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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 -
Applied and Environmental Microbiology Feb 2022The marine environment presents great potential as a source of microorganisms that possess novel enzymes with unique activities and biochemical properties. Examples of...
The marine environment presents great potential as a source of microorganisms that possess novel enzymes with unique activities and biochemical properties. Examples of such are the quorum-quenching (QQ) enzymes that hydrolyze bacterial quorum-sensing (QS) signaling molecules, such as -acyl-homoserine lactones (AHLs). QS is a form of cell-to-cell communication that enables bacteria to synchronize gene expression in correlation with population density. Searching marine metagenomes for sequences homologous to an AHL lactonase from the phosphotriesterase-like lactonase (PLL) family, we identified new putative AHL lactonases (sharing 30 to 40% amino acid identity to a thermostable PLL member). Phylogenetic analysis indicated that these putative AHL lactonases comprise a new clade of marine enzymes in the PLL family. Following recombinant expression and purification, we verified the AHL lactonase activity for one of these proteins, named moLRP (marine-originated lactonase-related protein). This enzyme presented greater activity and stability at a broad range of temperatures and pH, tolerance to high salinity levels (up to 5 M NaCl), and higher durability in bacterial culture, compared to another PLL member, parathion hydrolase (PPH). The addition of purified moLRP to cultures of Pseudomonas fluorescens inhibited its extracellular protease activity, expression of the protease encoding gene, biofilm formation, and the sedimentation process in milk-based medium. These findings suggest that moLRP is adapted to the marine environment and can potentially serve as an effective QQ enzyme, inhibiting the QS process in Gram-negative bacteria involved in food spoilage. Our results emphasize the potential of sequence and structure-based identification of new QQ enzymes from environmental metagenomes, such as from the ocean, with improved stability or activity. The findings also suggest that purified QQ enzymes can present new strategies against food spoilage, in addition to their recognized involvement in inhibiting bacterial pathogen virulence factors. Future studies on the delivery and safety of enzymatic QQ strategy against bacterial food spoilage should be performed.
Topics: Carboxylic Ester Hydrolases; Metagenome; Phylogeny; Pseudomonas; Pseudomonas fluorescens; Quorum Sensing
PubMed: 34910563
DOI: 10.1128/AEM.01680-21 -
Toxics Jul 2022The intensive use of organophosphorus pesticides (OPPs) causes concern among authorities in different countries, as many of them, remaining unchanged for a long time,...
The intensive use of organophosphorus pesticides (OPPs) causes concern among authorities in different countries, as many of them, remaining unchanged for a long time, pose a threat to environmental sustainability. This study assessed the spatio-temporal trends of nine OPPs in the water dissolved phase (WDP), suspended particulate matter (SPM), and sediment samples from the Sele River estuary, Southern Italy. Samples were collected in 10 sampling sites during four seasons. The highest levels were found at the mouth (mean value 28.25 ng L as WDP + SPM) and then decreased moving southwards to the Mediterranean Sea. Moreover, highest concentrations were detected in the warm season (July) with a mean value of 27.52 ng L. The load contribution to the Mediterranean Sea was evaluated in about 61.5 kg year, showing that the river was an important source of OPPs through discharge into the sea. The risk assessment revealed that no high-risk indices for the general-case scenario were observed, but for the worst-case scenario, potential risks were associated with chlorpyrifos, pyrimifos-methyl, and parathion, suggesting that OPP contamination should not be neglected. This study makes up the first record of OPPs in the surface waters of the Sele River and provides helpful data as a starting point for future studies.
PubMed: 35878282
DOI: 10.3390/toxics10070377 -
Chemico-biological Interactions Aug 2022Epidemiological evidence suggests that people chronically exposed to organophosphorus pesticides are at increased risk of neurodegenerative disease. Covalently linked...
