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Journal of Mass Spectrometry : JMS Feb 2020Detection of pesticide residues in food samples is important for safeguarding food quality and safety. Conventional approaches for detection of pesticides in food...
Detection of pesticide residues in food samples is important for safeguarding food quality and safety. Conventional approaches for detection of pesticides in food samples typically involve labour-intensive and time-consuming sample pretreatment and chromatographic separation. In this study, solid phase micro-extraction fibres were used to rapidly extract and enrich pesticides in honey, a popular agricultural product with complex matrix, and then directly coupled with electrospray ionization mass spectrometry for qualitative and quantitative analysis. Three pesticides, ie, atrazine, benalaxyl, and pirimicarb, were investigated using the technique and their analytical performances were evaluated. The limits of detection and limits of quantitation of all the three pesticides could fulfil the cut-off values of the international standard. Linear calibration curves were constructed with good R coefficients, and the accuracy and precision were in acceptable ranges for all the pesticides. The analysis time is much reduced, with only minimum sample preparation and no chromatographic separation involved. The technique is simple and easy to set up, and can be extended for analysis of other analytes and sample systems.
Topics: Honey; Limit of Detection; Linear Models; Pesticide Residues; Reproducibility of Results; Solid Phase Microextraction; Spectrometry, Mass, Electrospray Ionization
PubMed: 31183930
DOI: 10.1002/jms.4380 -
The Science of the Total Environment Jun 2021The presence of carcinogenic N-nitrosamines and dissolved organic matter (DOM) in freshwater is a significant concern from the perspective of public health and drinking...
The presence of carcinogenic N-nitrosamines and dissolved organic matter (DOM) in freshwater is a significant concern from the perspective of public health and drinking water treatment plant operation. This study investigated the N-nitrosamines concentration and their precursors' distributions, and DOM composition in four reservoirs located in a southern city of China. A total of 22 renowned precursors were identified. Precursors from industrial and pharmaceutical origins were found to be dominant in all reservoirs; however, traces of pesticide-based precursors, i.e. pirimicarb and cycluron were also found. The distribution of nine N-nitrosamines was substantially different among the reservoirs. N-Nitrosodibutylamine (NDBA), N-Nitrosopiperidine (NPIP), N-Nitrosodimethylamine (NDMA), and N-Nitrosopyrrolidine (NPYR) were abundantly present in all reservoirs. Most of N-nitrosamines except NDMA and N-nitrosodiethylamine (NDEA) were far below the generally accepted cancer risk of 10, and NDMA/NDEA were found close to the risk level (10). Anthropogenic DOM was dominant in three reservoirs as depicted by a higher biological index (BIX) than the humification index (HIX). By the principle component analysis, BIX appeared as an indicator of N-nitrosamines (except NDEA and NPIP). A strong and direct relationship was observed between the NDMA-formation potential (FP) and concentration of total N-nitrosamines (∑NA), and BIX. These results confirmed that the anthropogenic activities were the leading source of DOM and N-nitrosamines in this city based on land-use.
PubMed: 33548708
DOI: 10.1016/j.scitotenv.2021.145409 -
Environmental Toxicology Apr 2024We performed multigenerational tests to clarify the chemical tolerance mechanisms of a nontarget aquatic organism, Daphnia magna. We continuously exposed D. magna to a...
