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1.
Epidemiology ; 35(2): 185-195, 2024 Mar 01.
Article in English | MEDLINE | ID: mdl-37934147

ABSTRACT

BACKGROUND: Hypospadias is a male genital tract defect for which an increase in prevalence has been documented over the last few decades. A role for environmental risk factors is suspected, including prenatal exposure to pesticides. OBJECTIVES: To study the risk of hypospadias in association with multiple pesticide measurements in meconium samples. METHODS: The Brittany Registry of Congenital Anomalies (France) conducted a case-control study between 2012 and 2018. Cases were hypospadias, ascertained by a pediatrician and a pediatric surgeon, excluding genetic conditions, following European Surveillance of Congenital Anomalies guidelines (N = 69). Controls (N = 135) were two male infants without congenital anomaly born after each case in the same maternity unit. Mothers in the maternity units completed a self-administered questionnaire, we collected medical data from hospital records, and medical staff collected meconium samples. We performed chemical analysis of 38 pesticides (parent compound and/or metabolite) by UHPLC/MS/MS following strict quality assurance/quality control criteria and blind to case-control status. We carried out logistic regression accounting for frequency-matching variables and major risk factors. RESULTS: Among the 38 pesticides measured, 16 (42%) were never detected in the meconium samples, 18 (47%) were in <5% of samples, and 4 (11%) in ≥5% of the samples. We observed an association between the detection of fenitrothion in meconium and the risk of hypospadias (OR = 2.6 [1.0-6.3] with n cases = 13, n controls = 21), but not the other pesticides. CONCLUSIONS: Our small study provides a robust assessment of fetal exposure. Fenitrothion's established antiandrogenic activities provide biologic plausibility for our observations. Further studies are needed to confirm this hypothesis.


Subject(s)
Hypospadias , Pesticides , Infant, Newborn , Infant , Child , Humans , Male , Female , Pregnancy , Hypospadias/chemically induced , Hypospadias/epidemiology , Meconium/chemistry , Pesticides/toxicity , Maternal Exposure/adverse effects , Case-Control Studies , Tandem Mass Spectrometry , Fenitrothion/analysis , France/epidemiology
2.
J AOAC Int ; 106(6): 1532-1541, 2023 Nov 02.
Article in English | MEDLINE | ID: mdl-37439707

ABSTRACT

BACKGROUND: Supercritical fluid extraction (SFE) is a fast, versatile, and solvent-efficient automatic extraction method. Despite its advantages, the results of our proficiency tests imply that the applicability assessments of SFE for pesticide residues were insufficient. OBJECTIVE: In this study, as analytical method using SFE was optimized and validated by testing the incurred and fortified brown rice samples with organophosphorus (OP), pyrethroid (PYR), and dithiolane (DIT) pesticides. METHOD: A validation study using the incurred sample with etofenprox, fenitrothion, and isoprothiolane was performed by comparing the analytical results obtained using the SFE and solid-liquid extraction with homogenization (SLE), which is a well-validated official multi-residue extraction method. The tests on the fortified samples were also performed for seven pesticide residues, chlorpyrifos, diazinon, O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN), etofenprox, fenitrothion, isoxathion, and isoprothiolane, at three fortification levels, 0.001, 0.01, and 0.1 mg/kg. RESULTS: In the test on the incurred samples, optimized SFE-to-SLE analytical values (CSFE/CSLE) were 99.2-100.1%, with RSD lower than 3%. In contrast, the analytical-to-spiked concentrations in the tests on the fortified samples were 96.4-105.0%, with RSD lower than 8.8%. CONCLUSIONS: These results indicate that the proposed SFE method, which is well validated with the incurred brown rice sample, is useful for determining OP, PYR, and DIT pesticide residues in brown rice. HIGHLIGHTS: The proposed SFE method satisfies EU and Japanese maximum residue limits (MRLs). The consumption of solvent can be reduced to one-fourth of that of SLE using the proposed SFE method.


