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Analytical and Bioanalytical Chemistry May 2021Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously,...
Development, validation, and application of a multi-method for the determination of mycotoxins, plant growth regulators, tropane alkaloids, and pesticides in cereals by two-dimensional liquid chromatography tandem mass spectrometry.
Mycotoxins and pesticides regularly co-occur in agricultural products worldwide. Thus, humans can be exposed to both toxic contaminants and pesticides simultaneously, and multi-methods assessing the occurrence of various food contaminants and residues in a single method are necessary. A two-dimensional high performance liquid chromatography tandem mass spectrometry method for the analysis of 40 (modified) mycotoxins, two plant growth regulators, two tropane alkaloids, and 334 pesticides in cereals was developed. After an acetonitrile/water/formic acid (79:20:1, v/v/v) multi-analyte extraction procedure, extracts were injected into the two-dimensional setup, and an online clean-up was performed. The method was validated according to Commission Decision (EC) no. 657/2002 and document N° SANTE/12682/2019. Good linearity (R > 0.96), recovery data between 70-120%, repeatability and reproducibility values < 20%, and expanded measurement uncertainties < 50% were obtained for a wide range of analytes, including very polar substances like deoxynivalenol-3-glucoside and methamidophos. However, results for fumonisins, zearalenone-14,16-disulfate, acid-labile pesticides, and carbamates were unsatisfying. Limits of quantification meeting maximum (residue) limits were achieved for most analytes. Matrix effects varied highly (-85 to +1574%) and were mainly observed for analytes eluting in the first dimension and early-eluting analytes in the second dimension. The application of the method demonstrated the co-occurrence of different types of cereals with 28 toxins and pesticides. Overall, 86% of the samples showed positive findings with at least one mycotoxin, plant growth regulator, or pesticide.
Topics: Alkaloids; Chromatography, Liquid; Edible Grain; Food Contamination; Mycotoxins; Pesticides; Plant Growth Regulators; Reproducibility of Results; Tandem Mass Spectrometry; Tropanes
PubMed: 33713146
DOI: 10.1007/s00216-021-03239-1 -
World Journal of Microbiology &... Sep 2020Acephate is widely used in agriculture, but its poisonous metabolites and poor sorption characteristics make it a serious environmental pollutant and toxicant to human...
Acephate is widely used in agriculture, but its poisonous metabolites and poor sorption characteristics make it a serious environmental pollutant and toxicant to human health. To screen novel bacteria for biodegradation of acephate and uncover its degradation pathway, a strain called NDZ that is capable of utilizing acephate as a sole carbon and energy source was isolated from severely contaminated cultivated land. The bacterium was identified as Bacillus paramycoides based on 16S rDNA sequence analyses. The growth and degradation capacities of B. paramycoides NDZ under different conditions were studied using optical density at 600 nm (OD) and high-performance liquid chromatography (HPLC). The results showed that B. paramycoides NDZ can grow well with acephate as its sole carbon source (OD = 0.76), and degraded about 76% of acephate in mineral salt medium with an initial concentration of 500 mg/L within 48 h. The results of response surface methodology revealed the optimal conditions for degradation was 36 ℃ and pH 6.85 with 526 mg/L acephate. Gas chromatography-mass spectrometry showed that methamidophos was the main metabolite of B. paramycoides NDZ, different from the degradation products of high-temperature steam (121 °C, 103 kPa). Based on the detection of this intermediate, we inferred that acephate was degraded to methamidophos through hydrolysis of the amide linkage, after which methamidophos was degraded to some small molecules, which can be metabolized easily by the bacterium. In summary, B. paramycoides NDZ is a potentially useful bacterium for acephate degradation and remediation of contaminated soils.
Topics: Bacillus; Biodegradation, Environmental; DNA, Bacterial; DNA, Ribosomal; Gas Chromatography-Mass Spectrometry; Hydrolysis; Metabolomics; Organothiophosphorus Compounds; Phosphoramides; RNA, Ribosomal, 16S; Soil Microbiology
PubMed: 32951077
DOI: 10.1007/s11274-020-02931-1 -
Toxicology and Applied Pharmacology Dec 2018Methamidophos (MET) is an organophosphate (OP) pesticide widely used in agriculture in developing countries. MET causes adverse effects in male reproductive function in...
