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1.
Sci Rep ; 14(1): 13064, 2024 06 06.
Article En | MEDLINE | ID: mdl-38844596

This study aimed to investigate carbamate pesticide residues in different varieties of date palm fruits in the UAE, utilizing UHPLC-MS/MS. For sample preparation and clean-up, the efficiency and performance of different QuEChERS dispersive solid-phase extraction kits were compared. Precision and recovery were assessed at 10 µg kg-1 for the three kits, revealing that Kit 2 demonstrated the best performance. The selected QuEChERS method was validated to detect 14 carbamate residues in 55 date samples. The method exhibited strong linearity with R2 > 0.999 and low LOD (0.01-0.005 µg kg-1) and LOQ (0.003-0.04 µg kg-1). Excellent accuracy (recovery: 88-106%) and precision (RSD: 1-11%) were observed, with negligible matrix effect (- 4.98-13.26%). All samples contained at least one carbamate residue. While most detected residues were below their MRLs, carbosulfan was found in 21 samples, propoxur in 2 samples, and carbofuran in 1 sample above their MRLs. The hazard index (HI) was calculated for carbosulfan, phenmedipham, carbaryl, propoxur, carbofuran, and methomyl to assess potential health risks for date consumers. All HI values were below the safety limit of 1.0, indicating that the consumption of dates does not pose a non-carcinogenic health risk for adults and children.


Carbamates , Fruit , Pesticide Residues , Phoeniceae , Tandem Mass Spectrometry , Phoeniceae/chemistry , Pesticide Residues/analysis , Chromatography, High Pressure Liquid/methods , Tandem Mass Spectrometry/methods , Carbamates/analysis , Fruit/chemistry , Humans , Risk Assessment , Solid Phase Extraction/methods , Food Contamination/analysis
2.
Anal Chim Acta ; 1314: 342796, 2024 Jul 25.
Article En | MEDLINE | ID: mdl-38876515

BACKGROUND: Excessive pesticide residues in agricultural products could accumulate in organisms through the food chain, causing potential harm to human health. The investigation of dissipation kinetics and residues of pesticides in crops is crucial for the scientific application of pesticides and the mitigation of their adverse effects on human health. In vivo solid-phase microextraction (in vivo SPME) has unique advantages, but the research on field plants is still lacking and the quantitative correction methods need to be further developed. RESULTS: A method combining in vivo solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (in vivo SPME-UPLC-MS/MS) was developed to monitor the presence of acetamiprid, cyromazine, thiamethoxam and imidacloprid in cowpea fruits grown in the field. The sampling rates (Rs) were determined using both in vitro SPME in homogenized cowpea samples and in vivo SPME in intact cowpea fruit samples. The in vivo-Rs values were significantly higher than the in vitro-Rs for the same analyte, which were used for in vivo SPME correction. The accuracy of this method was confirmed by comparison with a QuEChERS-based approach and subsequently applied to trace pesticide residues in field-grown cowpea fruits. The residual concentrations of each pesticide positively correlated with application doses. After 7 days of application at two different doses, all of the pesticides had residual concentrations below China's maximum residue limits. Both experimental data and predictions indicated that a safe preharvest interval for these pesticides is 7 days; however, if the European Union standards are to be met, a safe preharvest interval for cyromazine should be at least 13 days. SIGNIFICANCE: This study highlights the advantages of in vivo SPME for simultaneous analysis and tracking of multiple pesticides in crops under field conditions. This technique is environmentally friendly, minimally invasive, highly sensitive, accurate, rapid, user-friendly, cost-effective, and capable of providing precise and timely data for long-term pesticide surveillance. Consequently, it furnishes valuable insights to guide the safe utilization of pesticides in agricultural production.


Neonicotinoids , Pesticide Residues , Solid Phase Microextraction , Tandem Mass Spectrometry , Triazines , Vigna , Vigna/chemistry , Tandem Mass Spectrometry/methods , Neonicotinoids/analysis , Solid Phase Microextraction/methods , Chromatography, High Pressure Liquid/methods , Triazines/analysis , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Fruit/chemistry
3.
Anal Methods ; 16(23): 3784-3797, 2024 Jun 13.
Article En | MEDLINE | ID: mdl-38828558

