CN103308630B - Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables - Google Patents
Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables Download PDFInfo
- Publication number
- CN103308630B CN103308630B CN201310175339.0A CN201310175339A CN103308630B CN 103308630 B CN103308630 B CN 103308630B CN 201310175339 A CN201310175339 A CN 201310175339A CN 103308630 B CN103308630 B CN 103308630B
- Authority
- CN
- China
- Prior art keywords
- extraction
- purification
- vegetables
- fruits
- purification method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention belongs to the technical field of pesticide residue determination, relates to a vegetable and fruit pesticide residue pre-treatment method and in particular relates to an extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables. The extraction and purification method comprises the following steps of: sampling, adding an acetonitrile extracting solution, purifying by virtue of a MycoSep 226 AflaZon+ small column, and then determining. According to the extraction and purification method, dosage of an organic reagent is reduced, and nitrogen blowing or rotary steaming equipment is not required; a step of detecting organic phosphorus in a conventional method is not required, manpower is reduced, and detection efficiency is improved; purification degree of an organic phosphorus extracting solution is obviously improved, the obtained sample injection solution is clear and transparent, no obvious pollution on a detection system is produced after sample injection is carried out for multiple times, sensitivities of instrument and equipment are consistent, and a detection limit is constant; and peak height is not reduced and peak shape is constant after the sample injection is carried out for multiple times even if residues of organophosphorus pesticides, such as methamidophos, acephate, moncrotophos and omethoate with strong polarity, are determined. The extraction and purification method for detecting organophosphorus pesticide residues in fruits and vegetables has a good application prospect in the technical field of pesticide residue determination.
Description
Technical field
The invention belongs to pesticide residue determination technical field, relate to a kind of vegetables and fruits residues of pesticides pre-treating method, relate in particular to the extraction and purification methods of Organophosphorus Pesticide Residue in a kind of vegetables and fruits.
Background technology
Fruit, vegetables are important food sources in people's daily life, along with the raising of people's quality of the life, Consciousness of food security are constantly strengthened, and particularly food-safety problem takes place frequently in recent years, have more excited the popular sensitivity to fruit, Pesticide Residues in Vegetables problem.Fruit, Pesticide Residues in Vegetables are wheezy problems, the situation of having stopped using at organochlorine insecticide, and organophosphorus pesticide becomes main pollution by pesticides source in vegetables, even if supermarket also cannot ensure safety.The agricultural chemicals remaining in a large number on vegetables not only produces directly and poisons human body, causes acute poisoning or causes accumulation and the enrichment of agricultural chemicals in human body, thereby cause various diseases, even affects offspring.But also can cause objectionable impurities to cause serious pollution and harm to ecologic environment.But just as people can not survive in the environment of absolutesterility, definitely will have new problem without the food of agricultural chemicals noresidue, therefore we should carry out fruit, Organo-phosphorus Pesticide Residues in Vegetables detects, and allow people be able to eat safe, healthy quality-assured food.
The pre-treating method detecting about fruit, Organo-phosphorus Pesticide Residues in Vegetables is at present reported more, and is mainly reflected in the purified treatment after extract configuration and extraction.What be wherein most widely used at present is NY/T761-2008 " organophosphorus in vegetables and fruit, organochlorine, the mensuration that how residual pyrethroid and carbamate chemicals for agriculture be " [organophosphorus in NY/T761-2008 vegetables and fruit, organochlorine, the mensuration [S] that how residual pyrethroid and carbamate chemicals for agriculture be. Chinese agriculture publishing house, 2008, 5], method regulation Extraction of organophosphorus pesticide reagent is acetonitrile, then extract is through being spin-dried for, after acetone constant volume, treat Instrument measuring, the method has universality, but due to comparatively low to the purification efficiency of extract, be more suitable at the bottom of sample copy less, the sample that background is comparatively clean, and it is impracticable to some extract colors sample dark or local complicated, be mainly reflected in these samples and in the time of sample introduction, caused the very big pollution to checkout equipment, so that instrumental sensitivity declines, particularly to the stronger organophosphorus of some polarity as acephatemet, Azodrin, the falls such as flolimat are larger, so not only increase the detection limit of method, also can be to instrument component as injection port accessory, chromatographic columns etc. cause very big loss, even shorten the instrument life-span.
