蔬菜中有机磷农药残留研究及对策

以西安市为例，研究了蔬菜中有机磷农药的残留问题，分析了不同农药在蔬菜中的残留特征以及不同品种蔬菜、不同类型蔬菜中农药残留的特征，讨论了蔬菜中农药残留量超标的原因及相关对策。     

Effect of ultraviolet-absorbing vinyl film on organophosphorus insecticides dichlorvos and fenitrothion residues in spinach

Dichlorvos and fenitrothion residues found in spinach grown in greenhouse covered either by regular vinyl film or UV-absorbing vinyl film (UV-A) were analyzed by gas chromatography. After one day, dichlorvos residues in spinach covered with regular vinyl film and UV-A degraded by 97% and 80%, respectively, and degraded 100% after three days covered with regular vinyl film and six days covered with UV-A. After three days, fenitrothion residue in spinach covered with regular vinyl film degraded by 72% and then by 97% after six days; residue in spinach covered with UV-A degraded by 50% after three days and by 95% after six days. These results indicate that UV-A used to prevent the occurrence of insects and fungi in greenhouses reduced the degradation rates of dichlorvos and fenitrothion.     

Neurotoxicity of organophosphorus insecticides Leptophos and EPN.

Phosfolan, chlorpyrifos, and stirophos when applied to white mice at sublethal doses did not induce any delayed neurotoxic effect. On the other hand, Leptophos and EPN when administered orally at sublethal or lethal levels clearly produced a delayed neurotoxic ataxia in treated mice. The five tested organophosphorus insecticides were compared for their ability to inhibit cholinesterase, neurotoxic esterases and monoamine oxidase. I50 values were estimated for each case. The results revealed that all five compounds were inhibitors of cholinesterase, but only Leptophos and EPN were shown to be potent inhibitors for both neurotoxic esterase and monoamine oxidase in the mouse brain. Additional particular properties of both Leptophos and EPN were found in their ability to cause delayed neurotoxic ataxia in chickens and sheep fed once on sublethal doses of these compounds. It is believed that the phosphonate ester configuration of EPN and Leptophos has a specific mode of toxic action which is mainly located at the central nervous system. It is also postulated that these delayed neurotoxic agents might inhibit postganglionic sympathetic neurons, thus resulting in chronic paralytic effects.     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

In-vivo interaction of some organophosphorus insecticides with different biochemical targets in white rats

A comparative study between five organophosphorus insecticides: Leptophos, EPN, Cyanofenphos, Chlorpyrifos and Diazinon, was carried out for acute oral toxicity to white rats and for their in vivo interaction at 1/10th of LD50 doses with the activity of six serum enzymes after 4 wks from oral administration. Leptophos, Chlorpyrifos and diazinon exerted significant inhibition particularly to glutamic oxaloacetic transaminase (GOT), glutamic pyruvic transaminase (GPT), glutamyltransferase (GT) and lactate dehydrogenase (LDH). Adding ascorbic acid in the diet at 0.5% enhanced the acute oral toxicity of leptophos, chlorpyrifos and diazinon. For all the compounds, presence of ascorbic acid protected a number of the monitored serum enzymes from being inhibited except for leptophos. Ascorbic acid caused hypoglycemia with sublethal doses of leptophos, chlorpyrifos, and diazinon. The synergist piperonyl butoxide alone at 750 mg/kg dose inhibited the activity of the six serum enzymes. Presence of ascorbic acid in the diet intensified the inhibitory effect of piperonyl butoxide to all enzymes except for GOT.     

Solid phase microextraction applied to the analysis of organophosphorus insecticides in fruits

Trace amounts of organophosphorus pesticides (OPs) were determined in various fruits by headspace solid phase microextraction (HS-SPME) and gas chromatography–nitrogen phosphorous detection (GC-NPD). Sampling from the headspace enhanced method selectivity, whereas at the same time improved fiber life time and method sensitivity. Diazinon, parathion, methyl parathion, malathion and fenithrothion were determined in various fruits: more than 150 samples of 21 types of fruits were studied. SPME-GC-NPD provided a useful and very efficient analytical tool: method linearity ranged from 1.2 to 700 ng/ml. Limits of detection (LODs) and quantitation (LOQs) ranged from 0.03 to 3 ng/ml and 0.12 to 10 ng/ml respectively, values well below the residue limits set by the EU. Less than 2% of the samples were found positive containing amounts higher than the EU limits. The effect of fruit peeling and washing was also investigated.     