Newly designed micro-solid phase extraction cartridges are now available, reflecting the increasing shift towards laboratory automation, especially in the clean-up step for the analysis of pesticide residues in food and feed. In the present study, the introduction of different sorbents on the newly designed PAL µSPE CTC cartridges was investigated for the removal of matrix interferents and the recovery of pesticides. Eight cartridges containing different sorbent combinations and different amounts were used including EMR-lipid (not activated), Z-sep, chitin, C18, PSA, and GCB. The evaluation of co-extractive removal for each cartridge showed that the optimal choice for removing fatty acids was the cartridges containing PSA and Z-sep as clean-up sorbents. However, the presence of C18 and EMR-lipid was still required for the removal of sterols and tocopherols. Two grams of sample, fish feed (FF) and rapeseed cake (RSC) were extracted using QuEChERS citrate buffer, followed by a freeze-out step. The recoveries and repeatability of QuEChERS using µ-SPE clean-up were evaluated for 216 pesticide residues (112 compounds analyzed by GC-MS/MS and 143 compounds by LC-MS/MS, from which 39 compounds were analyzed using both techniques). The best results, with recovery between 70 and 120% and RSD <20%, were achieved when FF samples were cleaned-up with 15 mg EMR-lipid and 20 mg MgSO4. This was achieved for 94% of GC-amenable compounds and 86% of LC-amenable compounds. In the case of RSC, the best results were seen when samples were cleaned-up with the cartridge containing only 20 mg Z-sep and 20 mg MgSO4. This was achieved for 88% of GC-amenable compounds and 90% of LC-amenable compounds. Although these cartridges yielded optimal results in terms of recovery, their use could require more instrument maintenance, especially for GC-MS/MS, due to the lower removal of co-extractives.


Animal Feed , Pesticide Residues , Solid Phase Microextraction , Pesticide Residues/analysis , Solid Phase Microextraction/methods , Animal Feed/analysis , Tandem Mass Spectrometry/methods , Gas Chromatography-Mass Spectrometry/methods , Food Contamination/analysis , Solid Phase Extraction/methods , Animals
4.
Food Chem ; 454: 139831, 2024 Oct 01.
Article En | MEDLINE | ID: mdl-38838408

Diquat (DQ) and paraquat (PQ) residues in food are potential hazards to consumers' health. Point-of-care testing (POCT) of them remains challenging. Based on surface-enhanced Raman spectroscopy (SERS) technology, we developed a POCT strategy for DQ and PQ on apple surface and in apple juice. A point-of-use composite was fabricated using a piece of porous melamine sponge (MS) modified with silver nanoflowers (AgNFs), combining the specificity of the SERS fingerprint and the excellent adsorption capacity of MS. Using this dual-functional AgNFs@MS, the on-site determination of the DQ and PQ residues was completed within 3 min without pretreatment. Clear trends were observed between SERS intensity and logarithmic concentrations, with r values from 0.962 to 0.984. The limit of detection of DQ and PQ were 0.14-0.70 ppb in apple juice and on apple surface. This study provides a new point-of-use alternative for rapidly detecting DQ and PQ residues in nonlaboratory settings.


Diquat , Food Contamination , Malus , Paraquat , Point-of-Care Testing , Silver , Spectrum Analysis, Raman , Triazines , Silver/chemistry , Paraquat/analysis , Triazines/analysis , Diquat/analysis , Diquat/chemistry , Malus/chemistry , Food Contamination/analysis , Spectrum Analysis, Raman/methods , Pesticide Residues/analysis , Pesticide Residues/chemistry , Herbicides/analysis , Herbicides/chemistry , Metal Nanoparticles/chemistry , Limit of Detection , Fruit and Vegetable Juices/analysis
5.
Sci Total Environ ; 944: 173857, 2024 Sep 20.
Article En | MEDLINE | ID: mdl-38871333

