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1.
Bull Environ Contam Toxicol ; 113(1): 8, 2024 Jul 09.
Article de Anglais | MEDLINE | ID: mdl-38981915

RÉSUMÉ

Monitoring wildlife exposure to biological hazards is a critical component of the wildlife risk assessment. In this study 38 hair samples were collected from 8 different species from ten districts of Russian Far East and Siberia and analysed for the presence of organochlorine pesticides (OCP). 50% of the samples were contaminated with - p, p'-DDT, α-HCH and DDD. DDT was the main contaminant found in 13 sample at concentrations range of 14.3 to 369.5 pg/mg hair, mean 91.9 ± 89.7 pg/mg. α-HCH was detected in three samples with the concentrations range 29.9-180.2 pg/mg. The p, p'-DDD was found only in one hair sample of Siberian roe deer from Altai region at 52.6 pg/mg. The exposure level is depended on animals habitat location. The most contaminated region is Terney district which is in the proximity to the borders with China and North Korea where OCP are still in use.


Sujet(s)
Surveillance de l'environnement , Polluants environnementaux , Poils , Hydrocarbures chlorés , Pesticides , Animaux , Hydrocarbures chlorés/analyse , Poils/composition chimique , Sibérie , Pesticides/analyse , Polluants environnementaux/analyse , Russie , Mammifères , DDT/analyse , Herbivorie
2.
Molecules ; 29(13)2024 Jun 26.
Article de Anglais | MEDLINE | ID: mdl-38998975

RÉSUMÉ

The contamination risks of plant-derived foods due to the co-existence of pesticides and veterinary drugs (P&VDs) have not been fully understood. With an increasing number of unexpected P&VDs illegally added to foods, it is essential to develop a non-targeted screening method for P&VDs for their comprehensive risk assessment. In this study, a modified support vector machine (SVM)-assisted metabolomics approach by screening eligible variables to represent marker compounds of 124 multi-class P&VDs in maize was developed based on the results of high-performance liquid chromatography-tandem mass spectrometry. Principal component analysis and orthogonal partial least squares discriminant analysis indicate the existence of variables with obvious inter-group differences, which were further investigated by S-plot plots, permutation tests, and variable importance in projection to obtain eligible variables. Meanwhile, SVM recursive feature elimination under the radial basis function was employed to obtain the weight-squared values of all the variables ranging from large to small for the screening of eligible variables as well. Pairwise t-tests and fold changes of concentration were further employed to confirm these eligible variables to represent marker compounds. The results indicate that 120 out of 124 P&VDs can be identified by the SVM-assisted metabolomics method, while only 109 P&VDs can be found by the metabolomics method alone, implying that SVM can promote the screening accuracy of the metabolomics method. In addition, the method's practicability was validated by the real contaminated maize samples, which provide a bright application prospect in non-targeted screening of contaminants. The limits of detection for 120 P&VDs in maize samples were calculated to be 0.3~1.5 µg/kg.


Sujet(s)
Métabolomique , Pesticides , Machine à vecteur de support , Médicaments vétérinaires , Zea mays , Zea mays/composition chimique , Métabolomique/méthodes , Pesticides/analyse , Médicaments vétérinaires/analyse , Chromatographie en phase liquide à haute performance/méthodes , Spectrométrie de masse en tandem/méthodes , Analyse en composantes principales , Contamination des aliments/analyse
3.
Anal Methods ; 16(28): 4827-4834, 2024 Jul 18.
Article de Anglais | MEDLINE | ID: mdl-38967314

