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1.
J Food Sci ; 87(10): 4751-4760, 2022 Oct.
Article in English | MEDLINE | ID: mdl-36209472

ABSTRACT

Pesticide residues in radishes can induce serious health hazards, especially in children and toddlers. In order to assess potential health risk from pesticide residues in radishes, a total of 26 pesticides were evaluated by gas chromatography with mass spectrometry in 1690 samples, which were collected from the year 2016 to 2019 in Shandong Province of China. All the 26 pesticide residues were detected in 752 radish samples (44.50%), but only 221 samples (13.08%) contained detectable pesticide residues, which are above the maximum residue limits (MRLs). Multiple residues with two to nine pesticides were present in 5.09% (86 out of 1690) of samples. Hazard quotient (HQ) and the cumulative risk index were far below 100, while percentage value of acute reference dose (%ARfD) of triazophos exceeded 100 for adults, children, and toddlers. The %ARfD value for carbofuran, aldicarb, monocrotophos, and parathion was over 100 for toddlers. From the perspective of public health, the occurrence of pesticide residues in radishes could not pose a serious health risk problem, but the acute health risk should be paid more attention, especially to toddlers. It is recommended to make strict regulations on the management of pesticide residues and human health risk assessment about pesticide residues.


Subject(s)
Carbofuran , Monocrotophos , Parathion , Pesticide Residues , Pesticides , Raphanus , Adult , Humans , Pesticide Residues/analysis , Carbofuran/analysis , Food Contamination/analysis , Aldicarb/analysis , Monocrotophos/analysis , Gas Chromatography-Mass Spectrometry , Risk Assessment , Pesticides/analysis , Parathion/analysis
2.
Environ Sci Pollut Res Int ; 29(22): 33281-33294, 2022 May.
Article in English | MEDLINE | ID: mdl-35022966

ABSTRACT

Unregulated use of chlorpyrifos (CPF) and monocrotophos (MCP) in agriculture casts adverse effects on non-target freshwater mollusc, Pila globosa and humans. Levels of CPF and MCP were assessed in the paddy field from the edible foot tissue of apple snail (Pila globosa) exposed to low (1.5 ml l-1 water) and high (2.5 ml l-1 water) agricultural doses for 48 h to determine human health risk associated with consumption of tissue. CPF and MCP were extracted by liquid-liquid extraction and analysed by QuEChERS method using GC-MS/MS. For low and high concentrations of CPF exposure, the pesticide residue levels in the paddy field water ranged from 4.43 to 1.08 and 5.13 to 1.53 µg l-1, respectively, whereas, for low and high concentrations of MCP exposure, the residue levels in water ranged from 16.43 to 5.78 and 31.41 to 9. 27 µg l-1, respectively, for 3-48 h. In the foot tissue, residues ranged from 4.36 to 15.54 µg kg-1 for low-dose CPF, 7.1 to 18.05 µg kg-1for high-dose CPF and from 5.28 to 12.3 µg kg-1 and 8.94 to 18.21 µg kg-1 for low and high dose of MCP, respectively, during 3 to 48 h of exposure. Pesticides in the tissue were lower than the recommended maximum residue limits. Estimated health risk for adults and children revealed that the estimated daily intake values did not exceed the threshold values of acceptable daily intake. Non-carcinogenic and carcinogenic health effects were less than the safe value of 1.0 and 1 × 10-6, respectively, suggesting that CPF and MCP residues from ingestion of apple snail posed low risks to both children and adults. This preliminary result suggests regular monitoring of pesticides residues in Pila globosa collected from the paddy field of India.


Subject(s)
Chlorpyrifos , Gastropoda , Insecticides , Monocrotophos , Pesticide Residues , Pesticides , Adult , Animals , Child , Chlorpyrifos/analysis , Humans , Insecticides/analysis , Monocrotophos/analysis , Pesticide Residues/analysis , Pesticides/analysis , Tandem Mass Spectrometry , Water/analysis
3.
Arch Environ Occup Health ; 77(9): 702-710, 2022.
Article in English | MEDLINE | ID: mdl-34817298