Subject(s)
Chromatography, Supercritical Fluid , Oryza , Pesticide Residues , Pyrethrins , Pesticide Residues/analysis , Chromatography, Supercritical Fluid/methods , Tandem Mass Spectrometry , Fenitrothion/analysis , Pyrethrins/analysis , Chromatography, Liquid/methods , Solvents/chemistry
3.
Article in English | MEDLINE | ID: mdl-35588053

ABSTRACT

The fate of five pesticides comprising triadimefon, imidacloprid, fenitrothion, chlorpyrifos-methyl, and chlorpyrifos in wheat flour during noodle production and accelerated storage was systematically investigated. Pesticide residues were determined by high-performance liquid chromatography with diode array detection (HPLC-DAD) after each processing step and accelerated storage. The results indicated that dough mixing reduced the concentration of five pesticide residues by 23-42%, mainly owing to the increase of moisture content. Dough resting had little effect on the residues of triadimefon, imidacloprid, and fenitrothion, but decreased chlorpyrifos-methyl and chlorpyrifos significantly by 24% and 15%, respectively. The pesticide residues increased by 3% to 69% during the drying step, attributed to the different role played by thermal evaporation or thermal degradation and concentration of the different pesticides. Boiling lowered the pesticide residues significantly by 56% to 74% in both fresh noodles and dried noodles. All the pesticide residues decreased during accelerated storage, especially for fenitrothion, chlorpyrifos-methyl, and chlorpyrifos. The processing factors (PFs) of the five pesticides in the drying step were greater than 1, while the others were all less than 1. The whole process for noodle production was beneficial to reduce the pesticide residues with PFs ranging from 0.15 to 0.35. The PFs of five pesticides in accelerated storage were all below 1.


Subject(s)
Chlorpyrifos , Pesticide Residues , Pesticides , Chlorpyrifos/analysis , Fenitrothion/analysis , Flour/analysis , Pesticide Residues/analysis , Pesticides/analysis , Triticum/chemistry
4.
J Sci Food Agric ; 102(14): 6612-6622, 2022 Nov.
Article in English | MEDLINE | ID: mdl-35596658

ABSTRACT

BACKGROUND: Ultrasound has the potential to increase microbial metabolic activity, so this study explored the stimulatory effect of ultrasound pre-treatment on the degradation of four common pesticides (fenitrothion, chlorpyrifos, profenofos, and dimethoate) during milk fermentation by Lactobacillus plantarum and its effect on yogurt quality. RESULTS: Appropriate ultrasound pretreatment significantly enhanced the growth of L. plantarum. The degradation percentages of pesticides increased by 19-38% under ultrasound treatment. Ultrasonic intensity, pulse duty cycle, and duration time were key factors affecting microbial growth and pesticide degradation. Under optimal ultrasonic pre-treatment conditions, the degradation rate constants of four pesticides were at least 3.4 times higher than those without sonication. In addition, such ultrasound pretreatment significantly shortened yogurt fermentation time, increased the water holding capacity, hardness and antioxidant activity of the yogurt, and improved the flavor quality of the yogurt. CONCLUSION: Ultrasonic pretreatment significantly accelerated the degradation of the four pesticides during yogurt fermentation. In addition, such ultrasound pretreatment increased the efficiency of yogurt making and improved the quality of yogurt in terms of water holding capacity, firmness, antioxidant activity, and flavor. These findings provide a basis for the application of ultrasound to the removal of pesticide residues and quality improvement of yogurt. © 2022 Society of Chemical Industry.


Subject(s)
Chlorpyrifos , Pesticide Residues , Pesticides , Ultrasonic Therapy , Animals , Antioxidants/analysis , Chlorpyrifos/analysis , Dimethoate/analysis , Fenitrothion/analysis , Fenitrothion/metabolism , Fermentation , Milk/chemistry , Pesticide Residues/analysis , Pesticides/analysis , Water/analysis , Yogurt/analysis
5.
Int J Mol Sci ; 22(19)2021 Oct 07.
Article in English | MEDLINE | ID: mdl-34639187

