Chlorpyrifos (CPF) is a broad-spectrum chlorinated organophosphate (OP) pesticide used for the control of a variety of insects and pathogens in crops, fruits, vegetables, as well as households, and ...various other locations. The toxicity of CPF has been associated with neurological dysfunctions, endocrine disruption, and cardiovascular diseases (CVDs). It can also induce developmental and behavioral anomalies, hematological malignancies, genotoxicity, histopathological aberrations, immunotoxicity, and oxidative stress as evidenced by animal modeling. Moreover, eye irritation and dermatological defects are also reported due to CPF toxicity. The mechanism of action of CPF involves blocking the active sites of the enzyme, acetylcholinesterase (AChE), thereby producing adverse nervous system effects. Although CPF has low persistence in the body, its active metabolites, 3,5,6-trichloro-2-pyridinol (TCP), and chlorpyrifos-oxon (CPO) are comparatively more persistent, albeit equally toxic, and thus produce serious health complications. The present review has been compiled taking into account the work related to CPF toxicity and provides a brief compilation of CPF-induced defects in animals and humans, emphasizing the abnormalities leading to endocrine disruption, neurotoxicity, reproductive carcinogenesis, and disruptive mammary gland functionality. Moreover, the clinical signs and symptoms associated with the CPF exposure along with the possible pharmacological treatment are reported in this treatise. Additionally, the effect of food processing methods in reducing CPF residues from different agricultural commodities and dietary interventions to curtail the toxicity of CPF has also been discussed.
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•Chlorpyrifos (CPF) is an extensively used insecticide for fruits and vegetables.•CPF contributes towards the air, water, and land pollution.•Dietary sources are the foremost cause of non-occupational CPF exposure in humans.•A number of CPF intoxication incidents have been reported around the world.•CPF and its environmental degradation products are associated with endocrine disruption.
A field study was conducted to further our understanding about the fate and transport of the organophosphate insecticide, chlorpyrifos, and its degradation product, chlorpyrifos oxon. Leaf, soil and ...air sampling was conducted for 21 days after chlorpyrifos application to a field of purple tansy (Phacelia tanacetifolia). Air samples were collected using a high-volume air sampler (HVAS) and seven battery-operated medium-volume active air samplers placed around the field and on a 500-m transect extending away from the field. Chlorpyrifos was detected every day of the sampling period in all matrices, with concentrations decreasing rapidly after application. Chlorpyrifos oxon was only detected in air samples collected with the HVAS during the first three days after application. Wind direction played a significant role in controlling the measured air concentrations in near-field samples. The SCREEN3 model and chlorpyrifos’ Characteristic Travel Distance (CTD) were used to predict modelled chlorpyrifos concentrations in air along the transect. The concentration trend predicted by the SCREEN3 model was similar to that of measured concentrations whereas CTD-modelled concentrations decreased at a significantly slower rate, indicating that downwind chlorpyrifos concentrations in air were primarily controlled by air dispersion. The SCREEN3-predicted chlorpyrifos concentrations were >5 times higher than measured concentrations, indicating that simple approaches for calculating accurate pesticide volatilization fluxes from agricultural fields are still needed. Finally, we found that measured concentrations in air on Days 0–2 at locations up to 500 m from the field were at levels considered concerning for human health.
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•Chlorpyrifos and its oxon were found in leaves, soil, and air for 21 days.•The time to reach half of the initial concentration was 0.4 (leaves) and 2 h (soil).•The chlorpyrifos flux calculated from leaf trends was 0.29 mg m−2 h−1.•Agreement with SCREEN3 concentrations showed importance of air dispersion.•Chlorpyrifos concentration in air was concerning for human health up to 0.5 km away.
•This is the first assessment of pesticides using indoor dust, urine from Pakistan.•Combined influence of various factors explains pesticides content in studied sites.•Site specific differences were ...observed for Pesticide concentration.•Significant variations were noted in pesticides biomarkers level in exposed group.•Health status markers indicate that occupational groups at greater risk.
