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International Journal of Environmental... Dec 2022Organophosphates (OPPs) are an important element of modern agriculture; however, because they are being used excessively, their residues are leaching and accumulating in...
Organophosphates (OPPs) are an important element of modern agriculture; however, because they are being used excessively, their residues are leaching and accumulating in the soil and groundwater, contaminating aquatic and terrestrial food chains. An important OPP called disulfoton is frequently used to eradicate pests from a wide range of crops, including Brazil's coffee crops. Additionally, it does not easily degrade in the environment, and as such, this compound can slowly build up in living organisms such as humans. Moreover, this compound has been classified as "extremely hazardous" by the World Health Organization. This study evaluated the degradation efficiency of disulfoton using a Fenton-like reaction catalyzed by magnetite nanoparticles and determined the toxicity of the by-products of the degradation process using the bioindicator . Further, the removal efficiency of disulfoton was determined to be 94% under optimal conditions. On the other hand, the bioassay showed different toxic, cytotoxic, genotoxic, and mutagenic outcomes even after the remediation process. In conclusion, the Fenton process catalyzed by magnetite nanoparticles presents great efficiency for the oxidation of disulfoton. However, it is important to highlight that the high degradation efficiency of the Fenton-based process was not sufficient to achieve detoxification of the samples.
Topics: Humans; Disulfoton; Oxidation-Reduction; Agriculture; Soil; Crops, Agricultural
PubMed: 36613108
DOI: 10.3390/ijerph20010786 -
Se Pu = Chinese Journal of... Feb 2022Disulfoton, an organophosphorus pesticide, is used to control cotton, beet, potato, and other seedling period aphids, leaf moths, underground pests, etc., with internal...
[Determination of disulfoton and its metabolites in agricultural products by dispersive soild phase extraction-ultra high performance liquid chromatography-tandem mass spectrometry].
Disulfoton, an organophosphorus pesticide, is used to control cotton, beet, potato, and other seedling period aphids, leaf moths, underground pests, etc., with internal absorption, killing, gastric poisoning, and fumigation. Disulfoton is a highly toxic organophosphate pesticide, which can inhibit cholinesterase activity, resulting in neurophysiological disorders by inhalation, feeding, and transdermal absorption. Disulfoton is difficult to degrade in the environment, which leads to enrichment in organisms and interference with endocrine. This compound is harmful to the ecological environment and human health. To ensure the quality and safety of food, it is important to develop a detection method for disulfoton and its metabolites in agricultural products. A reliable method based on dispersive solid phase extraction (d-SPE) with ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination of disulfoton and its metabolites (disulfoton sulfone, disulfoton sulfoxide, demeton-, demeton- sulfone, and demeton- sulfoxide) in agricultural products (pea, asparagus, wheat, coffee bean, and peanut). The optimal extraction method was as follows: 5.0 g the samples were extracted with acetonitrile (wheat, coffee bean, and peanut presoaked in 5 mL water) in a 50 mL centrifuge tube, followed by 10 min vortex. Before 30 s vortex, 4 g NaCl was added. After 5 min centrifugation, 1.5 mL of the supernatant was cleaned up with 50 mg octadecylsilane bonded silica (C), 50 mg primary secondary amine (PSA), and 50 mg aminopropyl (NH) adsorbents. The analytes were separated on a Thermo Syncronis C column (150 mm×2.1 mm, 5 μm) with gradient elution using water and acetonitrile at a column temperature of 40 ℃. The injection volume was 2 μL. Disulfoton and its metabolites were analyzed in multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI) for the selective quantification. Qualitative and quantitative analyses were accorded to the retention times and characteristic ion pairs with one parent ion and two fragment ions. Quantitative analysis was performed by an external standard method using matrix-matched calibration curves. All the parameters that affected the extraction efficiencies were optimized. C, PSA, and NH gave good recoveries of 87.9%-109.0%. Other adsorbents, multiwalled carbon nanotubes (MWCNTs), hydroxylated multiwalled carbon nanotubes (OH-MWCNTs), carboxylated multiwalled carbon nanotubes (COOH-MWCNTs), octylsilane bonded silica (C), strong cation exchange (SCX) and neutral alumina (-AlO), led to recoveries below 56.2%. The combination of adsorbents was also considered. Seven different combinations of 50 mg C, 50 mg PSA, and 50 mg NH were chosen for the optimization experiments. There were no obvious differences in these combinations, and the target analytes recoveries ranged from 81.0% to 109.3% with relative standard deviations (RSDs) between 0.6% and 12.5%. The matrix effect could affect the extraction efficiency. The adsorbents of 50 mg C, 50 mg PSA, and 50 mg NH showed weaker matrix effects as compared with other combinations of adsorbents in the instrument. The results for the matrix effect showed that peanuts and asparagus exceeded 20%, requiring matrix-matched calibration curves. Under the optimized conditions, disulfoton and its metabolites showed good linearities (≥0.9981) in the range of 2.0-200.0 μg/L. The average spiked recoveries of disulfoton and its metabolites in peas, asparagus, wheat, peanuts, and coffee beans ranged from 75.0% to 110.0%, with RSDs of 0.7% to 14.9%. The limits of detection (LODs) were between 0.02 and 2.0 μg/kg, and the limits of quantification (LOQs) were 5.0 μg/kg. The method was applied for the detection of 80 commercial productions, and neither disulfoton nor its metabolites were found. The proposed method is rapid, accurate, highly selective, and sensitive, and it is suitable for the simultaneous determination of disulfoton and its metabolites in grain, oil crops, vegetables, and other matrices.