ABSTRACT

Fenitrothion is an insecticide belonging to the organophosphate family of pesticides that is widely used around the world in agriculture and living environments. Today, it is one of the most hazardous chemicals that causes severe environmental pollution. However, detection of fenitrothion residues in the environment is considered a significant challenge due to the small molecule nature of the insecticide and lack of molecular recognition elements that can detect it with high specificity. We performed in vitro selection experiments using the SELEX process to isolate the DNA aptamers that can bind to fenitrothion. We found that newly discovered DNA aptamers have a strong ability to distinguish fenitrothion from other organophosphate insecticides (non-specific targets). Furthermore, we identified a fenitrothion-specific aptamer; FenA2, that can interact with Thioflavin T (ThT) to produce a label-free detection mode with a Kd of 33.57 nM (9.30 ppb) and LOD of 14 nM (3.88 ppb). Additionally, the FenA2 aptamer exhibited very low cross-reactivity with non-specific targets. This is the first report showing an aptamer sensor with a G4-quadruplex-like structure to detect fenitrothion. Moreover, these aptamers have the potential to be further developed into analytical tools for real-time detection of fenitrothion from a wide range of samples.


Subject(s)
Aptamers, Nucleotide/chemistry , Biosensing Techniques/methods , Brassica/metabolism , Fenitrothion/analysis , Insecticides/analysis , Plant Extracts/analysis , SELEX Aptamer Technique/methods , Brassica/drug effects , Fenitrothion/toxicity , Insecticides/toxicity
6.
J Environ Sci Health B ; 56(2): 142-149, 2021.
Article in English | MEDLINE | ID: mdl-33287632

ABSTRACT

Enzyme inhibition assay was used as a biomarker for detection of organophosphates pesticides in food and environmental samples. The aim of the present study was to optimize the time of enzyme-inhibitor reaction for quantitative determination of fenitrothion organophosphate based on cholinesterase inhibition. The results showed that this method provides a time-efficient, best linearity and simple assay. The effect of reaction time on the linearity relationship of the noncompetitive inhibition equation was studied. The best linearity of the assay was found at an optimum reaction time of 3.0 min, with coefficient of determination r 2 of 0.9972, in the range of inhibitor concentrations from 0.016 to 2.0 µg mL-1. The enzyme inhibition reached a plateau at 5 min by addition of pesticide in vitro and then the inhibited enzyme reactivate spontaneously and approached steady state at 20 min. A theoretical kinetic model to explain the effect of reaction time on the enzyme inhibition by addition of pesticide in vitro was derived. The higher values of coefficient of determination r 2 for the predicted model and error functions of the minimum deviations suggest that this model can be used to represent the experimental data and explain the plasma cholinesterase inhibition by fenitrothion pesticide.


Subject(s)
Enzyme Inhibitors/chemistry , Fenitrothion/analysis , Pesticides/analysis , Models, Biological , Organophosphorus Compounds/analysis
7.
Mikrochim Acta ; 187(6): 337, 2020 05 19.
Article in English | MEDLINE | ID: mdl-32430628

ABSTRACT

A sensitive and readily deployable analytical method has been reported for the simultaneous analysis of pirimicarb (PRM) and fenitrothion (FEN) pesticide residues in environmental water samples using fabric phase sorptive extraction (FPSE) followed by high-performance liquid chromatography combined with photodiode array (HPLC-PDA) detector. Both pesticides were successfully determined with a Luna omega C18 column under isocratic elution mode by means of acetonitrile and phosphate buffer (pH 3.0) as the mobile phase. The quantitative data for PRM and FEN were obtained at their maximum wavelengths of 310 nm and 268 nm, respectively. The calibration plots were linear in the range 10.00-750.00 ng mL-1 and 10.00-900.00 ng mL-1 with correlation coefficient of 0.9984 and 0.9992 for PRM and FEN, respectively. Major FPSE experimental variables were investigated in detail, such as contact time with the FPSE membrane, pH and electrolyte concentration, and the volume and type of desorption solvent. Under the optimized conditions, the developed method showed satisfactory reproducibility with relative standard deviations less than 2.5% and low limits of detection of 2.98 and 3.02 ng mL-1 for PRM and FEN, respectively. The combined procedure allows for enhancement factors ranging from 88 to 113, with pre-concentration values of 125 for both analytes. The chromatographic resolutions were approx. 12 for FEN (retention factor of 3.52) and PRM (retention factor of 6.09), respectively, with a selectivity factor of 1.73. Finally, the validated method was successfully applied to real environmental water samples for the determination of these pesticides. Graphical abstract.