ABSTRACT

Epidemiological studies suggest suppression of the lymphocytes function through cholinergic stimulation due to organophosphorus pesticide exposure. The study aimed to assess the alteration in the levels of immune cell phenotypes among farm women (FW) and farm children (FC) who were occupationally exposed to pesticides and age/gender-matched control subjects belonging to Rangareddy district (Telangana, India). A total of 129 FW, 129 FC and 268 age/gender-matched controls were recruited. Blood samples were collected from the selected subjects to estimate the levels of nine organophosphorus pesticide residues and CD (CD3+, CD4+, CD8+, CD16+ and CD19+) cell markers using LC-MS/MS and flow cytometry, respectively. Independent t-test analysis was conducted to compare the immune cell phenotypes between exposed and control groups. Spearman's rank correlation test was further carried out to identify any possible correlation between the pesticide residues and CD markers. The mean percentage for CD4+, CD8+ and CD16+ was found to be significantly low, while for CD19 + itwas significantly high in the FW as compared to the CW group (p < 0.01). Further, the residues of chlorpyrifos and monocrotophos among FW were found to be significantly correlating with the mean percentages of CD19+ and CD8+ markers, respectively. The cell marker subsets of CD4+ and CD8+ were significantly low in FC children 9-12 years and 13-15 years age groups, respectively (p < 0.05). Also, these levels were significantly correlating with the residues of malathion and monocrotophos. The present study could indicate an alteration in the lymphocytes' subpopulations, which may thereby infer the toxicity in the first phase assessment of immunotoxicity. Therefore, further studies may be conducted to understand the suspected pesticides' mechanism along with various other factors in causing immune suppression coupled with nutritional and other related disorders.


Subject(s)
Monocrotophos , Pesticide Residues , Pesticides , Chromatography, Liquid , Farms , Female , Humans , Monocrotophos/analysis , Organophosphorus Compounds/toxicity , Phenotype , Tandem Mass Spectrometry
4.
Bioprocess Biosyst Eng ; 43(2): 293-301, 2020 Feb.
Article in English | MEDLINE | ID: mdl-31602490

ABSTRACT

Long-term and excessive use of monocrotophos (MPs) pesticide leads to an accumulation of MPs residues in agricultural products. Electrochemical biosensor technology was developed as a simple and efficient method for detecting MPs. However, commercial acetylcholinesterase (AChE) sensors are not applied in practical MPs detection due to poor stability and reliability. In this study, the advantages of functionalized carbon nanotubes (Cl/MWCNTs) and a bi-enzyme system (horseradish peroxidase (HRP)/AChE) were combined, a novel bi-enzyme electrode (Cl/MWCNTs/HRP/AChE/GCE) was constructed. Under optimal conditions, the bi-enzyme sensor had a wide detection range of 1.0 × 10-11 to 1.0 × 10-7 mol/L and low detection limit of 4.5 × 10-12 mol/L. The proposed AChE biosensor exhibited excellent stability and sensitivity for MPs determination and presented a promising tool for monitoring food safety.


Subject(s)
Acetylcholinesterase/chemistry , Biosensing Techniques , Enzymes, Immobilized/chemistry , Ionic Liquids/chemistry , Monocrotophos/analysis , Nanotubes, Carbon/chemistry , Horseradish Peroxidase/chemistry
5.
Anal Bioanal Chem ; 411(13): 2905-2914, 2019 May.
Article in English | MEDLINE | ID: mdl-31011780

ABSTRACT

Acetylcholinesterase (AChE) biosensor technology is widely applied in the detection of organophosphate pesticides in agricultural production via the inhibition of AChE activity by organophosphates. However, the AChE electrode has some drawbacks, such as low stability and high overpotential. Combining the advantages of multiwalled carbon nanotubes (MWCNTs) and ionic liquids, we constructed a novel bienzyme electrode [Cl/iron porphyrin (FePP)-modified MWCNTs/AChE/glassy carbon electrode], which included AChE and mimetic oxidase FePP. In this electrode, FePP is covalently bound to the AChE carrier via ionic liquid for increased electrode sensitivity and stability. Under optimal conditions, this novel biosensor has a monocrotophos detection limit of 3.2 × 10-11 mol/L and good recovery of 89-104%. After 5 weeks of storage at 4 °C, the oxidation current was 97.8% of its original value. The biosensor has high stability and sensitivity for monocrotophos detection and is a promising device for monitoring food safety. Graphical abstract The complete synthesis process of Cl/FePP-MWCNTs/AChE/GCE.