Topics: Chromatography, High Pressure Liquid; Disulfoton; Humans; Nanotubes, Carbon; Organophosphorus Compounds; Pesticides; Solid Phase Extraction; Tandem Mass Spectrometry
PubMed: 35080159
DOI: 10.3724/SP.J.1123.2021.04028 -
Environmental Health Perspectives Apr 2017Growing evidence suggests that pesticide use may contribute to respiratory symptoms.
BACKGROUND
Growing evidence suggests that pesticide use may contribute to respiratory symptoms.
OBJECTIVE
We evaluated the association of currently used pesticides with allergic and non-allergic wheeze among male farmers.
METHODS
Using the 2005-2010 interview data of the Agricultural Health Study, a prospective study of farmers in North Carolina and Iowa, we evaluated the association between allergic and non-allergic wheeze and self-reported use of 78 specific pesticides, reported by ≥ 1% of the 22,134 men interviewed. We used polytomous regression models adjusted for age, BMI, state, smoking, and current asthma, as well as for days applying pesticides and days driving diesel tractors. We defined allergic wheeze as reporting both wheeze and doctor-diagnosed hay fever ( = 1,310, 6%) and non-allergic wheeze as reporting wheeze but not hay fever ( = 3,939, 18%); men without wheeze were the referent.
RESULTS
In models evaluating current use of specific pesticides, 19 pesticides were significantly associated ( < 0.05) with allergic wheeze (18 positive, 1 negative) and 21 pesticides with non-allergic wheeze (19 positive, 2 negative); 11 pesticides were associated with both. Seven pesticides (herbicides: 2,4-D and simazine; insecticides: carbaryl, dimethoate, disulfoton, and zeta-cypermethrin; and fungicide pyraclostrobin) had significantly different associations for allergic and non-allergic wheeze. In exposure-response models with up to five exposure categories, we saw evidence of an exposure-response relationship for several pesticides including the commonly used herbicides 2,4-D and glyphosate, the insecticides permethrin and carbaryl, and the rodenticide warfarin.
CONCLUSIONS
These results for farmers implicate several pesticides that are commonly used in agricultural and residential settings with adverse respiratory effects.
Topics: Adult; Agricultural Workers' Diseases; Agriculture; Farmers; Humans; Iowa; Male; North Carolina; Occupational Exposure; Pesticides; Prospective Studies; Respiratory Sounds
PubMed: 27384423
DOI: 10.1289/EHP315 -
The Journal of Dairy Research May 2016This Research Communication reports analysis of 37 compounds comprising polycyclic aromatic hydrocarbons (PAHs), organochlorine and organophosphate pesticides (OCPS and...
This Research Communication reports analysis of 37 compounds comprising polycyclic aromatic hydrocarbons (PAHs), organochlorine and organophosphate pesticides (OCPS and OPPS) in milk powder (one brand each of commercial infant formulae, follow-on formulae and baby formulae purchased from a local supermarket in Romania). The selected analytes were investigated using gas chromatography-mass spectrometry (GC-MS), gas chromatography with electron capture detector (GC-ECD) and gas chromatography with thermionic sensitive detection (GC-TSD). The estimated limits of detection for most target analytes were in the μg/kg level (range 0·001-0·320 µg/kg). The purpose of the study was to determine the selected analytes, to assess the exposure of babies and infants and to produce data for comparison with tolerable limits according to the European Union Regulations. In most of the samples the organochlorine pesticides values were under the limit of detection. Exceptions were heptachlor epoxide and endosulfan sulphate, the last of which was found in all analysed samples at low concentrations. We also found detectable levels of ethoprophos, parathion-methyl, chlorpyrifos, prothiofos, guthion, disulfoton and fenchlorphos in most of the analysed samples. Benzo[a]pyrene, which is used as an indicator for the presence of PAHs, was not detected in selected samples. The low level of exposure to contaminants indicates that there are no health risks for the infants and babies that consume this brand of milk powder formulae.
