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Journal of Water and Health Jun 2024Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the...
Despite the negative effects that the use of pesticides (such as herbicides and insecticides) have on human health and water resources, a significant portion of the world's agricultural production depends on them. The purpose of this study was to determine selected residual concentrations of pesticides (diazinon, ethion, malathion, alachlor, methyl-parathion, trifluralin, atrazine, chlorpyrifos, and azinphos-methyl) in samples from Shiraz potable water sources. For this purpose, water treatment plant, groundwater wells, treated surface water, and a mixture of groundwater and treated surface water were taken. In addition, statistical and risk analyses (carcinogenic and non-carcinogenic) were used. According to the results, chlorpyrifos with 84.4% had the highest removal efficiency and methyl-parathion with 10% had the lowest removal rate in the Shiraz water treatment plant process. The highest mean concentration was related to azinphos-methyl (1.5 μg/L) and chlorpyrifos (0.59 μg/L) in the groundwater samples. All measured compounds in water source samples were below standard levels, except for chlorpyrifos and azinphos-methyl, which were reported in groundwater above the limit recommended by the Environmental Protection Agency (EPA). The results showed that while the selected pesticides measured had a low non-carcinogenic risk for both adults and children, malathion and trifluralin posed a high carcinogenic risk for adults.
Topics: Water Pollutants, Chemical; Herbicides; Risk Assessment; Insecticides; Groundwater; Water Wells; Environmental Monitoring; Water Purification; Drinking Water; Humans; Iran
PubMed: 38935459
DOI: 10.2166/wh.2024.076 -
Journal of Molecular Recognition : JMR Jul 2024Organophosphorus are typically hazardous chemicals used in the pharmaceutical, agricultural, and other industries. They pose a serious risk to human life and can be...
Organophosphorus are typically hazardous chemicals used in the pharmaceutical, agricultural, and other industries. They pose a serious risk to human life and can be fatal upon direct exposure. Hence, studying the interaction between such compounds with proteins is crucial for environmental, health, and food safety. In this study, we investigated the interaction mechanism between azinphos-methyl (AZM) and β-lactoglobulin (BLG) at pH 7.4 using a combination of biophysical techniques. Intrinsic fluorescence investigations revealed that BLG fluorescence was quenched in the presence of increasing AZM concentrations. The quenching mechanism was identified as static, as evidenced by a decrease in the fluorescence quenching constant (1.25 × 10, 1.18 × 10, and 0.86 × 10 M) with an increase in temperatures. Thermodynamic calculations (ΔH > 0; ΔS > 0) affirmed the formation of a complex between AZM and BLG through hydrophobic interactions. The BLG's secondary structure was found to be increased due to AZM interaction. Ultraviolet -visible spectroscopy data showed alterations in BLG conformation in the presence of AZM. Molecular docking highlighted the significant role of hydrophobic interactions involving residues such as Val43, Ile56, Ile71, Val92, Phe105, and Met107 in the binding between BLG and AZM. A docking energy of -6.9 kcal mol, and binding affinity of 1.15 × 10 M suggest spontaneous interaction between AZM and BLG with moderate to high affinity. These findings underscore the potential health risks associated with the entry of AZM into the food chain, emphasizing the need for further consideration of its impact on human health.
Topics: Lactoglobulins; Molecular Docking Simulation; Cattle; Animals; Thermodynamics; Azinphosmethyl; Pesticides; Spectrometry, Fluorescence; Hydrophobic and Hydrophilic Interactions; Protein Binding; Protein Structure, Secondary
PubMed: 38686702
DOI: 10.1002/jmr.3086 -
Toxicological Sciences : An Official... Apr 2024Organophosphorus pesticides (OPPs) having a phosphate ester moiety, such as malathion (MA) and methidathion (DMTP), are widely used and have been detected in many fatal...