Spatiotemporal monitoring of pesticide residues in river water is urgently needed due to its negative environmental and human health consequences. The present study is to investigate the occurrence of multiclass pesticide residue in the surface water of the Feni River, Bangladesh, using an optimized salting-out assisted liquid-liquid microextraction (SALLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). The optimized SALLME method was developed and validated following the SANTE/11312/2021 guidelines. A total of 42 water samples were collected and analyzed to understand the spatiotemporal distribution of azoxystrobin (AZ), buprofezin (BUP), carbofuran (CAR), pymetrozine (PYM), dimethoate (DMT), chlorantraniliprole (CLP), and difenoconazole (DFN). At four spike levels (n = 5) of 20, 40, 200, and 400 µg/L, the recovery percentages were satisfactory, ranging between 71.1 % and 107.0 % (RSD ≤13.8 %). The residues ranged from below the detection level (BDL) to 14.5 µg/L. The most frequently detected pesticide was DMT (100 %), followed by CLP (52.3809-57.1429), CAR (4.7619-14.2867), and PYM (4.7619-9.5238). However, AZ and BUP were below the detection limit in the analyzed samples of both seasons. Most pesticides and the highest concentrations were detected in March 2023, while the lowest concentrations were present in August 2023.Furthermore, ecological risk assessment based on the general-case scenario (RQm) and worst-case scenario (RQex) indicated a high (RQ > 1) risk to aquatic organisms, from the presence of PYM and CLP residue in river water. Human health risk via dietary exposure was estimated using the hazard quotient (HQ). Based on the detected residues, the HQ (<1) value indicated no significant health risk. This report provides the first record of pesticide residue occurrences scenario and their impact on the river environment of Bangladesh.


Environmental Monitoring , Pesticide Residues , Rivers , Water Pollutants, Chemical , Bangladesh , Water Pollutants, Chemical/analysis , Rivers/chemistry , Pesticide Residues/analysis , Risk Assessment , Humans , Tandem Mass Spectrometry , Chromatography, Liquid , Spatio-Temporal Analysis , Liquid Phase Microextraction
6.
Environ Monit Assess ; 196(7): 656, 2024 Jun 25.
Article En | MEDLINE | ID: mdl-38916777

Previous research on pesticides in green tea mainly focused on detection technology but lacked insights into pesticide use during cultivation. To address this gap, a survey was conducted among Rizhao green tea farmers. The survey results showed that most tea farmers were approximately 60 years old and managed small, scattered tea gardens (< 0.067 ha). Notably, tea farmers who had received agricultural training executed more standardized pesticide application practices. Matrine and thiazinone are the most used pesticides. A total of 16 types of pesticides were detected in the tested green tea samples, with 65% of the samples containing residues of at least one pesticide. Notably, higher levels of residues were observed for bifenthrin, cyfluthrin, and acetamiprid. The presence of pesticide residues varied significantly between seasons and regions. The risk assessment results indicated that the hazard quotient (HQ) values for all 16 pesticides detected in green tea were < 1, suggesting that these residue levels do not pose a significant public health concern.


Pesticide Residues , Pesticides , Tea , Tea/chemistry , Risk Assessment , Pesticides/analysis , Pesticide Residues/analysis , Environmental Monitoring , Humans , Farmers , Agriculture , Camellia sinensis/chemistry , Pyrethrins/analysis , China , Occupational Exposure/analysis
7.
J Agric Food Chem ; 72(19): 11241-11250, 2024 May 15.
Article En | MEDLINE | ID: mdl-38709728

The fungicide phenamacril has been employed to manage Fusarium and mycotoxins in crops, leading to persistent residues in the environment and plants. Detecting phenamacril is pivotal for ensuring environmental and food safety. In this study, haptens and artificial antigens were synthesized to produce antiphenamacril monoclonal antibodies (mAbs). Additionally, gold nanoparticles coated with a polydopamine shell were synthesized and conjugated with mAbs, inducing fluorescence quenching in quantum dots. Moreover, a dual-readout immunochromatographic assay that combines the positive signal from fluorescence with the negative signal from colorimetry was developed to enable sensitive and precise detection of phenamacril within 10 min, achieving detection limits of 5 ng/mL. The method's reliability was affirmed by using spiked wheat flour samples, achieving a limit of quantitation of 0.05 mg/kg. This analytical platform demonstrates high sensitivity, outstanding accuracy, and robust tolerance to matrix effects, making it suitable for the rapid, onsite, quantitative screening of phenamacril residues.


Colorimetry , Food Contamination , Fungicides, Industrial , Pesticide Residues , Fungicides, Industrial/analysis , Food Contamination/analysis , Colorimetry/methods , Pesticide Residues/analysis , Antibodies, Monoclonal/chemistry , Chromatography, Affinity/methods , Chromatography, Affinity/instrumentation , Fluorescence , Triticum/chemistry , Metal Nanoparticles/chemistry , Gold/chemistry , Limit of Detection , Flour/analysis
8.
PLoS One ; 19(5): e0303040, 2024.
Article En | MEDLINE | ID: mdl-38713652

