Gas chromatographic method for determination of fenitrothion in technical and in emulsifiable concentrate and water-dispersible powder formulations: collaborative study

A variety of column packings and internal standards were evaluated to determine the most satisfactory system to use in a gas chromatographic (GC) method for analysis of fenitrothion, technical and formulations. Fenitrothion and the most closely related isomer, O,O-dimethyl O-(4-methyl-3-nitrophenyl) phosphorothioate, were resolved on columns packed with OV-210 and with polyphenyl ether, 6-ring (PPE-6R). A method based on the separation of fenitrothion on a PPE-6R column with fluoranthene as internal standard was selected for use in a limited collaborative trial and later for use in a full-scale collaborative trial with 21 collaborators participating. Each collaborator was furnished matched pairs of samples of technical fenitrothion, emulsifiable concentrate, and water-dispersible powder. The coefficients of variation (CV) for the paired samples were 1.02, 1.11, and 1.01, respectively, for technical fenitrothion, emulsifiable concentrates, and water-dispersible powders. Data are also presented for an alternative method in which compounds are separated on an OV-210 column with dibutyl sebacate as the internal standard. The method has been adopted official first action.     

Simultaneous determination of carbaryl, malathion, fenitrothion, and diazinon residues in sesame seeds (Sesamum indicum L.)

A method is described for the simultaneous determination of carbaryl (1-naphthyl methylcarbamate), malathion [diethyl (dimethoxythiophosphorylthio) succinate], fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), and diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate) in sesame (Sesamum indicum L.) seeds. Sesame seeds were Soxhlet extracted with n-hexane, and the extract was subjected to a liquid-liquid partitioning and column cleanup to remove the oily coextractives prior to analysis by high performance liquid chromatography (HPLC). The mean percent recoveries (+/- standard deviations) from sesame seeds fortified with carbaryl (0.004 to 0.035 microgram/g), malathion (0.53 to 4.25 microgram/g), fenitrothion (0.22 to 1.78 microgram/g), and diazinon (0.54 to 4.35 microgram/g) were 83.3 +/- 5.7, 85.5 +/- 6.6, 85. 6 +/- 7.2, and 88.4 +/- 4.8, respectively. The method was used for the simultaneous analysis of carbaryl, malathion, fenitrothion, and diazinon residues in sesame seeds obtained from an Ethiopian field crop that had been treated with the pesticides during its growing period.     

Metabolism of fenitrothion and conjugation of 3-methyl-4-nitrophenol in tomato plant (Lycopersicon esculentum)

The metabolism of (14)C-labeled fenitrothion (Sumithion, [O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate]) in tomato plant (Lycopersicon esculentum Mill., cv. Ponderosa) grown in the greenhouse equipped with quartz glass was conducted to investigate the effect of sunlight on the behavior of fenitrothion and to elucidate the detailed structure of conjugated metabolites. Tomato plants (BBCH 85) were topically treated with (14)C-labeled fenitrothion twice with a 2 week interval between applications. At 15 days after the second application, more than half of the recovered (14)C was detected as unaltered fenitrothion, glucose, and cellobiose esters of 3-methyl-4-nitrophenol (NMC) in extracts from tomato fruit. The photoinduced formation of the S-methyl isomer of fenitrothion via thiono-thiolo rearrangement was detected only in the surface rinse but at trace amounts. In the whole tomato fruit, fenitrothion, the S isomer, NMC-beta-glucoside, and NMC cellobioside were detected at 34.16, 1.28, 7.47, and 15.07% of the recovered (14)C, respectively. Trace amounts of the oxon analogue of fenitrothion were detected only on tomato leaves. The chemical structure of the cellobiose conjugate of NMC, 1-O-beta-d-glucopyranosyl-(1-->4)-beta-d-glucopyranosyl-3-methyl-4-nitrophenol, was determined by spectroscopic analyses (liquid chromatography-mass spectrometry, NMR), using the metabolite obtained from leaves and stems of tomato plant hydroponically grown with (14)C-labeled NMC.     

Comparison of soxhlet and microwave-assisted extractions for the determination of fenitrothion residues in beans

White and black "niebe" beans [Vigna unguiculata (L.) Walp] from Senegal were treated with fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), and the residues were determined by high-performance liquid chromatography (HPLC) and electron capture gas chromatography (EC-GC). Fenitrothion residues from the beans were extracted by Soxhlet extraction (SE) and microwave-assisted extraction (MAE). A column cleanup procedure was used to remove the coextractives in the extract before HPLC and EC-GC analyses. The overall mean recoveries of fenitrothion residues in the 0.19-1.90 microg/kg fortification range determined from extracts obtained by SE and MAE were 88.4 and 89.8%, respectively, with respective relative standard deviations of <4%. The results show that MAE is a viable alternative to the commonly used SE for the determination of fenitrothion residues in beans.     