RÉSUMÉ

A cloud point method was developed and applied for the first time to extract and preconcentrate thiabendazole (TBZ) from commercial whole grape juice samples, with determination by high performance liquid chromatography coupled to electrochemical detection (HPLC/EC), using a cathodically pretreated boron-doped diamond electrode (BDD). The best conditions for extraction and preconcentration of TBZ by cloud point extraction (CPE) were performed at pH 6.0, by adding 1 mL of the surfactant Tergitol TMN-6 at 10% (mass-to-mass ratio), without heating (at 27 °C) and ultrasonic stirring time of (20 kHz) for 60 min. The HPLC/EC determination was duly validated in a C8 column, in mobile phase with a 69 : 31 ratio (V/V) of phosphate buffer (pH 7.0):ACN, at a flow rate of 1.2 mL min-1 and electrochemical detection with BDD electrode by applying 1.40 V × Ag/AgCl (3.0 mol L-1). Under these conditions, the procedure showed a preconcentration factor (FC) of 21.7, and limits of detection (LOD) and quantification (LOQ) of 6.64 × 10-9 mol L-1 (or 1.33 µg L-1) and 1.66 × 10-8 mol L-1 (or 3.34 µg L-1), respectively. The method provided a percent recovery of 81% to 98%, with a coefficient of variation between 3% and 15%.


Sujet(s)
Techniques électrochimiques , Jus de fruits et de légumes , Tiabendazol , Vitis , Chromatographie en phase liquide à haute performance/méthodes , Tiabendazol/analyse , Tiabendazol/isolement et purification , Jus de fruits et de légumes/analyse , Vitis/composition chimique , Techniques électrochimiques/méthodes , Limite de détection , Électrodes , Pesticides/analyse , Contamination des aliments/analyse
4.
Sensors (Basel) ; 24(12)2024 Jun 08.
Article de Anglais | MEDLINE | ID: mdl-38931527

RÉSUMÉ

The identification and detection of pesticides is crucial to protecting both the environment and human health. However, it can be challenging to conveniently and rapidly differentiate between different types of pesticides. We developed a supramolecular fluorescent sensor array, in which calixarenes with broad-spectrum encapsulation capacity served as recognition receptors. The sensor array exhibits distinct fluorescence change patterns for seven tested pesticides, encompassing herbicides, insecticides, and fungicides. With a reaction time of just three minutes, the sensor array proves to be a rapid and efficient tool for the discrimination of pesticides. Furthermore, this supramolecular sensing approach can be easily extended to enable real-time and on-site visual detection of varying concentrations of imazalil using a smartphone with a color scanning application. This work not only provides a simple and effective method for pesticide identification and quantification, but also offers a versatile and advantageous platform for the recognition of other analytes in relevant fields.


Sujet(s)
Calixarènes , Pesticides , Calixarènes/composition chimique , Pesticides/analyse , Techniques de biocapteur/méthodes , Ordiphone , Spectrométrie de fluorescence/méthodes
5.
Environ Sci Pollut Res Int ; 31(30): 43432-43450, 2024 Jun.
Article de Anglais | MEDLINE | ID: mdl-38862805

RÉSUMÉ

The progress in chemical analytics and understanding of pesticide dynamics in surface waters allows establishing robust data on compounds with frequent exceedances of quality standards. The current chemical, temporal, and spatial coverage of the pesticide monitoring campaigns differs strongly between European countries. A questionnaire revealed differences in monitoring strategies in seven selected European countries; Nordic countries prioritize temporal coverage, while others focus on spatial coverage. Chemical coverage has increased, especially for non-polar classes like synthetic pyrethroids. Sweden combines monitoring data with agricultural practices for derived quantities, while the Netherlands emphasizes spatial coverage to trace contamination sources. None of the EU member states currently has established a process for linking chemical surface water monitoring data with regulatory risk assessment, while Switzerland has recently established a legally defined feedback loop. Due to their design and objectives, most strategies do not capture concentration peaks, especially 2-week composite samples, but also grab samples. Nevertheless, for substances that appear problematic in many data sets, the need for action is evident even without harmonization of monitoring programs. Harmonization would be beneficial, however, for cross-national assessment including risk reduction measures.