Subject(s)
Acetylcholinesterase/chemistry , Biosensing Techniques/methods , Enzymes, Immobilized/chemistry , Metalloporphyrins/chemistry , Monocrotophos/analysis , Nanotubes, Carbon/chemistry , Pesticides/analysis , Biomimetic Materials/chemistry , Brassica/chemistry , Ionic Liquids/chemistry , Iron Compounds/chemistry , Lactuca/chemistry , Limit of Detection , Nanotubes, Carbon/ultrastructure , Onions/chemistry
6.
J Cell Biochem ; 120(6): 10777-10786, 2019 06.
Article in English | MEDLINE | ID: mdl-30672607

ABSTRACT

Toxic contamination of commonly consumed food products and water due to food chain vulnerability via agricultural products and commodities is a serious health hazard. This study reports on Santa Barbara Amorphous (SBA-15), a type of mesoporous silica nanoparticles, for efficient and stable acetylcholinesterase (AChE) adhesion toward detection of toxic pesticides. AChE was immobilized to the inert framework of mesoporous materials viz. SBA-15 with a proficient hydrolytic response toward acetylthiocholine. The immobilized system acts as a biosensor for the detection of pesticides, which are organophosphorus compounds in food. Both the SBA-15 and immobilized SBA-15 were characterized to give an insight on the physiochemical and morphological modification properties. The enzyme activity was accessed by Ellman's spectrophotometric bioassay for bare and enzyme-immobilized SBA-15 that resulted in promising enzymatic activity with the counterpart. Enzyme stability was also studied, which exhibited that immobilized AChE retained its catalytic activity up to 60 days and retained 80% of the hydrolytic activity even at 37°C. On the basis of the success of immobilized enzyme (covalent) being inhibited by acetylthiocholine, the sensor was administered for the inhibition by monocrotophos and dimethoate that are used widely as pesticides in agricultural. The inhibitory concentration (IC50 ) value was found to be 2.5 ppb for monocrotophos and 1.5 ppb for dimethoate inhibiting immobilized AChE. This was verified using cyclic voltammetry, an electrochemical analysis thus proving that the SBA-15@AChE complex could be used as a sensitive and highly stable sensor for detecting the concentration of hazardous pesticide compounds.


Subject(s)
Acetylcholinesterase/chemistry , Dimethoate/analysis , Electrochemical Techniques , Enzymes, Immobilized/chemistry , Monocrotophos/analysis , Pesticides/analysis , Acetylthiocholine/chemistry , Adsorption , Biosensing Techniques/methods , Carbonated Beverages/analysis , Enzyme Assays , Food Contamination/analysis , Humans , Nanoparticles/chemistry , Porosity , Sensitivity and Specificity , Silicon Dioxide/chemistry
7.
Anal Biochem ; 560: 12-18, 2018 11 01.
Article in English | MEDLINE | ID: mdl-30172744

ABSTRACT

Monocrotophos (Ops) has been widely used as pesticide in crop production but simultaneously could accumulate in the nature and seriously impact food safety and human health. It is necessary to develop a high sensitivity biosensor for accurate and fast detection of OPs. In this study, multi-walled carbon nanotubes (MWCNTs) were selected as acetylcholinesterase (AChE) carrier and their surface was modified by introducing different functional groups (-SH, -NH2, -Cl, -OH), hydrophobic alkyl groups (-CH3, -(CH2)2CH3, -(CH2)7CH3, -(CH2)15CH3) and ionic liquids (-IL1, -IL2). The interaction mechanism of MWCNTs functionalized surface and AChE has been revealed by studying characteristics of AChE immobilized on different carrier surface. Finally, compared with reported references and above other modifiers, we found that MWCNTs surface modified by -IL1 was the best carrier for AChE and the detection limit of IL1-MWCNTs/AChE/GCE was 3.3 × 10-11 M. At optimum reaction condition (pH 7.0, AChE loading 0.25 U, Inhibition time 14 min), storability test indicated reactivity of IL1-MWCNTs/AChE/GCE remained above 98.5% within two weeks. For real vegetable sample detection, the recoveries of IL1-MWCNTs/AChE/GCE were found to be between 90.0% and 104%. These results demonstrated novel biosensors could act as device of high sensitivity for accurate and fast detection of OPs.


Subject(s)
Acetylcholinesterase/chemistry , Biosensing Techniques/methods , Insecticides/analysis , Monocrotophos/analysis , Nanotubes, Carbon/chemistry , Pesticides/chemistry , Plant Leaves/chemistry , Electrochemical Techniques/methods , Electrodes , Enzymes, Immobilized/chemistry , Limit of Detection
8.
Environ Sci Pollut Res Int ; 25(5): 4942-4950, 2018 Feb.
Article in English | MEDLINE | ID: mdl-29204940