Subject(s)
Carbamates/analysis , Fenitrothion/analysis , Pesticide Residues/analysis , Pyrimidines/analysis , Cellulose/chemistry , Chromatography, High Pressure Liquid , Dimethylpolysiloxanes/chemistry , Lakes/analysis , Limit of Detection , Polyesters/chemistry , Ponds/analysis , Reproducibility of Results , Rivers/chemistry , Solid Phase Extraction/instrumentation , Solid Phase Extraction/methods , Textiles , Water Pollutants, Chemical/analysis
8.
Toxicol Mech Methods ; 30(2): 134-138, 2020 Feb.
Article in English | MEDLINE | ID: mdl-31532269

ABSTRACT

Kinetic and validation of the enzymatic method for the determination of fenitrothion organophosphorus based on cholinesterase inhibition were studied. A Linear relationship was obtained with a determination coefficient R2 of 0.9989 suggesting that the noncompetitive inhibition kinetic equation is suitable to represent the enzymatic assay of fenitrothion. The value of the inhibition constant KI was 0.374 µg/ml/min. The analytical logarithmic curve for the determination of fenitrothion concentration using the percentage of cholinesterase inhibition presented good linear relations at concentrations of 0.05-2 µg/ml (R2 = 0.9889). The maximum inhibition 83% was observed at 2.0 µg/ml final assay concentration. The lower inhibition 3.3% was observed at 0.05 µg/ml detection limit. The experimental measurement condition was optimized. The enzymatic method exhibited detection limits (LOD) in the range of 0.05-2.0 µg/ml. The limit of quantification (LOQ) was 0.06 µg/ml with inhibition 13%. The concentration of fenitrothion that inhibited the hydrolysis of substrate by 50% (IC50 value) was 0.4 µg/ml. Standard deviations and coefficients of variation indicate a good precision of the enzymatic method for the detection of organophosphate insecticides at an incubation time of 20 min.


Subject(s)
Cholinesterase Inhibitors/analysis , Cholinesterases/blood , Fenitrothion/analysis , Insecticides/analysis , Models, Biological , Organophosphorus Compounds/analysis , Cholinesterases/metabolism , Dose-Response Relationship, Drug , Enzyme Assays , Humans , Kinetics , Limit of Detection , Time Factors
9.
Molecules ; 24(24)2019 Dec 17.
Article in English | MEDLINE | ID: mdl-31861155

ABSTRACT

A sensitive, rapid, reliable, and easily applicable method based on magnetic solid phase extraction (MSPE) combined with HPLC-PDA was developed for monitoring propoxur (PRO) and fenitrothion (FEN) pesticides in environmental water samples. The effect of major experimental variables on the extraction efficiency of both the pesticides was investigated and optimized systematically. For this purpose, a new magnetic material containing decanoic acid on the surface of particles was synthesized and characterized by XRD, FT-IR, SEM, EDX, and TGA analysis in detail. The simultaneous determination of pesticide molecules was carried out by using a Luna Omega C18 column, isocratic elution of acetonitrile (ACN): Water (70:30 v/v) with a flow rate of 1.2 mL min-1. After MSPE, the linear range for pesticide molecules (r2 > 0.9982) was obtained in the range of 5-800 and 10-800 ng mL-1, respectively. The limit of detections (LOD) are 1.43 and 4.71 ng mL-1 for PRO and FEN, respectively while RSDs % are below 3.5%. The applicability of the proposed method in four different environmental samples were also investigated using a standard addition-recovery procedure. Average recoveries at two spiking levels were over the range of 91.3-102.5% with RSD < 5.0% (n = 3). The obtained results show that decanoic acid grafted magnetic particles in MSPE combined with HPLC-PDA is a fast and simple method for the determination of PRO and FEN in environmental water samples.