Methamidophos (MET) is an organophosphate (OP) pesticide widely used in agriculture in developing countries. MET causes adverse effects in male reproductive function in humans and experimental animals, but the underlying mechanisms remain largely unknown. We explored the effect of MET on mice testes (5 mg/kg/day/4 days), finding that this pesticide opens the blood-testis barrier and perturbs spermatogenesis, generating the appearance of immature germ cells in the epididymis. In the seminiferous tubules, MET treatment changed the level of expression or modified the stage-specific localization of tight junction (TJ) proteins ZO-1, ZO-2, occludin, and claudin-3. In contrast, claudin-11 was barely altered. MET also modified the shape of claudin-11, and ZO-2 at the cell border, from a zigzag to a more linear pattern. In addition, MET diminished the expression of ZO-2 in spermatids present in seminiferous tubules, induced the phosphorylation of ZO-2 and occludin in testes and reduced the interaction between these proteins assessed by co-immunoprecipitation. MET formed covalent bonds with ZO-2 in serine, tyrosine and lysine residues. The covalent modifications formed on ZO-2 at putative phosphorylation sites might interfere with ZO-2 interaction with regulatory molecules and other TJ proteins. MET bonds formed at ZO-2 ubiquitination sites likely interfere with ZO-2 degradation and TJ sealing, based on results obtained in cultured epithelial cells transfected with ZO-2 mutated at a MET target lysine residue. Our results shed light on MET male reproductive toxicity and are important to improve regulations regarding the use of OP pesticides and to protect the health of agricultural workers.
Topics: Animals; Blood-Testis Barrier; Claudins; Insecticides; Male; Mice; Mice, Inbred ICR; Occludin; Organophosphates; Organothiophosphorus Compounds; Phosphoproteins; Phosphorylation; Seminiferous Tubules; Spermatogenesis; Tight Junctions; Zonula Occludens-1 Protein; Zonula Occludens-2 Protein
PubMed: 30291936
DOI: 10.1016/j.taap.2018.10.003 -
Journal of Economic Entomology Feb 2019A piezoelectric quartz crystal impedance (PQCI) sensor was used to investigate influences of the insecticide methamidophos on proteinase activity in midguts of the wolf...
A piezoelectric quartz crystal impedance (PQCI) sensor was used to investigate influences of the insecticide methamidophos on proteinase activity in midguts of the wolf spider, Pardosa pseudoamulata (Araneae: Lycosidae). Results from PQCI indicated that low-concentration dose methamidophos (0.008%) can activate the proteinase but high-concentration dose methamidophos (0.016-0.032%) can inhibit the enzyme activity. The changes in subcellular structure of spider midgut cells were also observed. Electron micrographs of spider midgut epithelial cells showed that the low-dose methamidophos did not visibly impact the structure of these cells. Conversely, high-concentration dose methamidophos led to severe changes in the cell structure, including the karyotheca dissolved, the nucleolus, and the endoplasmic reticulum disappeared. These may contribute to changes in proteinase activity of spider. This work documents a feasible method for rapid and reliable detection of proteinase activity.
Topics: Animals; Female; Gastrointestinal Tract; Hydrolysis; Insect Proteins; Insecticides; Organothiophosphorus Compounds; Peptide Hydrolases; Spiders
PubMed: 30321348
DOI: 10.1093/jee/toy318 -
Environmental Science and Pollution... Jan 2017Pesticide handling in farming activities involves substantial hazards for the rural population and for the environment. In Latin America, it is estimated that the...
Pesticide handling in farming activities involves substantial hazards for the rural population and for the environment. In Latin America, it is estimated that the population at risk of being affected by heavy metals is over 4 million. This research describes the different types of exposure to pesticides and heavy metals in a rural population (Loma del Gallo), considering both environmental and occupational exposure. This study consists of an inspection in a former pesticide factory (QUIMAGRO), analysis of heavy metals in samples from surface and ground water in the community close to the factory, and a survey to the local population about their perceptions of pesticide exposures. Containers with 34.6 tons of chemicals improperly stored were identified in the former factory and removed by the government. Arsenic and cadmium were found in groundwater, and the highest values were 0.012 and 0.004 mg/l, respectively. These contaminants were also detected in most surface water samples, with maximum values of 0.026 and 0.0001 mg/l, respectively. Results of the survey show that of the 44 participants 42 % were farmers. Farmers used 19 different pesticide products containing 11 active ingredients. The most used active ingredients were paraquat (65 %), methamidophos (35 %), and atrazina (29 %). Eighty-two percent of the farmers did not use personal protective equipment. In addition to the pesticides used in the agriculture of the area, pesticide containers were removed from the QUIMAGRO area, but the pollution was still present at time of sampling and it is evident by the odor of the site. Surface water had the major concentration of heavy metals than the groundwater. Loma del Gallo population has been exposed to toxic pesticide from QUIMAGRO and agriculture for many years. The farmers carry out mishandling of pesticides and they not use PPE.