Toxic and developmental effects of organophosphorus insecticides in embryos of the South African clawed frog

Four organophosphorus insecticides and the active metabolites of two phosphorothionate insecticides were tested for their toxic and teratogenic effects on embryos of Xenopus laevis. All compounds caused dose-dependent developmental defects, such as abnormal pigmentation, abnormal gut development, notochordal defects and reduced growth. Malathion, malaoxon, parathion, and paraoxon produced severe defects, while monocrotophos and dicrotophos produced considerably milder defects. All compounds reduced NAD+ levels to a similar extent, regardless of the severity of the defects induced. Thus some commonly used organophosphorus insecticides and their metabolites are teratogenic to Xenopus embryos, but reduced NAD+ level does not appear to be important in causing the developmental defects.     

Delayed neurotoxicity in the wild mallard duckling caused by the organophosphorus insecticides cyanofenphos and leptophos

The susceptibility of wild mallard ducklings to the delayed neurotoxic effect of the neurotoxic organophosphorus insecticides cyanofenphos and leptophos was evaluated following a daily dosing regimen. Ducklings were treated daily with either cyanofenphos or with leptophos at different dose levels for 90 days, or until they died, or became paralyzed. A control group of ducklings given corn oil at 1 ml/kg daily for 90 days was used for comparison. All treated birds were observed daily for any clinical signs of neurotoxicity during the course of this study. All of the surviving ducklings that were treated with cyanofenphos at 4 mg/kg/day or leptophos at 10 mg/kg/day developed clinical signs of delayed neurotoxicity after 7 to 11 weeks of intoxication. Symptoms included leg weakness, ataxia, severe ataxia and paralysis. The observed clinical signs were confirmed by histological changes found in the spinal cords of the treated birds. These changes were of the type associated with organophosphorus-induced delayed neuropathy (OPIDN). These results demonstrate that wild mallard ducklings are susceptible to OPIDN and this avian species can be used in screening organophosphorus compounds for such effect.     

Delayed neurotoxicity in the wild mallard duckling caused by the organophosphorus insecticides cyanofenphos and leptophos

Abstract

The susceptibility of wild mallard ducklings to the delayed neurotoxic effect of the neurotoxic organophosphorus insecticides cyanofenphos and leptophos was evaluated following a daily dosing regimen. Ducklings were treated daily with either cyanofenphos or with leptophos at different dose levels for 90 days, or until they died, or became paralyzed. A control group of ducklings given corn oil at 1 ml/kg daily for 90 days was used for comparison. All treated birds were observed daily for any clinical signs of neurotoxicity during the course of this study. All of the surviving ducklings that were treated with cyanofenphos at 4 mg/kg/day or leptophos at 10 mg/kg/day developed clinical signs of delayed neurotoxicity after 7 to 11 weeks of intoxication. Symptoms included leg weakness, ataxia, severe ataxia and paralysis. The observed clinical signs were confirmed by histological changes found in the spinal cords of the treated birds. These changes were of the type associated with organophosphorus‐induced delayed neuropathy (OPIDN). These results demonstrate that wild mallard ducklings are susceptible to OPIDN and this avian species can be used in screening organophos‐phorus compounds for such effect.     

Simultaneous determination of organophosphorus and organonitrogen pesticides residues in Angelica sinensis

Gas chromatography with nitrogen phosphorus detector (GC-NPD) was applied to the simultaneous determination of 15 organophosphorus and 6 organonitrogen pesticides residues in Angelica sinensis. The pesticides were extracted by microwave-assisted extraction (MAE) and ultrasound-assisted extraction (UAE) techniques, respectively. The experimental variables were optimized through orthogonal array experimental design. Cleanup of extracts was performed with column chromatography using florisil and neutral aluminum as the sorbents. The determination of pesticides in the final extracts was carried out by GC-NPD. Under optimized conditions, the average recoveries obtained from MAE and UAE are in the range of 75.1–129% and 70.6–129%, respectively, and the relative standard deviations of MAE and UAE were 3.1–10.6% and 1.0–17.8%, respectively.     

A method for the analysis of organophosphorus pesticide residues in Mexican axolotl

A method based on matrix solid-phase dispersion (MSPD) was developed for quantitative extraction of three organophosphorus pesticides (OPPs) from the Mexican axolotl, Ambystoma mexicanum. The determination was carried out using high- performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection (DAD). The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, fenthion and methyl parathion. The method was validated, yielding recovery values higher than 90%. The precision, expressed as the relative standard deviation (RSD), was less than or equal to 6% in muscle samples at spiking levels of 10 and 5 ppm. Linearity was studied from 15 to 60 ppm for chlorpyrifos and fenthion, and from 7.5 to 30 ppm for methyl parathion. The limits of detection (LODs) were found to be less than or equal to 0.5 ppm_.This method was applied to the analysis of samples from a chlorpyrifos-exposed axolotl, demonstrating its use as an analytical tool for toxicological studies.     