In the present study, we attempted to use melatonin combined with germination treatment to remove pesticide residues from contaminated grains. High levels of pesticide residues were detected in soybean seeds after soaking with chlorothalonil (10 mM) and malathion (1 mM) for 2 hours. Treatment with 50 µM melatonin for 5 days completely removed the pesticide residues, while in the control group, only 61-71% of pesticide residues were removed from soybean sprouts. Compared with the control, melatonin treatment for 7 days further increased the content of ascorbic acid (by 48-66%), total phenolics (by 52-68%), isoflavones (by 22-34%), the total antioxidant capacity (by 37-40%), and the accumulated levels of unsaturated fatty acids (C18:1, C18:2, and C18:3) (by 17-30%) in soybean sprouts. Moreover, melatonin treatment further increased the accumulation of ten components of phenols and isoflavones in soybean sprouts relative to those in the control. The ability of melatonin to accelerate the degradation of pesticide residues and promote the accumulation of antioxidant metabolites might be related to its ability to trigger the glutathione detoxification system in soybean sprouts. Melatonin promoted glutathione synthesis (by 49-139%) and elevated the activities of glutathione-S-transferase (by 24-78%) and glutathione reductase (by 38-61%). In summary, we report a new method in which combined treatment by melatonin and germination rapidly degrades pesticide residues in contaminated grains and improves the nutritional quality of food.


Antioxidants , Germination , Glycine max , Melatonin , Nutritive Value , Pesticide Residues , Seeds , Melatonin/pharmacology , Germination/drug effects , Pesticide Residues/analysis , Seeds/drug effects , Seeds/chemistry , Seeds/metabolism , Seeds/growth & development , Glycine max/drug effects , Glycine max/growth & development , Glycine max/metabolism , Glycine max/chemistry , Antioxidants/metabolism , Edible Grain/drug effects , Edible Grain/metabolism , Phenols/analysis , Food Contamination/analysis , Glutathione/metabolism
9.
J Agric Food Chem ; 72(21): 11980-11989, 2024 May 29.
Article En | MEDLINE | ID: mdl-38758169

Compound-specific isotope analysis stands as a promising tool for unveiling the behavior of pesticides in agricultural environments. Using the commercial formulations of persistent fungicide procymidone (PRO) and less persistent insecticide diazinon (DIA), respectively, we analyzed the concentration and carbon isotope composition (δ13C) of the residual pesticides through soil incubation experiments in a greenhouse (for 150 days) and lab conditions (for 50-70 days). Our results showed that the magnitude of δ13C variation depends on pesticide specificity, in which PRO in the soil exhibited little variation in δ13C values over the entire incubation times, while DIA demonstrated an increased δ13C value, with the extent of δ13C variability affected by different spiking concentrations, plant presence, and light conditions. Moreover, the pesticides extracted from soils were isotopically overlapped with those from crop lettuce. Ultimately, the isotope composition of pesticides could infer the degradation and translocation processes and might contribute to identifying the source(s) of pesticide formulation in agricultural fields.


Carbon Isotopes , Diazinon , Pesticide Residues , Soil Pollutants , Soil , Diazinon/analysis , Diazinon/chemistry , Carbon Isotopes/analysis , Soil/chemistry , Pesticide Residues/chemistry , Pesticide Residues/analysis , Soil Pollutants/chemistry , Soil Pollutants/analysis , Fungicides, Industrial/chemistry , Fungicides, Industrial/analysis , Insecticides/chemistry , Insecticides/analysis , Bridged Bicyclo Compounds
10.
Sci Total Environ ; 937: 173507, 2024 Aug 10.
Article En | MEDLINE | ID: mdl-38797413

The widespread use of herbicides impacts non-target organisms, promotes weed resistance, posing a serious threat to the global goal of green production in agriculture. Although the herbicide residues have been widely reported in individual environmental medium, their presence across different media has received scant attention, particularly in Mollisols regions with intensive agricultural application of herbicides. A systematic investigation was conducted in this study to clarify the occurrence of herbicide residues in soil, surface water, sediments, and grains from a typical agricultural watershed in the Mollisols region of Northeast China. Concentrations of studied herbicides ranged from 0.30 to 463.49 µg/kg in soil, 0.31-29.73 µg/kg in sediments, 0.006-1.157 µg/L in water, and 0.32-2.83 µg/kg in grains. Among these, Clomazone was the most priority herbicide detected in soil, sediments, and water, and Pendimethalin in grains. Crop types significantly affected the residue levels of herbicides in grains. Clomazone posed high ecological risks in soil and water, with 86.4 % of water samples showing high risks from herbicide mixtures (RQ > 1). These findings aid in enhancing our comprehension of the pervasive occurrence and potential ecological risks of herbicides in different media within typical agricultural watersheds, providing detailed data to inform the development of targeted mitigation strategies.