Sujet(s)
Surveillance de l'environnement , Pesticides , Polluants chimiques de l'eau , Pesticides/analyse , Polluants chimiques de l'eau/analyse , Europe , Appréciation des risques
6.
Sci Total Environ ; 945: 173971, 2024 Oct 01.
Article de Anglais | MEDLINE | ID: mdl-38876342

RÉSUMÉ

Pesticides are widely used in agriculture where they do not only reach their targets but also distribute to other environmental compartments and negatively affect non-target organisms. To prospectively assess their environmental risk, several tools and models using pesticide persistence (DT50) and leaching potential (groundwater ubiquity score (GUS), EXPOSIT) have been developed. Here, we simultaneously quantified 18 pesticides in soil and drainage water during a conventionally grown potato culture at field scale with high temporal resolution and compared our findings with predictions of the above models. Overall dissipations of all freshly applied compounds in soil were in line with published DT50 field values and their occurrences in drainage water were generally consistent with GUS and EXPOSIT models, respectively. In contrast, soil concentrations of the legacy pesticide atrazine and one of its transformation products (atrazine-2-hydroxy) were constant during the entire sampling campaign. Moreover, during peak discharge atrazine concentrations in drainage water were diluted whereas those of freshly applied pesticides were maximal. This difference demonstrates that the applied risk assessment tools were capable of predicting environmental concentrations and dissipation of pesticides at the short and medium time scale of a few half-lives after application, but fell short of capturing long-term trace residues.


Sujet(s)
Agriculture , Surveillance de l'environnement , Pesticides , Polluants du sol , Sol , Solanum tuberosum , Polluants chimiques de l'eau , Pesticides/analyse , Polluants du sol/analyse , Surveillance de l'environnement/méthodes , Polluants chimiques de l'eau/analyse , Sol/composition chimique , Agriculture/méthodes , Modèles chimiques , Appréciation des risques , Atrazine/analyse
7.
ACS Appl Mater Interfaces ; 16(27): 35245-35254, 2024 Jul 10.
Article de Anglais | MEDLINE | ID: mdl-38935865

RÉSUMÉ

An alarming increase in the use of pesticides and organoarsenic compounds and their toxic impacts on the environment have inspired us to develop a selective and highly sensitive sensor for the detection of these pollutants. Herein, a bio-friendly, low-cost Al-based luminescent metal-organic framework (1')-based fluorescent material is demonstrated that helps in sustaining water quality by rapid monitoring and quantification of a long-established pesticide (pendimethalin) and a widely employed organoarsenic feed additive (roxarsone). A pyridine-functionalized porous aluminum-based metal-organic framework (Al-MOF) was solvothermally synthesized. After activation, it was used for fast (<10 s) and selective turn-off detection of roxarsone and pendimethalin over other competitive analytes. This is the first MOF-based recyclable sensor for pendimethalin with a remarkably low limit of detection (LOD, 14.4 nM). Real-time effectiveness in detection of pendimethalin in various vegetable and food extracts was successfully verified. Moreover, the aqueous-phase recyclable detection of roxarsone with an ultralow detection limit (13.1 nM) makes it a potential candidate for real-time application. The detection limits for roxarsone and pendimethalin are lower than the existing luminescent material based sensors. Furthermore, the detection of roxarsone in different environmental water and a wide pH range with a good recovery percentage was demonstrated. In addition, a cheap and bio-friendly 1'@chitosan@paper strip composite was prepared and successfully employed for the hands-on detection of pendimethalin and roxarsone. The turn-off behavior of 1' in the presence of pendimethalin and roxarsone was examined systematically, and plausible mechanistic pathways were proposed with the help of multiple experimental evidences.


Sujet(s)
Dérivés de l'aniline , Chitosane , Réseaux organométalliques , Papier , Roxarsone , Légumes , Polluants chimiques de l'eau , Réseaux organométalliques/composition chimique , Dérivés de l'aniline/composition chimique , Polluants chimiques de l'eau/analyse , Légumes/composition chimique , Roxarsone/analyse , Roxarsone/composition chimique , Chitosane/composition chimique , Pesticides/analyse , Contamination des aliments/analyse , Limite de détection , Additifs alimentaires/analyse
8.
Toxins (Basel) ; 16(6)2024 May 26.
Article de Anglais | MEDLINE | ID: mdl-38922139

