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1.
Environ Geochem Health ; 46(6): 191, 2024 May 02.
Article in English | MEDLINE | ID: mdl-38696024

ABSTRACT

Pesticides are frequently used to protect crop yields and manage malaria vectors; however, their inadvertent transport into aquatic habitats poses a significant concern. Various anthropogenic activities influence the Indus River in Pakistan. This study aimed to assess the presence of eight pesticide residues at three different sites (Kalabagh, Kundian, and Chashma) in water, sediment, and the fish species (Labeo rohita) during both dry and wet seasons to measure the intensity of this pressure. Pesticide analysis was carried out using gas chromatography equipped with an electron capture detector. The results revealed the highest concentrations of pesticides during both dry and wet seasons at all sites, measuring 0.83 and 0.62 µg/l (water), 12.37 and 9.20 µg/g/dw (sediment), and 14.27 and 11.29 µg/g/ww (L. rohita), respectively. Overall, pesticide concentrations were higher in the dry season than in the wet season across all study sites. Based on detection frequency and concentration in both seasons at all sites, dominant pesticides included cypermethrin and carbofuran (in water), as well as endosulfan and cypermethrin (in sediment and fish tissue). Levels of endosulfan and cypermethrin exceeded standard limits. Moreover, principal component analysis (PCA) indicated no correlation among pesticides in fish tissue, sediment, and water. However, pesticides exhibited different behavior in different seasons. Furthermore, endosulfan and triazophos impose great human health risk, as indicated by the THQ value (> 1). The overall HI value was greater for site 1 in the dry season (8.378). The study concluded that the presence of agricultural pesticides in the Indus River poses a risk to aquatic life and has the potential to disrupt the entire food chain. This highlights the importance of sustainable practices for the study area and Pakistan overall agricultural and environmental sustainability. It is further recommended to strengthen regulations for reduced pesticide use and promote eco-friendly pest management.


Subject(s)
Environmental Monitoring , Geologic Sediments , Pesticides , Rivers , Water Pollutants, Chemical , Geologic Sediments/chemistry , Water Pollutants, Chemical/analysis , Animals , Rivers/chemistry , Pakistan , Humans , Risk Assessment , Pesticides/analysis , Environmental Monitoring/methods , Seasons , Pesticide Residues/analysis , Cyprinidae , Fishes
2.
PLoS One ; 19(5): e0303040, 2024.
Article in English | MEDLINE | ID: mdl-38713652

ABSTRACT

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.


Subject(s)
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
3.
Molecules ; 29(9)2024 May 03.
Article in English | MEDLINE | ID: mdl-38731605

ABSTRACT

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.


Subject(s)
Gas Chromatography-Mass Spectrometry , Pesticide Residues , Tandem Mass Spectrometry , Tandem Mass Spectrometry/methods , Pesticide Residues/analysis , Gas Chromatography-Mass Spectrometry/methods , Pesticides/analysis , Crops, Agricultural/chemistry , Republic of Korea , Food Contamination/analysis , Limit of Detection , Solid Phase Extraction/methods
4.
J Agric Food Chem ; 72(19): 11241-11250, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38709728

ABSTRACT

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.


Subject(s)
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
5.
PLoS One ; 19(5): e0298371, 2024.
Article in English | MEDLINE | ID: mdl-38758738

ABSTRACT

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.


Subject(s)
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
6.
Rapid Commun Mass Spectrom ; 38(15): e9770, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-38773864

ABSTRACT

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.


Subject(s)
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
7.
Rev Saude Publica ; 58: 19, 2024.
Article in English | MEDLINE | ID: mdl-38747867

ABSTRACT

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.


Subject(s)
Lactation , Milk, Human , Pesticides , Humans , Milk, Human/chemistry , Female , Latin America , Pesticides/analysis , Pesticide Residues/analysis , Prevalence , DDT/analysis , Maternal Exposure/adverse effects
8.
J Chromatogr A ; 1726: 464967, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38749275

ABSTRACT

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.