We performed multigenerational tests to clarify the chemical tolerance mechanisms of a nontarget aquatic organism, Daphnia magna. We continuously exposed D. magna to a carbamate insecticide (pirimicarb) at lethal or sublethal concentrations (0, 3.8, 7.5, and 15 μg/L) for 15 generations (F0-F14). We then determined the 48 h-EC values and mRNA expression levels of acetylcholinesterase, glutathione S-transferase, and ATP (Adenosine triphosphate)-binding cassette transporter (ABCt) in neonates (<24 h old) from F0, F4, F9, and F14. To ascertain the effects of DNA methylation on pirimicarb sensitivity, we measured 5-methylcytosine levels (DNA methylation levels) in neonates of parents in the last generation (F14). In addition, we cultured groups exposed to 0 and 7.5 μg/L (the latter of which acquired chemical tolerance to pirimicarb) with or without 5-azacytidine (de-methylating agent) and determined methylation levels and 48 h-EC values in neonates (<24 h old) from the treated parents. The EC values (30.3-31.6 μg/L) in F14 of the 7.5 and 15 μg/L groups were approximately two times higher than that in the control (16.0 μg/L). A linear mixed model analysis showed that EC and ABCt mRNA levels were significantly increased with generational alterations; further analysis showed that the ABCt mRNA level was positively related to the EC . Therefore, ABCt may be associated with altered pirimicarb sensitivity. In addition, the EC value and DNA methylation levels in pirimicarb-tolerant clones decreased after exposure to 5-azacytidine, suggesting that DNA methylation contributes to chemical tolerance. These findings improved our knowledge regarding the acquisition of chemical tolerance in aquatic organisms.
Topics: Animals; Cladocera; Daphnia magna; Daphnia; Acetylcholinesterase; DNA Methylation; ATP-Binding Cassette Transporters; Water Pollutants, Chemical; Aquatic Organisms; Azacitidine; RNA, Messenger; Carbamates; Pyrimidines
PubMed: 38073494
DOI: 10.1002/tox.24077 -
Insects Sep 2023The invasive apricot aphid ( Matsumura) is an important pest of apricot trees ( L.). In the presented study, laboratory bioassays using treated leaf disks of apricot...
The invasive apricot aphid ( Matsumura) is an important pest of apricot trees ( L.). In the presented study, laboratory bioassays using treated leaf disks of apricot were conducted to test the efficacy of twelve insecticides according to the maximum field dose. Additionally, dose-response curves were established for selected insecticides, and the effects on colony development were evaluated. Furthermore, a field trial was conducted to investigate the effectiveness of commonly used insecticides in apricot cultivation. The dose-response curves showed LC values ranging from 0.08 mg/L for flupyradifurone, 0.15 mg/L for acetamiprid, 0.70 mg/L for etofenprox, 1.89 mg/L for sulfoxaflor, 2.64 mg/L for pirimicarb, 3.97 mg/L for deltamethrin, up to 6.79 mg/L for tau-fluvalinate. These aforementioned insecticides resulted in mortality rates ranging from 95 to 100% at the field dose. Azadirachtin, flonicamid, and pyrethrins showed mortality rates of 27 to 45%. Spirotetramat reduced the colony development and decreased the number of infested shoots by 86%. Spinosad, which is not recommended against aphids, showed minimal impact; reducing the number of exuviae in nymphs in the colony development bioassay. It can be concluded that the majority of the tested insecticides are effective against .
PubMed: 37754715
DOI: 10.3390/insects14090746 -
Journal of Chromatography. B,... Jun 2023Carbamate pesticides are extensively used in agriculture for their inhibition to acetylcholinesterase and damages to the insects' neural systems. Because of their...
A retrospective screening method for carbamate toxicant exposure based on butyrylcholinesterase adducts in human plasma with ultra-high performance liquid chromatography-tandem mass spectrometry.
