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Metabolites Nov 2022Ultrahigh-performance liquid chromatography system coupled to a hybrid quadrupole time-of-flight mass spectrometer (UPLC-QTOF/MS) technology was used to investigate the...
Ultrahigh-performance liquid chromatography system coupled to a hybrid quadrupole time-of-flight mass spectrometer (UPLC-QTOF/MS) technology was used to investigate the degradation and metabolism of chlorpyrifos during wheat growth by spraying plants with different doses of chlorpyrifos 7 days after the flowering and filling stage. We analyzed and identified chlorpyrifos metabolites in different parts of wheat in full-scan MSE mode, and established a chlorpyrifos metabolite screening library using UNIFI software. The results show that the residues of chlorpyrifos in wheat ears, leaves, and stems exhibited a decreasing trend with the prolongation of application time, and the degradation kinetics could be fitted with the first-order kinetic equation Ct = C0 e−kt. The initial residues of chlorpyrifos in different parts of the wheat were different, in the order of leaves > wheat ears > stems. The degradation rate of chlorpyrifos under field conditions is relatively fast, and the half-life value is 2.33−5.05 days. Chlorpyrifos can undergo a nucleophilic addition substitution reaction under the action of hydrolase to generate secondary metabolite 3,5,6-trichloro-2-pyridinol (3,5,6-TCP). The residual amount of 3,5,6-TCP in each part of wheat first showed an increasing trend and then decreased over time. It reached the maximum on the 3rd, 7th, or 11th day after application, and then gradually degraded. Considering that 3,5,6-TCP is a biomarker with potential threats to humans and animals, it is recommended that 3,5,6-TCP be included in the relevant regulations for dietary exposure risk assessment.
PubMed: 36557199
DOI: 10.3390/metabo12121162 -
Environment International Aug 2022Only few studies have compared environmental pesticide air concentrations with specific urinary metabolites to evaluate pathways of exposure. Therefore, we compared...
BACKGROUND
Only few studies have compared environmental pesticide air concentrations with specific urinary metabolites to evaluate pathways of exposure. Therefore, we compared pyrimethanil and chlorpyrifos concentrations in air with urinary 4-hydroxypyrimethanil (OHP, metabolite of pyrimethanil) and 3,5,6-trichloro-2-pyridinol (TCPy, metabolite of chlorpyrifos) among pregnant women from the Infant's Environmental Health Study (ISA) in Matina County, Costa Rica.
METHODS
During pregnancy, we obtained repeat urinary samples from 448 women enrolled in the ISA study. We extrapolated pyrimethanil and chlorpyrifos concentrations measured with passive air samplers (PAS) (n = 48, from 12 schools), across space and time using a Bayesian spatiotemporal model. We subsequently compared these concentrationswith urinary OHP and TCPy in 915 samples from 448 women, usingseparatemixed models andconsidering several covariables.
RESULTS
A 10% increase in air pyrimethanil (ng/m) was associated with a 5.7% (95% confidence interval (CI 4.6, 6.8) increase in OHP (μg/L). Women living further from banana plantations had lower OHP: -0.7% (95% CI -1.2, -0.3) for each 10% increase in distance (meters) as well as women who ate rice and beans ≥15 times a week -23% (95% CI -38, -4). In addition, each 1 ng/m increase in chlorpyrifos in air was associated with a 1.5% (95% CI 0.2, 2.8) increase in TCPy (μg/L), and women working in agriculture tended to have increased TCPy (21%, 95% CI -2, 49).
CONCLUSION
The Bayesian spatiotemporal models were useful to estimate pyrimethanil and chlorpyrifos air concentrations across space and time. Our results suggest inhalation of pyrimethanil and chlorpyrifos is a pathway of environmental exposure. PAS seems a useful technique to monitor environmental current-use pesticide exposures. For future studies, we recommend increasing the number of locations of environmental air measurements, obtaining all air and urine measurements during the same month, and, ideally, including dermal exposure estimates as well.