ABSTRACT

The bacterial strain Sphingobium sp. YW16, which is capable of degrading monocrotophos, was isolated from paddy soil in China. Strain YW16 could hydrolyze monocrotophos to dimethylphosphate and N-methylacetoacetamide and utilize dimethylphosphate as the sole carbon source but could not utilize N-methylacetoacetamide. Strain YW16 also had the ability to hydrolyze other organophosphate pesticides. A fragment (7067 bp) that included the organophosphorus hydrolase gene, opdA, was acquired from strain YW16 using the shotgun technique combined with SEFA-PCR. Its sequence illustrated that opdA was included in TnopdA, which consisted of a transpose gene, a putative integrase gene, a putative ATP-binding protein gene, and opdA. Additionally, a conjugal transfer protein gene, traI, was located downstream of TnopdA. The juxtaposition of TnopdA with TraI suggests that opdA may be transferred from strain YW16 to other bacteria through conjugation. OpdA was able to hydrolyze a wide range of organophosphate pesticides, with the hydrolysis efficiency decreasing as follows: methyl parathion > fenitrothion > phoxim > dichlorvos > ethyl parathion > trichlorfon > triazophos > chlorpyrifos > monocrotophos > diazinon. This work provides the first report of opdA in the genus Sphingobium.


Subject(s)
Bacterial Proteins/genetics , DNA Transposable Elements , Mixed Function Oxygenases/genetics , Monocrotophos/analysis , Soil Microbiology , Soil Pollutants/analysis , Sphingomonadaceae/isolation & purification , Biodegradation, Environmental , China , Cloning, Molecular , Hydrolysis , RNA, Ribosomal, 16S/genetics , Sequence Analysis, DNA , Sphingomonadaceae/genetics
9.
Environ Sci Pollut Res Int ; 23(4): 3727-35, 2016 Feb.
Article in English | MEDLINE | ID: mdl-26498809

ABSTRACT

A bacteria strain, YW6, capable of utilizing monocrotophos (MCP) as the sole carbon and nitrogen sources for growth was isolated from paddy soil and identified as Starkeya novella. Strain YW6 completely degraded 0.2 mM MCP within 36 h without any lag period. Addition of carbon source resulted in slowing down of the initial rate of degradation of MCP, while the presence of a more favorable source of nitrogen enhanced the degradation of MCP. In addition to the degradation of MCP, strain YW6 was also able to degrade a wide range of organophosphorus pesticides (OPs) containing P-O-C bond, but not dimethoate, which has P-S-C bond. A MCP degradation pathway was proposed on the basis of metabolite production patterns and identification of the metabolites. MCP is hydrolyzed at the P-O-C bond to form N-methylacetoacetamide and dimethyl phosphate; N-methylacetoacetamide is transformed to N-methyl-4-oxo-pentanamide, which was subsequently converted to 5-(methylamino)-5-oxo-pentanoic acid, and 5-(methylamino)-5-oxo-pentanoic acid is cleaved to glutaric acid and methylamine. These findings provide new insights into the microbial metabolism of MCP. To the best of our knowledge, this is the first report on the degradation of MCP by Starkeya bacteria.


Subject(s)
Alphaproteobacteria/growth & development , Monocrotophos/analysis , Pesticides/analysis , Soil Pollutants/analysis , Alphaproteobacteria/isolation & purification , Alphaproteobacteria/metabolism , Biodegradation, Environmental , Hydrolysis , Monocrotophos/chemistry , Pesticides/chemistry , Soil/chemistry , Soil Microbiology , Soil Pollutants/chemistry
10.
Appl Biochem Biotechnol ; 172(7): 3570-82, 2014 Apr.
Article in English | MEDLINE | ID: mdl-24557957

ABSTRACT

Continuous and repeated use of pesticides affects soil microbial flora and fauna and hence indirectly affects the activity of diverse microbial enzymes present within it. The present study investigates the interaction effect of different concentrations of monocrotophos on diverse hydrolases and oxidases, viz., protease, alkaline phosphatase, acid phosphatase, cellulase, amylase, invertase, arginine deaminase, and dehydrogenase, present in sandy loam soil of Rajasthan under in vitro conditions for 30 days. Soil sample was inoculated with three different concentrations of monocrotophos, viz., 50, 100, and 150 µg kg(-1), and incubated in dark at room temperature. At regular interval of 5 days, sample was withdrawn and enzyme activity was calculated and compared with that of control. Application of various concentrations of monocrotophos enhanced the activity of diverse enzymes present in soil. Therefore, the study revealed synergistic or additive effect of monocrotophos on all the tested microbial enzyme entities. Increasing concentration of the pesticide, however, poses an antagonistic interaction on the increment of different enzymes activities. Therefore, it can be concluded from the study that monocrotophos impose a positive effect at low concentration of pesticide, whereas high concentration poses negative effect on the activity of different enzymes present in soil.