Removal of Mixed Pesticides from Drinking Water System Using Surfactant-Assisted Nano-TiO2

The present study focused on the degradation of mixed pesticides using UV-induced photocatalytic degradation of lindane (1α,2α,3β,4α,5α,6β-hexachlorocyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate), and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate). Different grades of TiO₂ were prepared through the acid route (AR), alcohol route (AlR), and surfactant route (SR) and their photocatalytic activity were compared with commercially available Degussa P-25 TiO₂. The rate of degradation of pesticides was high for TiO₂ prepared through the SR compared to the other three catalysts. The crystalline structure and morphology of SR TiO₂ was identified with scanning electron microscope, energy dispersive X-ray analyzer, UV, and transmission electron microscope analyses and was compared with that of Degussa P-25 TiO₂. Degradation studies of individual as well as mixed pesticides were carried out. The intermediate formed during the photodegradation of methyl parathion, lindane, and dichlorvos were identified by gas chromatography–mass spectrometry analysis.     

Biologically-induced hydrolysis of parathion in soil: Kinetics and modelling

The hydrolysis of the organophosphorus insecticide, parathion (O,O-diethyl O-p-nitrophenyl phosphorothioate) in a silty loam sierozem soil (Gilat, Israel) occurred primarily through microbial action. Parathion (labelled with ¹⁴C in the alkyl chain) was applied at levels of 10–160 μg dry soil^?1 to soil remoistened to 20% and incubated at 25°C for 8 days. Bacterial numbers increased to a maximum 4–5 days after application of parathion and the increase was proportional to the concentration of parathion added. The rate of hydrolysis of parathion per μg applied was independent of the concentration of parathion. A model developed to predict the relationship between parathion concentration, microbial numbers and hydrolysis kinetics was in general agreement with the data experimentally obtained. The course of decomposition of successive additions of parathion, determined experimentally and predicted by the model, was characterized by rapid hydrolysis of parathion and successive increases in bacterial numbers. A portion of the ¹⁴C applied in these experiments was strongly absorbed by the soil and was not used by the soil microorganisms during the incubation period tested.     

Persistence and biodegradation of selected organophosphorus insecticides in flooded versus non-flooded soils

Summary The persistence of parathion, methyl parathion and fenitrothion in five tropical soils of varying physicochemical characteristics was compared under flooded and non-flooded conditions. The degradation of all the three insecticides was more rapid under flooded conditions than under non-flooded conditions in four out of five soils. Degradation of these insecticides proceeded by hydrolysis under non-flooded conditions and essentially by nitro group reduction and to a minor extent by hydrolysis under flooded conditions. Kinetic analysis indicated that degradation of the three insecticides followed a first-order reaction irrespective of the soil and water regime. The degradation of these organophosphorus insecticides was accelerated after repeated applications to flooded alluvial soil. Nitro group reduction was the major pathway of degradation for all the three insecticides after the first addition while the rate of hydrolysis increased after each successive addition.     

Thin layer chromatography of parathion as paraoxon with cholinesterase inhibition detection.

A simple, sensitive, and rapid method is described for the quantitative estimation of ng amounts of parathion (O,O-diethyl O-p-nitrophenyl phosphorothioate) as paraoxon (O,O-diethyl O-p-nitrophenyl phosphate) on thin layer chromatograms. Paraoxon is detected by inhibition, using p-nitrobenzenediazonium fluoroborate as the chromogenic reagent. This chromogenic reagent is more sensitive than Fast Blue B or indoxyl acetate; 0.1 ng may be detected and amounts from 5 to 50 ng may be estimated. The method is a viable alternative to gas chromatographic analysis for parathion.     

Rapid and sensitive determination of 4-nitrophenol, 3-methyl-4-nitrophenol, 4,6-dinitro-o-cresol, parathion-methyl, fenitrothion, and parathion-ethyl by liquid chromatography with electrochemical detection

Liquid chromatography with electrochemical detection has been used to determine various nitropesticides, DNOC, fenitrothion, and parathion (methyl and ethyl), and some of their main metabolites, 4-nitrophenol for parathion (methyl and ethyl) and 3-methyl-4-nitrophenol for fenitrothion, by using indirect detection. Analysis of them in river water samples has been performed without a preconcentration step. The recovery efficiencies of the tested compounds yielded values between 96 and 112% at the fortification level of 0.5 ppb in a river water sample, and their relative standard deviations were between 1 and 15%. The detection limits of these compounds ranged between 0.05 and 0.14 ppb.     