Organophosphorus pesticides (OPPs) having a phosphate ester moiety, such as malathion (MA) and methidathion (DMTP), are widely used and have been detected in many fatal cases of accidental exposure or suicide in Japan. In forensic toxicology, the accurate determination of blood OPP concentration is mandatory to prove death by OPP poisoning. However, fatal pesticide concentration in blood at autopsy varies depending on the circumstances surrounding the dead body. In this study, we found that 16 OPPs were degraded by human serum albumin (HSA) in a temperature-dependent fashion. The mechanism underlying MA, DMTP, azinphos-methyl, etrimfos, fenthion (MPP), pirimiphos-methyl, (E)-dimethylvinphos, (Z)-dimethylvinphos, vamidothion, edifenphos (EDDP), fosthiazate, and pyraclofos degradation involves the formation of adducts with tyrosine residues in HSA. The mass spectra obtained by liquid chromatography quadrupole Orbitrap mass spectrometry revealed that phosphate ester amino acid adducts such as Y-adduct1, Y-adduct2, Y-adduct3, Y-adduct4, and Y-adduct5 were formed in HSA solution incubated with OPPs. These results indicate that the 16 OPPs are postmortem changed by HSA. The detection of phosphate ester amino acid adducts such as Y-adduct1, Y-adduct2, Y-adduct3, Y-adduct4, and Y-adduct5, instead of MA, DMTP, azinphos-methyl, etrimfos, MPP, pirimiphos-methyl, (E)-dimethylvinphos, (Z)-dimethylvinphos, vamidothion, EDDP, fosthiazate, and pyraclofos per se, may be used to determine death by these OPPs poisoning.
Topics: Humans; Organophosphorus Compounds; Tyrosine; Pesticides; Serum Albumin, Human; Postmortem Changes; Chromatography, Liquid; Mass Spectrometry; Forensic Toxicology
PubMed: 38366941
DOI: 10.1093/toxsci/kfae023 -
Ecotoxicology and Environmental Safety Jan 2024The insect cuticle consists of chitin and cuticular proteins (CPs), which stabilize the body shape and provide an effective physical barrier against the external...
The insect cuticle consists of chitin and cuticular proteins (CPs), which stabilize the body shape and provide an effective physical barrier against the external environment. They are also potential target sites for developing environmentally friendly insect management through the utilization of physiology-based methods. The codling moth, Cydia pomonella, is a pest afflicting fruit orchards worldwide. This study used a comparative genomic approach, whole-genome resequencing, and transcriptome data to understand the role that CPs played in the environmental adaptation of the codling moth. A total of 182 putative CPs were identified in the codling moth genome, which were classified into 12 CP families. 119 CPR genes, including 54 RR-1, 60 RR-2, and 5 RR-3 genes were identified and accounted for 65.4% of the total CPs. Eight and seven gene clusters are formed in RR1 and RR2 subfamily and the ancestor-descendant relationship was explained. Five CPAP genes were highly expressed during the egg stage and exposed to high temperature, which indicated their potential role in aiding codling moth eggs in acclimating to varying external heat conditions. Moreover, six CPs belonging to the CPR and CPLCP families were identified in association with insecticide resistance by population resequencing. Their expression levels increased after exposure to insecticides, suggesting they might be involved in codling moth resistance to the insecticides azinphos-methyl or deltamethrin. Our results provide insight into the evolution of codling moth CPs and their association with high temperature adaptation and insecticide resistance, and provide an additional information required for further analysis of CPs in environmental adaptation.
Topics: Humans; Animals; Moths; Insecticides; Temperature; Azinphosmethyl; Insecticide Resistance
PubMed: 38141334
DOI: 10.1016/j.ecoenv.2023.115852 -
Talanta Apr 2024Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule,...
Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5-3.7 mg g and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d-SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d-SPE-HPLC method displayed low detection limits of 1.2-4.5 μg kg and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1-119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides.
Topics: Pesticides; Vegetables; Molecularly Imprinted Polymers; Organophosphorus Compounds; Edible Grain; Fruit; Solid Phase Extraction; Molecular Imprinting; Adsorption; Chromatography, High Pressure Liquid
PubMed: 38101032
DOI: 10.1016/j.talanta.2023.125536 -
Dalton Transactions (Cambridge, England... Dec 2023The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b)...
