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The Science of the Total Environment Mar 2020Data obtained from samples of poisoned domestic and wild animals sent for toxicological evaluation during the period between 2005 and 2014 have been analyzed. Among the...
Data obtained from samples of poisoned domestic and wild animals sent for toxicological evaluation during the period between 2005 and 2014 have been analyzed. Among the 4606 tested samples, the majority of which were collected in the northern regions of Italy, 2006 (43.55%) were found positive for pesticides. Analytical detections were performed via solvent extraction followed by separation and chromatographic characterization and all the methods applied for the toxicological investigations were developed by IZSLER. Insecticides, mainly represented by acetylcholinesterase inhibitors (carbamates 17.55%, n = 352; organophosphates 15.15%, n = 304) and organochlorines (29.21%, n = 586), were found to be the first category of pesticides involved in intoxications, in both domestic and in wild animals, followed by rodenticides (anticoagulant rodenticides 21.09%, n = 423; zinc phosphide 2.59%, n = 52; chloralose 0.95%, n = 19 and thallium 0.15%, n = 3) and molluscicides (metaldehyde 6.63%, n = 133). Second and third generation anticoagulants (bromadiolone and brodifacoum) were the most represented (10.52%, n = 211) but also first generation compounds (i.e. coumatetralyl and warfarin) were still found responsible of intoxications. Even if some pesticides are frequently involved in domestic animal poisoning (i.e. metaldehyde and strychnine), they did not show the same diffusion in wild animals. In particular, unlike domestic species, cyanide and pyrethroids have not been found responsible of intoxications in wild animals. Interestingly, a great number of positive samples involved banned pesticides like α- (14.41%, n = 289) and β- (14.16%, n = 284) endosulfan, carbofuran (5.73%, n = 115), methamidophos (9.47%, n = 190), strychnine (6.23%, n = 125) but, on the other hand, many positives were due to the exposure to commercially available products (i.e. metaldehyde and anticoagulant rodenticides). Thus, together with measures aimed to reduce illegal uses, educational campaigns and a wider range of compounds to detect would be beneficial in order to address the issue of animal poisoning, which besides has also repercussions on environmental and public health.
Topics: Animals; Animals, Domestic; Animals, Wild; Anticoagulants; Italy; Pesticides; Poisoning; Rodenticides
PubMed: 31869614
DOI: 10.1016/j.scitotenv.2019.136129 -
Chemosphere Dec 2020Triazophos (TAP), methamidophos (MAP) and carbofuran (CF) pesticides are highly toxic, soluble and absorbable. Efficient co-degradation of multi-pesticides is rare...
Simultaneous degradation of triazophos, methamidophos and carbofuran pesticides in wastewater using an Enterobacter bacterial bioreactor and analysis of toxicity and biosafety.
Triazophos (TAP), methamidophos (MAP) and carbofuran (CF) pesticides are highly toxic, soluble and absorbable. Efficient co-degradation of multi-pesticides is rare reported. The objectives of this study were to investigate TAP, MAP and CF co-degradative ability of Enterobacter sp. Z1 and study the degradation mechanisms. Strain Z1 was shown to efficiently co-degrade TAP, MAP and CF when they were used as primary carbon sources. The degradation occurred over a wide range of temperatures, pH values and pesticide concentrations and followed first-order kinetics. Under the optimum conditions (37 °C, pH 7 and 100 mg/L of each pesticide), the degradation efficiencies were 100%, 100%, and 95.3% for TAP, MAP and CF, respectively. In addition, strain Z1 could simultaneously degrade TAP, MAP, CF and total nitrogen in wastewater in a batch bioreactor, with high removal efficiencies of 98.3%, 100%, 98.7% and 100%, respectively. Genomics, proteomics, qRT-PCR and gene overexpression analyses revealed that the degradation mechanisms involved the activities of multiple proteins, among which, organophosphorus hydrolase (Oph) and 3-hydroxyacyl-CoA dehydrogenase (PaaC) are primarily responsible for TAP and MAP degradation, while carbofuran hydrolase (Mcd) and amidohydrolase (RamA) primarily degrade CF. Among these enzymes, PaaC and RamA are newly identified pesticide-degrading enzymes. Toxicity assays of strain Z1 using reporter recombinase gene (recA) and zebrafish showed that there was no accumulation of toxic metabolites during the degradation process. Biosafety test using zebrafish showed that the strain was nontoxic toward zebrafish. Strain Z1 provides a good purification effect for pesticides-containing wastewater and novel microbial pesticide-degrading mechanisms were discovered.