Agriculture , Environmental Monitoring , Herbicides , Water Pollutants, Chemical , Herbicides/analysis , China , Water Pollutants, Chemical/analysis , Risk Assessment , Soil/chemistry , Soil Pollutants/analysis , Pesticide Residues/analysis
11.
J Chromatogr A ; 1727: 464999, 2024 Jul 19.
Article En | MEDLINE | ID: mdl-38788403

A reliable and greener alternative to the usual extraction methods is reported for the determination of pesticide residues in soybeans. This novel approach combines the classical QuEChERS extraction method with a DLLME (dispersive liquid-liquid microextraction) step, utilizing a deep eutectic solvent (DES) - camphor: hexanoic acid (1:1 molar ratio) - as the microextraction solvent. This DES has never been employed in pesticide analysis by gas chromatography-mass spectrometry of complex matrices like soybeans. A Plackett-Burman screening design was employed to optimize sample preparation variables of QuEChERS (amount of sodium chloride and magnesium sulfate, and amount of PSA and C18 sorbents) and DLLME (pH of medium, amount of sodium chloride, and volume of microextraction solvent). This design allowed for a systematic evaluation of the impact of each parameter on the method's performance. The optimized method was evaluated using a certified reference material and commercial samples of soybeans. The method exhibited high accuracy and precision for most of the analytes under study, demonstrating its applicability for pesticide residue analysis in soybeans. To assess the greenness and practicality of the developed method, the Analytical Greenness (AGREE) and Blue Applicability Grade Index (BAGI) metric systems were employed, respectively. Overall, the proposed QuEChERS-DLLME method using a DES solvent is a reliable and greener alternative to conventional extraction methods for the determination of pesticide residues in soybeans. Its high performance, coupled with its environmental friendliness, makes it a promising tool for food safety analysis.


Gas Chromatography-Mass Spectrometry , Glycine max , Liquid Phase Microextraction , Pesticide Residues , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Glycine max/chemistry , Gas Chromatography-Mass Spectrometry/methods , Liquid Phase Microextraction/methods , Deep Eutectic Solvents/chemistry , Limit of Detection , Reproducibility of Results
12.
Biosens Bioelectron ; 259: 116371, 2024 Sep 01.
Article En | MEDLINE | ID: mdl-38761742

The work was based on N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)-functionalized Fe-MIL-101 and gold nanoparticles (AuNPs) as sensing materials, and an electrochemiluminescence (ECL) aptasensor was constructed for detecting acetamiprid. As a metal-organic framework (MOF) material, Fe-MIL-101, was renowned for its unique three-dimensional network structure and efficient catalytic capability. ABEI, a common ECL reagent, was widely applied. ABEI was introduced into the Fe-MIL-101 structure as a luminescence functionalization reagent to form Fe-MIL-101@ABEI. This approach avoided limitations on the loading capacity of luminescent reagents imposed by modification and encapsulation methods. With character of excellent catalytic activity and ease of bioconjugation, AuNPs offered significant advantages in biosensing. Leveraging the reductive properties of ABEI, AuNPs were reduced around Fe-MIL-101@ABEI, resulting in the modified luminescent functionalized material denoted as Fe-MIL-101@ABEI@AuNPs. An aptamer was employed as a recognition element and was modified accordingly. The aptamer was immobilized on Fe-MIL-101@ABEI@AuNPs through gold-sulfur (Au-S) bonds. After capturing acetamiprid, the aptamer induced a decrease in the ECL signal intensity within the ABEI-hydrogen peroxide (H2O2) system, enabling the quantitative detection of acetamiprid. The aptasensor displayed remarkable stability and repeatability, featured a detection range of 1×10-3-1×102 nM, and had a limit of detection (LOD) of 0.3 pM (S/N=3), which underscored its substantial practical application potential.