Given this, there is people to be improved by changing extract polarity or increasing purifying step.The people such as Ou Yangpuyue adopt methylene chloride, acetone mixed extract to extract organophosphorus in vegetables [Ou Yangpuyue, Huang Zhixuan, Zhou Jinsen, Deng. Organo-phosphorus Pesticide Residues in Vegetables pretreatment technology pre-test [J]. Tropical China medical science, 2009,9(4): 757-758,760]; Song Xinguo [Song Xinguo. the extracting method of cowpea residues of pesticides. China, 2012, G01N30/06 (2006.01) I G01N30/02 (2006.01) I:1-5] adopt mixed extract, by acetonitrile 25%, acetone 25%, ether 25%, methylene chloride 25% by volume number percent form, and in follow-up test, increased nh 2 column purifying step and introduced toluene as eluent extraction and determination cowpea Pesticide Residues.Huang Zhiqiang[Zhiqiang Huang, Yongjun Li, Bo Chen.Simultaneous determination of102pesticide residues in Chinese teas by gas chromatography – mass spectrometry[J] .Journal of Chromatography B, 2007,853 (1-2): 154-162.] etc. people adopt gel permeation chromatography and solid phase extraction to extract Determination of Organophosphorus Pesticide in tealeaves.These improvement have all been carried out strong extension and expansion to NY/T761-2008, make organophosphorus detection technique obtain very big lifting.But these are through improved various schemes, though can improve the extraction efficiency of various agricultural chemicals as mixed extract, also increase the extracted amount to non-object simultaneously, and the burden that these non-objects must be detection methods.The application of various Solid phase extraction pillars certainly will additionally increase the consumption of organic reagent, increases environmental pollution, increases method applying step simultaneously, increases and detects labor capacity.
Summary of the invention
The present invention finds that there is a kind of pillar (MycoSep226AflaZon+ purifies pillar) that purifies can directly apply to the acetonitrile extract that purifies organophosphorus in fruit, residue of organic phosphorus pesticides in vegetable detection, directly filter in this pillar at the acetonitrile extract after NY/T761-2008 method is extracted organophosphorus, acetonitrile extract after the purification of gained is as clear as crystal, can be directly used in examination with computer.Wherein, MycoSep226AflaZon+ purifies pillar and is the immune affine pillar of MycoSep series, on sale on the market, when being mainly used in multiple trichothecenes compound, analyzes in prior art.And the present invention is introduced in pesticide residue determination pre-treating method.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
An extraction and purification methods for Organophosphorus Pesticide Residue in vegetables and fruits, is made up of following step successively,
A. take the fruits and vegetables sample grinding in centrifuge tube;
B. add acetonitrile extract;
C. carry out dispersion extraction with refiner, then add sodium chloride, the violent jolting of cover lid;
D. static, treat the distinct after purification of layering;
E. get supernatant, cross the little column purification of MycoSep226AflaZon+;
F. get acetonitrile extract after purification in sample injection bottle, treat that on gas chromatograph, machine is measured.
As preferably, formed by following step successively,
A. accurately take fruits and vegetables sample that 25g grinds in 100ml centrifuge tube;
B. accurately add 50ml acetonitrile extract;
C. carry out dispersion extraction 1min with refiner with the rotating speed of 10kr/min, then add 5g sodium chloride, the violent jolting 10s of cover lid;
D. static 30～45min, treats the distinct after purification of layering;
E. get 10ml supernatant, cross the little column purification of MycoSep226AflaZon+;
F. get acetonitrile extract 1ml after purification in sample injection bottle, treat that on gas chromatograph, machine is measured.