Subject(s)
Hydrolases/analysis , Monocrotophos/analysis , Oxidoreductases/analysis , Pesticides/analysis , Soil/chemistry , India
11.
J Sci Food Agric ; 94(7): 1409-15, 2014 May.
Article in English | MEDLINE | ID: mdl-24122545

ABSTRACT

BACKGROUND: Organophosphate pesticide residues are harmful to human health because of their potential mutagenic and carcinogenic properties. Therefore, it is of great importance to development an accurate and reliable analytical method to prevent their uncontrolled effects on environmental pollution and human health. RESULTS: This study reports a new method of molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography (MISPE-HPLC) for simultaneous determination of two organophosphate pesticides residues. Two types of molecularly imprinted polymers (MIPs) were prepared using the trichlorfon and monocrotophos as the template molecule, respectively, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The recognition ability and adsorption-desorption dynamic of each imprinted polymer toward the trichlorfon or monocrotophos were characterised. Using the mixture of trichlorfon-MIP and monocrotophos-MIP (20:80, wt/wt) as solid-phase extraction sorbent, the factors affecting the pre-concentration on the analytes and the sensitivity of the MISPE-HPLC method were optimised. Under optimal condition, the linear range was 0.005-1.0 mg L⁻¹. The limit of detection was 4.2 µg g⁻¹ for trichlorfon, and 1.2 ng g⁻¹ for monocrotophos. The peak area precision [Relative standard deviation (RSD)] for three replicates was 2.9-4.5%. The blank rape and cauliflower samples spiked with trichlorfon and monocrotophos at 0.05 and 0.005 µg g⁻¹ levels were extracted and determined by this method with recoveries ranging from 88.5% to 94.2%. Moreover, this method was successfully applied to the quantitative detection of the trichlorfon and monocrotophos residues in leek samples. CONCLUSION: With good properties of high sensitivity, simple pre-treatment and low cost, this MISPE-HPLC method could provide a new tool for the rapid determination of multi-pesticide residues in the complicated food samples.


Subject(s)
Food Contamination , Food Inspection/methods , Insecticides/analysis , Monocrotophos/analysis , Pesticide Residues/analysis , Trichlorfon/analysis , Vegetables/chemistry , Brassica/chemistry , Brassica rapa/chemistry , Carcinogens, Environmental/analysis , China , Chromatography, High Pressure Liquid , Limit of Detection , Molecular Imprinting , Mutagens/analysis , Onions/chemistry , Reproducibility of Results , Solid Phase Extraction
12.
J Agric Food Chem ; 61(22): 5397-403, 2013 Jun 05.
Article in English | MEDLINE | ID: mdl-23687955

ABSTRACT

This article presents a novel application of dispersive microextraction based on "magnetic water" (m-water) for the purification of organophosphorus pesticides (methamidophos, omethoate, monocrotophos) from cold-pressed vegetable oils. In the present study, a trace amount of water (extractant) was adsorbed on bare Fe3O4 by hydrophilic interaction to form m-water. Rapid extraction can be achieved while the m-water is dispersed in the sample solution with the aid of a vigorous vortex. After extraction, the analyte-adsorbed m-water can be readily isolated from the sample solution by a magnet, which could greatly simplify the operation and reduce the whole pretreatment time. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for pesticide analysis was established by coupling with gas chromatography/mass spectrometry (GC/MS). The linearity range of the proposed method was 2-100 ng/g with satisfactory correlation coefficients (R) of 0.9997-0.9998, and the limits of quantification (LOQ) for the target compounds were in the range of 0.70-1.27 ng/g. In addition, the reproducibility was obtained by evaluating the intra- and interday precisions with relative standard deviations (RSDs) less than 7.2% and 6.5%, respectively. Finally, the established "magnetic water" microextraction method was successfully applied for the determination of pesticide residues in several kinds of cold-pressed vegetable oils.