Subject(s)
Decanoic Acids/chemistry , Fenitrothion/chemistry , Magnetite Nanoparticles/chemistry , Pesticide Residues/chemistry , Propoxur/chemistry , Chromatography, High Pressure Liquid , Decanoic Acids/analysis , Decanoic Acids/isolation & purification , Environmental Monitoring , Fenitrothion/analysis , Fenitrothion/isolation & purification , Limit of Detection , Molecular Structure , Pesticide Residues/analysis , Pesticide Residues/isolation & purification , Propoxur/analysis , Propoxur/isolation & purification , Reproducibility of Results , Solid Phase Extraction
10.
Mikrochim Acta ; 187(1): 8, 2019 12 03.
Article in English | MEDLINE | ID: mdl-31797057

ABSTRACT

A surface plasmon resonance study was carried out for the identification and determination of the organophosphate pesticide fenitrothion via an optical fiber sensor. A thin layer of silver was deposited on the unclad core of silica optical fiber for plasmon generation. This was followed by the deposition of a sensing surface comprising a layer of tantalum(V) oxide nanoparticles sequestered in a nano-scaled matrix of reduced graphene oxide. The sensing mechanism is due to the interaction of fenitrothion with the silver film which leads to a change in refractive index.. Characterized by a wavelength interrogation scheme, the fiber-optic sensor exhibited a red shift equalling 56 nm corresponding to fenitrothion concentration in the range 0.25-4 µM including the blank solution. The spectral sensitivity is 24 nm µM-1, the limit of detection is 38 nM, and the response time is as short as 23 s. The sensor is selective, repeatable and works at ambient temperature. Graphical abstractSchematic representation of the sensing mechanism of an SPR based fiber-optic fenitrothion sensor utilizing modification in refractive index of sensing surface comprising of tantalum(V) oxide (Ta2O5) nanoparticles embedded in reduced graphene oxide (rGO) caused by interaction with fenitrothion entities.


Subject(s)
Fenitrothion/analysis , Graphite/chemistry , Nanotechnology/instrumentation , Optical Fibers , Oxides/chemistry , Pesticides/analysis , Surface Plasmon Resonance/instrumentation , Tantalum/chemistry , Calibration , Fenitrothion/chemistry , Limit of Detection , Oxidation-Reduction , Pesticides/chemistry , Time Factors
11.
Shokuhin Eiseigaku Zasshi ; 59(5): 228-233, 2018.
Article in Japanese | MEDLINE | ID: mdl-30429422

ABSTRACT

We measured the concentrations of organophosphorus pesticide (chlorpyrifos-methyl, pirimiphos-methyl and fenitrothion) residues in domestic and imported commercial wheat products (flour, noodles, cookies) collected from 2008 to 2016. Chlorpyrifos-methyl and fenitrothion in domestic flour samples were detected in 16 out of 34 samples at levels of <0.001 to 0.016 ppm, and in 14 out of 34 samples at levels of <0.001 to 0.004 ppm. Chlorpyrifos-methyl was detected in 22 out of 38 domestic cookies at levels of <0.001 to 0.054 ppm (median: 0.001 ppm). Relatively high concentrations of chlorpyrifos-methyl (0.005 to 0.054 ppm) were found in six domestic cookies containing wheat bran. Pirimiphos-methyl was detected in 32 out of 68 cookies from foreign countries at levels of <0.001 to 0.11 ppm. Pirimiphos-methyl was detected frequently in products imported from Europe.


Subject(s)
Chlorpyrifos/analogs & derivatives , Fenitrothion/analysis , Food Analysis/methods , Food Contamination/analysis , Pesticide Residues/analysis , Triticum/chemistry , Chlorpyrifos/analysis , Europe , Insecticides/analysis
12.
Anal Chim Acta ; 1030: 52-60, 2018 Nov 07.
Article in English | MEDLINE | ID: mdl-30032773

ABSTRACT

We have reported an effective electrochemical sensor for assorted pesticide (i.e., Fenitrothion). Exact tracking of these pesticides has become more important for protecting the environment and food resources owing to their high toxicity. Hence, the development of compatible sensors for the real-time detection of pesticides is imperative to overcome practical limitations encountered in conventional methodologies. In this regard, the role of the novel, advanced functional materials such as niobium carbide (NbC) supported on molybdenum nanoparticles (NbC@Mo) has drawn great consideration in conventional sensory systems because of their numerous advantages over other nanomaterials. The nanocomposite was characterized by XRD, XPS, HR-TEM, and EIS. Under optimized working conditions, the modified electrode NbC@Mo/SPCE responds linearly as 0.01-1889 µM concentration range and the detection limit is 0.15 nM. Most importantly, the method was successfully demonstrated in fruit samples.