The invention provides the extraction and purification methods of Organophosphorus Pesticide Residue in a kind of vegetables and fruits, reduced the consumption of organic reagent, and do not need to use nitrogen and blow or revolve steaming equipment; Reduce detecting step and the manpower of conventional method to organophosphorus, promoted detection efficiency; The degree of purification that obviously promotes organophosphorus extract, gained sample introduction liquid is as clear as crystal, and repeatedly after sample introduction to detection system without obvious pollution, instrument and equipment sensitivity is consistent, detection limit is constant; Even the stronger organophosphorus pesticide of polarity is as acephatemet, orthene, Azodrin, flolimat etc., repeatedly after sample introduction, peak height does not subtract, peak shape is constant; The consumption degree that has simultaneously also obviously reduced gas chromatography consumables associated therewith, has extended the service time of capillary column and the serviceable life of gas chromatograph.Have a good application prospect in pesticide residue determination technical field.
Brief description of the drawings
Fig. 1 is the acetonitrile extract purification process schematic diagram of organophosphorus of the present invention.
Fig. 2 is that in embodiment 2, red bayberry mark-on reclaims chromatogram.
Fig. 3 is that in embodiment 2, cucumber mark-on reclaims chromatogram.
Fig. 4 is that in embodiment 2, capsicum mark-on reclaims chromatogram.
Fig. 5 is only column purification mark-on recovery chromatogram of art methods capsicum in embodiment 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
An extraction and purification methods for Organophosphorus Pesticide Residue in vegetables and fruits, taking red bayberry as example, as shown in Figure 1, is made up of following step successively:
A. accurately take fruits and vegetables sample that 25g grinds in 100ml centrifuge tube;
B. accurately add 50ml acetonitrile extract;
C. carry out dispersion extraction 1min with refiner with the rotating speed of 10kr/min, then add 5g sodium chloride, the violent jolting 10s of cover lid;
D. static 30min, treats the distinct after purification of layering;
E. get 10ml supernatant, cross the little column purification of MycoSep226AflaZon+;
F. get acetonitrile extract 1ml after purification in sample injection bottle, treat that on gas chromatograph, machine is measured.
Acetonitrile extracting liquid colourless after MycoSep226AflaZon+ purifies little column purification is transparent, can significantly reduce the pollution level to instrument.
Embodiment 2
The extraction and purification methods of Organophosphorus Pesticide Residue in a kind of vegetables and fruits, 19 kinds of organophosphorus pesticides such as the DDVP that is 0.08mg/kg in red bayberry, cucumber, capsicum interpolation mass concentration, Profenofos, orthene, sulfotep, thimet, flolimat, diazinon, Azodrin, dichlofenthion, Rogor, Nankor, parathion, Entex, isofenphos, isocarbophos, quinalphos, methidathion, Ethodan, phosfolan, under following chromatographic condition, the mark-on of gained reclaims spectrogram, and result as shown in Figures 2 to 4.The chromatogram that purifies cucumber sample mark-on recovery continuous sample introduction the 10th pin of little column purification in prior art without MycoSep226AflaZon+, adds pesticide variety, concentration with of the present invention consistent.As shown in Figure 5.And result spectrogram of the present invention and prior art are compared, illustrate that method of the present invention can reach effect of the prior art with easier method.
Chromatographic condition:
Injection port: 220 DEG C, Splitless injecting samples; Sample size: 1 μ l; Chromatographic column: DB17 fused-silica capillary column (30m × 0.25mm, 0.25 μ is m); Temperature programme: 80 DEG C of (0.5min)～240 DEG C/20 DEG C (10min); Detecting device: 250 DEG C; Dottle pin purges: 2ml/min; Current-carrying: 1ml/min; Hydrogen: 40ml/min; Air: 100ml/min; Tail blows: 30ml/min.
Comparing result: known through contrast spectrogram, extraction and purification methods of the present invention has reduced the consumption of organic reagent than prior art, and does not need to use nitrogen and blow or revolve steaming equipment; Reduce detecting step and the manpower of conventional method to organophosphorus, promoted detection efficiency; The degree of purification that obviously promotes organophosphorus extract, gained sample introduction liquid is as clear as crystal, and repeatedly after sample introduction to detection system without obvious pollution, instrument and equipment sensitivity is consistent, detection limit is constant; Even the stronger organophosphorus pesticide of polarity is as acephatemet, orthene, Azodrin, flolimat etc., repeatedly after sample introduction, peak height does not subtract, peak shape is constant; The consumption degree that has simultaneously also obviously reduced gas chromatography consumables associated therewith, has extended the service time of capillary column and the serviceable life of gas chromatograph.Illustrate that method of the present invention is obviously better than the mensuration pre-treating method of prior art.
