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Chemosphere Apr 2024This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential...
This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential risks to the aquatic health and human water consumption in the western region of Bahia state, Brazil. Two gas chromatography-mass spectrometry analytical methods were applied to monitor 34 pesticides in water samples collected during both the dry and rainy seasons at 17 sites. Upon individual analysis, only γ-HCH, methoxychlor, demeton-S, methyl parathion, fenitrothion, chlorpyrifos, and azoxystrobin exhibited statistically significant differences between seasons. During rainy season, concentration medians of residues were higher for γ-HCH (74.7 ng L), methoxychlor (25.1 ng L), and azoxystrobin (47.2 ng L), potentially linked to historical contamination or illegal use. Conversely, pesticides like methyl parathion, fenitrothion, and chlorpyrifos, belonging to the organophosphate class, showed higher concentration medians in the dry period, measuring 75.1, 5.50, and 10.8 ng L, respectively, probably due to region crop activities. The risk quotient (RQ) assessment for aquatic life indicated that 59.0% of the samples in the dry season and 76.0% in the rainy season had RQ values greater than one, signifying a critical scenario for species conservation. Regarding human consumption, elevated risks were observed for heptachlor in both sampling periods and for azoxystrobin during the rainy season, surpassing RQ levels above 1, indicating danger in untreated water ingestion. Additionally, 24.0% and 53.0% of the samples in the dry and rainy seasons, respectively, contained at least one pesticide exceeding the EU resolution limit (100 ng L). Therefore, considering this information, implementing mitigation measures to avoid the river's contamination becomes imperative.
Topics: Humans; Pesticides; Seasons; Rivers; Brazil; Water; Hexachlorocyclohexane; Chlorpyrifos; Methyl Parathion; Methoxychlor; Fenitrothion; Water Pollutants, Chemical; Risk Assessment; Environmental Monitoring; Strobilurins; Pyrimidines
PubMed: 38490616
DOI: 10.1016/j.chemosphere.2024.141659 -
Journal of Separation Science Mar 2024Herein, a deep eutectic solvent (DES)-based miniaturized pressurized liquid extraction in combination with DES-based dispersive liquid-liquid microextraction (DLLME) was...
Deep eutectic solvent-based pressurized liquid extraction combined with dispersive liquid-liquid microextraction of organophosphorus pesticide residues in egg powder prior to high-performance liquid chromatography analysis.
Herein, a deep eutectic solvent (DES)-based miniaturized pressurized liquid extraction in combination with DES-based dispersive liquid-liquid microextraction (DLLME) was developed for the extraction of organophosphorus pesticides (parathion-methyl, triazophos, parathion, diazinon, and phoxim) from egg powder samples prior to their analysis by a high-performance liquid chromatography-diode array detector. In this work, first, the analytes' extraction was done by a pressurized liquid phase extraction for effective extraction of the analytes from the solid matrix, and then they were concentrated on a DLLME for more concentration of the analytes to reach low limits of detections. The use of DESs was done in both steps to omit the use of toxic organic solvents. Satisfactory results including high extraction recoveries (74-90%), great repeatability (relative standard deviations equal or less than 4.3% and 5.3% for intra- and inter-day precisions), and low limits of detection (0.11-0.29 ng/g) and quantification (0.38-0.98 ng/g) were attained under the optimum conditions. Lastly, the suggested approach was utilized for the determination of the studied pesticides in various egg powder samples marketed in Tabriz, Iran.
Topics: Pesticide Residues; Liquid Phase Microextraction; Pesticides; Organophosphorus Compounds; Chromatography, High Pressure Liquid; Deep Eutectic Solvents; Powders; Parathion
PubMed: 38466171
DOI: 10.1002/jssc.202300070 -
Food Chemistry Jul 2024The unreasonable use of organophosphorus pesticides leads to excessive pesticide residues in food, seriously threatening public health, and the potential of...
The unreasonable use of organophosphorus pesticides leads to excessive pesticide residues in food, seriously threatening public health, and the potential of surface-enhanced Raman spectroscopy (SERS) technology, incorporating a metal-organic framework, is substantial for the rapid detection of trace pesticide residues. Here, a novel FeO@NH-MIL-101(Fe)@Ag (FNMA) SERS nanosensor was developed. Results indicated that the FNMA had a high enhancement factor of 1.53 × 10, a low limit of detection (LOD) of 4.55 × 10 M, and a relative standard deviation of 7.73 % for 4-nitrothiophenol, demonstrating its good SERS sensitivity and uniformity, and also possessed good storage stability for one month. In quantifying fenthion and methyl parathion in standard solutions and apple juice in the range of 0.05/0.02-20 mg/L, it showed LODs of 3.02 × 10 mg/L and 1.43 × 10 mg/L, and 0.0407 and 0.0075 mg/L, respectively, demonstrating potentials in ultrasensitive trace detection of pesticides in food.