Subject(s)
Electrochemical Techniques , Fenitrothion/analysis , Fruit/chemistry , Molybdenum/chemistry , Nanocomposites/chemistry , Niobium/chemistry , Pesticide Residues/analysis , Particle Size , Surface Properties
13.
Anal Biochem ; 553: 15-23, 2018 07 15.
Article in English | MEDLINE | ID: mdl-29777681

ABSTRACT

This paper reports the electrosynthesis and characterisation of a polymeric film derived from 2-hydroxybenzamide over a graphite electrode and its application as an enzymatic biosensor for the determination and quantification of the pesticide fenitrothion. The material was analysed by scanning electron microscopy and its electrochemical properties characterised by cyclic voltammetry and electrochemical impedance spectroscopy. The enzyme tyrosinase was immobilised over the modified electrode by the drop and dry technique. Catechol was determined by direct reduction of biocatalytically formed o-quinone by employing the flow injection analysis technique. The analytical characteristics of the proposed sensor were optimised as follows: phosphate buffer 0.050 M at pH 6.5, flow rate 5.0 mL min-1, sample injection volume 150 µL, catechol concentration 1.0 mM and maximum inhibition time by fenitrothion of 6 min. The biosensors showed a linear response to pesticide concentration from 0.018 to 3.60 µM. The limit of detection and limit of quantification were calculated as 4.70 nM and 15.9 nM (RSD < 2.7%), respectively. The intra- and inter-electrode RSDs were 3.35% (n = 15) and 8.70% (n = 7), respectively. In addition, water samples spiked with the pesticide showed an average recovery of 97.6% (±1.53).


Subject(s)
Benzamides/chemistry , Electrochemical Techniques/methods , Electrodes , Fenitrothion/analysis , Graphite/chemistry , Insecticides/analysis , Monophenol Monooxygenase/chemistry , Biosensing Techniques/methods , Polymerization
14.
J Sep Sci ; 41(11): 2411-2418, 2018 Jun.
Article in English | MEDLINE | ID: mdl-29493115

ABSTRACT

A simple, environmentally benign, and rapid method based on temperature-controlled liquid-liquid microextraction using a deep eutectic solvent was developed for the simultaneous extraction/preconcentration of diazinon and fenitrothion. The method involved the addition of deep eutectic solvent to the aqueous sample followed by heating the mixture in a 75°C water bath until the solvent was completely dissolved in the aqueous phase. Then, the resultant solution was cooled in an ice bath and a cloudy solution was formed. Afterward, the mixture was centrifuged and the enriched deep eutectic solvent phase was analyzed by high-performance liquid chromatography with ultraviolet detection for quantification of the analytes. The factors affecting the extraction efficiency were optimized. Under the optimized extraction conditions, the limits of detection for diazinon and fenitrothion were 0.3 and 0.15 µg/L, respectively. The calibration curves for diazinon and fenitrothion exhibited linearity in the concentration range of 1-100 and 0.5-100 µg/L, respectively. The relative standard deviations for five replicate measurements at 10.0 µg/L level of analytes were less than 2.8 and 4.5% for intra- and interday assays, respectively. The developed method was successfully applied to the determination of diazinon and fenitrothion in water and fruit juice samples.


Subject(s)
Chromatography, High Pressure Liquid/methods , Diazinon/analysis , Diazinon/isolation & purification , Fenitrothion/analysis , Fenitrothion/isolation & purification , Fresh Water/chemistry , Fruit and Vegetable Juices/analysis , Liquid Phase Microextraction/methods , Food Contamination/analysis , Insecticides/analysis , Insecticides/isolation & purification , Limit of Detection
15.
J Sep Sci ; 41(7): 1567-1575, 2018 Apr.
Article in English | MEDLINE | ID: mdl-29230971

ABSTRACT

A new type of adsorbent composed of magnetic three-dimensional graphene coated with silver nanoparticles was synthesized by an electroless technique and used in the magnetic solid-phase extraction of selected pesticides (fenitrothion, chlorpyrifos, and hexaconazole) before gas chromatography with a micro-electron capture detector. The adsorbent was characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometry, and field-emission scanning electron microscopy. The important extraction parameters such as pH, adsorbent dose, extraction time, and desorption conditions were investigated. Under the optimal conditions, the analytical figures of merit were obtained as: linear dynamic range of 0.1-5 ng/g with determination coefficients of 0.991-0.996; limit of detection of 0.07-0.13 ng/g; limit of quantification of 0.242-0.448 ng/g; and the intraday and interday relative standard deviations (C = 5 ng/g, n = 3) were 3.8-8.7 and 6.6-8.9%, respectively. The developed method was successfully applied for analysis of the selected pesticides in tomato and grape with extraction recoveries in the range of 72.8-109.6%.