Purification and partial characterization of an acid phosphatase from Spirodela oligorrhiza and its affinity for selected organophosphate pesticides

An acid phosphatase from the aquatic plant Spirodela oligorrhiza (duckweed) was isolated by fast protein liquid chromatography and partially characterized. The enzyme was purified 1871-fold with a total yield of 40%. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) of the pure acid phosphatase resolved a single protein band that migrated to approximately 60 kDa. Nondenaturing SDS-PAGE electrophoresis revealed a single protein band around 120 kDa after staining with Coomassie Brilliant blue. Quantitative gel filtration chromatography estimated a native molecular mass of this enzyme to be 120 kDa. Thus, this acid phosphatase likely functions as a homodimer, consisting of two similar 60 kDa subunits. An electrophoretic technique using the flourogenic substrate 4-methylumbelliferyl phosphate enabled visualization of an acid phosphatase activity that corresponded to the protein band at 120 kDa on a nondenaturing PAGE gel. It was determined that the acid phosphatase had a pH optimum of 6.0 at 25 degrees C. The enzyme activity appeared to be stable over a broad range of temperatures (10-40 degrees C) and in the presence of the metals Zn2+, Mn2+, and Mg2+ as well as the chelating agents ethylenedinitrilotetraacetic acid and ethylene glycol tetraacetic acid. It was shown that this acid phosphatase could hydrolyze a variety of physiological organophosphate compounds including beta-glycerophosphate, phosphoserine, adenosine triphosphate, adenosine diphosphate, adenosine monphosphate, and pyrophosphate. Furthermore, analysis using capillary electrophoresis demonstrated that this hydrolytic enzyme could transform a wide array of organophosphate pesticides including S-2-ethylthioethyl O,O-dimethylphosphorothioate (demeton-S-methyl); S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethylphosphorodithioate (malathion); O,O-dimethyl O-4-nitrophenyl (paraoxon); O,O,O,O-tetraethyldithiopyrophosphate (sulfatep); O-2-chloro-4-nitrophenyl O,O-dimethylphosphorothioate (dicapthon); and 2,2-dichlorovinyl dimethylphosphate (dichlorvos).     

Enzyme-linked immunosorbent assay based on a polyclonal antibody for the detection of the insecticide fenitrothion. Evaluation of antiserum and application to the analysis of water samples.

For development of an indirect competitive enzyme-linked immunosorbent assay (ELISA) for the organophosphorus insecticide fenitrothion, the specificity of the antiserum R-3 generated with the bifunctional hapten, LysMNPA (2-[[[(3-methyl-4-nitrophenyl)oxy]methylcarbonyl]amino]-6-(2,4-dinitrophenyl)aminohexanoic acid) and the application to the residual analysis of some water samples were evaluated. At optimized ELISA conditions, the quantitative working range was from 1 to 39 ng/mL with a limit of detection of 0.3 ng/mL and an IC(50) value of 6 ng/mL. Cross-reactivity to structurally similar organophosphorus compounds and related chemicals was determined. The antiserum R-3 showed significant cross-reactivity with fenitrooxon and 3-methyl-4-nitrophenol, which have a 3-methyl-4-nitrophenoxy group as common structures, but showed relatively low cross-reactivity with other compounds. Each water sample (river water, tap water, purified water, and bottled water) had a matrix effect and was investigated by adding Tween 20 in the assay buffer. These four kinds of water samples were fortified with fenitrothion at several concentration levels and were directly analyzed with only dilution with an equal volume of antiserum solution. The mean recovery was 105.9%, and the mean coefficient of variation was 10.9%. The results suggested that the developed ELISA would be very suitable for a preliminary screening for fenitrothion in water samples at such low levels.     

Stability of chlorpyrifos for termiticidal control in six Australian soils.

Chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate] is the most widely used soil-applied termiticide in Australia. It is relatively stable, has low water solubility, is absorbed by organic matter, and has a high affinity for soil with low partitioning potential from soil matter to soil water. The purpose of this degradation study is to determine the effect of soil alkalinity on the longevity of termite protection when chlorpyrifos is applied as a termiticide in a range of Australian soils, particularly high-pH substrates. The study also examines the effects of initial soil concentration on the degradation of chlorpyrifos in the range of soils. At an initial soil concentration of 1000 mg kg(-)(1) for termite control, the degradation rate of chlorpyrifos is very strongly retarded in soils tested when compared with lower soil concentrations of 100 and 10 mg kg(-)(1) in the same soils. The degradation data correlated with a logarithmic model of decay, and it was thus possible to produce half-lives and predict likely periods of termite control. Average half-lives for all soils for the three concentrations were 385, 155, and 41 days, respectively. Soil pH had no effect on the rate of degradation at all concentrations tested.     

Aminoparathion: a highly reactive metabolite of parathion. 1. Reactions with polyphenols and polyphenol oxidase

Spiking of tomato and apple fruits with parathion at different levels of about 1-4 mg/kg irradiation and under simulated sunlight conditions resulted in nearly complete photodegradation within 13 h, but extractable parathion degradation products could not be found in any case. However, after irradiation of an unrealistically spiked apple (134 mg/kg) different photoproducts including aminoparathion (AP) were detectable by HPLC, proving that the hitherto postulated photochemistry of parathion indeed takes place in the fruit cuticle environment. Besides the photoreduction pathway it was shown for the first time that AP is also easily formed by reduction of the primary photoproduct nitrosoparathion with thiols (cysteine, glutathione), while ascorbic acid only leaves hydroxylaminoparathion. In the presence of polyphenols, AP was effectively bound to quinone intermediates formed by both silver oxide and polyphenol oxidases. For pyrocatechol, a disubstituted o-quinone derivative could be isolated as a dark red addition product and structurally be elucidated. However, in the presence of caffeic acid, catechol, naringin, and quercetin, respectively, insoluble dark colored polymers precipitated within 48 h, while in the supernatants AP was not detectable any more. Polymer-bound and nonextractable AP was proven by transesterification with sodium ethoxide releasing O,O,O-triethyl thiophosphate which was determined by GC. Additionally, AP itself was a substrate for polyphenol oxidases, resulting in a quinone imine intermediate which in turn reacted with excessive AP yielding deep red colored di- and trimerization products.     

Degradation of diphenyl ether herbicides in soils

The gas chromatographic determination of CNP (2,4,6-trichlorophenyl 4-nitrophenyl ether), nitrofen (2,4-dichlorophenyl 4′-nitrophenyI ether), chlomethoxynil (2,4-dieblorophenyl 3′-methoxy-4′-nitrophenyl ether), CFNP (2,4-dichloro-6-fluorophenyl 4-nitrophenyl ether) and their amino derivatives in soils were carried out. Good recoveries from soils were obtained for the diphenyl ethers. On the other hand, satisfactory recoveries from soils were also obtained for the amino derivatives at high concentrations, but the recoveries at lower concentrations averaged about 66% for the least recovered compound.

The degradation of several diphenyl ether herbicides in two paddy soils were compared under flooded and upland conditions. The degradation was much slower under upland than under flooded conditions. Considerable amounts of their amino derivatives were produced in soils under flooded conditions, but not under upland conditions. It was suggested that the diphenyl ethers to the amino derivatives involved both chemical and microbial processes. CNP and chlomethoxynil degraded faster at lower concentrations than at higher ones.     

La（Ⅲ）对UV—B辐射胁迫下大豆幼苗光氧化作用的影响

采用水培实验法研究了稀土La（Ⅲ）对紫外辐射（UV—B：0．15Wm^-2，0．45Wm^-2）胁迫下大豆（Glycinemax）幼苗体内O2^-和H2O2积累、抗坏血酸过氧化物酶（AsA—POD）活性变化和叶绿素（chl）光氧化降解的影响。实验结果表明：La（Ⅲ）可降低大豆幼苗体内的O2^-和H2O2含量、提高AsA—POD的活性，从而减轻光氧化作用对大豆幼苗chl的降解及对植株的伤害。     

SBSE-GC-ECD/FPD in the analysis of pesticide residues in Passiflora alata Dryander herbal teas

Stir bar sorptive extraction (SBSE) in combination with GC-ECD/FPD analysis is here applied to the determination of the residues of 11 pesticides (hexachlorobenzene, lindane, chlorothalonil, parathion methyl, parathion ethyl, fenitrothion, malathion, dieldrin, alpha- and beta-endosulfan, and tetradifon) in herbal teas prepared with Passiflora alata Dryander spiked leaves. The method was optimized using spiked herbal teas in a range from 0.05 to 1 pg/microL for organochlorine pesticides and from 0.15 to 3 pg/microL for organophosphorus pesticides. The method is reproducible and repeatable with recoveries calculated from herbal teas prepared with spiked plant material versus spiked herbal teas, varying from about 30% for tetradifon to about 90% for parathion methyl and malathion. The limits of quantitation (LOQs) ranged from 0.017 pg/microL for lindane to 0.117 pg/microL for malathion.     