Epidemiological evidence suggests that people chronically exposed to organophosphorus pesticides are at increased risk of neurodegenerative disease. Covalently linked amyloid beta dimers have been isolated from the brains of Alzheimer's patients. The toxic forms of amyloid beta are amyloid dimers that spontaneously oligomerize. In the present report we treated recombinant and synthetic amyloid beta (1-42) with 1 mM chlorpyrifos oxon or 1 mM paraoxon. The trypsin-digested samples were analyzed by liquid chromatography tandem mass spectrometry on an Orbitrap Fusion Lumos mass spectrometer. Data were searched with Protein Prospector software. We found two new types of crosslinks in amyloid dimers. An isopeptide Asp-Asp link occurred between the N-terminal amine of Asp 1 in one peptide and the beta carboxyl group of Asp 1 in another peptide. An Asp-Arg link occurred between the guanidino group of Arg 5 in one peptide and the beta carboxyl group of Asp 1 in another peptide. These results show that the active metabolites of the pesticides chlorpyrifos and parathion catalyze the crosslinking of amyloid beta (1-42) into toxic dimers. It was concluded that the increased risk of neurodegenerative disease in people exposed to organophosphorus pesticides could be explained by the crosslinking activity of these chemicals. Data are available via ProteomeXchange with identifier PXD034163.
Topics: Alzheimer Disease; Amyloid beta-Peptides; Chlorpyrifos; Humans; Neurodegenerative Diseases; Organophosphorus Compounds; Peptide Fragments; Pesticides
PubMed: 35779611
DOI: 10.1016/j.cbi.2022.110029 -
Toxics Sep 2023New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic...
New approach methods (NAMs) can reduce the need for chronic animal studies. Here, we apply benchmark dose (concentration) (BMD(C))-response modeling to transcriptomic changes in the liver of mice and in fathead minnow larvae after short-term exposures (7 days and 1 day, respectively) to several dose/concentrations of three organophosphate pesticides (OPPs): fenthion, methidathion, and parathion. The mouse liver transcriptional points of departure (TPODs) for fenthion, methidathion, and parathion were 0.009, 0.093, and 0.046 mg/Kg-bw/day, while the fathead minnow larva TPODs were 0.007, 0.115, and 0.046 mg/L, respectively. The TPODs were consistent across both species and reflected the relative potencies from traditional chronic toxicity studies with fenthion identified as the most potent. Moreover, the mouse liver TPODs were more sensitive than or within a 10-fold difference from the chronic apical points of departure (APODs) for mammals, while the fathead minnow larva TPODs were within an 18-fold difference from the chronic APODs for fish species. Short-term exposure to OPPs significantly impacted acetylcholinesterase mRNA abundance (FDR -value <0.05, |fold change| ≥2) and canonical pathways (IPA, -value <0.05) associated with organism death and neurological/immune dysfunctions, indicating the conservation of key events related to OPP toxicity. Together, these results build confidence in using short-term, molecular-based assays for the characterization of chemical toxicity and risk, thereby reducing reliance on chronic animal studies.
PubMed: 37888672
DOI: 10.3390/toxics11100820 -
Environmental Research Sep 2019Organophosphate (OP) pesticides can be hazardous to human health if not applied with appropriate precautions. There is evidence in the Maule region of Chile that rural...
An educational intervention on the risk perception of pesticides exposure and organophosphate metabolites urinary concentrations in rural school children in Maule Region, Chile.
BACKGROUND
Organophosphate (OP) pesticides can be hazardous to human health if not applied with appropriate precautions. There is evidence in the Maule region of Chile that rural schoolchildren are exposed to OP pesticides.
OBJECTIVE
To evaluate the effectiveness of an educational intervention on OP exposure and understanding of pesticides and their hazards (risk perception) in two school communities in the Maule Region of Chile during 2016.
METHOD
We conducted a quasi-experimental study about the effects on OP pesticide exposure of a community outreach and education program (COEP) administered in four 2-h sessions that's included hands-on activities among 48 schoolchildren from two rural schools. The intervention was directed to groups of parents and school-children separately, and aimed to educate them about the risks of exposure to pesticides and their effects on health. We measured 3,5,6-trichloro-2-pyridinol (TCPy), 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMPY), malathion dicarboxylic acid (MDA), p-nitrophenol (PNP), specific urinary metabolites of the OP pesticides chlorpyrifos, diazinon, malathion and parathion, respectively, as well as the non-specific diethylakylphosphates (DEAPs) and dimethylalkylphosphates (DMAPs) in 192 urine samples of schoolchildren collected before and after the intervention. The risk perception of school children and their parents was also assessed through a questionnaire before and after the intervention. Generalized Estimated Equations were used to account for each child's repeated measures during four sessions, two in September 2016 (pre-intervention) and two in November 2016 (post-intervention).