Chlorpyrifos residues levels in fruits and vegetables after field treatment

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate) was applied with three different formulations on oranges, peaches, tomatoes, wine and table grapes, and its behaviour was evaluated after field treatment. The formulations applied were emulsifiable concentrates (EC), microencapsulates (ME), and wettable granules (WG). The residues were similar in all crops studied in the EC and WG experiments, except peaches with WG treatment, the residue amount was lower than EC values. Tomatoes which were grown in greenhouse showed similar residues in all treatments just after treatment. Wine and table grapes showed different decline curves in the EC experiments ascribable to the different growing technology. Instrumental limit of determination (LOD) and limit of quantification (LOQ) for all matrices were 0.01, and 0.03 mg kg?1, respectively. Repeated treatments showed that Chlorpyrifos can accumulate leading to residue levels at the preharvest interval (PHI) over the maximum residue level (MRL), especially on oranges and peaches. Among the formulates used ME showed the higher risk of residues over the MRL at harvest.     

LC-MS/MS determination of pesticide residues in fruits and vegetables

The aim of the research is to evaluate pesticide residue contamination of fresh and frozen fruits and vegetables, agricultural raw material, purchased from Polish farmers for production of frozen fruits and vegetables, and the estimation of the multiresidue method effectiveness expressed as the proportion of pesticides detected in food samples to the total number of pesticides analyzed by multiresidue methods. A total of 144 samples (of black currants, red currants, raspberries, cherries, strawberries, blackberries, cauliflowers and broccoli) were analyzed using LC-MS/MS method for the determination of 60 pesticides. QuEChERS extraction, matrix-matched calibration and dynamic multiple reaction monitoring method were used. Residues of 15 compounds, mainly fungicides and insecticides, were detected in 46 samples. The percentage of samples with residues above the maximum residue levels (MRL) was 15%, whereas samples with residues below MRL were 17%. A total of 13 samples contained more than one pesticide residue. Pesticide residues were detected most often in samples of black currants (50%), broccoli (36.4%), raspberries (29%) and red currants (21.8%). The most frequently detected pesticides were carbendazim and acetamiprid. The proportion of pesticides detected during our study to the total number of analyzed pesticides amounted to 25%. It was compared to literature findings. For three fourth of multiresidue methods, the proportion was below 50% for methods developed for the analysis of less than 100 pesticides, and below 30% for methods developed for the analysis of more than 100 pesticides. It appears that a lot of efforts and means is lost on pesticides never or rarely detected in examined samples. The workload and cost effectiveness of the development and application of multiresidue methods along with the range of pesticides covered by the method should be carefully and thoroughly considered anytime when a new method or workflow is developed. Including non-targeted screenings in pesticide residue control seems to be an alternative worth considering.     

Effects of two organophosphorus insecticides on some biochemical constituents in the nervous system and liver of rabbits

Abstract

Male Baladi rabbits were acutely and sub‐chronically intoxicated with cyanofenphos and profenophos. The levels of cholesterol, triglycerides, B‐lipoproteins and total proteins were determined in the serum, brain, spinal cord and sciatic nerve of rabbits. Moreover, the activities of alkaline phosphatase, acid phosphatase and glutamic‐pyruvic transaminase were determined in the liver of the animals. The whole Studie revealed that the biochemical constituents were highly affected by the tested insecticides. Also, the liver function suffered from adverse effects of the tested insecticides.     

Pesticide residues in fruits and vegetables in Ghana: a review

Pesticides are known to improve agriculture yield considerably leading to an increase in its application over the years. The use of pesticides has shown varying detrimental effects in humans as well as the environment. Presently, enough evidence is available to suggest their misuse and overuse in the last few decades in most developing nations primarily due to lack of education, endangering the lives of farmers as well as the entire population and environment. However, there is paucity of data especially over long durations in Ghana resulting in the absence of effective monitoring programs regarding pesticide application and subsequent contamination in fruits and vegetables. Therefore, this review discusses comprehensively pesticide type and use, importation, presence in fruits and vegetables, human exposure, and poisoning in Ghana. This is to alert the scientific community in Ghana of the need to further research into the potential implications of pesticide residues in food commodities in order to generate a comprehensive and reliable database which is key in drafting policies simultaneous with food regulation, suitable monitoring initiatives, assessment, and education to minimize their effects thereon.     

Effects of two organophosphorus insecticides on some biochemical constituents in the nervous system and liver of rabbits

Male Baladi rabbits were acutely and sub-chronically intoxicated with cyanofenphos and profenophos. The levels of cholesterol, triglycerides, B-lipoproteins and total proteins were determined in the serum, brain, spinal cord and sciatic nerve of rabbits. Moreover, the activities of alkaline phosphatase, acid phosphatase and glutamic-pyruvic transaminase were determined in the liver of the animals. The whole studies revealed that the biochemical constituents were highly affected by the tested insecticides. Also, the liver function suffered from adverse effects of the tested insecticides.     