Subject(s)
Chlorpyrifos/analysis , Fenitrothion/analysis , Fruit/chemistry , Insecticides/analysis , Triazoles/analysis , Graphite/chemistry , Magnetic Fields , Metal Nanoparticles/chemistry , Silver/chemistry , Solid Phase Extraction
16.
J Agric Food Chem ; 65(49): 10711-10718, 2017 Dec 13.
Article in English | MEDLINE | ID: mdl-29144738

ABSTRACT

In this study, the detailed metabolic pathways of fenitrothion (FNT), an organophosphorus insecticide by Cunninghamella elegans, were investigated. Approximately 81% of FNT was degraded within 5 days after treatment with concomitant accumulation of four metabolites (M1-M4). The four metabolites were separated by high-performance liquid chromatography, and their structures were identified by mass spectroscopy and/or nuclear magnetic resonance. M3 is confirmed to be an initial precursor of others and identified as fenitrothion-oxon. On the basis of their metabolic profiling, the possible metabolic pathways involved in phase I and II metabolism of FNT by C. elegans was proposed. We also found that C. elegans was able to efficiently and rapidly degrade other organophosphorus pesticides (OPs). Thus, these results will provide insight into understanding of the fungal degradation of FNT and the potential application for bioremediation of OPs. Furthermore, the ability of C. elegans to mimic mammalian metabolism would help us elucidate the metabolic fates of organic compounds occurring in mammalian liver cells and evaluate their toxicity and potential adverse effects.


Subject(s)
Cunninghamella/metabolism , Fenitrothion/metabolism , Insecticides/metabolism , Biodegradation, Environmental , Chromatography, High Pressure Liquid/methods , Fenitrothion/analysis , Insecticides/analysis , Magnetic Resonance Spectroscopy/methods , Mass Spectrometry/methods
17.
Leg Med (Tokyo) ; 29: 44-50, 2017 Nov.
Article in English | MEDLINE | ID: mdl-29054069

ABSTRACT

We herein report a fatal intoxication case caused by the ingestion of the insecticides chlorpyrifos-methyl (CPFM) and fenitrothion (MEP). A 70-year-old man was found dead in his house and a cup containing a small amount of agricultural chemicals was on the table near his body. External and internal examinations revealed no injuries. In a gas chromatography-mass spectrometry (GC-MS) screening test, CPFM, MEP, and their metabolites, 3,5,6-trichloro-2-pyridinol (TCPY) and 3-methyl-4-nitrophenol (3MNP), respectively, were qualitatively detected in his stomach contents. The concentrations (µg/g) of CPFM, TCPY, MEP, and 3MNP in the extracts of each body fluid and organ tissue were assessed by GC-MS and were as follows: 27.8, 56.2, 17.2, and 2.82 (heart blood); 6.60, 42.9, 1.80, and 2.59 (peripheral blood); 0.0821, 45.9, 2,09, and 102 (urine); 21.4, 26.6, 76.2, and 3.83 (brain (frontal portion)); 16.1, 101, 9.67, and 1.26 (liver); 7.45, 101, 21.4, and 26.1 (right kidney); and 73,500, 9750, 232,000, and 1880 (stomach contents), respectively. Based on these results and autopsy findings, the cause of death was acute fatal intoxication by CPFM and MEP.