The lanthanide metal organic framework compounds [Ln(BPTA)(Bpy)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1a-5a) and [Ln(BPTA)(Phen)]·0.5DMF (Ln = Y, Eu, Gd, Tb, Dy; 1b-5b) were prepared by employing 2,5-bis(prop-2-yn-1-yloxy)terephthalic acid (2,5-BPTA) as the primary ligand and 2,2'-bipyridine (1a-5a) and 1,10-phenanthroline (1b-5b) as the secondary ligands. Single-crystal structural studies on [Gd(BPTA)(Bpy)]·0.5DMF (3a) and [Dy(BPTA)(Phen)]·0.5DMF (5b) indicated that the compounds have a two-dimensional structure. The Y compound exhibits blue emission, and the other compounds exhibit emission in the expected regions ( = 350 nm). White light emission was achieved by careful mixing of the red (Eu) and green (Tb) components in the blue emitting Y compound. Thus, YTbEu (bpy) and YTbEu (phen) were found to show white emission when excited using a wavelength of 350 nm. The introduction of N-N-containing ancillary ligands (, bpy and phen) increased the overall quantum yield (QY) of white light emission to 31% and 43%, respectively. The high QY observed for the Tb and Eu compounds was found to be sensitive and selective for the fluorometric detection of azinphos-methyl pesticide and trinitrophenol (TNP) in an aqueous medium at the ppb level. The same behaviour was observed when utilising the compounds as onsite paper strip sensors. Their magnetic properties were also studied, revealing for the Tb and Dy derivatives slow relaxation of the magnetisation at low temperature. The present study highlights the usefulness of rigid π-conjugated molecules such as 2,2'-bipyridine and 1,10-phenanthroline in enhancing the many utilities of rare-earth-containing MOFs towards white light emission, the sensing of harmful and dangerous substances and magnetic properties.
PubMed: 38013491
DOI: 10.1039/d3dt01882b -
Water Research Jan 2024Assessing spatial variation in the chemical sensitivity of natural assemblages will enhance ecological relevance and reduce uncertainty in ecological risk assessments...
Assessing spatial variation in the chemical sensitivity of natural assemblages will enhance ecological relevance and reduce uncertainty in ecological risk assessments and the derivation of environmental quality standards (EQSs). However, the majority of species in natural communities have not undergone toxicity testing for any chemical, which poses a major challenge when assessing their sensitivity. We investigated spatial variation and patterns in the sensitivity of 4084 freshwater macroinvertebrate assemblages across England to 5 general-acting chemicals (heavy metals) and 13 specifically acting chemicals (insecticides) using a novel hierarchical species sensitivity distribution method based on taxonomic relatedness. Furthermore, we explored how river typology relates to spatial variation in assemblage sensitivity to chemicals and the potential impacts of such variation on current EQSs. Our findings revealed that, whereas assemblages with similar taxonomic compositions exhibit comparable sensitivity distributions, assemblages with different taxonomic compositions could have very similar or very different sensitivity distributions. The variation in assemblage sensitivity was greater for specifically acting chemicals than for general-acting chemicals and exhibited spatial clustering patterns. These spatial clustering patterns varied depending on the chemical, and the regions where assemblages were most sensitive to metals were generally not the same as the regions where assemblages were most sensitive to insecticides. Spatial variation in assemblage sensitivity was related to river typology with sensitive assemblages being more common than expected in lowland calcareous (or mixed geology) rivers within very small to small catchments. Comparing spatial variation in assemblage-specific chemical sensitivity to EQSs, we found that the operational EQSs in England would protect most study assemblages (i.e., > 99.5 %), although a small proportion of assemblages may face potential risks associated with azinphos-methyl, copper, and malathion. In many cases the EQSs were very precautionary, potentially requiring expensive control measures or restricting beneficial chemical use with no additional environmental benefit. The development of spatially defined EQSs, possibly based on river types, could be developed to target areas that require the highest level of protection and thus strike a balance between the benefits of chemical use and environmental protection.