Organochlorine and organophosphorus pesticide residues in the Atoya river basin, Chinandega, Nicaragua

The hydrographic basin of the Atoya river, located in the Department of Chinandega, one of the main cotton producing regions in Nicaragua, is intensively contaminated by pesticides. Samples of river waters and sediments, as well as strategically selected wells have been analyzed to study variations in the concentrations of organochlorine and organophosphorus pesticide residues between the dry season (November-April) and the rainy season (May-June). Generally, higher concentrations of pesticides have been detected in the river waters and sediments in the dry season. DDT, DDD, DDE compounds and toxaphene are the most frequent organochlorine residues found in the water and sediment samples, while endrin, aldrin, dieldrin and lindane are mainly found in the waters of rivers and wells. Organophosphorus compounds were rarely detected. However, residues of ethion, methyl-parathion and ethyl-parathion were found in high concentrations in some river and well water samples. Generally, organochlorine compounds tend to accumulate in the fine grain-size fractions, rich in organic matter, except DDE, which concentrates basically in the coarse grain-size fractions.     

Determination of etoxazole residues in fruits and vegetables by SPE clean-up and HPLC-DAD

A method for determination of etoxazole residues in apples, strawberries and green beans was developed and validated. The analyte was extracted with acetonitrile from foodstuff and a charcoal-celite cartridge was used for clean-up of raw extracts. Reversed phase high performance liquid chromatography with photodiode array detector (HPLC-DAD) was used for the determination and quantification of etoxazole residues in the studied samples. The calibration graphs of etoxazole in a solvent or three blank matrixes were linear within the tested intervals 0.01–2 mg L^?1, with correlation coefficient of determination >0.999. The combined solid phase extraction (SPE) clean-up and the chromatographic method steps were sensitive and reliable for simultaneous determination of etoxazole residues in the studied samples. The average recoveries of etoxazole in the tested foodstuffs were between 93.4 to 102% at spiking levels of 0.01, 0.10, and 0.50 mg kg^?1, with relative standard deviations ranging from 2.8 to 4.7%, in agreement with directives for method validation in residue analyses. The limit of detection (LOD) of the HPLC-DAD system was 100 pg. The limit of quantification of the entire method was 0.01 mg kg^?1.     

Determination of organochlorine and organophosphate pesticide residues in fruits,vegetables and sediments

Abstract

A method is described for the determination of organochlorine and organophosphate pesticide residues in fruits, vegetables and sediments. The concentrated solvent extract was sealed in a polymeric membrane tube, dialysed in cyclohexane and the solvent replaced with hexane. The organophosphates were analysed on a specific thermionic detector without further clean‐up. For the organochlorine pesticides the extract was eluted through 3 g of alumina and analysed on GC/ECD. The clean‐up for sediment extract was carried out on a10 g alumina column with 100 mL hexane containing 5% acetone and the eluate was concentrated to 5 mL.

The detection limit for organophosphates on a 40 g sample and a final volume of 10 mL was on the average 0.01 mg/kg. The detection limit for organochlorine pesticides, with the final volume of 25 mL, was 0.005 mg/kg for all pesticides except for p,p'‐DDT and endosulfan sulphate, which was 0.01 mg/kg.

The detection limit for oganochlorine pesticides in sediment, with the final volume of 2 mL, was less than 1 μg/kg and for organophosphate pesticides less than 10 μg/kg when the final volume was made to 0.5 mL. At the detection limits the method produced a very high coefficient of variation for both organochlorine and organophosphate pesticides.     

The effect of certain intrinsic and extrinsic variables on the acute toxicity of selected organophosphorus insecticides to the mummichog,Fundulus heteroclitus

Abstract

The acute toxicity of two organophosphorus (OP) insecticides, azinphosmethyl and acephate, was evaluated in the mummichog, Fundulus heteroclitus. In addition, the effects of certain intrinsic (sex) and extrinsic (salinity and multiple toxicant interraction) variables on the toxic response were also investigated. Azinphosmethyl was by far the most toxic of the two OP insecticides with a 96h LC50 ～ 100,000 x lower than that for acephate. Slight sex differences were observed in the sensitivity of mummichogs to each of the OP insecticides with male fish being marginally more sensitive. Significant effects of low salinity stress were observed only with acephate exposure and, in this case, low salinity appeared to be slightly protective. In general, all of the insecticide mixtures (azinphosmethyl/endosulfan, azinphosmethyl/fenvalerate and acephate/fenvalerate) tested exhibited simple additive toxicity.