Carbamate pesticides are extensively used in agriculture for their inhibition to acetylcholinesterase and damages to the insects' neural systems. Because of their toxicity, human poisoning incidents caused by carbamate pesticide exposure have occurred from time to time. What's more, some lethally toxic carbamate toxicants known as carbamate nerve agents (CMNAs) have been supplemented in Schedule 1 of the Annex on Chemicals in the Chemical Weapons Convention (CWC) by Organisation of the Prohibition of Chemical Weapons (OPCW) from 2020. And some other carbamates, like physostigmine, have been used in clinical treatment as anticholinergic drugs and their misuse may also cause damages to the body. Similar to organophosphorus toxicants, carbamate toxicants would react with butyrylcholinesterase (BChE) in plasma when entering the human body, resulting in the BChE adducts, based on which the exposure of carbamate toxicants could be detected retrospectively. In this study, methylcarbamyl nonapeptide and dimethylcarbamyl nonapeptide from pepsin digestion of BChE adducts were identified with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) in product ion scan mode. Carbofuran was chosen as the target to establish the detection method of carbamate toxicant exposure based on methylcarbamyl nonapeptide digested from methylcarbamyl BChE. Procainamide-gel affinity purification, pepsin digestion and UHPLC-MS/MS analysis in multiple reaction monitoring (MRM) mode were applied. Under the optimized conditions of sample preparation and UHPLC-MS/MS MRM analysis, the limits of detection (LODs) reached 10.0 ng/mL of plasma exposed to carbofuran with satisfactory specificity. The quantitation approach was established with d-carbofuran-exposed plasma as the internal standard (IS) and the linearity range was 30.0-1.00 × 10 nmol/L (R >0.998) with the accuracy of 95.6%-107% and precision of ≤9% relative standard deviation (RSD). The applicability was also evaluated by N,N-dimethyl-carbamates with the LODs of 30.0 nmol/L for pirimicarb-exposed plasma based on dimethylcarbamyl nonapeptide. Because most of carbamate toxicants has methylcarbamyl or dimethylcarbamyl groups, this approach could be applied on the retrospective screening of carbamate toxicant exposure including CMNAs, carbamate pesticides or carbamate drugs. This study could provide an effective means in the fields of CWC verification, toxicological mechanism investigation and down-selection of potential treatment options.
Topics: Humans; Butyrylcholinesterase; Chromatography, High Pressure Liquid; Tandem Mass Spectrometry; Retrospective Studies; Carbofuran; Acetylcholinesterase; Pepsin A; Nerve Agents; Pesticides
PubMed: 37285767
DOI: 10.1016/j.jchromb.2023.123775 -
Nanomaterials (Basel, Switzerland) Aug 2022A three-steps sol-gel method was used to obtain a CuO/SnO/WO heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final...
A three-steps sol-gel method was used to obtain a CuO/SnO/WO heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final heterostructure was constructed starting with fiber-like WO acting as substrate for SnO development. The SnO/WO sample provide nucleation and grew sites for CuO formation. Diffraction evaluation indicated that all samples contained crystalline structures with crystallite size varying from 42.4 Å (CuO) to 81.8 Å (WO). Elemental analysis confirmed that the samples were homogeneous in composition and had an oxygen excess due to the annealing treatments. Photocatalytic properties were tested in the presence of three pesticides-pirimicarb, S-metolachlor (S-MCh), and metalaxyl (MET)-chosen based on their resilience and toxicity. The photocatalytic activity of the CuO/SnO/WO heterostructure was compared with WO, SnO, CuO, CuO/SnO, CuO/WO, and SnO/WO samples. The results indicated that the three-component heterostructure had the highest photocatalytic efficiency toward all pesticides. The highest photocatalytic efficiency was obtained toward S-MCh (86%) using a CuO/SnO/WO sample and the lowest correspond to MET (8.2%) removal using a CuO monocomponent sample. TOC analysis indicated that not all the removal efficiency could be attributed to mineralization, and by-product formation is possible. CuO/SnO/WO is able to induce 81.3% mineralization of S-MCh, while CuO exhibited 5.7% mineralization of S-MCh. The three-run cyclic tests showed that CuO/SnO/WO, WO, and SnO/WO exhibited good photocatalytic stability without requiring additional procedures. The photocatalytic mechanism corresponds to a Z-scheme charge transfer based on a three-component structure, where CuO exhibits reduction potential responsible for O production and WO has oxidation potential responsible for HO· generation.
PubMed: 35957078
DOI: 10.3390/nano12152648 -
Talanta May 2022Research of detection of low molecular weight compounds on human health and biological systems become increasingly important. Matrix-assisted laser desorption/ionization...