Subject(s)
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
9.
Food Chem ; 453: 139660, 2024 Sep 30.
Article in English | MEDLINE | ID: mdl-38761738

ABSTRACT

A novel dispersive solid-phase microextraction method based on a metal-organic framework (MIL-100(Fe)) combined with a dispersive liquid-liquid microextraction technique was proposed for the extraction and enrichment of four insecticides in beverages. The qualitative and quantitative analysis of these insecticides was conducted using HPLC-MS/MS. To optimize the extraction process, several parameters were investigated, and the main variables were optimized using CCD-based RSM. The developed method displayed a wide linear range of 1.000-1000 ng/L and R2 values >0.993 for all four calibration curves. The method demonstrated high sensitivity, with LODs and LOQs of 0.3-0.6 ng/L and 0.8-1.0 ng/L, respectively. In addition, the greenness of the proposed method was assessed using the Complex GAPI tool, and the results showed that the proposed method exhibits benefits, such as minimal usage of organic solvents and negligible matrix influence, making it a suitable method for the detection of insecticide residues in beverages.


Subject(s)
Beverages , Food Contamination , Insecticides , Liquid Phase Microextraction , Pesticide Residues , Solid Phase Microextraction , Tandem Mass Spectrometry , Liquid Phase Microextraction/methods , Chromatography, High Pressure Liquid , Insecticides/analysis , Insecticides/isolation & purification , Insecticides/chemistry , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Pesticide Residues/chemistry , Tandem Mass Spectrometry/methods , Food Contamination/analysis , Beverages/analysis , Solid Phase Microextraction/methods , Metal-Organic Frameworks/chemistry , Liquid Chromatography-Mass Spectrometry
10.
Chemosphere ; 359: 142309, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38735491

ABSTRACT

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.


Subject(s)
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
11.
Biosens Bioelectron ; 259: 116371, 2024 Sep 01.
Article in English | MEDLINE | ID: mdl-38761742

ABSTRACT

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.


Subject(s)
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
12.
J Chromatogr A ; 1727: 464999, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-38788403

ABSTRACT

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.


Subject(s)
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
13.
Food Chem ; 452: 139463, 2024 Sep 15.
Article in English | MEDLINE | ID: mdl-38718451

ABSTRACT

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.


Subject(s)
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 in English | MEDLINE | ID: mdl-38718452

ABSTRACT

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.


Subject(s)
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.
Food Chem ; 452: 139535, 2024 Sep 15.
Article in English | MEDLINE | ID: mdl-38728890

ABSTRACT

This study systematically investigates the residue changes, processing factors (PFs), and relation between the physicochemical properties of pesticides during peanut processing. Results revealed that peeling, washing, and boiling treatments removed partial or substantial pesticide residues from peanuts with PFs of 0.29-1.10 (most <1). By contrast, pesticides appeared to be partially concentrated during roasting, stir-frying, and deep-frying peanuts with PFs of 0.16-1.25. During oil pressing, 13 of the 28 pesticides were concentrated in the peanut oil (PF range: 1.06-2.01) and 25 of the pesticides were concentrated in the peanut meal (1.07-1.46). Physicochemical parameters such as octanol-water partition coefficient, degradation point, molecular weight, and melting point showed significant correlations with PFs during processing. Notably, log Kow exhibited strong positive correlations with the PFs of boiling, roasting, and oil pressing. Overall, this study describes the fate of pesticides during multiproduct processing, providing guidance to promote the healthy consumption of peanuts for human health.


