CN1243967C - Rapid measuring method for residual carbamate pesticide weight in vegetables - Google Patents
Rapid measuring method for residual carbamate pesticide weight in vegetables Download PDFInfo
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- CN1243967C CN1243967C CN 200410059679 CN200410059679A CN1243967C CN 1243967 C CN1243967 C CN 1243967C CN 200410059679 CN200410059679 CN 200410059679 CN 200410059679 A CN200410059679 A CN 200410059679A CN 1243967 C CN1243967 C CN 1243967C
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Abstract
The present invention relates to a rapid measuring method for carbamate pesticide residue in vegetables. Carbamate pesticide in vegetables is extracted with an organic solvent, and pigments and other interfering substances in extraction liquid are removed by active carbon; a solvent in the purified extraction liquid is completely blown off by air or nitrogen, and strong alkali solution is added into residue to hydrolyze the carbamate pesticide into methylamine; then derived methylamine as a derivatization reagent is added, and finally, derivant is measured by a fluorescence detector; the total residue of the carbamate pesticide in vegetable samples is calculated by a standardized work curve. The present invention has the advantages of rapid measuring speed, high precision, low detection limit, simple device and low cost, the needed time for measuring 12 samples by a person is about 40 minutes at a time, a measuring result has good consistency with a measuring result by chromatography, a detection limit to various kinds of carbamate pesticide is lower than 0.1 mg/kg, and the needed expense for measuring a sample is less than 1 yuan RMB.
Description
Technical field
The present invention relates to the rapid assay methods of carbamate pesticide residue amount in a kind of vegetables.
Background technology
At present, the method for carbamate pesticide residue mainly contains vapor-phase chromatography, liquid phase chromatography and enzyme inhibition method in the mensuration vegetables.Chromatographic advantage is that the result is accurate, but needs expensive instrument, skilled operating personnel, and operate loaded down with trivial details, time-consuming, the organic solvent consumption is big, comprises sample pretreatment, analyzing single sample needed about 2 hours and hundreds of milliliter organic solvent.Chromatography is difficult to be applied to the fast measuring of carbamate pesticide residue in a large amount of samples generally as standard method or referee method.The advantage that enzyme suppresses method is consuming time few, and the mensuration of single sample is time-consuming to obtaining a result from sample pretreatment to be 15～30 minutes, has been widely used in the fast detecting of organophosphorus and carbamate pesticide residue in the vegetables.But the sensitivity of this method and the enzyme of use, the chromogenic reaction of being utilized and reaction time, temperature of reaction have confidential relation, and measurement result is subjected to the interference of other material easily, omission and flase drop often occur.The detectability of this method has very big difference with the difference of pesticide variety, and measurement result and chromatographic correlativity are poor, really the residual quantity of agricultural chemicals in the response sample.Publication number provides a kind of residual organophosphorus, carbamate pesticide fast determining method and rapidly measuring device for the patented claim of CN1349094.This method is by detected water sample and do not contain the common water sample of agricultural chemicals to substrate (ester type compound) hydrolysis, with enzyme as catalyzer, substrate after two kinds of hydrolysis of comparison and detection or hydrolysate judge with coloration method whether enzyme is suppressed by agricultural chemicals, and make its catalytic activity forfeiture or reduction, measure persticide residue with this.Rapidly measuring device is made up of plastics reaction tube, plastics stopple coupon, insulated column, sealing compound, and the glass capillary of enzyme and buffering agent and interior dress developer is housed in the plastics reaction tube, glass capillary, the cotton of dress substrate solution in being equipped with in the plastics stopple coupon.
Summary of the invention
The object of the present invention is to provide a kind of highly sensitively, can fast and accurately measure the method for carbamate pesticide residue amount in the vegetables, be mainly used in the fast detecting of occasions such as the market of farm produce and vegetables production base.
Step of the present invention is as follows:
(1) extraction
With vegetables chopping or rubbing, take by weighing 5～20g in centrifuge tube, the organic solvent that adds 2～10g anhydrous sodium sulfate and 10～20ml, place ultrasound wave or mechnical oscillator to extract at least 2 minutes centrifuge tube, extract is transferred in another centrifuge tube, said organic solvent is an ethyl acetate, normal hexane or their potpourri.
