10⁻³, carcinogenic risk: less than 10⁻⁶). Full article

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. Full article

The development of efficient methods for evaluating pesticide residues is essential in order to ensure the safety and quality of agricultural products since the Republic of Korea implemented the Positive List System (PLS). The objective of this research was to establish a method for the simultaneous analysis of 322 pesticide residues in fruits and vegetables (such as coffee, potato, corn, and chili pepper), using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS). This study introduces a robust, high-throughput GC-MS/MS method for screening the target pesticide residues in agricultural products, achieving the PLS criterion of 0.01 mg/kg LOQ. Despite some compounds not aligning with the CODEX recovery guideline, sufficient reproducibility was confirmed, attesting to the method’s applicability in qualitative analyses. A health risk assessment conducted using estimated daily intake/acceptable daily intake ratios indicated low risks associated with product consumption (<0.035391%), thereby confirming their safety. This efficient method holds significant implications for the safe distribution of agricultural products, including during import inspections. 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

The aim of this study was the optimization of the clean–up step in the widely applied QuEChERS method for the determination of 39 representative multiclass pesticides in olive oil with Ultra-High-Performance Chromatography–Orbitrap Mass Spectrometry (UHPLC-Orbitrap-MS). The analytical methodology combines the original version of QuEChERS extraction with two different clean-up-step approaches, using firstly a combination of Z-Sep⁺, PSA and MgSO₄ and secondly EMR-lipid. The methods were compared for their efficiency in the removal of fats and co-extractives and their effect on the analytical performance characteristics. Both methods were evaluated in terms of linearity, matrix effects (ME), recovery, precision, limits of detection (LOD) and quantification (LOQ) and expanded uncertainty in three spiking levels of 30, 100 and 300 μg/kg. The recoveries ranged between 70–113% for 95% of analytes (RSD_r < 14%) when EMR-lipid was used as a sorbent, while in the case of Z-Sep⁺/PSA/MgSO₄ recoveries ranged between 72–107% for 92% of analytes (RSD_r < 18%). ME showed low signal suppression for 77% of analytes in the case of Z-Sep⁺/PSA/MgSO₄ and for 85% of analytes in the case of EMR-lipid. According to the results, both methodologies provided good analytical performances fulfilling validation criteria; however, the EMR-lipid sorbent showed better clean-up capacity (i.e., less matrix effects and lower variability in extraction recoveries) and validation parameter values for more analytes. The validated method was successfully applied to 30 olive oil samples from different regions of Greece. No residues have been identified in the analyzed samples. Full article