Topics: Agriculture; Chemical Industry; El Salvador; Female; Groundwater; Humans; Male; Metals, Heavy; Occupational Exposure; Pesticides; Rural Population; Surveys and Questionnaires; Water Pollutants, Chemical; Young Adult
PubMed: 27796975
DOI: 10.1007/s11356-016-7899-z -
Applied Spectroscopy Jul 2015A protocol created for acephate detection on particulates and vapors surrounding farmworkers as well as in urine samples is reported. Acephate is detected to the low...
A protocol created for acephate detection on particulates and vapors surrounding farmworkers as well as in urine samples is reported. Acephate is detected to the low parts-per-billion (ppb) range using surface-enhanced Raman spectroscopy (SERS). Optimal SERS sensor metal choice and post-production treatments to improve sensor stability in aqueous solutions containing acephate are presented. Acephate is detected in the vapor phase and can be differentiated from urine components and structurally similar pesticides, including the acephate metabolite-degradation product methamidophos. Protocol evaluation and preliminary field tests from North Carolina farms are discussed.
Topics: Humans; Occupational Exposure; Organothiophosphorus Compounds; Pesticides; Phosphoramides; Spectrum Analysis, Raman; Urinalysis; Volatilization; Water
PubMed: 26036870
DOI: 10.1366/14-07594 -
Journal of Exposure Science &... Jul 2020The use of pesticides has increased during the past decades, also increasing the risk of exposure to toxic pesticides that can cause detrimental health effects in the...
The use of pesticides has increased during the past decades, also increasing the risk of exposure to toxic pesticides that can cause detrimental health effects in the future. This is of special concern among farmers in low-to-middle-income countries that may lack proper training in the safe use of these chemicals. To assess the situation in Bolivia a cross-sectional study in three agricultural communities was performed (n = 297). Handling, use of personal protective equipment (PPE) and pesticide exposure were assessed by a questionnaire and measurements of urinary pesticide metabolites (UPMs). Results showed that methamidophos (65%) and paraquat (52%) were the most commonly used pesticides and that 75% of the farmers combined several pesticides while spraying. Notably, only 17% of the farmers used recommended PPEs while 84% reported to have experienced symptoms of acute pesticide poisoning after spraying. UPM measurements indicated high levels of exposure to chlorpyrifos, pyrethroids and 2,4D and that men generally were more highly exposed compared to women. Our study demonstrates that farmers who are better at following recommendations for pesticide handling and use of PPE had a significantly lower risk of having high UPM levels of most measured pesticides. Our results thus confirm the need of proper training of farmers in low-to-middle-income countries in proper protection and pesticide handling in order to reduce exposure levels and health problems.
Topics: Adult; Agriculture; Biomarkers; Bolivia; Cross-Sectional Studies; Farmers; Female; Health Knowledge, Attitudes, Practice; Hispanic or Latino; Humans; Male; Occupational Exposure; Pesticides; Surveys and Questionnaires
PubMed: 30787424
DOI: 10.1038/s41370-019-0128-3 -
The Science of the Total Environment Mar 2023Pesticide exposure has consistently been associated with Parkinson's disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD...
BACKGROUND
Pesticide exposure has consistently been associated with Parkinson's disease (PD) onset. Yet, fewer epidemiologic studies have examined whether pesticides influence PD motor and non-motor symptom progression.
OBJECTIVES
Using a geographic information system tool that integrates agricultural pesticide use reports and land use records to derive ambient exposures at residences and workplaces, we assessed associations between specific pesticides previously related to PD onset with PD symptom progression in two PD patient cohorts living in agricultural regions of California.
METHODS
We calculated the pounds of pesticide applied agriculturally near each participant's residential or occupational addresses from 1974 to the year of PD diagnosis, using a geographic information system tool that links the California Pesticide Use Reports database to land use data. We examined 53 pesticides selected a priori as they have previously been associated with PD onset. We longitudinally followed two PD patient cohorts (PEG1 N = 242, PEG2 N = 259) for an average of 5.0 years (SD ± 3.5) and 2.7 years (SD ± 1.6) respectively and assessed PD symptoms using the movement disorder specialist-administered Unified Parkinson's disease Rating Scale part III (UPDRS), Mini-Mental State Examination (MMSE), and Geriatric Depression Scale (GDS). Weighted time-to-event regression models were implemented to estimate effects.
RESULTS
Ten agricultural pesticides, including copper sulfate (pentahydrate), 2-methyl-4-chlorophenoxyacetic acid (MCPA) dimethylamine salt, tribufos, sodium cacodylate, methamidophos, ethephon, propargite, bromoxynil octanoate, monosodium methanearsonate (MSMA), and dicamba, were associated with faster symptom progression. Among these pesticides, residential or workplace proximity to higher amounts of copper sulfate (pentahydrate) and MCPA (dimethylamine salt) was associated with all three progression endpoints (copper sulfate: HRs = 1.22-1.36, 95 % CIs = 1.03-1.73; MCPA: HRs = 1.27-1.35, 95 % CIs = 1.02-1.70).