Research of detection of low molecular weight compounds on human health and biological systems become increasingly important. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), a soft ionization equipment, is a rapid, reliable, high-sensitivity, high-throughput and simple test instrument. However, the application of MALDI-TOF MS in the analysis of small molecules (<500 Da) has become a great challenge because of the interference from the conventional matrices in low mass region when using conventional matrices. In this research, tricobalt tetraoxide (CoO) nanocrystals with rich surface hydroxyl groups were synthesized and served as novel matrices for the detection of small molecules by MALDI-TOF MS. In comparison with conventional organic matrices, the use of as-prepared CoO nanocrystal matrices showed little matrix background interference, good reproducibility and high signal intensity in the analyses of amino acids, harmful additives and pesticide residues. For the detection of most amino acids, CoO nanocrystal matrices have good detection performance both in the positive and negative ion modes and have a unique decarboxylation peak in the positive ion mode, which is conducive to the identification of amino acids. In addition, CoO nanocrystals are completely feasible to test triadimefon, pirimicarb and other pesticide residues, as well as additives such as bisphenol A and melamine in the positive ion mode. It is also feasible to detect small molecule compounds in practical samples using CoO nanocrystals as matrices. We believe the work provides an alternative approach for the detection of small molecules and expands the application scope of CoO nanocrystals.
Topics: Amino Acids; Cobalt; Humans; Nanoparticles; Oxides; Pesticide Residues; Reproducibility of Results; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
PubMed: 35183982
DOI: 10.1016/j.talanta.2022.123299 -
Pest Management Science May 2024Failures in controlling Myzus persicae by pyrethroids and carbamates have been observed in Czechia since 2018. Eleven populations collected from Czech oilseed rape...
BACKGROUND
Failures in controlling Myzus persicae by pyrethroids and carbamates have been observed in Czechia since 2018. Eleven populations collected from Czech oilseed rape fields during 2018-2021 were tested for susceptibility to 11 insecticides. The presence of a single nucleotide polymorphism (SNP) leading to knockdown resistance in M. persicae populations was screened using allelic discriminating quantitative real-time polymerase chain reaction (qPCR). The presence of mutations related with the resistance of M. persicae to pyrethroids and carbamates was detected by sequencing paratype voltage-gated sodium channel and acetylcholinesterase 2 genes, respectively.
RESULTS
Resistance to alpha-cypermethrin and pirimicarb was detected in most of the tested populations. The L1014F mutation was detected in 44.5% of M. persicae individuals surviving the field-recommended dose of alpha-cypermethrin. Sequencing of partial para gene for paratype voltage-gated sodium channel detected five different SNPs leading to four amino acid substitutions (kdr L1014F; s-kdr M918L; s-kdr M918T; and L932F). No pyrethroid-sensitive genotype was detected. The S431F amino acid substitution conferring resistance to carbamates was detected in 11 of 20 individuals with different pyrethroid-resistance genotypes.
CONCLUSION
Resistance of M. persicae to both pyrethroids and carbamates was detected in nine of 11 populations. High resistance of M. persicae was correlated with mutations of the sodium channel. Sulfoxaflor, flonicamid, and spirotetramat are proposed as effective compounds to control pyrethroid- and carbamate-resistant populations of M. persicae. © 2023 Society of Chemical Industry.
Topics: Animals; Humans; Aphids; Acetylcholinesterase; Czech Republic; Pyrethrins; Insecticides; Mutation; Carbamates; Voltage-Gated Sodium Channels; Brassica napus; Insecticide Resistance
PubMed: 37402271
DOI: 10.1002/ps.7646 -
Chemosphere Oct 2022Pirimicarb as a pesticide is used to control the aphids in the agriculture field; however, it affects the groundwater ecosystem by leaching through the soil profile. The...