RÉSUMÉ

Monitoring agricultural toxins such as mycotoxins is crucial for a healthy society. High concentrations of these toxins lead to the cause of several chronic diseases; therefore, developing analytical systems for detecting/monitoring agricultural toxins is essential. These toxins are found in crops such as vegetables, fruits, food, and beverage products. Currently, screening of these toxins is mostly performed with sophisticated instrumentation such as chromatography and spectroscopy techniques. However, these techniques are very expensive and require extensive maintenance, and their availability is limited to metro cities only. Alternatively, electrochemical biomimetic sensing methodologies have progressed hugely during the last decade due to their unique advantages like point-of-care sensing, miniaturized instrumentations, and mobile/personalized monitoring systems. Specifically, affinity-based sensing strategies including immunosensors, aptasensors, and molecular imprinted polymers offer tremendous sensitivity, selectivity, and stability to the sensing system. The current review discusses the principal mechanisms and the recent developments in affinity-based sensing methodologies for the detection and continuous monitoring of mycotoxins and pesticides. The core discussion has mainly focused on the fabrication protocols, advantages, and disadvantages of affinity-based sensing systems and different exploited electrochemical transduction techniques.


Sujet(s)
Techniques de biocapteur , Techniques électrochimiques , Mycotoxines , Pesticides , Mycotoxines/analyse , Pesticides/analyse , Techniques de biocapteur/instrumentation , Techniques de biocapteur/méthodes , Biomimétique , Humains , Contamination des aliments/analyse , Matériaux biomimétiques/composition chimique
9.
Biosensors (Basel) ; 14(6)2024 Jun 10.
Article de Anglais | MEDLINE | ID: mdl-38920608

RÉSUMÉ

Agricultural products are vitally important for sustaining life on earth and their production has notably grown over the years worldwide in general and in Brazil particularly. Elevating agricultural practices consequently leads to a proportionate increase in the usage of pesticides that are crucially important for enhanced crop yield and protection. These compounds have been employed excessively in alarming concentrations, causing the contamination of soil, water, and air. Additionally, they pose serious threats to human health. The current study introduces an innovative tool for producing appropriate materials coupled with an electrochemical sensor designed to measure carbendazim levels. The sensor is developed using a molecularly imprinted polymer (MIP) mounted on a glassy carbon electrode. This electrode is equipped with multi-walled carbon nanotubes (MWCNTs) for improved performance. The combined system demonstrates promising potential for accurately quantifying carbendazim. The morphological characteristics of the synthesized materials were investigated using field emission scanning electron microscopy (FESEM) and the Fourier-transform infrared (FTIR) technique. The analytical curve was drawn using the electrochemical method in the range of 2 to 20 ppm while for HPLC 2-12 ppm; the results are presented as the maximum adsorption capacity of the MIP (82.4%) when compared with NIP (41%) using the HPLC method. The analysis conducted using differential pulse voltammetry (DPV) yielded a limit of detection (LOD) of 1.0 ppm and a repeatability of 5.08% (n = 10). The results obtained from the analysis of selectivity demonstrated that the proposed electrochemical sensor is remarkably efficient for the quantitative assessment of carbendazim, even in the presence of another interferent. The sensor was successfully tested for river water samples for carbendazim detection, and recovery rates ranging from 94 to 101% were obtained for HPLC and 94 to 104% for the electrochemical method. The results obtained show that the proposed electrochemical technique is viable for the application and quantitative determination of carbendazim in any medium.


Sujet(s)
Benzimidazoles , Carbamates , Techniques électrochimiques , Nanotubes de carbone , Pesticides , Carbamates/analyse , Benzimidazoles/analyse , Pesticides/analyse , Nanotubes de carbone/composition chimique , Techniques de biocapteur , Électrodes , Matériaux biomimétiques/composition chimique , Limite de détection
10.
Mikrochim Acta ; 191(7): 368, 2024 06 04.
Article de Anglais | MEDLINE | ID: mdl-38833176

RÉSUMÉ

A colorimetric analysis platform has been successfully developed based on FeCo-NC dual-atom nanozyme (FeCo-NC DAzyme) for the detection of organophosphorus pesticides (OPPs). The FeCo-NC DAzyme exhibited exceptional oxidase-like activity (OXD), enabling the catalysis of colorless TMB to form blue oxidized TMB (oxTMB) without the need for H2O2 involvement. By combining acid phosphatase (ACP) hydrolase with FeCo-NC DAzyme, a "FeCo-NC DAzyme + TMB + ACP + SAP" colorimetric system was constructed, which facilitated the rapid detection of malathion. The chromogenic system was applied to detect malathion using a smartphone-based app and an auxiliary imaging interferogram device for colorimetric measurements, which have a linear range of 0.05-4.0 µM and a limit of detection (LOD) as low as 15 nM in real samples, comparable to UV-Vis and HPLC-DAD detection methods. Overall, these findings present a novel approach for convenient, rapid, and on-site monitoring of OPPs.