Topics: Humans; Female; Infant; Pregnancy; Chlorpyrifos; Pregnant Women; Costa Rica; Bayes Theorem; Pesticides; Environmental Health; Insecticides
PubMed: 35728412
DOI: 10.1016/j.envint.2022.107328 -
International Journal of Environmental... Sep 2022Chlorpyrifos (CPF) was the most frequently used pesticide in food production in the European Union (EU) until 2020. Unfortunately, this compound is still being applied... (Review)
Review
Chlorpyrifos (CPF) was the most frequently used pesticide in food production in the European Union (EU) until 2020. Unfortunately, this compound is still being applied in other parts of the world. National monitoring of pesticides conducted in various countries indicates the presence of CPF in soil, food, and water, which may have toxic effects on consumers, farmers, and animal health. In addition, CPF may influence changes in the population of fungi, bacteria, and actinomycete in soil and can inhibit nitrogen mineralization. The mechanisms of CPF activity are based on the inhibition of acetylcholinesterase (AChE) activity. This compound also exhibits reproductive toxicity, neurotoxicity, and genotoxicity. The problem seems to be the discrepancy between the actual observations and the final conclusions drawn for the substance's approval in reports presenting the toxic impact of CPF on human health. Therefore, this influence is still a current and important issue that requires continuous monitoring despite its withdrawal from the market in the EU. This review traces the scientific reports describing the effects of CPF resulting in changes occurring in both the environment and at the cellular and tissue level in humans and animals. It also provides an insight into the hazards and risks to human health in food consumer products in which CPF has been detected.
Topics: Acetylcholinesterase; Animals; Chlorpyrifos; Humans; Insecticides; Nitrogen; Pesticides; Soil; Water
PubMed: 36231509
DOI: 10.3390/ijerph191912209 -
3 Biotech Jun 2016Fungi are important natural product sources that have enormous potential for the production of novel compounds for use in pharmacology, agricultural applications and... (Review)
Review
Fungi are important natural product sources that have enormous potential for the production of novel compounds for use in pharmacology, agricultural applications and industry. Compared with other natural sources such as plants, fungi are highly diverse but understudied. However, research on Cladosporium cladosporioides revealed the existence of bioactive products such as p-methylbenzoic acid, ergosterol peroxide (EP) and calphostin C as well as enzymes including pectin methylesterase (PME), polygalacturonase (PG) and chlorpyrifos hydrolase. p-Methylbenzoic acid has ability to synthesise 1,5-benzodiazepine and its derivatives, polyethylene terephthalate and eicosapentaenoic acid. EP has anticancer, antiangiogenic, antibacterial, anti-oxidative and immunosuppressive properties. Calphostin C inhibits protein kinase C (PKC) by inactivating both PKC-epsilon and PKC-alpha. In addition, calphostin C stimulates apoptosis in WEHI-231 cells and vascular smooth muscle cells. Based on the stimulation of endoplasmic reticulum stress in some types of cancer, calphostin C has also been evaluated as a potential photodynamic therapeutic agent. Methylesterase (PME) and PG have garnered attention because of their usage in the food processing industry and significant physiological function in plants. Chlorpyrifos, a human, animal and plant toxin, can be degraded and eliminated by chlorpyrifos hydrolase.
PubMed: 28330073
DOI: 10.1007/s13205-015-0323-4 -
Molecules (Basel, Switzerland) Mar 2019Xenobiotics and their reactive metabolites are conjugated with native biomolecules such as glutathione and glucoside during phase II metabolism. Toxic metabolites are...
Xenobiotics and their reactive metabolites are conjugated with native biomolecules such as glutathione and glucoside during phase II metabolism. Toxic metabolites are usually detoxified during this step. On the other hand, these reactive species have a potential health impact by disrupting many enzymatic functions. Thus, it is crucial to understand phase II conjugation reactions of xenobiotics in order to address their fate and possible toxicity mechanisms. Additionally, conventional methods (in vivo and in vitro) have limitation due to matrix complexity and time-consuming. Hence, developing fast and matrix-free alternative method is highly demandable. In this work, oxidative phase I metabolites and reactive species of chlorpyrifos (insecticide) and fluopyram (fungicide) were electrochemically produced by using a boron-doped diamond electrode coupled online to electrospray mass spectrometry (ESI-MS). Reactive species of the substrates were trapped by biomolecules (glutathione and glucoside) and phase II conjugative metabolites were identified using liquid chromatography (LC)-MS/MS, and/or Triple time of flight (TripleTOF)-MS. Glutathione conjugates and glucosylation of chlorpyrifos, trichloropyridinol, oxon, and monohydroxyl fluopyram were identified successfully. Glutathione and glucoside were conjugated with chlorpyrifos, trichloropyridinol, and oxon by losing a neutral HCl. In the case of fluopyram, its monohydroxyl metabolite was actively conjugated with both glutathione and glucoside. In summary, seven bioconjugates of CPF and its metabolites and two bioconjugates of fluopyram metabolites were identified using electrochemistry (EC)/MS for the first time in this work. The work could be used as an alternative approach to identify glutathione and glucosylation conjugation reactions of other organic compounds too. It is important, especially to predict phase II conjugation within a short time and matrix-free environment.