Topics: Animals; Food Contamination; Food, Preserved; Gas Chromatography-Mass Spectrometry; Humans; Hydrocarbons, Chlorinated; Infant; Infant Formula; Infant, Newborn; Maximum Allowable Concentration; Milk; Organophosphates; Pesticides; Polycyclic Aromatic Hydrocarbons; Romania
PubMed: 27210498
DOI: 10.1017/S0022029916000169 -
Food Chemistry Aug 2017The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio)...
The dissipation/degradation of the pesticides dimethoate, terbufos, disulfoton, and pirimiphos-methyl were evaluated in milled toasted maize and wheat flour (gofio) during three months of storage. Their dissipation kinetics and residual levels were determined, as well as their possible decomposition into some of their main transformation products (disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone). For this purpose, pesticide-free milled toasted maize and wheat samples were spiked with the pesticides, and they were then stored in the darkness at ambient temperature in a closed container to simulate current storage conditions of such packed food. A multiresidue analysis based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was performed for the simultaneous determination of these pesticides and their metabolites. After three months of storage, the dissipation of residues ranged between 34% (pirimiphos-methyl) and 86% (disulfoton) for maize gofio and between 69% (terbufos) and 92% (disulfoton and pirimiphos-methyl) for wheat gofio. The results demonstrated that the degradation was slower in gofio than in wheat gofio and that none of the selected metabolites were detected in any of the samples. Dissipation curves of all studied pesticides fitted to a first-order decay curve in both types of cereals.
Topics: Chromatography, Gas; Edible Grain; Flour; Food Storage; Kinetics; Organophosphorus Compounds; Pesticide Residues; Pesticides; Triticum; Zea mays
PubMed: 28372254
DOI: 10.1016/j.foodchem.2017.02.148 -
Analytica Chimica Acta Mar 2020Magnetic restricted-access carbon nanotubes (M-RACNTs) were synthesised and used for dispersive solid phase extraction of organophosphates (chlorpyriphos, malathion,...
Magnetic restricted-access carbon nanotubes (M-RACNTs) were synthesised and used for dispersive solid phase extraction of organophosphates (chlorpyriphos, malathion, disulfoton, pirimiphos) from commercial bovine raw milk samples. Due to their magnetic susceptibility, M-RACNTs were easily separated from the samples/solvents using a neodymium magnet, and the extracted organophosphates were analysed by gas chromatography-mass spectrometry. The protein exclusion capacity was about 100%. Kinetic and isotherm data (for M-RACNTs - malathion interaction) were adequately adjusted to the pseudo-second order and Sips models, respectively, and the maximum adsorption capacity was about 0.55 mg g. The method presented linear ranges from 5.0 to 40.0 μg L for all analytes, with determination coefficients from 0.9902 to 0.9963. The intra-assay precisions (as relative standard deviation) and accuracies (as relative error) ranged from 10.47 to 19.85% and from -0.18 to -18.80%, respectively, whereas the inter-assay precisions ranged from 6.48 to 18.76% and from -0.22 to 19.49%, respectively for 5.0, 20.0 and 40.0 μg L organophosphates levels. The organophosphates were not stable at 4 and 24 h (relative errors ranged from -39.30 to 72.07% and -69.64 to 75.95%, respectively). Limits of detection ranged from 0.36 to 0.95 μg L, and 5 μg L was defined as the limit of quantification for all the analytes. The proposed method was applied in the determination of organophosphates in five commercial milk samples, and no pesticides were detected.
Topics: Adsorption; Animals; Food Contamination; Gas Chromatography-Mass Spectrometry; Limit of Detection; Magnetic Phenomena; Milk; Nanotubes, Carbon; Organophosphates; Pesticides; Reproducibility of Results; Solid Phase Extraction
PubMed: 32043990
DOI: 10.1016/j.aca.2019.12.039 -
Ecotoxicology and Environmental Safety Jul 2018The use of multiple biomarkers has been shown to be an efficient method for evaluating environmental contamination. In this work, we evaluate neurotoxic effects and the...
The use of multiple biomarkers has been shown to be an efficient method for evaluating environmental contamination. In this work, we evaluate neurotoxic effects and the antioxidant system responses of the R. branneri collected in two streams of lower Iguazu River basin, relating them with different percentage of vegetation coverture, presence of pesticides and fall and winter seasons. The biological samples were collected in March and August of 2015, from two streams that belong to the lower Iguazu River basin (Brazil): the Manoel Gomes River and the Arquimedes Stream. Soil analyses were performed, and the results showed the presence of the following organophosphates in the Manoel Gomes River and the Arquimedes Stream: disulfoton, methyl parathion, and ronnel. The present study detected inhibition of cholinesterase activity in the brain and muscle of fish samples during the fall from the Manoel Gomes River and the Arquimedes Stream. In the Manoel Gomes River, elevated lipoperoxidation was also observed during the fall. It was observed that the increase or decrease of biomarkers was related to temporal variation and, possibly, to the exposure of animals to agrochemicals. Although the Manoel Gomes River and the Arquimedes Stream are located in regions with large areas of vegetation, the soil analyses show that agrochemical residues are able to reach these locations, which suggests that the fauna are in contact with oxidant and anti-cholinesterase agents during the fall, in addition to respond differently during each season.