Subject(s)
Arachis , Food Contamination , Food Handling , Pesticide Residues , Arachis/chemistry , Pesticide Residues/chemistry , Pesticide Residues/analysis , Food Contamination/analysis , Cooking , Hot Temperature
16.
Molecules ; 29(10)2024 May 14.
Article in English | MEDLINE | ID: mdl-38792172

ABSTRACT

Pyrethroid pesticides (PYRs) have found widespread application in agriculture for the protection of fruit and vegetable crops. Nonetheless, excessive usage or improper application may allow the residues to exceed the safe limits and pose a threat to consumer safety. Thus, there is an urgent need to develop efficient technologies for the elimination or trace detection of PYRs from vegetables. Here, a simple and efficient magnetic solid-phase extraction (MSPE) strategy was developed for the simultaneous purification and enrichment of five PYRs in vegetables, employing the magnetic covalent organic framework nanomaterial COF-SiO2@Fe3O4 as an adsorbent. COF-SiO2@Fe3O4 was prepared by a straightforward solvothermal method, using Fe3O4 as a magnetic core and benzidine and 3,3,5,5-tetraaldehyde biphenyl as the two building units. COF-SiO2@Fe3O4 could effectively capture the targeted PYRs by virtue of its abundant π-electron system and hydroxyl groups. The impact of various experimental parameters on the extraction efficiency was investigated to optimize the MSPE conditions, including the adsorbent amount, extraction time, elution solvent type and elution time. Subsequently, method validation was conducted under the optimal conditions in conjunction with gas chromatography-mass spectrometry (GC-MS). Within the range of 5.00-100 µg·kg-1 (1.00-100 µg·kg-1 for bifenthrin and 2.5-100 µg·kg-1 for fenpropathrin), the five PYRs exhibited a strong linear relationship, with determination coefficients ranging from 0.9990 to 0.9997. The limits of detection (LODs) were 0.3-1.5 µg·kg-1, and the limits of quantification (LOQs) were 0.9-4.5 µg·kg-1. The recoveries were 80.2-116.7% with relative standard deviations (RSDs) below 7.0%. Finally, COF-SiO2@Fe3O4, NH2-SiO2@Fe3O4 and Fe3O4 were compared as MSPE adsorbents for PYRs. The results indicated that COF-SiO2@Fe3O4 was an efficient and rapid selective adsorbent for PYRs. This method holds promise for the determination of PYRs in real samples.


Subject(s)
Pesticides , Pyrethrins , Silicon Dioxide , Solid Phase Extraction , Vegetables , Solid Phase Extraction/methods , Silicon Dioxide/chemistry , Vegetables/chemistry , Pyrethrins/isolation & purification , Pyrethrins/analysis , Pyrethrins/chemistry , Pesticides/isolation & purification , Pesticides/chemistry , Pesticides/analysis , Gas Chromatography-Mass Spectrometry , Adsorption , Food Contamination/analysis , Limit of Detection , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Ferric Compounds/chemistry , Cobalt
17.
J Hazard Mater ; 472: 134534, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38733786

ABSTRACT

Cowpea plants, renowned for their high edibility, pose a significant risk of pesticide residue contamination. Elucidating the behavior of pesticide residues and their key metabolic pathways is critical for ensuring cowpea safety and human health. This study investigated the migration of pesticide residues and their key metabolic pathways in pods throughout the growth process of cowpea plants via in situ mass spectrometry. To this end, four pesticides--including systemic (thiram), and nonsystemic (fluopyram, pyriproxyfen, and cyromazine) pesticides--were selected. The results indicate the direct upward and downward transmission of pesticides in cowpea stems and pods. Systemic pesticides gradually migrate to the core of cowpea plants, whereas nonsystemic pesticides remain on the surface of cowpea peels. The migration rate is influenced by the cowpea maturity, logarithmic octanol-water partition coefficient (log Kow) value, and molecular weight of the pesticide. Further, 20 types of key metabolites related to glycolysis, tricarboxylic acid cycle, and flavonoid synthesis were found in cowpea pods after pesticide treatment. These findings afford insights into improving cowpea quality and ensuring the safe use of pesticides.


Subject(s)
Mass Spectrometry , Pesticide Residues , Vigna , Vigna/growth & development , Vigna/metabolism , Vigna/drug effects , Pesticide Residues/metabolism , Pesticide Residues/analysis , Metabolic Networks and Pathways
18.
J Agric Food Chem ; 72(21): 11980-11989, 2024 May 29.
Article in English | MEDLINE | ID: mdl-38758169

ABSTRACT

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.