Topics: Pesticides; Malus; Pesticide Residues; Organophosphorus Compounds; Spectrum Analysis, Raman; Fruit; Magnetic Phenomena; Metal Nanoparticles
PubMed: 38460279
DOI: 10.1016/j.foodchem.2024.138846 -
Environmental Research May 2024Pesticide exposure has been linked to some autoimmune diseases and colorectal cancer, possibly via alteration of gut microbiota or other mechanisms. While pesticides...
BACKGROUND
Pesticide exposure has been linked to some autoimmune diseases and colorectal cancer, possibly via alteration of gut microbiota or other mechanisms. While pesticides have been linked to gut dysbiosis and inflammation in animal models, few epidemiologic studies have examined pesticides in relation to inflammatory bowel disease (IBD).
OBJECTIVES
We evaluated use of pesticides and incident IBD in 68,480 eligible pesticide applicators and spouses enrolled in the Agricultural Health Study.
METHODS
Self-reported IBD cases were identified from follow-up questionnaires between enrollment (1993-1997) and 2022. We evaluated IBD incidence in relation to self-reported ever use of 50 pesticides among applicators and spouses. We also explored associations with intensity-weighted lifetime days (IWLD) of pesticide use among male applicators. Covariate-adjusted hazard ratios (HR) and 95% confidence intervals (CI) were calculated using Cox regression.
RESULTS
We identified 454 IBD cases, including 227 among male applicators. In analyses with applicators and spouses combined, associations were positive (HR > 1.2) for ever vs. never use of five organochlorine insecticides, three organophosphate insecticides, one fungicide, and five herbicides. HRs were highest for dieldrin (HR = 1.59, 95%CI: 1.03, 2.44), toxaphene (HR = 1.61, 95%CI: 1.17, 2.21), parathion (HR = 1.42, 95%CI: 1.03, 1.95), and terbufos (HR = 1.53, 95%CI: 1.19, 1.96). We had limited power in many IWLD of pesticide use analyses and did not find clear evidence of exposure-response trends; however, we observed elevated HRs in all tertiles of IWLD use of terbufos compared to never use (T1 vs. never use HR = 1.52, 95%CI: 1.03, 2.24; T2 vs. never use HR = 1.53, 95%CI: 1.04, 2.26; T3 vs. never use HR = 1.51, 95%CI: 1.03, 2.23).
CONCLUSIONS
Exposure to specific pesticides was associated with elevated hazards of IBD. These findings may have public health importance given the widespread use of pesticides and the limited number of known modifiable environmental risk factors for IBD.
Topics: Humans; Male; Pesticides; Middle Aged; Female; Occupational Exposure; Inflammatory Bowel Diseases; Spouses; Adult; Aged; Farmers; Incidence; Iowa; Agriculture
PubMed: 38354883
DOI: 10.1016/j.envres.2024.118464 -
Environmental Research May 2024Organophosphorus adulteration in the environment creates terrestrial and aquatic pollution. It causes acute and subacute toxicity in plants, humans, insects, and... (Review)
Review
Organophosphorus adulteration in the environment creates terrestrial and aquatic pollution. It causes acute and subacute toxicity in plants, humans, insects, and animals. Due to the excessive use of organophosphorus pesticides, there is a need to develop environmentally friendly, economical, and bio-based strategies. The microbiomes, that exist in the soil, can reduce the devastating effects of organophosphates. The use of cell-free enzymes and yeast is also an advanced method for the degradation of organophosphates. Plant-friendly bacterial strains, that exist in the soil, can help to degrade these contaminants by oxidation-reduction reactions, enzymatic breakdown, and adsorption. The bacterial strains mostly from the genus Bacillus, Pseudomonas, Acinetobacter, Agrobacterium, and Rhizobium have the ability to hydrolyze the bonds of organophosphate compounds like profenofos, quinalphos, malathion, methyl-parathion, and chlorpyrifos. The native bacterial strains also promote the growth abilities of plants and help in detoxification of organophosphate residues. This bioremediation technique is easy to use, relatively cost-effective, very efficient, and ensures the safety of the environment. This review covers the literature gap by describing the major effects of organophosphates on the ecosystem and their bioremediation by using native bacterial strains.