There are few studies documenting the dust loaded with pesticides as a potential non-dietary exposure source for occupational worker and populations living near agricultural farms and pesticides formulation plants. In present study we have evaluated the pesticide concentration in dust from potential sites and relevant health risk from dust ingestion. Furthermore, the effect of currently used pesticides was investigated on blood and urine parameters of subjects: farmer, factory worker, urban resident and rural resident and controlled subjects with presumably different levels of exposure. The urinary metabolites (TCPY and IMPY) were quantified as biomarkers of exposure to chlorpyrifos and diazinon in relation with biomarkers of effect including BuChE, LH, FSH, testosterone and oxidative stress. Results showed that chlorpyrifos and diazinon were present in higher concentration in dust and posed a high health risk to exposed subjects. The mean SOD value was high among the farmer (3048U/g Hb) followed by factory worker (1677.6U/g Hb). The urinary biomarkers – TCPY and IMPY- were found higher in exposed subjects as compared to control. Furthermore, testosterone was found in higher concentration in factory worker than control (12.63ng/ml vs 4.61ng/ml respectively). A decreased BuChE activity was noticed in occupational group and significant differences were observed in control verses exposed subjects. The PCA analysis evidenced the impact of pesticides on exposure biomarkers and male reproductive hormones. The study suggests that dust contaminated with pesticides engenders significant health risk particularly related to the nervous and endocrine system, not only for occupational workers exposed to direct ingestion but also for nearby residential community. Succinctly putting: Pesticides loaded dust in the city of Lahore, being a high priority concern for the government of Pakistan, demands to be addressed.
This review examines the large body of toxicological and epidemiological information on human exposures to chlorpyrifos, with an emphasis on the controversial potential for chlorpyrifos to induce ...neurodevelopmental effects at low doses. The results of this review demonstrate that the use of urinary 3,5,6-trichlorpyridinol (TCPy), a metabolite of chlorpyrifos as a biomarker of nonoccupational exposure is problematic and may overestimate nonoccupational exposures to chlorpyrifos by 10-to 20-fold because of the widespread presence of both TCPy and chlorpyrifos-methyl in the food supply. Current "background" (nonoccupational) levels of exposure to chlorpyrifos are several orders of magnitude lower than those required to inhibit plasma cholinesterase activity, which is a more sensitive target than nervous system cholinesterase. However, several in vitro studies have identified putative neurodevelopmental mechanisms that are altered at concentrations of chlorpyrifos below those that inhibit cholinesterases. Although one human cohort study reported an association between maternal and cord blood chlorpyrifos levels and several measures of neurodevelopment, two other cohort studies that utilized urinary TCPy as a surrogate for chlorpyrifos exposure did not demonstrate an association. Although the weight of the scientific evidence demonstrates that current levels of chlorpyrifos exposure will not have any adverse effects on neurodevelopment that might result from inhibition of nervous system cholinesterases, several recent studies propose alternative mechanisms. Thus, further in vivo investigation on neurodevelopment in an appropriate animal model is needed; additional epidemiological studies may be warranted if a suitable, chlorpyrifos-exposed cohort can be identified and more rigorous measures of exposure are utilized.
In this study, the removal of nutrients and chlorpyrifos as well as shifts of planktonic bacterial communities in constructed microcosms were investigated to evaluate the influence of Phragmites ...australis, Nymphaea alba, and Myriophyllum verticillatum, and their combination, on the restoration of eutrophic water containing chlorpyrifos. Plant-treated groups showed a higher pollutant removal rate than did no-remediation controls, indicating that treatment with plants is effective at remediation of eutrophic water containing chlorpyrifos. Different plants showed different performance on the remediation of eutrophic water, e.g., P. australis manifested stronger capacity for removal of sediment chlorpyrifos. This finding indicated that an appropriate plant combination is needed to deal with complex wastewater. During the treatments, the planktonic bacterial communities were influenced by the concentrations of nutrients and pollutants. The changes of composition of bacterial communities indicated a strong correlation between the bacterial communities and the concentrations of pollutants. The plants also influenced the planktonic bacterial communities, especially at the early phase of treatments. For example, P. australis increased the abundance of Limnohabitans and Nevskia significantly and decreased the abundance of Devosia, Luteolibacter, Methylibium, and Caulobacter significantly. The abundance of Hydrocarboniphaga significantly increased in N. alba-treated microcosms, whereas in M. verticillatum-treated microcosms, the abundance of Limnohabitans and Bdellovibrio significantly increased. Our results suggest that the planktonic bacterial communities may be altered during phytoremediation, and the functions of the affected bacteria should be concerned.