(2) purify
In the centrifuge tube that extract is housed, add the anhydrous sodium sulfate of 2～5g and the activated charcoal of 0.01～0.2g, tube shaken, at least 1 minute time, activated charcoal is fully contacted with solution, left standstill at least 1 minute, and drew upper solution, and directly insert the syringe-type filtrator, filter the suspension of removing in the solution, filtrate is collected in the test tube.
(3) concentrate
It is 35～70 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges the solvent in the test tube clean just fully with nitrogen or air.
(4) hydrolysis and derivatization
Adding 0.5ml concentration in the test tube is the NaOH solution of 0.05M, leaves standstill 5～15 minutes, adds 0.5ml derivatization reagent solution again, leaves standstill 1～5 minute.
(5) measure
In excitation wavelength is 340nmT, and emission wavelength is under the condition of 445～460nm, fluorescence intensity of solution behind the mensuration derivatization.The molecular weight of overwhelming majority carbamate chemicals for agriculture is about 200, obtains the methylamine of a part after the carbamate chemicals for agriculture hydrolysis of each molecule.The molecular weight of typical carbamate chemicals for agriculture carbaryl (sevin) is 201, therefore can come the total residue of carbamate chemicals for agriculture in the experiment with computing sample with the standard working curve of carbaryl.
In step (1), the vegetables that take by weighing are decided by the residual quantity of carbamate chemicals for agriculture in the sample, and the anhydrous sodium sulfate that is added is decided by sample moisture content, and the organic solvent that is added is decided by sample volume, need the sample submergence.In addition, the composition of derivatization reagent solution can be: contain 19.1g sodium tetraborate, 0.1g o-phthalaldehyde(OPA), 50 μ l mercaptoethanols in the 1L deionized water.In step (2), the activated charcoal of adding will be decided on the volume and the color of extract.In step (3), the bath temperature that the test tube of filtrate is housed is decided by the boiling point of organic solvent.
Method principle of the present invention is that carbamate chemicals for agriculture is hydrolyzed to methylamine under alkali condition, and methylamine and derivatization reagent (o-phthalaldehyde(OPA) and mercaptoethanol) reaction generates the hyperfluorescence material, detects with fluorescence detector again.Calculate the total residue of the carbamate chemicals for agriculture in the vegetable sample at last by standard working curve.The present invention has following characteristics; (1) finding speed is fast: use this method, disposable to measure a required time of sample and be about 15 minutes.The extraction of this method, concentrate, hydrolysis and derivatization step can be implemented on a plurality of samples simultaneously, use this method disposable to measure 12 required times of sample and be about 40 minutes.(2) accuracy height: this method is used the carbamate chemicals for agriculture in a small amount of organic solvent extracting sample thief, reference be chromatographic pre-treating method, one of standard determination method of carbamate chemicals for agriculture when belonging to no substrate and disturbing.So the stability and the reliability height of this method.Measurement result of this method and chromatographic measurement result have good consistance.(3) detectability is low: this method all is lower than 0.1mg/kg to the detectability of various carbamates chemicals for agriculture, is significantly less than the maximum residue limit (1-2mg/kg) of typical carbamate chemicals for agriculture in the national pollution-free vegetable.Utilize activated charcoal that extract is purified, removed pigment wherein and other chaff interference, make the fluorescence intensity of blank sample as far as possible little, thereby obtain very low detectability.(4) equipment is simple, cost is low: the used equipment of this method all is some mini-plants, buys easily on market and cheap.Agents useful for same is common reagent, cheaply is easy to get.Measure the required expense of sample less than 1 yuan.
Embodiment
Embodiment 1:
Green vegetables 10g, chopping is in the centrifuge tube of packing into; In centrifuge tube, add 10ml ethyl acetate and 3g anhydrous sodium sulfate, centrifuge tube is placed ultrasonic oscillator extraction 2 minutes, draw about 7ml extract in another centrifuge tube with micropipettor.
In the centrifuge tube that extract is housed, add 2g anhydrous sodium sulfate and 0.025g activated charcoal, vibrated 1 minute, and left standstill after 1 minute and draw the 1ml upper solution, micropipette tip is directly inserted the syringe-type filtrator with micropipettor, release solution, filter and remove the activated charcoal that is suspended in the solution.Filtrate is collected in the test tube.
It is 65 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges the ethyl acetate in the test tube clean just fully with pressurized air.