Topics: Biodegradation, Environmental; Organophosphorus Compounds; Ecosystem; Pesticide Residues; Bacteria; Soil Pollutants
PubMed: 38301757
DOI: 10.1016/j.envres.2024.118291 -
Food Chemistry Jun 2024In this study, a cascade nanobioreactor was developed for the highly sensitive detection of methyl parathion (MP) in food samples. The simultaneous encapsulation of...
In this study, a cascade nanobioreactor was developed for the highly sensitive detection of methyl parathion (MP) in food samples. The simultaneous encapsulation of acetylcholinesterase (AChE) and choline oxidase (CHO) in a zeolitic imidazole ester backbone (ZIF-8) effectively improved the stability and cascade catalytic efficiency of the enzymes. In addition, glutathione-stabilized gold nanoclusters (GSH-AuNCs) were encapsulated in ZIF-8 by ligand self-assembly, conferring excellent fluorescence properties. Acetylcholine (ATCh) is catalyzed by a cascade of AChE/CHO@ZIF-8 as well as Fe(II) to generate hydroxyl radicals (·OH) with strong oxidizing properties. The ·OH radicals then oxidize Au(0) in GSH-AuNCs@ZIF-8 to Au(I), resulting in fluorescence quenching. MP, as an inhibitor of AChE, hinders the cascade reaction and thus restores the fluorescence emission, enabling its quantitative detection. The limit of detection of the constructed nanobioreactor for MP was 0.23 µg/L. This MOF-based cascade nanobioreactor has great potential for the detection of trace hazards.
Topics: Methyl Parathion; Metal-Organic Frameworks; Acetylcholinesterase; Metal Nanoparticles; Acetylcholine; Gold; Limit of Detection
PubMed: 38219569
DOI: 10.1016/j.foodchem.2024.138389 -
Food Chemistry May 2024Advances in flexible SERS substrates has made it possible to approach the ultimate goal of rapid in-situ monitoring of fruit and vegetable safety, but its vulnerability...
Advances in flexible SERS substrates has made it possible to approach the ultimate goal of rapid in-situ monitoring of fruit and vegetable safety, but its vulnerability under laser ablation results in low utilization. In order to solve this problem, a 3D framework of TiO-doped PVDF\PVP polymer was utilized to self-assemble gold-silver core-shell nanorods (Au@Ag NRs) to prepare a flexible SERS substrate with good physical stability and self-cleaning properties. This substrate showed excellent detection limit and recyclability after the detection of three pesticide residues in apple peel. The LOD of methyl-parathion (MP) was as low as 0.037 ng/cm, with an RSD of 5.61 % for 5 cycle-detection. The recoveries of two additional pesticides thiram (TMTD) and chlorpyrifos (CPF) were 86.32 %-112.47 %. We hoped that this research will contribute to providing a recyclable and facile method for in-situ analysis of fruit and vegetable surface residues and functional manufacture of flexible SERS substrates.
Topics: Malus; Spectrum Analysis, Raman; Metal Nanoparticles; Pesticides; Pesticide Residues; Thiram; Vegetables; Gold
PubMed: 38185049
DOI: 10.1016/j.foodchem.2023.138345 -
The Science of the Total Environment Feb 2024The ecological risks posed by widespread organophosphorus pesticide (OPs) pollution in the surface waters of China remain unclear. In this study, species sensitivity...