Subject(s)
Food Contamination , Food Inspection/methods , Organophosphorus Compounds/analysis , Pesticide Residues/analysis , Pesticides/analysis , Plant Oils/chemistry , Water/chemistry , Analytic Sample Preparation Methods , China , Dimethoate/analogs & derivatives , Dimethoate/analysis , Dimethoate/chemistry , Gas Chromatography-Mass Spectrometry , Liquid Phase Microextraction , Magnetic Phenomena , Monocrotophos/analysis , Monocrotophos/chemistry , Organophosphorus Compounds/chemistry , Organothiophosphorus Compounds/analysis , Organothiophosphorus Compounds/chemistry , Pesticide Residues/chemistry , Pesticides/chemistry
13.
J Environ Sci (China) ; 24(5): 956-62, 2012.
Article in English | MEDLINE | ID: mdl-22893976

ABSTRACT

An amperometric biosensor based on screen-printed electrodes (SPEs) was developed for the determination of organophosphorus pesticides in water samples. The extent of acetylcholinesterase (AChE) deactivation was determined and quantified for pesticide concentrations in water samples. An enzyme immobilization adsorption procedure and polyacrylamide gel matrix polymerization were used for fabrication of the biosensor, with minimal losses in enzyme activity. The optimal conditions for enzyme catalytic reaction on the SPEs surfaces were acetylthiocholine chloride (ATChCl) concentration of 5 mmol/L, pH 7 and reaction time of 4 min. The detection limits for three organophosphorus pesticides (dichlorvos, monocrotophs and parathion) were in the range of 4 to 7 microg/L when an AChE amount of 0.1 U was used for immobilization.


Subject(s)
Biosensing Techniques/instrumentation , Electrochemistry/instrumentation , Organophosphorus Compounds/analysis , Pesticides/analysis , Water Pollutants, Chemical/analysis , Water/chemistry , Acetylcholinesterase/metabolism , Adsorption , Biocatalysis , Calibration , Dichlorvos/analysis , Electricity , Electrodes , Hydrogen-Ion Concentration , Monocrotophos/analysis , Parathion/analysis , Polymerization
14.
Biosens Bioelectron ; 27(1): 82-7, 2011 Sep 15.
Article in English | MEDLINE | ID: mdl-21752626

ABSTRACT

An ultrasensitive amperometric acetylcholinesterase (AChE) biosensor was fabricated by controlled immobilization of AChE on gold nanoparticles/poly(dimethyldiallylammonium chloride) protected Prussian blue (Au-PDDA-PB) nanocomposite modified electrode surface for the detection of organophorous pesticide. The Au-PDDA-PB membrane served as an excellent matrix for the immobilization of enzyme, which not only enhanced electron transfer but also possessed a relatively large surface area. In addition, the surface hydrophilicity of the Au-PDDA-PB nanocomposite was finely controlled in the static water contact angle range of 25.6-78.1° by adjusting the ratio of gold nanoparticles to PDDA-PB. On an optimized hydrophobic surface, the AChE adopts an orientation with both good activity and stability, which has been proven by electrochemical methods. Benefit from the advantages of the Au-PDDA-PB nanocomposite and the good activity and stability of AChE, the biosensor shows significantly improved sensitivity to monocrotophos, a typical highly toxic organophorous pesticide, with wide linear range (1.0-1000 pg/mL and 1.0-10 ng/mL) and an ultra-low detection limit of 0.8 pg/mL. The biosensor exhibits accuracy, good reproducibility and stability. This strategy may therefore provide useful information for the controlled immobilization of protein and the design of highly sensitive biosensors.


Subject(s)
Acetylcholinesterase/chemistry , Biosensing Techniques , Enzymes, Immobilized/chemistry , Gold/chemistry , Metal Nanoparticles/chemistry , Organophosphates/analysis , Pesticides/analysis , Electrochemical Techniques , Ferrocyanides/chemistry , Hydrophobic and Hydrophilic Interactions , Limit of Detection , Monocrotophos/analysis , Sensitivity and Specificity , Water/chemistry
15.
Environ Sci Technol ; 45(10): 4609-15, 2011 May 15.
Article in English | MEDLINE | ID: mdl-21510672

ABSTRACT

Currently, the determination of health risks to pesticide applicators from dermal exposure to these chemicals is assessed using either a concentrate of the compound or a relevant aqueous dilution. Neither of these conditions reflects a normal exposure of an individual when re-entering an area after pesticide application, that is, contact with dried residue of the diluted product on foliage. Methodology has therefore been developed to determine a relevant estimate of this potential dermal re-entry exposure from pesticide residues. Potential delivery platforms have been characterized for the transfer of pesticide residue to skin. Spin coating has been used to deposit uniform pesticide layers on to each platform. Five pesticides have been chosen to encompass a wide range of physicochemical properties: atrazine, 2,4-dichlorophenoxyacetic acid (2,4-D), chlorpyrifos, monocrotophos, and acetochlor. In vitro (Franz diffusion cell) experiments have been performed to monitor the transfer of these pesticides from the delivery platforms onto and through excised porcine skin. Parallel experiments were also conducted with aqueous pesticide dilutions for comparison, and a final in vivo measurement using ibuprofen (as a model compound) complemented the in vitro data. The results demonstrate that transfer of chemical residue onto and subsequently through the skin is dependent on the physical attributes of the residue formed. Thus, assessing dermal exposure to pesticides based on skin contact with either the chemical concentrate or a relevant aqueous dilution may incorrectly estimate the risk for re-entry scenarios.