Topics: Biodegradation, Environmental; Bioreactors; Carbofuran; Containment of Biohazards; Enterobacter; Hydrolases; Organothiophosphates; Organothiophosphorus Compounds; Pesticides; Triazoles; Wastewater; Water Pollutants, Chemical; Water Purification
PubMed: 33113645
DOI: 10.1016/j.chemosphere.2020.128054 -
RSC Advances Apr 2022A colloidal silver nanoparticle (AgNP)-based lateral flow immunoassay (LFIA) was evaluated in terms of the rapid detection of profenofos (PEO) pesticide residue in...
A colloidal silver nanoparticle (AgNP)-based lateral flow immunoassay (LFIA) was evaluated in terms of the rapid detection of profenofos (PEO) pesticide residue in vegetables. Colloidal AgNPs, of a diameter of approximately 20 nm, were surface-modified with trisodium citrate dehydrate (TSC) in order to improve their stability and dispersion. An anti-profenofos polyclonal antibody (pAb) was successfully immobilized on the surface of the AgNPs by ionic interaction and characterized using UV-vis, SEM, TEM, FTIR and XPS analyses. Surface modification of Ag-pAb conjugates of varying pH, pAb content and cross-reactivity was employed to design and prepare labels for use in an LFIA to examine whether these factors affect the performance of the assay. The visible detection limit and optical detection limit of the PEO test strip were 0.20 and 0.01 ppm, respectively, in PEO standard solution. This assay showed no cross-reaction with omethoate, methamidophos or pyraclofos. Finally, the PEO test strip was effectively applied for the detection of PEO in liquid vegetables A and B, with optical detection limits of 0.09 and 0.075 ppm, respectively.
PubMed: 35497005
DOI: 10.1039/d2ra01654k -
Industrial Health Feb 2020This study explored the potential association between chronic exposure to pesticide mixtures including paraquat and respiratory outcomes among Colombian farmers....
This study explored the potential association between chronic exposure to pesticide mixtures including paraquat and respiratory outcomes among Colombian farmers. Sociodemographic and occupational data, respiratory symptoms and spirometric data were collected. Paraquat in spot urine samples were quantified with solid-phase extraction high-performance liquid chromatography. Multiple Poisson regressions with robust variance were used to determine factors associated with respiratory outcomes. Profiles of pesticide mixtures used were identified among 217 farmworkers, but profenofos and methamidophos-based mixtures were more frequent. Chronic paraquat exposure was slightly associated with self-reported asthma (PR: 1.06; 95% CI 1.00 to 1.13). Different pesticide mixtures were associated with flu, thoracic pain, allergic rhinitis, and obstructive pattern in spirometry. Although acute exposure to paraquat is low among Colombian farmers participating in the study, associations between respiratory outcomes and chronic pesticide mixtures exposure including profenofos, methamidophos or glyphosate require further specific studies.
Topics: Adolescent; Adult; Aged; Chest Pain; Colombia; Farmers; Female; Humans; Male; Middle Aged; Occupational Exposure; Organothiophosphates; Organothiophosphorus Compounds; Paraquat; Pesticides; Respiratory Tract Diseases; Rhinitis, Allergic; Spirometry
PubMed: 30996154
DOI: 10.2486/indhealth.2018-0111 -
Food Chemistry Aug 2021Based on the successful synthesis of mercaptomethamidophos as a substrate, a novel nanogold/mercaptomethamidophos multi-residue electrochemical biosensor was designed...