Pirimicarb as a pesticide is used to control the aphids in the agriculture field; however, it affects the groundwater ecosystem by leaching through the soil profile. The post-synthetic amine and BWO modified MIL-100 (Fe) nanofillers were synthesized. The photocatalytic property of amine-functionalized and BWO@MIL-100(Fe) nanofillers was confirmed by the lesser bandgap energy than the unmodified MIL-100 (Fe) nanofiller. Herein, we constructed a nanofillers grafted PVDF membrane via in-situ polymerization technique for the pirimicarb reduction and photodegradation. Furthermore, the nanofiller's grafted membranes were characterized by FESEM, XRD, FTIR, and contact angle analysis. The carboxylic acid peak was observed on the FTIR which demonstrated the PAA grafted on the membrane surface and similar crystalline peaks evident that the nanofillers were grafted on the membrane surface. Furthermore, surface morphology studies have exhibited the dispersion of nanofillers and enhanced microvoids in the cross-section of the membrane. The decrease in the water contact angle of the membrane depicted the improved antifouling properties and surface energy. The nanofiller's grafted membranes have shown higher hydrophilicity correlated well with the enhanced pure water flux in the order M4 > M5 > M2 > M3 > M6 > M7 compared to the neat membrane (M1). In BWO@MIL-100(Fe) membrane has shown a higher permeate flux (25.99 L m.h) than the neat PVDF membrane. The BWO@MIL-100(Fe) grafted PVDF membrane has also shown excellent pirimicarb photodegradation of 81% at pH 5. The proposed MIL-100 (Fe) and bismuth tungsten nanocomposite will pave the way for the different MOF-based photocatalytic materials for membrane-based pesticide degradation.
Topics: Amines; Bismuth; Ecosystem; Fluorocarbon Polymers; Pesticides; Photolysis; Polymerization; Polyvinyls; Tungsten Compounds; Water
PubMed: 35690168
DOI: 10.1016/j.chemosphere.2022.135286 -
Archives of Toxicology Dec 2020In chemical risk assessment, default uncertainty factors are used to account for interspecies and interindividual differences, and differences in toxicokinetics and... (Comparative Study)
Comparative Study
Acetylcholinesterase inhibition in electric eel and human donor blood: an in vitro approach to investigate interspecies differences and human variability in toxicodynamics.
In chemical risk assessment, default uncertainty factors are used to account for interspecies and interindividual differences, and differences in toxicokinetics and toxicodynamics herein. However, these default factors come with little scientific support. Therefore, our aim was to develop an in vitro method, using acetylcholinesterase (AChE) inhibition as a proof of principle, to assess both interspecies and interindividual differences in toxicodynamics. Electric eel enzyme and human blood of 20 different donors (12 men/8 women) were exposed to eight different compounds (chlorpyrifos, chlorpyrifos-oxon, phosmet, phosmet-oxon, diazinon, diazinon-oxon, pirimicarb, rivastigmine) and inhibition of AChE was measured using the Ellman method. The organophosphate parent compounds, chlorpyrifos, phosmet and diazinon, did not show inhibition of AChE. All other compounds showed concentration-dependent inhibition of AChE, with ICs in human blood ranging from 0.2-29 µM and ICs ranging from 0.1-18 µM, indicating that AChE is inhibited at concentrations relevant to the in vivo human situation. The oxon analogues were more potent inhibitors of electric eel AChE compared to human AChE. The opposite was true for carbamates, pointing towards interspecies differences for AChE inhibition. Human interindividual variability was low and ranged from 5-25%, depending on the concentration. This study provides a reliable in vitro method for assessing human variability in AChE toxicodynamics. The data suggest that the default uncertainty factor of ~ 3.16 may overestimate human variability for this toxicity endpoint, implying that specific toxicodynamic-related adjustment factors can support quantitative in vitro to in vivo extrapolations that link kinetic and dynamic data to improve chemical risk assessment.
Topics: Acetylcholinesterase; Animals; Bayes Theorem; Biological Variation, Population; Cholinesterase Inhibitors; Dose-Response Relationship, Drug; Electrophorus; Female; GPI-Linked Proteins; Humans; Male; Proof of Concept Study; Reproducibility of Results; Risk Assessment; Species Specificity; Toxicity Tests; Toxicokinetics; Uncertainty
PubMed: 33037899
DOI: 10.1007/s00204-020-02927-8