Topics: Animals; Biomarkers; Brain; Brazil; Catfishes; Cholinesterase Inhibitors; Cholinesterases; Environmental Monitoring; Muscles; Organophosphates; Pesticides; Rivers; Seasons; Water Pollutants, Chemical
PubMed: 29522881
DOI: 10.1016/j.ecoenv.2018.02.063 -
PloS One 2019Senescence Marker Protein (SMP30) is a metalloenzyme that shows lactonase activity in the ascorbic acid (AA) biosynthesis pathway in non-primate mammals such as a mouse....
Senescence Marker Protein (SMP30) is a metalloenzyme that shows lactonase activity in the ascorbic acid (AA) biosynthesis pathway in non-primate mammals such as a mouse. However, AA biosynthesis does not occur in the primates including humans. Several studies have shown the role of SMP30 in maintaining calcium homeostasis in mammals. In addition, it is also reported to have promiscuous enzyme activity with an organophosphate (OP) substrate. Hence, this study aims to recombinantly express and purify the SMP30 proteins from both mouse and human, and to study their structural alterations and functional deviations in the presence of different divalent metals. For this, mouse SMP30 (MoSMP30) as well as human SMP30 (HuSMP30) were cloned in the bacterial expression vector. Proteins were overexpressed and purified from soluble fractions as well as from inclusion bodies as these proteins were expressed largely in insoluble fractions. The purified proteins were used to study the folding conformations in the presence of different divalent cations (Ca2+, Co2+, Mg2+, and Zn2+) with the help of circular dichroism (CD) spectroscopy. It was observed that both MoSMP30 and HuSMP30 acquired native folding conformations. To study the metal-binding affinity, dissociation constant (Kd values) were calculated from UV-VIS titration curve, which showed the highest affinity of MoSMP30 with Zn2+. However, HuSMP30 showed the highest affinity with Ca2+, suggesting the importance of HuSMP30 in maintaining calcium homeostasis. Enzyme kinetics were performed with γ-Thiobutyrolactone and Demeton-S in the presence of different divalent cations. Interestingly, both the proteins showed lactonase activity in the presence of Ca2+. In addition, MoSMP30 and HuSMP30 also showed lactonase activity in the presence of Co2+ and Zn2+ respectively. Moreover, both the proteins showed OP hydrolase activities in the presence of Ca2+ as well as Zn2+, suggesting the metal-dependent promiscuous nature of SMP30.
Topics: 4-Butyrolactone; Animals; Binding Sites; Calcium-Binding Proteins; Cations, Divalent; Disulfoton; Humans; Intracellular Signaling Peptides and Proteins; Kinetics; Mice; Mice, Inbred BALB C; Molecular Dynamics Simulation; Protein Binding; Sequence Homology, Amino Acid
PubMed: 31220150
DOI: 10.1371/journal.pone.0218629 -
Environmental Science and Pollution... Dec 2023Pesticide deposits post-treatment and before diffusing inside the plants are exposed to sunlight. Many of them degrade into a variety of photoproducts that may be...
Pesticide deposits post-treatment and before diffusing inside the plants are exposed to sunlight. Many of them degrade into a variety of photoproducts that may be harmful to living beings through accidental ingestion. The addition of ultraviolet light absorbers to the pesticide formulations is an attractive strategy to prevent photodegradation of the pesticides. Water-soluble quaternary ammonium ultraviolet light absorbers (QAUVAs) were synthesized from 2,4-dihydroxy benzophenones (BP-1) and their structures were confirmed by H NMR, C NMR, UV, and FTIR. A cost-saving approach for the photoprotection of disulfoton insecticide using these QAUVAs is presented. All the four QAUVAs exhibit excellent UV screening effect. The insecticide disulfoton was recovered in much higher amounts (22.27 ~ 25.64% higher than control) when it was irradiated in the presence of QAUVAs in comparison with the amount of recovery of pesticide exposed in absence of them.
Topics: Photolysis; Disulfoton; Insecticides; Ultraviolet Rays; Pesticides; Benzophenones
PubMed: 35687284
DOI: 10.1007/s11356-022-21247-1