RESULTS
The intervention level had significant effect on the risk perception of adults and children, which increased after the intervention. However, the intervention was not associated with reduced of urinary metabolites levels, with no significant differences between the pre and post measures. The detection frequencies were 1.1% (MDA), 71.4% (TCPy), 43.3% (IMPY), 98.96% (PNP), and 100% (DEAPs and DMAPs). Higher DEAPs urine concentrations were associated with eating more fruit at school (p = 0.03), a younger age (p = 0.03), and being male (p = 0.01). DMAPs showed no associations with potential predictor variables (e.g. OPs applied at home, fruit consumption at school, among others). Higher TCPy was associated with attending a school closer to farms (p = 0.04) and living in a home closer to farm fields (p = 0.01); higher PNP was marginally associated with children younger age (p = 0.035).
CONCLUSION
Environmental exposure to OP pesticides was unchanged even after behavior changes. It is possible that a longer time period is needed to observe changes in both behavior and urinary metabolites. The levels of DEP and DMP metabolites found here are above the reference population of the US, and our findings indicate exposure to a wide variety of OP pesticides. Given that individual-level interventions were not associated with lower exposures, efforts to reduce exposure must occur upstream and require stricter regulation and control of pesticide use by government agencies.
Topics: Adult; Agriculture; Child; Chile; Chlorpyrifos; Environmental Exposure; Female; Health Knowledge, Attitudes, Practice; Humans; Insecticides; Male; Organophosphorus Compounds; Pesticides
PubMed: 31288198
DOI: 10.1016/j.envres.2019.108554 -
F1000Research 2020: Developmental delay among children under 5 years of age is a serious global public health problem and much research has been carried out to find potential causes....
: Developmental delay among children under 5 years of age is a serious global public health problem and much research has been carried out to find potential causes. Pesticides - especially organophosphates - are suspected to be one of the main causes of the problem. This study aimed to investigate the association between pesticide use by the mother during pregnancy and preschool children development using a case-control study. : Data on prenatal and postnatal pesticide exposure of 442 children with suspected developmental delay, and 413 controls with normal development were included for analysis. The children were matched for gender, age, and residency. Data on pesticide exposure were collected via interview with the mother, and data on pregnancy outcomes abstracted from hospital records. : Chlorpyrifos exposure significantly increased the risk of developmental delay with an odds ratio (OR) of 3.71 (95% CI 1.03-13.36) for ever use of the pesticide, and an OR of 5.92 (95% CI 1.01-34.68) for postnatal exposure (p <0.05). Some other pesticides also had a positive association with developmental delay but none were statistically significant (p <0.05). Those pesticides were insecticide, fungicide, herbicide, and molluscicide. Individual pesticides with a positive association were glyphosate, paraquat, butachlor, methyl parathion (pholidon), savin, methomyl, endosulfan, carbosulfan, methamidophos, monochrotofos, mancozeb, and bordeaumixture. : This case-control study found that chlorpyrifos and some other pesticides exposure during pregnancy were positively associated with developmental delay in children aged under 5 years. Further research should be conducted to better understand this potential effects of pesticides on child neurodevelopment, and the public - especially those who plan to have families - should be informed.
Topics: Case-Control Studies; Child, Preschool; Chlorpyrifos; Female; Humans; Pesticides; Pregnancy; Pregnancy Outcome; Thailand
PubMed: 34557296
DOI: 10.12688/f1000research.27874.5 -
ACS Omega Dec 2022Pesticide usage is one of the significant issues in modern agricultural practices; hence, monitoring pesticide content and its degradation is of utmost importance. A...