Add the NaOH solution 0.5ml of concentration 0.05mol/L in the test tube, left standstill 5 minutes, add the derivative reagent solution of 0.5ml again, left standstill 2 minutes.In excitation wavelength is 340nm, emission wavelength is under the condition of 445nm, recording the blank back of deduction fluorescence intensity of solution is that I is 0.228, and according to the standard working curve C=0.502I-0.02 of carbaryl, the total residue that can calculate carbamate chemicals for agriculture in the laboratory sample is 0.09mg/kg.
Embodiment 2:
Cucumber 10g, chopping is in the centrifuge tube of packing into; In centrifuge tube, add 15ml normal hexane and 2g anhydrous sodium sulfate, centrifuge tube is placed ultrasonic oscillator extraction 4 minutes, draw about 7ml extract in another centrifuge tube with micropipettor.
In the centrifuge tube that extract is housed, add 5g anhydrous sodium sulfate and 0.2g activated charcoal, vibrated 3 minutes, and left standstill after 2 minutes and draw the 1ml upper solution, micropipette tip is directly inserted the syringe-type filtrator with micropipettor, release solution, filter and remove the activated charcoal that is suspended in the solution.Filtrate is collected in the test tube.
It is 55 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges the normal hexane in the test tube clean just fully with pressurized air.
Add the NaOH solution 0.5ml of concentration 0.05mol/L in the test tube, left standstill 15 minutes, add the derivative reagent solution of 0.5ml again, left standstill 5 minutes.In excitation wavelength is 340nm, emission wavelength is under the condition of 445nm, recording the blank back of deduction fluorescence intensity of solution is that I is 0.100, and according to the standard working curve C=0.502I-0.02 of carbaryl, the total residue that can calculate carbamate chemicals for agriculture in the laboratory sample is 0.03mg/kg.
Embodiment 3:
Tomato 10g, chopping is in the centrifuge tube of packing into; In centrifuge tube, add 5ml normal hexane, 5ml ethyl acetate and 5g anhydrous sodium sulfate, centrifuge tube is placed ultrasonic oscillator extraction 5 minutes, draw about 5ml extract in another centrifuge tube with micropipettor.
In the centrifuge tube that extract is housed, add 3g anhydrous sodium sulfate and 0.015g activated charcoal, vibrated 2 minutes, and left standstill after 3 minutes and draw the 1ml upper solution, micropipette tip is directly inserted the syringe-type filtrator with micropipettor, release solution, filter and remove the activated charcoal that is suspended in the solution.Filtrate is collected in the test tube.
It is 70 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges normal hexane in the test tube and ethyl acetate clean just fully with pressurized air.
Add the NaOH solution 0.5ml of concentration 0.05M in the test tube, left standstill 10 minutes, add the derivative reagent solution of 0.5ml again, left standstill 3 minutes.In excitation wavelength is 340nm, emission wavelength is under the condition of 445nm, recording the blank back of deduction fluorescence intensity of solution is that I is 0.500, and according to the standard working curve C=0.502I-0.02 of carbaryl, the total residue that can calculate carbamate chemicals for agriculture in the laboratory sample is 0.23mg/kg.
Embodiment 4:
Tomato 10g, chopping is in the centrifuge tube of packing into; In centrifuge tube, add 5ml normal hexane, 10ml ethyl acetate and 10g anhydrous sodium sulfate, centrifuge tube is placed ultrasonic oscillator extraction 6 minutes, draw about 5ml extract in another centrifuge tube with micropipettor.
In the centrifuge tube that extract is housed, add 4g anhydrous sodium sulfate and 0.01g activated charcoal, vibrated 4 minutes, and left standstill after 4 minutes and draw the 1ml upper solution, micropipette tip is directly inserted the syringe-type filtrator with micropipettor, release solution, filter and remove the activated charcoal that is suspended in the solution.Filtrate is collected in the test tube.
It is 35 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges normal hexane in the test tube and ethyl acetate clean just fully with pressurized air.
Add the NaOH solution 0.5ml of concentration 0.05M in the test tube, left standstill 8 minutes, add the derivative reagent solution of 0.5ml again, left standstill 4 minutes.In excitation wavelength is 340nm, emission wavelength is under the condition of 445nm, recording the blank back of deduction fluorescence intensity of solution is that I is 0.500, and according to the standard working curve C=0.502I-0.02 of carbaryl, the total residue that can calculate carbamate chemicals for agriculture in the laboratory sample is 0.23mg/kg.