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•Chlorpyrifos in eutrophic water is successfully removed by phytoremediation.•Combination of aquatic plants can remove chlorpyrifos both in water and sediment.•The bacterial communities changed during phytoremediation.
The organophosphate chlorpyrifos, and its active metabolite chlorpyrifos-oxon (CPO), have been attributed to a number of neurodevelopmental disorders. It is unclear if the adverse effects associated ...with developmental exposure to the active CPO persist into adulthood and future generations. The goal of this study was to investigate whether CPO-associated changes in embryo-larval zebrafish (ZF) behavior at the F0 5 dpf were manifest throughout the life of the exposed F0, and are inherited by subsequent generations. For this study, embryos were exposed to chlorpyrifos-oxon at the environmentally relevant concentration of 0.01 μg/L and a high concentration of 50 μg/L starting at 4 hpf to 5 dpf, and then raised to F2. There was a significant decrease in distance traveled with 5 dpf F0 ZF exposed to the 50 μg/L CPO, with alterations in noncholinergic genes CFOS and LINGO, and alterations in global DNA methylation. CPO-related behavioral effects were ameliorated by day 21 through the F1 generation. This trend changed with hyperactive behavior, increase acetylcholine concentration in F2 zebrafish that were exposed to 50 μg/L CPO during the F0 development. There was also an increase in AChE activity and hypermethylation in F2 0.01 μg/L exposure larvae, indicating that even low dose exposures can have transgenerational effects. Results from this study demonstrate that early life stage exposures to CPO can lead to epigenetic changes in neurological activity, which may lead to alterations in response to CPO in future generations.
This study identified a correlation between CPO exposure during F0 development and significant differences in F2 behavioral, AChE activity and neurotransmitter concentration.
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•F0 developmental exposure to CPO causes hyperactivity in F2 generation.•F0 developmental exposure to CPO causes increased acetylcholine concentration in F2.•Increased global methylation and AChE activity in F2 from F0-exposed ZF at 0.01 μg/L.
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•A temperature-responsive microcapsule loaded chlorpyrifos (CM@CPF) was constructed.•The release process is controlled by the phase transition of hexadecane in the core.•The control ...efficacy of CPF@CM against P. xylostella was correlated with temperature.•CM@CPF showed a higher adhesion ability on cucumber and peanut leaves.•CM@CPF could enhance the light stability and biosecurity of CPF technical.
Controlled pesticide release in response to environmental stimuli by encapsulating pesticide in carrier is a feasible approach to improve the effective utilization rate. Here, a temperature-responsive release microcapsule loaded with chlorpyrifos (CPF@CM) was prepared from n-hexadecane-in-water emulsions via interfacial polymerization. The microcapsule was consisted of nanofibrillated cellulose (NFC) as the shell wall material and isophorone diisocyanate (IPDI) as the crosslinker. The prepared CPF@CM had pesticide-loading efficiency (33.1 wt%) and favorable adhesion on the surface of cucumber and peanut foliage compared with conventional formulation. Additionally, CPF@CM could protect chlorpyrifos against photodegradation effectively. The in vitro release test showed that microcapsule had adjustable controlled-release characteristics with the change in temperature based on phase transition of the n-hexadecane core. Bioassay studies showed that control efficacy of CPF@CM microcapsule against P. xylostella was positively correlated with temperature because of temperature-induced changes in release rate. The acute toxicity of CPF@CM to zebrafish was reduced more than 5-fold compared with that of CPF technical. These results indicated that the microcapsule release system has great potential in the development of an effective and environmentally friendly pesticide formulation.