Subject(s)
Environmental Exposure/statistics & numerical data , Environmental Pollutants/analysis , Pesticide Residues/analysis , Plant Leaves/chemistry , Skin/metabolism , 2,4-Dichlorophenoxyacetic Acid/analysis , 2,4-Dichlorophenoxyacetic Acid/metabolism , Adult , Animals , Atrazine/analysis , Atrazine/metabolism , Chlorpyrifos/analysis , Chlorpyrifos/metabolism , Environmental Exposure/analysis , Environmental Pollutants/metabolism , Female , Humans , Monocrotophos/analysis , Monocrotophos/metabolism , Pesticide Residues/metabolism , Skin Absorption , Swine/metabolism , Toluidines/analysis , Toluidines/metabolism
16.
Biosens Bioelectron ; 26(6): 2864-9, 2011 Feb 15.
Article in English | MEDLINE | ID: mdl-21185711

ABSTRACT

A sensitive amperometric acetylcholinesterase (AChE) biosensor was fabricated based on mesocellular silica foam (MSF), which functioned as both an enzyme immobilization matrix and a solid phase extraction (SPE) material for the preconcentration of target molecules. The hydrophilic interface, the good mechanical/chemical stability, and the suitable pore dimension of MSF provided the entrapped AChE a good environment to well maintain its bioactivity at basic condition. The AChE immobilized in MSF showed improved catalytic ability for the hydrolysis of acetylthiocholine, as evidenced by the increasing of the oxidation current of thiocholine, the enzymatic catalytic hydrolysis production of acetylthiocholine. In addition, the MSF with large surface area showed a modest adsorption capacity for monocrotophos, a model organophosphate used in this study, via the hydrogen bond or physical adsorption interaction. The combination of the SPE and the good enzyme immobilization ability in MSF significantly promoted the sensitivity of the biosensor, and the limit of detection has lowered to 0.05 ng/mL. The biosensor exhibited accuracy, good reproducibility, and acceptable stability when used for garlic samples analysis. The strategy may provide a new method to fabricate highly sensitive biosensors for the detection of ultra-trace organophosphorous pesticide infield.


Subject(s)
Biosensing Techniques/methods , Organophosphorus Compounds/analysis , Pesticides/analysis , Silicon Dioxide , Acetylcholinesterase/metabolism , Acetylthiocholine/metabolism , Biosensing Techniques/statistics & numerical data , Enzymes, Immobilized/metabolism , Food Contamination/analysis , Garlic/chemistry , Monocrotophos/analysis
17.
J Environ Monit ; 12(5): 1119-25, 2010 May.
Article in English | MEDLINE | ID: mdl-21491630

ABSTRACT

Information regarding pesticide mobility is critical for the evaluation of pesticide management practices. For this purpose, lysimetric studies were conducted to develop assessment schemes to protect groundwater from unacceptable effects caused by pesticide use. By using these studies, specific monitoring actions and prevention measures for the protection of waters can be studied, and the results thus obtained can provide the local authorities and the decision makers with an identification tool for demarcating risk areas. Pesticide residues were found at the bottom of lysimeters in the following pattern i.e., 1.52 > 2.1 > 2.74 m which could represent an "index of risk" for groundwater pollution. Regressions built for carbofuran and monocrotophos against watertable depths showed a decreasing trend of pesticide in higher watertable treatments. These findings support the existence of a significant role for chromatographic flow in sandy texture soil. Moreover, the higher values of pesticide residue at the bottom of lysimeters reflect that chromatographic flow as well as preferential flow pattern prevails during higher precipitation events. The precipitation received during the study was higher than the 10 year average and can be considered relatively as a worst case scenario. Finally, the authors have recommended a standardized pesticide monitoring scheme for groundwater in accordance with the already validated generic schemes in developed countries.