Claims (2)
1, the rapid assay methods of carbamate pesticide residue amount in the vegetables is characterized in that its step is as follows:
(1) extraction
With vegetables chopping or rubbing, take by weighing 5～20g in centrifuge tube, the organic solvent that adds 2～10g anhydrous sodium sulfate and 10～20ml, place ultrasound wave or mechnical oscillator to extract at least 2 minutes centrifuge tube, extract is transferred in another centrifuge tube, said organic solvent is an ethyl acetate, normal hexane or their potpourri;
(2) purify
In the centrifuge tube that extract is housed, add the anhydrous sodium sulfate of 2～5g and the activated charcoal of 0.01～0.2g, tube shaken, at least 1 minute time, activated charcoal is fully contacted with solution, left standstill at least 1 minute, and drew upper solution, and directly insert the syringe-type filtrator, filter the suspension of removing in the solution, filtrate is collected in the test tube;
(3) concentrate
It is 35～70 ℃ water-bath that the test tube that filtrate is housed is placed temperature, purges the solvent in the test tube clean just fully with nitrogen or air;
(4) hydrolysis and derivatization
Adding 0.5ml concentration in the test tube is the NaOH solution of 0.05M, leaves standstill 5～15 minutes, adds 0.5ml derivatization reagent solution again, leaves standstill 1～5 minute;
(5) measure
In excitation wavelength is 340nm, and emission wavelength is under the condition of 445～460nm, and fluorescence intensity of solution behind the mensuration derivatization is with the total residue of carbamate chemicals for agriculture in the standard working curve experiment with computing sample of carbaryl.
2, the rapid assay methods of carbamate pesticide residue amount in the vegetables as claimed in claim 1, it is characterized in that in step (4) the consisting of of derivatization reagent solution: contain 19.1g sodium tetraborate, 0.1g o-phthalaldehyde(OPA), 50 μ l mercaptoethanols in the 1L deionized water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410059679 CN1243967C (en) | 2004-06-15 | 2004-06-15 | Rapid measuring method for residual carbamate pesticide weight in vegetables |
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| CN 200410059679 CN1243967C (en) | 2004-06-15 | 2004-06-15 | Rapid measuring method for residual carbamate pesticide weight in vegetables |
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| CN1584557A CN1584557A (en) | 2005-02-23 |
| CN1243967C true CN1243967C (en) | 2006-03-01 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183513A (en) * | 2011-05-31 | 2011-09-14 | 杨亚玲 | Method for detecting residual quantity of sulfonamide in milk and meat products |
| CN108444946A (en) * | 2018-05-10 | 2018-08-24 | 苏州农业职业技术学院 | A kind of Practice for Pesticide Residue in Agricultural Products detection method and device |
| CN108872139A (en) * | 2018-05-09 | 2018-11-23 | 苏州农业职业技术学院 | Organophosphorus pesticide detection method in a kind of vegetable and fruit |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464187C (en) * | 2006-11-03 | 2009-02-25 | 南通市农产品质量检验测试中心 | Method for detecting residue of Metalaxyl, badistan, thiophanate-methyl in vegetable |
| CN102749404B (en) * | 2012-07-18 | 2014-07-16 | 国家海洋局天津海水淡化与综合利用研究所 | Method for detecting N-methyl carbamate pesticide residues |
| CN105510284A (en) * | 2015-11-13 | 2016-04-20 | 北京工商大学 | Fluorescence detection method of pesticide carbaryl in paper-based food package |
| CN111220602A (en) * | 2018-11-27 | 2020-06-02 | 上海尚湾信息技术有限公司 | Quick detection device of carbamate pesticide residue |
-
2004
- 2004-06-15 CN CN 200410059679 patent/CN1243967C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183513A (en) * | 2011-05-31 | 2011-09-14 | 杨亚玲 | Method for detecting residual quantity of sulfonamide in milk and meat products |
| CN108872139A (en) * | 2018-05-09 | 2018-11-23 | 苏州农业职业技术学院 | Organophosphorus pesticide detection method in a kind of vegetable and fruit |
| CN108444946A (en) * | 2018-05-10 | 2018-08-24 | 苏州农业职业技术学院 | A kind of Practice for Pesticide Residue in Agricultural Products detection method and device |
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