Covalent-immobilization of the laccase enzyme onto the iron oxide nanoparticles was achieved using N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDAC) as cross-linkers. The presence ...of sulphur moeity in the laccase immobilized nanoparticles (LNPs) observed through Scanning Electron Microscopy- Energy dispersive X-ray spectroscopy (SEM-EDS) spectra confirmed the immobilization of laccase enzyme. The TEM analysis of iron oxide nanoparticles (FNPs), chitosan coated iron nanoparticles (CNPs) and laccase immobilized nanoparticles (LNPs) confirmed their sizes around 12, 15 and 20 nm, respectively. The effect of LNPs in degrading chlorpyrifos under field conditions was studied by simulating the conditions in a column. Column A, which was used as control showed more leaching of chlorpyrifos as compared to column B containing LNPs. The sorption coefficient (Kd) value obtained for control (column A) and LNPs containing column B were 21.6 and 112.3 L/kg, respectively. LNPs altered the Kd values of soil thereby showing lesser leaching potential. Higher the Kd value, lesser will be the leaching potential in the ground water. Copper in laccase enzyme resulted in hydrolysis of chlorpyrifos. Chitosan used for coating on FNPs and soil organic matter resulted in the adsoption of chlorpyrifos. Current results will allow a better assessment of the role of LNPs as a competent deterrent in chlorpyrifos mobility and degradation.
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•Laccase immobilized nanoparticles degraded chlorpyrifos at simulated field condition.•Soil column with laccase immobilized nanoparticles showed reduced chlorpyrifos leaching.•Laccase immobilized nanoparticles altered the sorption coefficient of the soil.
Bioaccumulation of Chlorpyrifos (CP) as pesticides due to their aggrandized use in agriculture has raised serious concern on the health of ecosystem and human beings. Moreover, their degraded ...products like 3,5,6-trichloro-2-pyridinol (TCP) has enhanced the distress due to their unpredictable biotoxicity. This study evaluates and deduce the comparative in vivo mechanistic biotoxicity of CP and TCP with zebrafish embryos through experimental and computational approach. Experimental cellular and molecular analysis showed higher induction of morphological abnormalities, oxidative stress and apoptosis in TCP exposed embryos compared to CP exposure due to upregulation of metabolic enzymes like Zhe1a, Sod1 and p53. Computational analysis excavated the differential discrepancies in intrinsic atomic interaction as a reason of disparity in biotoxicity of CP and TCP. The mechanistic differences were deduced due to the differential accumulation and internalisation leading to variable interaction with metabolic enzymes for oxidative stress and apoptosis causing physiological and morphological abnormalities. The study unravelled the information of in vivo toxicity at cellular and molecular level to advocate the attention of taking measures for management of CP as well as TCP for environmental and human health.
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•Chlorpyrifos (CP) and 3,5,6-trichloro-2-pyridinol (TCP) bioaccumulation possess in environmental concern of toxicity.•Uptake of TCP in zebrafish embryos is higher than CP due to molecular structure.•TCP induces higher deformities, oxidative stress and apoptosis than CP in zebrafish embryos.•Intrinsic atomic interaction of TCP with Sod1, Zhe1a and p53 proteins vary at molecular level.•Proximal discrepancies in intrinsic atomic interaction of CP and TCP determines in vivo biotoxicity in zebrafish embryos.
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•Chlorpyrifos is found worldwide in up to 1/3 of all conventionally citrus fruits.•Potential neurotoxicity of CPS in food from both China and Denmark.•Remediation using photoreactive ...nanoparticle is recommended.•Water, mechanical and heat treatment reduce the hazard quotients.•More research needed on health risks and socioeconomic impacts.
Pollution with pesticides is a widespread global problem and biomonitoring of the environment and human populations is necessary to assess potential harmful biological effects. One of the pesticides that are showing up in vegetables and fruit is chlorpyrifos (CPS). CPS is a nerve-poisoning organophosphorus insecticide, which is in up to 1/3 of all conventionally produced citrus fruits. Our review shows that CPS is a hazardous material that poses risks to human health and also pollutes the environment. There is numerous risk assessment of CPS reported, however, the assessment is easily affected by factors such as climate change, exposure period and CPS concentration. Therefore, rigorous update of the hazardous level of CPS is needed to determine the threshold level safe for humans and animals. There is a need for remediation using for example photoreactive nanoparticle methods and microbial degeneration possessing high degradation efficiency (73–97%). In addition, stringent biomonitoring of food, environment and human exposure should occur to avoid exposure to chemicals via citrus fruits and vegetables. This is necessary to assess health risks and socioeconomic impacts which also require collaboration between private and public sectors to facilitate the growth, sale and manufacturing of biopesticides.
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