Aptamers, Nucleotide , Biosensing Techniques , Electrochemical Techniques , Gold , Limit of Detection , Luminescent Measurements , Metal Nanoparticles , Metal-Organic Frameworks , Neonicotinoids , Neonicotinoids/analysis , Neonicotinoids/chemistry , Metal-Organic Frameworks/chemistry , Biosensing Techniques/methods , Metal Nanoparticles/chemistry , Gold/chemistry , Aptamers, Nucleotide/chemistry , Luminescent Measurements/methods , Electrochemical Techniques/methods , Vegetables/chemistry , Luminol/chemistry , Luminol/analogs & derivatives , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Food Contamination/analysis
13.
Food Chem ; 452: 139463, 2024 Sep 15.
Article En | MEDLINE | ID: mdl-38718451

In this study, a QuEChERS method based on citrate was developed and utilized for the analysis of twelve neonicotinoid pesticides in fresh red chilies, fresh green chilies, and dried chilies, coupled with ultra-high performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF/MS). In the sample preparation, acetonitrile containing 1% formic acid was used as the extraction solvent. Anhydrous sodium sulfate replaced the traditional anhydrous magnesium sulfate for water removal, effectively eliminating the issues of salt caking. Graphitized carbon black, octadecyl silica, and primary secondary amine were used as cleaning agents. The method showed good sensitivity, with the limits of quantification below 0.03 mg/kg for fresh chilies and below 0.15 mg/kg for dried chilies. Values of matrix effects ranged from -19.5% to 8.4%, and the recovery was 86.9% - 105.2%. The analytical method provided an effective tool for the high throughput detection of neonicotinoid pesticide residues in multiple chili matrices.


Capsicum , Food Contamination , Pesticide Residues , Chromatography, High Pressure Liquid , Capsicum/chemistry , Food Contamination/analysis , Pesticide Residues/analysis , Pesticide Residues/chemistry , Pesticide Residues/isolation & purification , Mass Spectrometry/methods , Neonicotinoids/analysis , Neonicotinoids/chemistry , Tandem Mass Spectrometry/methods
14.
Food Chem ; 452: 139510, 2024 Sep 15.
Article En | MEDLINE | ID: mdl-38718452

Lettuce, a globally consumed nutritious vegetable, is often linked to concerns regarding pesticide residues. To address this issue, we conducted field trials and utilized dynamiCROP modeling to examine the uptake, distribution, translocation, and dissipation of five pesticides (λ-cyhalothrin, difenoconazole, acetamiprid, dimethomorph, and ß-cypermethrin) commonly detected in lettuce. At harvest, pesticides residues were below the maximum residue limits (MRLs) at 0.05, 0.39, 0.047, 0.72, and 0.072 mg kg-1, respectively. Simulation results elucidated distinct behaviors of the pesticides following application to lettuce foliage across various compartments. However, all pesticides exhibited a common dissipation trend, initially stabilizing or increasing before gradually declining. For all five pesticides, the largest contribution of residues on lettuce leaves came from the leaf surface during the early period after application, and from the soil in the long term. Health risk assessments indicated negligible risks associated with consuming lettuce containing these pesticides, both in the short and long term.


Food Contamination , Lactuca , Pesticide Residues , Lactuca/chemistry , Lactuca/growth & development , Lactuca/metabolism , Food Contamination/analysis , Pesticide Residues/analysis , Pesticide Residues/chemistry , Plant Leaves/chemistry , Plant Leaves/metabolism , Humans , Consumer Product Safety
15.
J Chromatogr A ; 1726: 464967, 2024 Jul 05.
Article En | MEDLINE | ID: mdl-38749275

Infant formulas (IF) can contain harmful chemical substances, such as pesticides and mycotoxins, resulting from the contamination of raw materials and inputs used in the production chain, which can cause adverse effects to infants. Therefore, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) methodology prior ultra-high performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPL-QqQ-MS/MS) analysis was applied for the determination of 23 contaminants, in 30 samples of Brazilian IF. The method was validated in terms of limit of detection (0.2 to 0.4 µg/kg), limits of quantification (1 and 10 µg/kg), and recovery (64 % to 122 %); precision values, in terms of relative standard deviation (RSD), were ≤ 20 %. Fenitrothion, chlorpyrifos, and bifenthrin were the pesticides detected in the samples, but the values did not exceed the limit set by the European Union (EU), and ANVISA, and they were detected under their limits of quantification. Additionally, suspect screening and unknown analysis were conducted to tentatively identify 32 substances, including some compounds not covered in this study, such as pesticides, hormones, and veterinary drugs. Carbofuran was identified, confirmed and quantified in 10 % of the samples.