Subject(s)
Body Fluids/chemistry , Chlorpyrifos/analogs & derivatives , Fenitrothion/analysis , Fenitrothion/metabolism , Insecticides/analysis , Insecticides/metabolism , Aged , Autopsy/methods , Chlorpyrifos/adverse effects , Chlorpyrifos/analysis , Chlorpyrifos/metabolism , Fenitrothion/adverse effects , Gas Chromatography-Mass Spectrometry , Gastrointestinal Contents/chemistry , Humans , Insecticides/adverse effects , Male
18.
Anal Chem ; 89(17): 8995-9001, 2017 09 05.
Article in English | MEDLINE | ID: mdl-28783323

ABSTRACT

Three-dimensional (3D) printing has proven to be a versatile and useful technology for specialized applications in industry and also for scientific research. We demonstrate its potential use toward the electrochemical detection of nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and fenitrothion (FT). The detection of these compounds is of utmost importance in military and forensic applications. Stainless steel electrodes were fabricated by 3D printing, and the surface was electroplated with gold. The electrochemical performance of the 3D printed electrodes was compared to that of the conventionally employed glassy carbon electrode (GCE) and proved to be more sensitive toward the detection of all three nitroaromatic compounds. 3D printing of customizable electrodes provides a viable alternative to traditional electrodes for the analysis of samples with electrochemical methods.


Subject(s)
Electrochemical Techniques/methods , Nerve Agents/analysis , Dinitrobenzenes/analysis , Electrodes , Explosive Agents/analysis , Fenitrothion/analysis , Gold/chemistry , Printing, Three-Dimensional , Stainless Steel/chemistry , Trinitrotoluene/analysis
19.
Food Chem ; 229: 814-819, 2017 Aug 15.
Article in English | MEDLINE | ID: mdl-28372248

ABSTRACT

A simple and rapid gas chromatography with flame photometric detector (GC-FPD) determination method was developed to detect residue levels and investigate the dissipation pattern and safe use of fenitrothion in tomatoes. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) using an ethyl acetate-based extraction, followed by a dispersive solid-phase extraction (d-SPE) with primary-secondary amine (PSA) and graphite carbon black (GCB) for clean up, was applied prior to GC-FPD analysis. The method showed satisfactory linearity, recovery and precision. The limits of detection (LOD) and quantification (LOQ) were 0.005 and 0.01mg/kg, respectively. The residue levels of fenitrothion were best described by first order kinetics with a half-life of 2.2days in tomatoes. The potential health risks posed by fenitrothion were not significant, based on supervised residue trial data. The current findings could provide guidance for safe and reasonable use of fenitrothion in tomatoes and prevent health problems to consumers.


Subject(s)
Fenitrothion/analysis , Food Contamination , Pesticide Residues/analysis , Photometry/standards , Solanum lycopersicum/chemistry , Chromatography, Gas/methods , Chromatography, Gas/standards , Gas Chromatography-Mass Spectrometry/methods , Gas Chromatography-Mass Spectrometry/standards , Limit of Detection , Photometry/methods , Reproducibility of Results , Risk Assessment , Solid Phase Extraction/methods , Solid Phase Extraction/standards
20.
Talanta ; 168: 113-120, 2017 Jun 01.
Article in English | MEDLINE | ID: mdl-28391829

ABSTRACT

A combination of a novel synthesized azo dye (E)-1-(4-((4-(phenylamino)phenyl)diazenyl) phenyl)ethanone and reduced graphene oxide was used to electrochemically modify the surface of a pencil graphite electrode. The surfaces of the modified electrodes were characterized using electrochemical techniques (cyclic voltammetry and electrochemical impedance spectroscopy) and spectroscopic techniques (scanning electron microscopy and attenuated total reflectance). This azo dye/reduced graphene oxide modified electrode was applied first time for the electrochemical detection of an organophosphorus pesticide, fenitrothion. The modified pencil graphite electrode displayed excellent performance for the detection of fenitrothion. Cyclic voltammetry was used to study the dependence of the scan rate on the peak current and peak potential and to determine the kinetic parameters for fenitrothion. Square wave voltammetry was used to determine the effect of pH on the peak potential and for the sensitive and selective detection of fenitrothion using the modified electrode. Satisfactory results were obtained with the proposed sensor for the analysis of FT in tomato samples.


Subject(s)
Azo Compounds/chemistry , Electrochemical Techniques/methods , Electrodes , Fenitrothion/analysis , Graphite/chemistry , Insecticides/analysis , Biosensing Techniques , Hydrogen-Ion Concentration
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