Pesticide usage is one of the significant issues in modern agricultural practices; hence, monitoring pesticide content and its degradation is of utmost importance. A novel and simple one-pot deep eutectic solvent-based solvothermal method has been developed for the synthesis of FeVO/reduced graphene oxide (FeV/RGO) nanocomposite. The band gap of FeV decreased upon anchoring with RGO. Enhanced activity in the detection and photocatalytic degradation has been achieved in the FeV/RGO nanocomposite compared to pure FeV and RGO. FeV/RGO was used to modify glassy carbon electrode (GCE), and the fabricated electrode was evaluated for its electrochemical detection of methyl parathion (MP). The amperometric technique was found to be more sensitive with a 0.001-260 μM (two linear ranges; 0.001-20 and 25-260 μM) wide linear range and low limit of detection value (0.70 nM). The practical applicability of modified GCE is more selective and sensitive to real samples like river water and green beans. Photocatalytic degradation of MP has been examined using FeV, RGO, and FeV/RGO nanocomposite. FeV/RGO managed to degrade 95% of MP under solar light in 80 min. Degradation parameters were optimized carefully to attain maximum efficiency. Degradation intermediates were identified using liquid chromatography-mass spectrometry analysis. The degradation mechanism has been studied in detail. FeV/RGO could serve as a material of choice in the field of electrochemical sensors as well as heterogeneous catalysis toward environmental remediation.
PubMed: 36530306
DOI: 10.1021/acsomega.2c05729 -
Archives of Toxicology May 2023The current approach for the risk assessment of chemicals does not account for the complex human real-life exposure scenarios. Exposure to chemical mixtures in everyday...
The current approach for the risk assessment of chemicals does not account for the complex human real-life exposure scenarios. Exposure to chemical mixtures in everyday life has raised scientific, regulatory, and societal concerns in recent years. Several studies aiming to identify the safety limits of chemical mixtures determined hazardous levels lower than those of separate chemicals. Following these observations, this study built on the standards set by the real-life risk simulation (RLRS) scenario and investigated the effect of long-term exposure (18 months) to a mixture of 13 chemicals (methomyl, triadimefon, dimethoate, glyphosate, carbaryl, methyl parathion, aspartame, sodium benzoate, EDTA, ethylparaben, butylparaben, bisphenol A and acacia gum) in adult rats. Animals were divided into four dosing groups [0xNOAEL (control), 0.0025xNOAEL (low dose-LD), 0.01xNOAEL (medium dose-MD) and 0.05xNOAEL (high dose-HD) (mg/kg BW/day)]. After 18 months of exposure, all animals were sacrificed, and their organs were harvested, weighed, and pathologically examined. While organ weight tended to be higher in males than in females, when sex and dose were taken into account, lungs and hearts from female rats had significantly greater weight than that of males. This discrepancy was more obvious in the LD group. Histopathology showed that long-term exposure to the chemical mixture selected for this study caused dose-dependent changes in all examined organs. The main organs that contribute to chemical biotransformation and clearance (liver, kidneys, and lungs) consistently presented histopathological changes following exposure to the chemical mixture. In conclusion, exposure to very low doses (below the NOAEL) of the tested mixture for 18 months induced histopathological lesions and cytotoxic effects in a dose and tissue-dependent manner.
Topics: Male; Humans; Rats; Female; Animals; No-Observed-Adverse-Effect Level; Rats, Sprague-Dawley; Pesticides; Food Additives; Organ Size
PubMed: 36892595
DOI: 10.1007/s00204-023-03455-x -
Beilstein Journal of Nanotechnology 2020Methyl parathion (MP) is one of the most neurotoxic pesticides. An inexpensive and reliable one-step degradation method of MP was achieved through an aqueous suspension...
Methyl parathion (MP) is one of the most neurotoxic pesticides. An inexpensive and reliable one-step degradation method of MP was achieved through an aqueous suspension of copper(I) oxide nanoparticles (NPs). Three different NPs sizes (16, 29 and 45 nm), determined with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), were synthesized using a modified Benedict's reagent. H nuclear magnetic resonance (NMR) results show that the hydrolytic degradation of MP leads to the formation of 4-nitrophenol (4-NPh) as the main product. While the P=S bond of MP becomes P=O, confirmed by P NMR. Although CuO is a widely known photocatalyst, the degradation of methyl parathion was associated to the surface basicity of CuO NPs. Indirect evidence for the basicity of CuO NPs was achieved through UV-vis absorption of 4-NPh. Likewise, it was shown that the surface basicity increases with decreasing nanoparticle size. The presence of CuCO on the surface of CuO, identified using X-ray photoelectron spectroscopy (XPS), passivates its surface and consequently diminishes the degradation of MP.
PubMed: 33133999
DOI: 10.3762/bjnano.11.137