Food Contamination , Infant Formula , Limit of Detection , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Chromatography, High Pressure Liquid/methods , Brazil , Infant Formula/chemistry , Food Contamination/analysis , Pesticides/analysis , Humans , Pesticide Residues/analysis , Reproducibility of Results , Mycotoxins/analysis , Infant , Pyrethrins/analysis
16.
Rapid Commun Mass Spectrom ; 38(15): e9770, 2024 Aug 15.
Article En | MEDLINE | ID: mdl-38773864

RATIONALE: Chlorothalonil (CHT), a broad-spectrum fungicide, has been employed widely to control foliar diseases, whereas with a major metabolite of polar 4-hydroxychlorothalonil (CHT-4-OH), only an acceptable nonpolar CHT residue is allowed by most countries. This study involves the method development for CHT residue in vegetables/fruits using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a novel modified discharge-adaptor (DA) interface. METHODS: CHT residue was analyzed using LC-MS/MS with DA interface (LC-DA-MS/MS), developed in our previous works. A DA was placed on the electrospray tip to switch the ionization modes. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied to extract CHT residue of vegetables/fruits efficiently with less sample preparation time and analysis cost. RESULTS: CHT and CHT-4-OH spiked in four different vegetables/fruits were extracted using the modified QuEChERS method. After LC with isocratic elution, CHT and CHT-4-OH were separated within 3 min. Using LC-DA-MS/MS, the ion signals of CHT were improved two to three times, and the limit of quantification of 5 ng/g and linearity (r2 > 0.99) in the range of 5-200 ng/g were achieved using 10 g of vegetables/fruits. The precision and accuracy were within 15% each. The modified QuEChERS and LC-DA-MS/MS were applied to examine eight field-grown vegetables/fruits; 9.5 and 2588.9 ng/g of CHT were detected in two vegetables/fruits. CONCLUSION: LC-DA-MS/MS combined with modified QuEChERS was successfully applied to determine CHT residue <10 ng/g in vegetables/fruits and with satisfied validation results. The developed method could reduce both analysis cost and time, attributing to simplifications in modified QuEChERS, isocratic elution, and DA interface in LC-DA-MS/MS.


Fruit , Fungicides, Industrial , Nitriles , Pesticide Residues , Tandem Mass Spectrometry , Vegetables , Tandem Mass Spectrometry/methods , Vegetables/chemistry , Nitriles/analysis , Nitriles/chemistry , Chromatography, Liquid/methods , Pesticide Residues/analysis , Fruit/chemistry , Fungicides, Industrial/analysis , Limit of Detection , Reproducibility of Results , Food Contamination/analysis
17.
Rev Saude Publica ; 58: 19, 2024.
Article En | MEDLINE | ID: mdl-38747867

OBJECTIVE: To identify the prevalence of contamination by pesticides and their metabolites in the milk of lactating mothers in Latin America. METHODS: In this systematic review, the PubMed, LILACS, Embase, and Scopus databases were searched up to January 2022 to identify observational studies. The Mendeley software was used to manage these references. The risk of bias assessment was evaluated according to the checklist for prevalence studies and writing design, by the Prisma guidelines. RESULTS: This study retrieved 1835 references and analyzed 49 studies. 69.38% of the analyzed studies found a 100% prevalence of breast milk contamination by pesticides among their sample. Main pesticides include dichlorodiphenyltrichloroethane (DDT) and its isomers (75.51%), followed by the metabolite dichlorodiphenyldichloroethylene (DDE) (69.38%) and hexachlorocyclohexane (HCH) (46.93%). This study categorized most (65.30%) studies as having a low risk of bias. CONCLUSIONS: This review shows a high prevalence of pesticide contamination in the breast milk of Latin American women. Further investigations should be carried out to assess contamination levels in breast milk and the possible effects of these substances on maternal and child health.


Lactation , Milk, Human , Pesticides , Humans , Milk, Human/chemistry , Female , Latin America , Pesticides/analysis , Pesticide Residues/analysis , Prevalence , DDT/analysis , Maternal Exposure/adverse effects
18.
Environ Pollut ; 352: 124143, 2024 Jul 01.
Article En | MEDLINE | ID: mdl-38735465