Sujet(s)
Colorimétrie , Limite de détection , Pesticides , Ordiphone , Colorimétrie/méthodes , Pesticides/analyse , Composés organiques du phosphore/analyse , Composés organiques du phosphore/composition chimique , Malathion/analyse , Malathion/composition chimique , Oxidoreductases/composition chimique , Fer/composition chimique , Acid phosphatase/analyse , Acid phosphatase/composition chimique , Benzidines
11.
Analyst ; 149(14): 3765-3772, 2024 Jul 08.
Article de Anglais | MEDLINE | ID: mdl-38842353

RÉSUMÉ

Molecularly imprinted polymer (MIP)-based chromatographic separation materials, owing to their advantages of unique selectivity, low cost, suitable reproducibility, and acceptable stability, have attracted a great deal of research in different fields. In this investigation, a new type of MIP-coated silica (MIP/SiO2) separation material was developed using sulfamethoxazole as a template; the specific recognition ability of MIP and appropriate physicochemical properties (abundant Si-OH, suitable pore structure, good stability, etc.) of SiO2 microbeads were combined. The MIP/SiO2 separation materials were characterized carefully. Then, various compounds (such as sulfonamides, ginsenosides, nucleosides, and several pesticides) were used to comprehensively evaluate the chromatographic performances of the MIP/SiO2 column. Furthermore, the chromatographic performances of the MIP/SiO2 column were compared with those of other separation materials (such as non-imprinted polymer-coated silica, C18/SiO2, and bare silica) packed columns. The resolution value of all measured compounds was more than 1.51. The column efficiencies of 13 510 plates per meter (N m-1) for sulfamethoxazole, 11 600 N m-1 for ginsenoside Rd, and 10 510 N m-1 for 2'-deoxyadenosine were obtained. The acceptable results verified that the MIP/SiO2 column can be applied to separate highly polar drugs such as sulfonamides, ginsenosides, nucleosides, and pesticides.


Sujet(s)
Microsphères , Polymères à empreintes moléculaires , Silice , Silice/composition chimique , Chromatographie en phase liquide à haute performance/méthodes , Polymères à empreintes moléculaires/composition chimique , Ginsénosides/composition chimique , Ginsénosides/analyse , Ginsénosides/isolement et purification , Empreinte moléculaire/méthodes , Nucléosides/composition chimique , Nucléosides/isolement et purification , Nucléosides/analyse , Pesticides/analyse , Pesticides/composition chimique , Pesticides/isolement et purification , Polymères/composition chimique
12.
Environ Res ; 257: 119379, 2024 Sep 15.
Article de Anglais | MEDLINE | ID: mdl-38851374

RÉSUMÉ

A large number of pesticides have been widely manufactured and applied, and are released into the environment with negative impact on human health. Pesticides are largely used in densely populated urban environments, in green zones, along roads and on private properties. In order to characterize the potential exposure related health effects of pesticide and their occurrence in the urban environment, 222 pesticides were screened and quantified in 228 road dust and 156 green-belt soil samples in autumn and spring from Harbin, a megacity in China, using GC-MS/MS base quantitative trace analysis. The results showed that a total of 33 pesticides were detected in road dust and green-belt soil, with the total concentrations of 650 and 236 ng/g (dry weight = dw), respectively. The concentrations of pesticides in road dust were significantly higher than that in green-belt soil. Pesticides in the environment were influenced by the seasons, with the highest concentrations of insecticides in autumn and the highest levels of herbicides in spring. In road dust, the concentrations of highways in autumn and spring (with the mean values of 94.1 and 68.2 ng/g dw) were much lower than that of the other road classes (arterial roads, sub-arterial roads and branch ways). Whereas in the green-belt soil, there was no significant difference in the concentration of pesticides between the different road classes. A first risk assessment was conducted to evaluate the potential adverse health effects of the pesticides, the results showed that the highest hazard index (HI) for a single pesticide in dust and soil was 0.12, the hazard index for children was higher than that for adults, with an overall hazard index of less than 1. Our results indicated that pesticide levels do not have a significant health impact on people.