Topics: Benzamides; Chlorpyrifos; Chromatography, High Pressure Liquid; Electrochemical Techniques; Electrodes; Glucosides; Glutathione; Molecular Structure; Oxidation-Reduction; Pesticides; Pyridines; Tandem Mass Spectrometry; Xenobiotics
PubMed: 30836697
DOI: 10.3390/molecules24050898 -
Ecotoxicology and Environmental Safety Oct 2022Chironomids are characterized by their ubiquitous distribution, global diversity and tolerant ability to deal with environmental stressors. To our knowledge, this is the...
Chironomids are characterized by their ubiquitous distribution, global diversity and tolerant ability to deal with environmental stressors. To our knowledge, this is the first study presenting the gut microbial structure of chironomid larvae and examining the microbial alteration induced by invading chlorpyrifos and copper with different dosages. Lethal bioassay displayed a significantly decreased percentage survival of Propsilocerus akamusi larvae exposed to 800 mg/L copper and 50 μg/L chlorpyrifos at 96 h. Larvae with deficient gut microbiota exhibited a depressed level of glutathione S-transferase activity after stressful exposure. The high-throughput 16S rRNA gene sequencing was adopted to investigate the community structure and it turned out that both copper and chlorpyrifos were able to generate distinguished variations of gut microbiota in the stressor-specific and concentration-dependent manner. Of note, the relative abundance of Comamonas, Stenotrophomonas, and Yersinia remarkably elevated in the presence of copper while chlorpyrifos exposure upregulated the prevalence of certain genera (e.g. Serratia). Flavobacterium was greatly attenuated in chlorpyrifos group with lethal dosage exhibiting more severe impacts. The predicted gene functions of the gut commensals differed between normal samples and those subjected to distinct toxins. Besides, more positive associations and limited modularity of microbial interactions were observed in stressor-challenged larvae, presenting a network with impaired complexity and stability. The appearance of either copper or chlorpyrifos exhibited strong positive correlations with genera belonging to Proteobacteria and Firmicutes. Collectively, this investigation introduces a general outline of gut microbiota obtained from chironomid individuals with latent adaptive tactics to nocuous factors (heavy metal and pesticide), which could build a fundamental basis for us to further explore the protective roles of chironomid gut bacterial colonizers in defending against aquatic contaminants.
Topics: Animals; Chironomidae; Chlorpyrifos; Copper; Gastrointestinal Microbiome; Glutathione Transferase; Humans; Larva; Pesticides; RNA, Ribosomal, 16S
PubMed: 36049336
DOI: 10.1016/j.ecoenv.2022.114027 -
Food Science & Nutrition Jun 2021To investigate the fractioning of chlorpyrifos, omethoate, cypermethrin, and deltamethrin during wheat milling and the fate of four pesticides during Chinese steamed...
To investigate the fractioning of chlorpyrifos, omethoate, cypermethrin, and deltamethrin during wheat milling and the fate of four pesticides during Chinese steamed bread (CSB) processing, wheat samples, which were sprayed twice with chlorpyrifos, omethoate, cypermethrin, and deltamethrin at three levels of concentrations during the grain-filling stage, were milled, and wheat flour was processed to CSB. The residues of four pesticides in the milling products, kneaded dough, fermented dough, and CSB were determined with GC-MS/MS. The concentrations of chlorpyrifos, omethoate, cypermethrin, and deltamethrin in bran were 1.46-1.57, 1.85-2.13, 1.27-1.86, and 1.63-2.33 times higher than those in wheat, respectively, while the residues of the four pesticides in shorts decreased approximately 27.97% to 57.02% for chlorpyrifos, 6.22% to 44.77% for cypermethrin, and 13.13% to 61.15% for deltamethrin compared with the residues in wheat ( < .05); however, omethoate levels approximately doubled in the ten-fold treatment group in shorts compared with those in wheat ( < .05). The residues of the four pesticides in flour were significantly lower than those in wheat, ranging from 38.68% to 98.04%. Chlorpyrifos and omethoate levels showed a slight decrease during the kneading and fermentation process, and further decreases of 2.46%-29.51% for chlorpyrifos and 14.22%-71.11% for omethoate were found in CSB; however, most of the groups of cypermethrin and deltamethrin showed various degrees of increases in kneaded and fermented dough and steamed bread compared with flour. The mechanism of this increase is unknown and needs further research.