Fruits consistently hold a prominent position in healthy dietary habits. Pesticides are used to manage plant diseases, achieve sustainable production, and maintain high food standards. This study utilized a comprehensive analytical technique that involved both targeted analysis and suspect screening. Analysis was conducted using Ultra-high-performance liquid chromatography coupled with hybrid Linear Trap Quadrupole (LTQ)/Orbitrap High Resolution Mass Spectrometry (HRMS) to examine pesticide levels in fruits. The matrices chosen comprised fruit commodities that are commonly consumed in Greece, including table grapes, apples, pears, citrus fruits, and strawberries. The QuEChERS approach was effectively validated for 30 specific pesticides. According to the method acceptance criteria established by SANTE, the QuEChERS method have shown exceptional efficiency in extracting the chosen pesticides, with recovery rates ranging from 70% to 120% in three concentration levels (10, 50, 100 µg kg-1). It also exhibited outstanding linearity, with an R2 more than 0.99. The method exhibited exceptional precision, with relative standard deviations (RSDs) below 20%. Additionally, the combined measurement uncertainty (MU%) was found to be acceptable, remaining below 50% The quantification limits were below 10 µg kg-1 for the majority of the analytes, satisfying the Maximum Residue Levels (MRLs) established by the European Commission. Following targeted analysis, a dietary risk assessment was performed, revealing that both acute and chronic hazard quotients (aHQ and cHQ), along with chronic hazard index (cHI) were below 1, which indicated that the studied commodities are safe for human consumption. In addition, a suspect screening workflow was developed based on an in-house database comprising 355 pesticides commonly applied to the relevant commodities and related transformation products (TPs). Overall, through suspect screening, twenty-two additional pesticides and TPs not included in the target list were identified. Hence, this approach is anticipated to function as proactive alert system guaranteeing the long-term viability of agricultural production.


Dietary Exposure , Food Contamination , Fruit , Pesticide Residues , Pesticide Residues/analysis , Fruit/chemistry , Food Contamination/analysis , Greece , Chromatography, High Pressure Liquid , Mass Spectrometry/methods , Humans
19.
PLoS One ; 19(5): e0298371, 2024.
Article En | MEDLINE | ID: mdl-38758738

Malathion® is a persistent organophosphate pesticide used against biting and chewing insects on vegetables. It is a difficult-to-remove surface contaminant of vegetables and contaminates surface and ground water and soils. Malathion® is only partially water soluble, but use of detergent carriers makes adhering Malathion® residues difficult to subsequently remove. Magnetically treated water (MTW) successfully removed Malathion® from Chinese Kale (Brassica oleracea L.), meeting Maximum Residue Load (MRL) standards. Samples were soaked in MTW for 30 min prior to detection with GC/MS/MS, 98.5±3.02% of Malathion® was removed after washing by MTW. Removal by simple washing was only ≈42±1.2% which was not nearly sufficient to meet MRL criteria.


Brassica , Malathion , Brassica/chemistry , Water Pollutants, Chemical/analysis , Water/chemistry , Insecticides/analysis , Pesticide Residues/analysis , Water Purification/methods , Food Contamination/analysis , Gas Chromatography-Mass Spectrometry
20.
Chemosphere ; 359: 142309, 2024 Jul.
Article En | MEDLINE | ID: mdl-38735491

Pesticides play vital roles in controlling pests and boosting crop yields. Imidacloprid is widely used all over the world and may form in agricultural products. The presence of pesticide residues in apples raises serious health concerns. Understanding the residual fate of imidacloprid is critical for food safety and human health. In this study, the dissipation behavior, metabolism, household processing and risk assessment of imidacloprid and its metabolites in apple were investigated from filed to products. Field experiment results suggested that the half-lives of imidacloprid at 5 times the recommended dosage was 1.5 times that of the standard dosage. And the final residues of imidacloprid were less than the established maximum residue limits (MRLs). Clarification and simmering had little effect on the reduction the residues of imidacloprid and its metabolites. The calculated processing factors were lower than 1 for imidacloprid and its metabolites, implying that the residual ratios of imidacloprid and its metabolites in each steps of the food processing were reduced. The risk quotients were <1 for all Chinese people, indicating that acceptable risks associated with dietary exposure to imidacloprid in apple. However, the higher risks were observed in young people than adults, and females faced higher risks than males. Given high residue levels in pomace, imidacloprid and its metabolites should be further studied in commercial byproducts.


Insecticides , Malus , Neonicotinoids , Nitro Compounds , Pesticide Residues , Malus/chemistry , Malus/metabolism , Neonicotinoids/metabolism , Neonicotinoids/analysis , Nitro Compounds/analysis , Nitro Compounds/metabolism , Risk Assessment , Pesticide Residues/analysis , Pesticide Residues/metabolism , Insecticides/analysis , Insecticides/metabolism , Humans , Food Contamination/analysis , Dietary Exposure/analysis , China , Female , Imidazoles/metabolism , Imidazoles/analysis , Imidazoles/chemistry
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