Sujet(s)
Villes , Poussière , Exposition environnementale , Surveillance de l'environnement , Pesticides , Chine , Pesticides/analyse , Humains , Exposition environnementale/analyse , Poussière/analyse , Surveillance de l'environnement/méthodes , Population urbaine , Saisons , Polluants du sol/analyse , Tests de criblage à haut débit
13.
Environ Monit Assess ; 196(7): 656, 2024 Jun 25.
Article de Anglais | MEDLINE | ID: mdl-38916777

RÉSUMÉ

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.


Sujet(s)
Résidus de pesticides , Pesticides , Thé , Thé/composition chimique , Appréciation des risques , Pesticides/analyse , Résidus de pesticides/analyse , Surveillance de l'environnement , Humains , Agriculteurs , Agriculture , Camellia sinensis/composition chimique , Pyréthrines/analyse , Chine , Exposition professionnelle/analyse
14.
Molecules ; 29(11)2024 Jun 03.
Article de Anglais | MEDLINE | ID: mdl-38893504

RÉSUMÉ

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water's taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL-1 and RSDs in the range of 0.8-12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples.


Sujet(s)
Pesticides , Microextraction en phase solide , Polluants chimiques de l'eau , Microextraction en phase solide/méthodes , Pesticides/analyse , Pesticides/isolement et purification , Polluants chimiques de l'eau/analyse , Polluants chimiques de l'eau/isolement et purification , Chromatographie gazeuse-spectrométrie de masse/méthodes , Agriculture , Polydiméthylsiloxanes/composition chimique , Eau/composition chimique , Spectroscopie infrarouge à transformée de Fourier , Limite de détection , Aiguilles
15.
Anal Methods ; 16(25): 4124-4135, 2024 Jun 27.
Article de Anglais | MEDLINE | ID: mdl-38860427

RÉSUMÉ

This paper describes an extensive study in which a multiclass QuEChERS based approach was optimized for determination of 150 pesticides and 7 mycotoxins in table olives. Three versions of QuEChERS were evaluated and compared (unbuffered, citrate and acetate buffering). A combination of EMR-Lipid cartridges and liquid nitrogen or freezer freezing out were tested for clean-up of the oily olive extracts. Analysis of the extracts were performed by LC-MS/MS triple quadrupole. The best results were achieved using acetate QuEChERS with liquid nitrogen for clean-up. For validation, organic olives were ground and spiked at 4 concentrations with pesticides and mycotoxins (n = 5). The linearity of the calibration curves was assessed by analyzing calibration standards of 7 concentrations which were prepared separately in acetonitrile and in blank olive extract (n = 5). The validation study demonstrated that the calculated r2 was ≥0.99 for 144 pesticides and 6 mycotoxins, when the calibration curves were prepared in matrix extract, showing satisfactory linearity. Matrix effects were within the range of ±20% for only 46 pesticides and one mycotoxin. Then, to ensure reliable quantification, calibration standards had to be matrix-matched. In accuracy experiments 138 pesticides and 6 mycotoxins presented recoveries from 70 to 120% and RSD ≤ 20% for at least 2 of the 4 spike concentrations evaluated, being successfully validated. The integrated QuEChERS and LC-MS/MS method meet MRL for 11 of the 21 pesticides regulated for olives in Brazil and for 132 pesticides which are regulated in the EU law. Eleven commercial table olive samples were analyzed and 4 of them tested positive for pesticides. All the positive samples violate the Brazilian law and one sample violates also the European law.