Based on the successful synthesis of mercaptomethamidophos as a substrate, a novel nanogold/mercaptomethamidophos multi-residue electrochemical biosensor was designed and fabricated by combining nanoscale effect, strong Au-S bonds as well as interaction between acetylcholinesterase (AChE) and mercaptomethamidophos, which can simultaneously detect 11 kinds of organophosphorus pesticides (OPPs) and total amount of OPPs using indirect competitive method. Electrochemical behavior of the modified electrode was characterized by differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The AChE concentration and incubation time were optimized at 37.4 °C to achieve the best detection effect. This biosensor exhibits excellent electrochemical properties with a wider linear range of 0.1 ~ 1500 ng·mL, lower detection limit of 0.019 ~ 0.077 ng·mL, better stability and repeatability, which realizes the rapid detection of total amount of OPPs, and can simultaneously detect a large class of OPPs rather than one kind of OPP. Two OPPs (trichlorfon, dichlorvos) were detected in actual samples of apple and cabbage and achieved satisfactory test results.
Topics: Acetylcholinesterase; Biosensing Techniques; Brassica; Dielectric Spectroscopy; Electrodes; Enzymes, Immobilized; Gold; Limit of Detection; Metal Nanoparticles; Organophosphorus Compounds; Organothiophosphorus Compounds; Pesticides
PubMed: 33735695
DOI: 10.1016/j.foodchem.2021.129511 -
Reproductive Biology Sep 2020Methamidophos (MET) is a pesticide that has toxic properties, including effects on fertility. This study aimed to assess the joint action of treatment time and exposure...
Methamidophos (MET) is a pesticide that has toxic properties, including effects on fertility. This study aimed to assess the joint action of treatment time and exposure to methamidophos on the male reproductive system. MET was orally administered to adult male Swiss mice at a dose of 0.004 mg.kg for 15 and 50 consecutive days. The following parameters were evaluated: weight of reproductive organs, spermatogenesis, sperm and Sertoli cell count, daily sperm production and sperm transit time. Short-term exposure to methamidophos induced a decrease in epididymal weight. The frequency of stages V-VI of spermatogenesis increased and the frequency of stage IX decreased. In the epididymis, sperm transit time (caput/corpus) was reduced and the relative sperm number (cauda) increased. Long-term exposure induced an increase in the frequencies of stages I-IV and V-VI and decreased the stages VII-VIII and IX. The number of Sertoli cells with evident nucleoli was reduced in both exposures. These results confirm the reproductive toxicity of MET.
Topics: Animals; Epididymis; Insecticides; Male; Mice; Organ Size; Organothiophosphorus Compounds; Reproduction; Sertoli Cells; Sperm Count; Spermatogenesis; Spermatozoa; Testis
PubMed: 32405287
DOI: 10.1016/j.repbio.2020.05.003 -
Molecules (Basel, Switzerland) Jan 2020Over the last years, the detection of pesticide residues in the official food surveillance programs of Chile has been increased, mainly in fresh vegetables such as...
Over the last years, the detection of pesticide residues in the official food surveillance programs of Chile has been increased, mainly in fresh vegetables such as tomatoes and lettuces. The Metropolitana Region of Chile presents the highest detections in the country. The lack of evaluations of toxicological risks in human health have increased uncertainty of the potential effects of pesticides exposures in the Chilean population. This research aims to determinate health risks assessment of pesticide residues associated to tomatoes and lettuces produced in Metropolitana Region. The findings of this study reveal that tomatoes and lettuces cultivated in the MR show more than 50% of samples with one or multiple pesticides residues. From the total samples, 16% were over the Chilean Maximum Residue Levels (MRLs). The main pesticides detected in tomatoes and lettuces were methamidophos, methomyl, difenoconazole, cyprodinil and boscalid. The results obtained using the official data of the Ministry of Health of Chile (MINSAL) compared to the World Health Organization (WHO), describe relevant risks through the Estimated Daily Intakes (EDI), Hazard Quotients (HQ) and Hazard Index (HI) for the Chilean population due to high concentrations of methamidophos, methomyl and cyprodinil. More restrictions for the use of methamidophos, methomyl, difenoconazole, cyprodinil and boscalid and effective control programs should be implemented in order to mitigate the impacts on the Chilean population.
Topics: Environmental Monitoring; Farms; Food Contamination; Humans; Lactuca; Solanum lycopersicum; Pesticide Residues; Risk Assessment
PubMed: 31952243
DOI: 10.3390/molecules25020355 -
Scientific Reports Nov 2021Toxicity of organophosphorus compounds (OPs) remains a major public health concern due to their widespread use as pesticides and the existence of nerve agents. Their...