Subject(s)
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
19.
Environ Sci Pollut Res Int ; 31(23): 34355-34367, 2024 May.
Article in English | MEDLINE | ID: mdl-38700766

ABSTRACT

The present study focused on the optimization of the QuEChERS extraction method for the determination of 61 pesticide residues and associated health risk assessment in 144 samples of commonly consumed vegetables, viz., eggplant, cabbage, green chilli, okra, and tomato. The samples were collected between January and April 2022 from three different districts within Gujarat, India. The QuEChERS method was optimized and utilized for the extraction of samples. The samples were analyzed by UHPLC-q-TOF/MS and GC-MS/MS. The modified QuEChERS method was successfully validated, and the obtained results were satisfactory as per the 2021 SANTE guidelines. The residue analysis of the vegetable samples showed that about 4% of total samples contained single pesticide residues. Pesticide residues below the quantitation limit (BQL) were observed in eggplant, cabbage, and okra samples. In total, 15.62% (n = 5) samples of green chilli showed the presence of pesticides such as azoxystrobin, bifenthrin, cypermethrin, fenpropathrin, and propargite whereas 3% (n = 1) tomato samples contained cyfluthrin. In total, 97.22% of the samples had residues that were below the European Union Maximum Residue Limit (EU MRL). Two samples of green chilli had pesticide residues above EU MRL. The Hazard Index (HI) and Hazard Quotient (HQ) were used to assess the health risks associated with green chilli and tomato consumption. The HI and HQ values for adolescents and adults were found to be less than 1. The modified QuEChERS method was found to be easy and effective and can be implemented for routine sample analysis. The study revealed the presence of pesticide residues in tomato and green chilli samples. Further, the outcome provided information pertaining to current pesticide status, concluding that consumption of these commodities is unlikely to pose any health risk, though long-term monitoring studies focusing on dietary health risk assessment must be initiated.


Subject(s)
Pesticide Residues , Vegetables , Pesticide Residues/analysis , Vegetables/chemistry , Risk Assessment , Humans , India , Food Contamination/analysis
20.
J Hazard Mater ; 472: 134486, 2024 Jul 05.
Article in English | MEDLINE | ID: mdl-38714052

ABSTRACT

Peanuts, known for their nutritional value, health benefits, and delicious taste, are susceptible to agricultural chemical contamination, posing a challenge to the peanut industry in China. While tristyrylphenol ethoxylates (TSPEOs) have garnered attention for their widespread use in pesticide formulations, their dissipation and potential risks in peanuts remain a gap in knowledge. This study, unique in its focus on TSPEOs, investigates their dissipation and potential risks under two common application modes: spraying and root irrigation. The concentration of total TSPEOs in peanut plants was significantly higher when sprayed (435-37,693 µg/kg) than in root irrigation (24-1602 µg/kg). The dissipation of TSPEOs was faster in peanuts and soil when sprayed, with half-lives of 3.67-5.59 d (mean: 4.37 d) and 5.41-7.07 d (mean: 5.95 d), respectively. The residue of TSPEOs in peanut shells and soil were higher with root irrigation (8.9-65.2 and 25.4-305.1 µg/kg, respectively) than with spraying (5.4-30.6 and 8.8-146.5 µg/kg, respectively). These results indicated that the dissipation behavior of TSPEOs in peanuts was influenced by application modes. While the healthy and ecological risk assessments of TSPEOs in soil and peanut shells showed no risks, root irrigation might pose a higher potential risk than spraying. This research provides valuable data for the judicious application of pesticides during peanut cultivation to enhance pesticide utilization and reduce potential risks.


Subject(s)
Agricultural Irrigation , Arachis , Plant Roots , Soil Pollutants , Soil Pollutants/analysis , Soil Pollutants/chemistry , Risk Assessment , Pesticide Residues/analysis , Pesticides/toxicity , Pesticides/chemistry , Pesticides/analysis , Agriculture , China
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