Sujet(s)
Mycotoxines , Olea , Pesticides , Spectrométrie de masse en tandem , Olea/composition chimique , Brésil , Mycotoxines/analyse , Spectrométrie de masse en tandem/méthodes , Pesticides/analyse , Chromatographie en phase liquide/méthodes , Contamination des aliments/analyse , Reproductibilité des résultats
16.
Sci Total Environ ; 940: 173705, 2024 Aug 25.
Article de Anglais | MEDLINE | ID: mdl-38830419

RÉSUMÉ

Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.


Sujet(s)
Agriculture , Polluants atmosphériques , Surveillance de l'environnement , Pesticides , Pesticides/analyse , Polluants atmosphériques/analyse , Portugal , Pays-Bas , Humains
17.
Anal Chim Acta ; 1315: 342756, 2024 Aug 01.
Article de Anglais | MEDLINE | ID: mdl-38879204

RÉSUMÉ

BACKGROUND: Dried blood spots (DBSs) collected and archived in newborn screening programs (NSP) represent a potentially valuable resource for assessing exposure to a range of organic and inorganic chemicals in newborns. This study develops and optimizes a method to measure polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs) in DBS using the isotope dilution technique, ultrasonic-assisted liquid-liquid extraction, simple cleanup, triple quadrupole GC-MS/MS analysis, and background correction. RESULTS: We minimize the number of extraction repetitions and the volume of solvent, which helps increase throughput while minimizing the potential for contamination. We obtained high recovery and precision for most compounds, and method detection limits (MDLs) were sufficiently low to detect the more prevalent compounds based on representative sample of the US population. MDLs averaged 0.020 ng/mL (recovery: 107 %, precision: 4 %) for PCNs, 0.021 ng/mL (recovery: 97 %, precision: 4 %) for PCBs, 0.021 ng/mL (recovery: 117 %, precision: 2 %) for OCPs, and 0.021 ng/mL (recovery: 96 %, precision: 3 %) for PBDEs. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first study presenting an analytical method and for PCNs in DBS, and one of the few studies providing an assessment of method performance for persistent organic pollutants in DBS. The optimized method can be applied to a wide range of applications, including exposure assessment, environmental epidemiology, forensics, environmental surveillance, and ecological monitoring.


Sujet(s)
Dépistage sur goutte de sang séché , Naphtalènes , Polluants organiques persistants , Spectrométrie de masse en tandem , Dépistage sur goutte de sang séché/méthodes , Humains , Naphtalènes/sang , Polluants organiques persistants/sang , Spectrométrie de masse en tandem/méthodes , Éthers de polyhalogénophényle/sang , Éthers de polyhalogénophényle/analyse , Polychlorobiphényles/sang , Polychlorobiphényles/analyse , Extraction liquide-liquide/méthodes , Hydrocarbures chlorés/sang , Hydrocarbures chlorés/analyse , Nouveau-né , Chromatographie gazeuse-spectrométrie de masse/méthodes , Limite de détection , Pesticides/sang , Pesticides/analyse
18.
Sci Total Environ ; 944: 173690, 2024 Sep 20.
Article de Anglais | MEDLINE | ID: mdl-38825198

RÉSUMÉ

As one of the nine primary non-ferrous metal smelting bases in China, Daye Lake basin was polluted due to diverse human activities. But so far the pollution status and related ecological risks of this region have not been detailly investigated. In current study, pollutants including heavy metals, polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in eight sediment samples from Daye Lake were quantified. 18S rRNA gene sequencing was employed to profile the nematode community structure within these sediments. Model organism Caenorhabditis elegans (C. elegans) were further applied for a comprehensive ecological risk assessment of Daye Lake. Notably, Cadmium (Cd) was identified as a key driver of ecological risk, reaching an index of 1287.35. At sample point S4, OCPs particularly p,p'-DDT, displayed an extreme ecological risk with a value of 23.19. Cephalobidae and Mononchida showed strong sensitivity to pollutant levels, reinforcing their suitability as robust bioindicators. The composite pollutants in sampled sediments caused oxidative stress in C. elegans, with gene Vit-2 and Mtl-1 as sensitive biomarkers. By employing the multiple analysis methods, our data can offer valuable contributions to environmental monitoring and health risk assessment for composite polluted areas.