PubMed: 34136147
DOI: 10.1002/fsn3.1523 -
Environment International Mar 2023The extensive usage of pesticides has led to a ubiquitous exposure in the Chinese general population. Previous studies have demonstrated developmental neurotoxicity...
BACKGROUND
The extensive usage of pesticides has led to a ubiquitous exposure in the Chinese general population. Previous studies have demonstrated developmental neurotoxicity associated with prenatal exposure to pesticides.
OBJECTIVES
We aimed to delineate the landscape of internal pesticides exposure levels from pregnant women's blood serum samples, and to identify the specific pesticides associated with the domain-specific neuropsychological development.
METHODS
Participants included 710 mother-child pairs in a prospective cohort study initiated and maintained in Nanjing Maternity and Child Health Care Hospital. Maternal spot blood samples were collected at enrollment. Leveraging on an accurate, sensitive and reproducible analysis method for 88 pesticides, a total of 49 pesticides were measured simultaneously using gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS). After implementing a strict quality control (QC) management, 29 pesticides were reported. We assessed neuropsychological development in 12-month-old (n = 172) and 18-month-old (n = 138) children using the Ages and Stages Questionnaire (ASQ), Third Edition. Negative binomial regression models were used to investigate the associations between prenatal exposure to pesticides and ASQ domain-specific scores at age 12 and 18 months. Restricted cubic spline (RCS) analysis and generalized additive models (GAMs) were fitted to evaluate non-linear patterns. Longitudinal models with generalized estimating equations (GEE) were conducted to account for correlations among repeated observations. Weighted quantile sum (WQS) regression and Bayesian kernel machine regression (BKMR) were applied to examining the joint effect of the mixture of pesticides. Several sensitivity analyses were performed to assess the robustness of the results.
RESULTS
We observed that prenatal exposure to chlorpyrifos was significantly associated with a 4 % decrease in the ASQ communication scores both at age 12 months (RR, 0.96; 95 % CI, 0.94-0.98; P < 0.001) and 18 months (RR, 0.96; 95 % CI, 0.93-0.99; P < 0.01). In the ASQ gross motor domain, higher concentrations of mirex (RR, 0.96; 95 % CI, 0.94-0.99, P < 0.01 for 12-month-old children; RR, 0.98; 95 % CI, 0.97-1.00, P = 0.01 for 18-month-old children), and atrazine (RR, 0.97; 95 % CI, 0.95-0.99, P < 0.01 for 12-month-old children; RR, 0.99; 95 % CI, 0.97-1.00, P = 0.03 for 18-month-old children) were associated with decreased scores. In the ASQ fine motor domain, higher concentrations of mirex (RR, 0.98; 95 % CI, 0.96-1.00, P = 0.04 for 12-month-old children; RR, 0.98; 95 % CI, 0.96-0.99, P < 0.01 for 18-month-old children), atrazine (RR, 0.97; 95 % CI, 0.95-0.99, P < 0.001 for 12-month-old children; RR, 0.98; 95 % CI, 0.97-1.00, P = 0.01 for 18-month-old children), and dimethipin (RR, 0.94; 95 % CI, 0.89-1.00, P = 0.04 for 12-month-old children; RR, 0.93; 95 % CI, 0.88-0.98, P < 0.01 for 18-month-old children) were associated with decreased scores. The associations were not modified by child sex. There was no evidence of statistically significant nonlinear relationships between pesticides exposure and RRs of delayed neurodevelopment (P > 0.05). Longitudinal analyses implicated the consistent findings.
CONCLUSION
This study gave an integrated picture of pesticides exposure in Chinese pregnant women. We found significant inverse associations between prenatal exposure to chlorpyrifos, mirex, atrazine, dimethipin and the domain-specific neuropsychological development (i.e., communication, gross motor and fine motor) of children at 12 and 18 months of age. These findings identified specific pesticides with high risk of neurotoxicity, and highlighted the need for priority regulation of them.