Gas-liquid chromatographic determination of famphur and its oxygen analog in tissues of reindeer and cattle.

A gas chromatography equipped with a flame photometric detector operating in the phosphorus mode provided a sensitive method for determining residues of famphur, O,O-dimethyl O-[p-(dimethylsulfamoyl)phenyl]phosphorothioate, and its oxygen analog in reindeer and cattle tissues. With extraction and cleanup, 0.025 ppm famphur and 0.06 ppm oxygen analog could be detected in the body tissues. Recoveries of 73-100% were obtained from fat, muscle, liver, and kidney.     

Degradation products of chlomethoxynil (X-52) in soil

The degradation of unlabelled and ^l4C-labelled chlomethoxynil (2,4-dichlorophenyl 3′-methoxy-4′-nitrophenyl ether) in a flooded soil was studied in the laboratory, using thin-layer chromatography (TLC) and combined gas chromatography-mass spectrometry (GC-MS).

Chlomethoxynil was rapidly degraded, and labelled chlomethoxynil was largely transformed into substances which were unextractable with organic solvents. Moreover, most of the radioactive substances extracted with organic solvents were not “free” compounds but complexes. The degradation products identified were the amino derivative (2,4-dichlorophenyl 4′-amino-3-methoxyphenyl ether), the demethyl derivative (2,4-dichlorophenyl 3′-hydroxy-4′-nitrophenyl ether), the formylamino derivative (2,4-dichlorophenyl 4-formylamino-3′-methoxyphenyl ether), the acetylamino derivative (2,4-dichlorophenyl 3-methoxy-4′-acetylaminophenyl ether), thepropionylamino derivative (2,4-dichlorophenyl 4-propionylaminophenyl ether), 2,4-dichlorophenol, and several other minor compounds.     

基于构建微生物传感器的甲基对硫磷降解菌的分离鉴定及其降解特性研究

有机磷农药是目前环境中残留量最多的农药之一,对其残留量的检测及降解机制的研究对于环境污染及生态修复具有重要意义。微生物传感器由生物学元件与换能器构成,因具有成本低廉、易于微型化及选择性高等特点而被广泛应用于各种生化物质的分析和检测。本文从长期受农药污染的土壤中分离出4株能以甲基对硫磷为碳源生长的菌株,根据形态特征和16S r RNA基因序列同源性分析,对4株降解菌进行鉴定,利用高效液相色谱测定降解率,选取降解率最高的1株菌进行降解机制研究,以期将其应用于测定环境中甲基对硫磷残留的电位型微生物传感器的构建。结果表明,在甲基对硫磷初始浓度50 mg·L-1、30℃、p H 7.0的培养条件下培养7 d,4株菌对甲基对硫磷的降解率均在78%以上,其中1株菌的降解效率可达100%。16S r RNA基因序列测定表明,该菌株属于克雷伯氏菌属,命名为Klebsiella sp.MP-6。利用液相色谱-质谱联用对其降解产物的研究表明,菌株MP-6水解甲基对硫磷主要产生二甲基硫代磷酸(dimethyl thiophosphoric acid,DMTP)和对硝基苯酚(p-nitrophenol,PNP),极少部分PNP通过产生4-硝基邻苯二酚(4-nitrocatechol,4-NC)和1,2,4-苯三酚(1,2,4-BT)进一步代谢。结果表明,基于测定中间产物对硝基苯酚(p-nitrophenol,PNP)的电位响应信号,该菌株适用于构建测定海水及土壤等环境中有机磷农药的微生物传感器。     

Effect of the epicuticular waxes of fruits and vegetables on the photodegradation of rotenone

The effect of epicuticular waxes extracted from fruits (apple, nectarine, pear, and plum) and vegetables (tomato and eggplant) on the photodegradation of rotenone was studied. The waxes affected the decay rate and the degradation pathway of this botanical insecticide. Tomato, nectarine, and plum waxes decreased the photodegradation rate compared to controls, whereas apple and pear waxes increased it. Rotenone irradiated under sunlight without waxes gave seven photoproducts; in contrast, in the presence of waxes it changed its behavior, leading to different pathways according to the wax employed. The main photoproduct formed was 12abeta-rotenolone.