Subject(s)
Carbamates/analysis , Environmental Monitoring/methods , Monocrotophos/analysis , Soil Pollutants/analysis , Water Pollutants, Chemical/analysis , Carbofuran/analysis , Insecticides/analysis , Pakistan , Pesticide Residues/analysis , Regression Analysis , Soil/chemistry , Water Movements
18.
J Nanosci Nanotechnol ; 9(4): 2368-73, 2009 Apr.
Article in English | MEDLINE | ID: mdl-19437977

ABSTRACT

In this paper, a simple method for immobilization of acetylcholinesterase (AChE) on cysteamine assembled glassy carbon electrode coupled with gold nanoparticles (GNPs) was proposed and thus a sensitive, fast and stable amperometric biosensor for quantitative determination of monocrotophos was developed. The fabrication procedure was characterized by cyclic voltammetry, electrochemical impedance spectroscopy and contact angles. The presence of GNPs not only led to an increased effective surface to provide a sufficient amount of sites for binding enzyme, but also promoted electron transfer reactions and catalyzed the electro-oxidation of thiocholine, thus amplifying the detection sensitivity. Due to the notable decrease in voltammetric signal of the immobilized AChE, a simple method for determination of monocrotophos was established. The inhibition of monocrotophos was proportional to its concentration in two ranges, from 0.5 to 10 ng mL(-1) and from 10 to 600 ng mL(-1), with a detection limit lower than 0.3 ng mL(-1). The constructed biosensor processing prominent characteristics and performance such as good precision and reproducibility, acceptable stability and accuracy, fast response and low detection limit has potential application in detection of toxic compounds.


Subject(s)
Acetylcholinesterase/chemistry , Acetylcholinesterase/metabolism , Biosensing Techniques/methods , Gold/chemistry , Metal Nanoparticles/chemistry , Monocrotophos/analysis , Cholinesterase Inhibitors/analysis , Cholinesterase Inhibitors/metabolism , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/metabolism , Monocrotophos/metabolism , Sensitivity and Specificity
19.
J Environ Sci Eng ; 51(1): 33-8, 2009 Jan.
Article in English | MEDLINE | ID: mdl-21114151

ABSTRACT

Foliar application of monocrotophos in cabbage resulted in high initial residues of 6.00 and 7.54 microg g(-1) for the recommended dose (2 mL L(-1)) and double the recommended dose of monocrotophos (4 mL L(-1)) respectively. However, in farmer's practice treatment, it was found to be 2.54 microg g(-1) where it was sprayed once as fourth spray. Monocrotophos residues in cabbage after spray persisted for more than 30 days at both recommended and double the recommended dose of monocrotophos. The farmer's practice showed persistence of monocrotophos for only 15 days. Degradation of monocrotophos residues in cabbage followed first order exponential equation. Monocrotophos residues in cabbage degraded with a half-life of 2.87 to 3.05 days for four sprays at the recommended and double the recommended level of application. However, showed a half-life of 1.99 days for one spray of monocrotophos according to farmer's practice. Waiting periods /safe intervals for monocrotophos on cabbage were found to be 13.79, 15.90 and 8.55 days for the recommended, double the recommended dose and farmer's practice of monocrotophos application respectively.


Subject(s)
Brassica/chemistry , Insecticides/analysis , Monocrotophos/analysis , Pesticide Residues/analysis , Biodegradation, Environmental
20.
J Environ Sci Health B ; 43(7): 595-604, 2008 Sep.
Article in English | MEDLINE | ID: mdl-18803114

ABSTRACT

The dissipation of (O-methyl-14C) monocrotophos and U-ring labelled 14C-carbaryl was monitored for over two years in absence and presence of other insecticides using in situ soil columns. The dissipation of 14C-monocrotophos from soil treated with methomyl and carbaryl showed a faster rate of downward movement than in a control column tagged with the labelled insecticide alone. The same trend was observed in experiments with 14C-carbaryl that dissipated more readily in soil treated with non-labelled monocrotophos and methomyl. In the presence of other insecticides the percentage of bound residues was generally lower than in control experiments. The bound residues at the top of the column are released at a low rate under conditions prevailing in the field. The overall time required for dissipation of 50% of monocrotophos and carbaryl (t50) as estimated from control experiment was approximately 20 and 24 weeks, respectively. The data indicate that repeated applications of pesticides might enhance the release of 14C-bound residues.


Subject(s)
Carbaryl/chemistry , Carbaryl/metabolism , Monocrotophos/chemistry , Monocrotophos/metabolism , Soil Pollutants/chemistry , Soil Pollutants/metabolism , Soil/analysis , Carbon Isotopes/analysis , Monocrotophos/analysis , Pesticides , Time Factors
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