Topics: Humans; Female; Pregnancy; Infant; Infant, Newborn; Pesticides; Chlorpyrifos; Prenatal Exposure Delayed Effects; Prospective Studies; Mirex; Tandem Mass Spectrometry; Bayes Theorem; Atrazine; China; Neurotoxicity Syndromes; Maternal Exposure
PubMed: 36809709
DOI: 10.1016/j.envint.2023.107814 -
PloS One 2020The levels and activity of the enzyme paraoxonase 1 affect the vulnerability to the teratogenic effects of organophosphate pesticides. Mutant mice lacking the gene for...
The levels and activity of the enzyme paraoxonase 1 affect the vulnerability to the teratogenic effects of organophosphate pesticides. Mutant mice lacking the gene for paraoxonase1 (PON1-/-) are more susceptible to the toxic effects of chlorpyrifos, and were hypothesized to be more vulnerable to social behavior deficits induced by exposure to chlorpyrifos during gestation. Three experiments were performed comparing PON1-/- mice to PON1+/+ mice born to dams treated with 0.5 mg/kg chlorpyrifos or cornoil vehicle on gestational days 12-15. Chlofpyrifos-exposed male PON1-/- mouse pups had delayed development of reflexes in in the first experiment. In the second experiment, adult male and female PON1-/- mice and the female PON1+/+ mice all displayed lower social preference than the male vehicle-treated PON1+/+ mice. The PON1-/- mice and the female PON1+/+ mice displayed lower social preference compared to the PON1+/+ male mice. Male adult mice that had been exposed in utero to chlorpyrifos showed less conditioned social preference regardless of genotype. In the third study, the delayed reflex development was replicated in male and female PON1-/- mice, but chlorpyrifos did not augment this effect. Nest Odor Preference, a test of early social attachment to dam and siblings, was lower in PON1-/- mouse pups compared to PON1+/+ pups. This study shows for the first time that PON1-/- mice have a behavioral phenotype that indicates impaired reflex development and social behavior. Chlorpyrifos exposure during gestation tended to augment some of these effects.
Topics: Animals; Aryldialkylphosphatase; Chlorpyrifos; Cholinesterase Inhibitors; Developmental Disabilities; Female; Male; Mice; Pregnancy; Prenatal Exposure Delayed Effects; Reflex; Social Behavior; Teratogens
PubMed: 32976529
DOI: 10.1371/journal.pone.0239738 -
Chemical Research in Toxicology Sep 2022Exposure to organophosphorus pesticides (OP) can have chronic adverse effects that are independent of inhibition of acetylcholinesterase, the classic target for acute OP...
Exposure to organophosphorus pesticides (OP) can have chronic adverse effects that are independent of inhibition of acetylcholinesterase, the classic target for acute OP toxicity. In pure proteins, the organophosphorus pesticide chlorpyrifos oxon induces a cross-link between lysine and glutamate (or aspartate) with loss of water. Tubulin is particularly sensitive to OP-induced cross-linking. Our goal was to explore OP-induced cross-linking in a complex protein sample, MAP-rich tubulin from and to test 8 OP for their capacity to promote isopeptide cross-linking. We treated 100 μg of MAP-rich tubulin with 100 μM chlorpyrifos, chlorpyrifos oxon, methamidophos, paraoxon, diazinon, diazoxon, monocrotophos, or dichlorvos. Each sample was separated using sodium dodecyl sulfate-polyacrylamide gel electrophoresis and stained with Coomassie blue. Five gel slices (at about 30, 50, 150, and 300 kDa, and the top of the separating gel) were removed from the lanes for each of the eight OP samples and from untreated control lanes. These gel slices were subjected to in-gel trypsin digestion. MSMS fragmentation spectra of the tryptic peptides were examined for isopeptide cross-links. Sixteen spectra yielded convincing evidence for isopeptide cross-linked peptides. Ten were from the chlorpyrifos oxon reaction, 1 from dichlorvos, 1 from paraoxon, 1 from diazinon, and 3 from diazoxon. It was concluded that catalysis of protein cross-linking is a general property of organophosphorus pesticides and pesticide metabolites. Data are available via ProteomeXchange with identifier PXD034529.
Topics: Acetylcholinesterase; Aspartic Acid; Chlorpyrifos; Diazinon; Dichlorvos; Glutamates; Lysine; Monocrotophos; Organophosphorus Compounds; Paraoxon; Peptides; Pesticides; Sodium Dodecyl Sulfate; Trypsin; Tubulin; Water
PubMed: 36048166
DOI: 10.1021/acs.chemrestox.2c00194