Topics: Animals; Invertebrates; Insecticides; Fresh Water; Rivers; Conservation of Natural Resources; Ecosystem; Environmental Monitoring
PubMed: 37992635
DOI: 10.1016/j.watres.2023.120854 -
Foods (Basel, Switzerland) Jun 2023Pesticides are extensively used in the cultivation and postharvest protection of citrus fruits, therefore continuous monitoring and health risk assessments of their...
Pesticides are extensively used in the cultivation and postharvest protection of citrus fruits, therefore continuous monitoring and health risk assessments of their residues are required. This study aimed to investigate the occurrence of pesticide residues on citrus fruits and to evaluate the acute and chronic risk for adults and children. The risk ranking of twenty-three detected pesticides was carried out according to a matrix ranking scheme. Multiple residues were detected in 83% of 76 analyzed samples. In addition, 28% contained pesticides at or above maximum residue levels (MRLs). The most frequently detected pesticides were imazalil, azoxystrobin, and dimethomorph. According to the risk ranking method, imazalil was classified in the high-risk group, followed by prochloraz, chlorpyrifos, azinphos-methyl, tebufenpyrad, and fenpiroximate, which were considered to pose a medium risk. The majority of detected pesticides (74%) posed a low risk. The health risk assessment indicated that imazalil and thiabendazole contribute to acute (HQa) and chronic (HQc) dietary risk, respectively. The HQc was negligible for the general population, while the HQa of imazalil and thiabendazole exceeded the acceptable level in the worst-case scenario. Cumulative chronic/acute risk (HIc/HIa) assessment showed that chronic risk was acceptable in all samples for children and adults, while the acute risk was unacceptable in 5.3% of citrus fruits for adults and 26% of citrus fruits for children. Sensitivity analyses indicated that the ingestion rate and individual body weight were the most influential risk factors.
PubMed: 37444192
DOI: 10.3390/foods12132454 -
Chemosphere Oct 2023The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land...
The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.
Topics: Pesticides; Ecuador; Insecticides; Water Quality; Ecosystem; Palm Oil; Urbanization; Environmental Monitoring; Water Pollutants, Chemical; Agriculture; Fresh Water; Rivers; Chlorpyrifos
PubMed: 37379974
DOI: 10.1016/j.chemosphere.2023.139286 -
Marine Pollution Bulletin Jul 2023Micropollutants such as pesticides and the prediction of water quality in aquatic environments have been known as a serious risk to the environment and human health. The...
Micropollutants such as pesticides and the prediction of water quality in aquatic environments have been known as a serious risk to the environment and human health. The pollution level of six pesticides-three organochlorines (OCPs: aldrin, dieldrin, and endrin) and three organophosphates (OPPs: diazinon, malathion, and azinphosmethyl)- in water, sediment, and fish samples was examined in the Miankaleh wetland, Iran. Water quality, including dissolved oxygen (DO), biological oxygen demand (BOD), chemical oxygen demand (COD), salinity, electrical conductivity (EC), turbidity, total dissolved solids (TDS), pH, temperature, and physicochemical properties of sediments, was analyzed. Low concentrations of OCPs (0.70 ± 0.01 μg/L) and OPPs (1.31 ± 0.1 μg/L) were observed in water. In contrast, OCPs and OPPs were not detected in sediment and fish samples in the Miankaleh wetland. Low concentrations of OCPs and OPPs in water and no pesticide concentrations in sediment and fish samples indicate low contamination of the aquatic environment in Miankaleh. The results of this study could be used as an effective reference for policy makers in the field of water resource management.
Topics: Animals; Humans; Wetlands; Iran; Water Pollutants, Chemical; Environmental Monitoring; Pesticides; Hydrocarbons, Chlorinated; Insecticides; Organophosphates; Geologic Sediments
PubMed: 37267870
DOI: 10.1016/j.marpolbul.2023.115097