The ecological risks posed by widespread organophosphorus pesticide (OPs) pollution in the surface waters of China remain unclear. In this study, species sensitivity distribution (SSD) parametric statistical approaches were coupled with fully acute and chronic toxicity data to fit the sensitivity distributions of different aquatic species to five typical OPs: dimethoate, malathion, parathion-methyl, trichlorfon, and dichlorvos. Crustaceans exhibit the highest sensitivity to OPs, whereas algae are the least sensitive. The acute hazardous concentrations that affected 5 % of the species (HC) were 0.112, 0.001, 0.001, 0.001, and 0.001 mg/L for dimethoate, malathion, parathion-methyl, trichlorfon, and dichlorvos, respectively, whereas their chronic HC values were 0.004, 0.004, 0.053, 0.001, and 0.0005 mg/L, respectively. Hence, dichlorvos is highly toxic and poses greater risk to non-target aquatic species. The evaluation data revealed varying geographical distribution characteristics of the ecological risks from OPs in 15 freshwater aquatic systems across different regions of China. Dichlorvos posed the highest risk in the basins of Zhejiang and Guangdong Provinces, with the highest chronic Risk Quotient (RQ) and Hazard Index (HI) at 9.34 and 9.92, respectively. This is much higher than what was collected and evaluated for foreign rivers (the highest chronic RQ and HI in foreign rivers were 1.65 and 2.24, respectively). Thus, dichlorvos in the surface waters of China poses a substantial ecological risk to aquatic organisms, and may endanger human health.
Topics: Humans; Pesticides; Organophosphorus Compounds; Dichlorvos; Malathion; Dimethoate; Water; Trichlorfon; Methyl Parathion; Aquatic Organisms; China; Risk Assessment; Water Pollutants, Chemical
PubMed: 38181956
DOI: 10.1016/j.scitotenv.2023.169805 -
Journal of Environmental Management Feb 2024Sulfate radical (SO), formed by persulfate (PS) activation during advanced oxidation process (AOPs), can be used for the remediation of organic contaminated soil....
Sulfate radical (SO), formed by persulfate (PS) activation during advanced oxidation process (AOPs), can be used for the remediation of organic contaminated soil. However, the role of biochar and microwave (MW) in the activation of PS is not fully understood, especially the corresponding mechanism. Herein, biochar combined with MW was used to activate PS for the remediation of ethyl-parathion (PTH)-polluted soil. The dynamic evolutions of PTH under different conditions, such as biochar content, particle size, reaction temperature, and the degradation mechanisms of PTH were also systematically investigated. Significant enhancement performance on PTH removal was observed after adding biochar, which was 88.78% within 80 min. Meanwhile, activating temperature exhibited remarkable abilities to activate PS for PTH removal. The higher content of adsorption sites in nano-biochar facilitated the removal of PTH. Furthermore, chemical probe tests coupled with quenching experiments confirmed that the decomposition of PS into active species, such as SO, •OH, O and O, contributed to the removal of PTH in biochar combined with MW system, which could oxidize PTH into oxidative products, including paraoxon, 4-ethylphenol, and hydroquinone. The results of this study provide valuable insights into the synergistic effects of biochar and MW in the PS activation, which is helpful for the potential application of biochar materials combined with MW-activated PS in the remediation of pesticide-polluted soils.
Topics: Parathion; Soil; Microwaves; Environmental Pollution; Charcoal; Oxidation-Reduction; Water Pollutants, Chemical
PubMed: 38160544
DOI: 10.1016/j.jenvman.2023.119930 -
Water Research Feb 2024Rapid and precise quantification of organophosphorus pesticides (OPPs) in environmental water bodies is crucial for evaluating ecological risks and safeguarding human...
Rapid and precise quantification of organophosphorus pesticides (OPPs) in environmental water bodies is crucial for evaluating ecological risks and safeguarding human health. Traditional instrumental methods are complex, time-consuming, and expensive, while enzyme-based biosensors suffer from instability and require a constant supply of substrates. Hence, there is an urgent need for a fast, simple, and sensitive biosensor for OPPs. In this study, we developed a novel non-enzymatic biosensor for the detection of methyl parathion (MP) by employing the bioluminescence resonance energy transfer (BRET) Q-body strategy. Optimizing the spacer arm and screening fluorescent dyes identified the R6G BRET MP Q-body sensor with the best performance. Key parameters affecting the sensor's detection performance were optimized by using single-factor experiments. Under optimal conditions, the detection exhibited a detection limit of 5.09 ng·mL and a linear range of 16.21-848.81 ng·mL. The sensor's accuracy was validated using standard recovery experiments, yielding a recovery rate of 84.47 %-102.08 % with a standard deviation of 1.93 %-9.25 %. The detection results of actual water samples demonstrate that this fast, simple, and highly sensitive BRET Q-body sensor holds great promise for practical water quality monitoring.
Topics: Humans; Pesticides; Organophosphorus Compounds; Methyl Parathion; Energy Transfer; Biosensing Techniques
PubMed: 38157605
DOI: 10.1016/j.watres.2023.121051