Toxicity of organophosphorus compounds (OPs) remains a major public health concern due to their widespread use as pesticides and the existence of nerve agents. Their common mechanism of action involves inhibition of enzymes acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) which are crucial for neurotransmission. Both chronic and acute poisoning by OPs can leave long-lasting health effects even when the patients are treated with standard medical therapy. Therefore, an increasing urgency exists to find more effective oxime reactivators for compounds which are resistant to reactivation, especially phosphoramidates. Here, we investigated in silico and in vitro interactions and kinetics of inhibition for human cholinesterases with four organophosphate pesticides-ethoprophos, fenamiphos, methamidophos and phosalone. Overall, ethoprophos and fenamiphos displayed higher potency as inhibitors for tested cholinesterases. Our results show that methamidophos-inhibited hAChE was more susceptible to reactivation than hAChE inhibited by fenamiphos by selected oximes. Molecular modelling enabled an evaluation of interactions important for specificity and selectivity of both inhibition and reactivation of cholinesterases. Two newly developed reactivators-bispyridinium triazole oxime 14A and zwitterionic oxime RS194B possess remarkable potential for further development of antidotes directed against pesticides and related phosphoramidate exposures, such as nerve agents tabun or Novichoks.
Topics: Acetylcholinesterase; Butyrylcholinesterase; Cholinesterase Inhibitors; GPI-Linked Proteins; Humans; Kinetics; Organophosphorus Compounds; Pesticides
PubMed: 34728713
DOI: 10.1038/s41598-021-00953-9 -
Journal of the American Chemical Society Sep 2019Sensors based on graphene are promising devices for chemical and biological detection owing to their high sensitivity, biocompatibility, and low costs. However, for...
Sensors based on graphene are promising devices for chemical and biological detection owing to their high sensitivity, biocompatibility, and low costs. However, for chiral recognition, which is very important in biological systems, graphene sensors remain unable to discriminate enantiomers. Here, using chiral pesticide molecules as an example, we realized a highly sensitive graphene chiral sensor by modification with acetylcholinesterase (AChE). Quantum chemical simulations indicate that the inhibition effect of the enantiomer on AChE was transferred to graphene, which allowed for the electrical detection of chiral molecules. Under an operating voltage of 1 V, the sensitivity of the device reached 0.34 μg/L and 0.32 μg/L for (+)/(-)-methamidophos, respectively, which is much higher than by circular dichroism (6.90 mg/L and 5.16 mg/L, respectively). Furthermore, real-time, rapid detection was realized by combining with smartphones and wireless transmission.
Topics: Acetylcholinesterase; Circular Dichroism; Graphite; Limit of Detection; Organothiophosphorus Compounds; Pesticides; Quantum Theory; Radio Waves; Smartphone; Stereoisomerism
PubMed: 31448915
DOI: 10.1021/jacs.9b05724 -
Toxics Oct 2021In recent years, the official authorities in Chile have reported transgressions in the maximum residue levels of pesticides in fresh vegetables. There is no official...
In recent years, the official authorities in Chile have reported transgressions in the maximum residue levels of pesticides in fresh vegetables. There is no official information about traceability, pesticide levels, and potential health risks. The aim of this study was to analyse pesticide residues and their corresponding dietary risk assessments in tomatoes from supermarkets in the Metropolitan Region. Pesticides were extracted using the Quick, Easy, Cheap, Effective, Rugged and Safe, QuEChERS method, and their concentrations were determined by using chromatography with HPLC-FL/UV and GC-MS/ECD/NPD, following the Analytical Quality Control and Method Validation Procedures for Pesticides Residues Analysis in Food and Feed, SANTE guide and ISO 17025:2017 standard. In addition, a dietary risk assessment was carried out by comparing Chilean data to international references. The results reported that 9% of the samples had pesticide residue levels above the maximum residue levels permitted in Chile. All the scenarios evaluated revealed the highest estimated daily intake and hazard quotients for methamidophos and chlorpyrifos. Both the active substances used were acetylcholinesterase inhibitors and were neurotoxic under chronic risk assessment. The results showed the highest chronic hazard index in the Chilean scenario for all age groups and genders. The evidence obtained revealed that methamidophos, methomyl, and chlorpyrifos should be restricted for their use in Chilean agriculture.
PubMed: 34678945
DOI: 10.3390/toxics9100249