Sujet(s)
Surveillance de l'environnement , Hydrocarbures chlorés , Lacs , Métaux lourds , Polluants chimiques de l'eau , Lacs/composition chimique , Polluants chimiques de l'eau/analyse , Surveillance de l'environnement/méthodes , Chine , Animaux , Hydrocarbures chlorés/analyse , Appréciation des risques , Métaux lourds/analyse , Caenorhabditis elegans/effets des médicaments et des substances chimiques , Hydrocarbures aromatiques polycycliques/analyse , Sédiments géologiques/composition chimique , Pesticides/analyse
19.
Anal Chem ; 96(24): 9834-9841, 2024 Jun 18.
Article de Anglais | MEDLINE | ID: mdl-38832651

RÉSUMÉ

Complexed and tiresome pretreatment processes have significantly impeded in-field analysis of environmental specimens. Herein, an all-in-one sample separation and enrichment strategy based on a compact charge-selective capture/nanoconfined enrichment (CSC/NCE) device is exploited for marker-free surface-enhanced Raman spectroscopy (SERS) detection of charged pesticides in matrix specimens. This tactic incorporating in situ separations, seizing, and nanoconfined enhancement can greatly elevate the effectiveness of sample pretreatment. Importantly, CSC/NCE with excellent adsorption performances and excellent plasmonic features facilitates concentration and signal amplification of electrically charged pesticides. With the introduction of an electric field on this integrated CSC/NCE, the matrix effect in samples could be significantly eradicated, and a distinct SERS response is witnessed for targeted analytes. Accurate quantification of multipesticides is achieved by synergizing the CSC/NCE chip and chemometrics, and the contents found by the CSC/NCE-based sensing strategy agree with those obtained from chromatography assays with relative deviations lower than 10%. The facile and versatile all-in-one tactic infused in a compact chip exhibits enormous potential for field-test application in chemical measurement and food safety.


Sujet(s)
Pesticides , Analyse spectrale Raman , Pesticides/analyse , Miniaturisation , Nanoparticules métalliques/composition chimique , Propriétés de surface
20.
J Water Health ; 22(6): 1075-1087, 2024 Jun.
Article de Anglais | MEDLINE | ID: mdl-38935458

RÉSUMÉ

This study evaluated pesticide exposure practices, and the potential health risks of drinking water and consuming fish from the cultivated wetlands of Ndop, Cameroon. Six hundred and twenty-six questionnaires were conveniently administered to farmers (≥ 26 years old) in a cross-sectional study to assess exposure practices and dietary risks. The Chi-square and Pearson correlation coefficients were used to establish relationships between variables. The PRIMET model was used to predict a worst-case dietary risk. The pesticide handling practices of 90% of farmers were inadequate. Chlorpyriphos, lambda-cyhalothrin, fipronil, and paraquat dichloride posed a possible dietary risk at recommended and applied doses, with chlorpyrifos having the highest exposure toxicity ratio (ETRdiet = 36.72). Paraquat dichloride, fipronil, and lambda-cyhalothrin posed a possible dietary risk at 26.3%, 58.3%, and 62.2% of their recommended concentrations, respectively. Remarkably, the dietary risk for cypermethrin was acceptable at 5.8 times its recommended dose (ETRdietR = 0.29). The significant positive correlation (p = 0.000) between PECfish and ETRdiet, suggests a possible health risk of consuming fish and drinking water harvested from the wetlands, thus the need for replacing pesticides posing possible risks at lower or recommended concentrations with less toxic alternatives and to train farmers on pesticide application practices.


Sujet(s)
Eau de boisson , Poissons , Pesticides , Polluants chimiques de l'eau , Zones humides , Eau de boisson/analyse , Eau de boisson/composition chimique , Animaux , Appréciation des risques , Humains , Polluants chimiques de l'eau/analyse , Pesticides/analyse , Cameroun , Études transversales , Contamination des aliments/analyse , Régime alimentaire , Exposition alimentaire/analyse , Adulte , Agriculture , Enquêtes et questionnaires
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