CONCLUSIONS
Our findings suggest that pesticide exposure may not only be relevant for PD onset but also PD progression phenotypes. We have implicated ten specific pesticide active ingredients in faster PD motor and non-motor decline.
Topics: Humans; Parkinson Disease; Pesticides; Copper Sulfate; 2-Methyl-4-chlorophenoxyacetic Acid; Workplace; California
PubMed: 36526213
DOI: 10.1016/j.scitotenv.2022.160851 -
Food Additives & Contaminants. Part A,... Aug 2020To assess the dietary exposure risks of pesticide residues in snow fungus for the general population and young children, 91 snow fungus samples were collected from major...
To assess the dietary exposure risks of pesticide residues in snow fungus for the general population and young children, 91 snow fungus samples were collected from major production areas in Fujian Province, China and the presence of 44 pesticides was determined. A total of thirteen pesticides were detected; 65.9% of the samples contained one or more pesticide residues. The most frequently found pesticide was carbofuran, followed by acetamiprid and then imidacloprid. Data obtained were used for chronic, acute, and chronic cumulative dietary exposure risk assessments. The chronic hazard quotient (cHQ) was extremely low for both the general population and young children. The values of cumulative dietary exposures to organophosphorus pesticides and carbamates ranged from 0.53% to 1.49%, and did not exceed their corresponding ADIs. However, the acute dietary risks from all 13 pesticides, especially carbofuran and methamidophos, were of concern due to the relatively high acute hazard quotient. The risk ranking scheme showed that carbofuran could pose a high risk to snow fungus consumers. Finally, suggestions are made about the potential use in snow fungus cultivation of the pesticides with detected residues.
Topics: Basidiomycota; China; Dietary Exposure; Food Analysis; Food Contamination; Humans; Pesticide Residues; Risk Assessment
PubMed: 32429748
DOI: 10.1080/19440049.2020.1766119 -
Journal of Chromatography. A Nov 2014To assess food safety emergencies caused by highly hazardous chemical-tainted foods, simultaneous analysis of organophosphorus insecticides in fatty foods such as...
To assess food safety emergencies caused by highly hazardous chemical-tainted foods, simultaneous analysis of organophosphorus insecticides in fatty foods such as precooked foods was conducted using thin-layer chromatography/direct analysis in real time time-of-flight mass spectrometry (TLC/DART-TOFMS) and isotope dilution technique. Polar (methamidophos and acephate) and nonpolar organophosphorus insecticides (fenitrothion, diazinon, and EPN) were studied. Experiments to ascertain chromatographic patterns using TLC/DART-TOFMS reveal that it was more useful than GC/MS or GC/MS/MS for the simultaneous analyses of polar and nonpolar pesticides, while obviating the addition of a protective agent for tailing effects of polar pesticides. Lower helium gas temperature (260°C) for DART-TOFMS was suitable for the simultaneous analysis of target pesticides. Linearities were achieved respectively at a lower standard concentration range (0.05-5 μg) for diazinon and EPN and at a higher standard concentration range (2.5-25 μg) for methamidophos, acephate, and fenitrothion. Their respective coefficients of determination were ≥ 0.9989 and ≥ 0.9959. A few higher repeatabilities (RSDs) for diazinon and EPN were found (>20%), although isotope dilution technique was used. Application to the HPTLC plate without an automatic TLC sampler might be inferred as a cause of their higher RSDs. Detection limits were estimated in the higher picogram range for diazinon and EPN, and in the lower nanogram range for methamidophos, acephate, and fenitrothion. Aside from methamidophos, recovery results (n=3) obtained using a highly insecticide-tainted fatty food (dumpling) and raw food (grapefruit) samples (10mg/kg) using TLC/DART-TOFMS with both complex and simpler cleanups were not as susceptible to matrix effects (95-121%; RSD, 1.3-14%) as those using GC/MS/MS (102-117%; RSD, 0.4-8.5%), although dumpling samples using GC/MS were remarkably susceptible to matrix effects. The coupled method of TLC with simpler cleanup and DART-TOFMS can be regarded as the same analytical tool as GC/MS/MS, which is useful to assess food safety emergencies caused by highly hazardous chemical-tainted foods.
Topics: Chromatography, High Pressure Liquid; Chromatography, Thin Layer; Fats; Food Analysis; Indicator Dilution Techniques; Insecticides; Isotopes; Mass Spectrometry; Phosphorus; Time Factors
PubMed: 25454149
DOI: 10.1016/j.chroma.2014.10.037