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (2)
1. an extraction and purification methods for Organophosphorus Pesticide Residue in vegetables and fruits, is characterized in that: formed by following step successively,
A. take the fruits and vegetables sample grinding in centrifuge tube;
B. add acetonitrile extract;
C. carry out dispersion extraction with refiner, then add sodium chloride, the violent jolting of cover lid;
D. static, treat the distinct after purification of layering;
E. get supernatant, cross the little column purification of MycoSep226AflaZon+;
F. get acetonitrile extract after purification in sample injection bottle, treat that on gas chromatograph, machine is measured.
2. the extraction and purification methods of Organophosphorus Pesticide Residue in a kind of vegetables and fruits according to claim 1, is characterized in that: formed by following step successively,
A. accurately take fruits and vegetables sample that 25g grinds in 100ml centrifuge tube;
B. accurately add 50ml acetonitrile extract;
C. carry out dispersion extraction 1min with refiner with the rotating speed of 10kr/min, then add 5g sodium chloride, the violent jolting 10s of cover lid;
D. static 30～45min, treats the distinct after purification of layering;
E. get 10ml supernatant, cross the little column purification of MycoSep226AflaZon+;
F. get acetonitrile extract 1ml after purification in sample injection bottle, treat that on gas chromatograph, machine is measured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310175339.0A CN103308630B (en) | 2013-05-10 | 2013-05-10 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310175339.0A CN103308630B (en) | 2013-05-10 | 2013-05-10 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103308630A CN103308630A (en) | 2013-09-18 |
| CN103308630B true CN103308630B (en) | 2014-07-23 |
Family
ID=49134081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310175339.0A Expired - Fee Related CN103308630B (en) | 2013-05-10 | 2013-05-10 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103308630B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105203377A (en) * | 2015-09-29 | 2015-12-30 | 齐国良 | Purifying device for pretreatment of Aspergillus flavus and method adopting same |
| CN106290692A (en) * | 2016-11-02 | 2017-01-04 | 百奥森（江苏）食品安全科技有限公司 | A kind of pesticide method |
| CN108645939B (en) * | 2018-02-28 | 2021-04-16 | 浙江省林产品质量检测站（浙江省林木种苗质量监督检验站） | Method for extracting and purifying phthalate plasticizer in vegetable oil |
| CN115684420A (en) * | 2022-11-04 | 2023-02-03 | 中轻检验认证有限公司 | Method for detecting pesticide residue in hops |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
| CN102121928A (en) * | 2010-12-20 | 2011-07-13 | 天津市农业科学院中心实验室 | Method for processing onion sample containing several pesticide residues before determination |
-
2013
- 2013-05-10 CN CN201310175339.0A patent/CN103308630B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1563976A (en) * | 2004-03-24 | 2005-01-12 | 南京大学 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
| CN102121928A (en) * | 2010-12-20 | 2011-07-13 | 天津市农业科学院中心实验室 | Method for processing onion sample containing several pesticide residues before determination |
Non-Patent Citations (10)
| Title |
|---|
| Carlo G.Zambonin等.Solid-phase microextraction–gas chromatography mass spectrometry: A fast and simple screening method for the assessment of organophosphorus pesticides residues in wine and fruit juices.《Food Chemistry》.2004,第86卷(第2期),269-274. |
| M.A. Farajzadeh等.Solid-Phase Microextraction Gas Chromatography for Determination of Some Organophosphorus Pesticides.《Chromatographia》.2004,第59卷(第3-4期),第259-262页. |
| Solid-Phase Microextraction Gas Chromatography for Determination of Some Organophosphorus Pesticides;M.A. Farajzadeh等;《Chromatographia》;20040228;第59卷(第3-4期);第259-262页 * |
| Solid-phase microextraction–gas chromatography mass spectrometry: A fast and simple screening method for the assessment of organophosphorus pesticides residues in wine and fruit juices;Carlo G.Zambonin等;《Food Chemistry》;20040630;第86卷(第2期);269-274 * |
| SPME-GC联用在鸭梨有机磷农药残留测定中的应用;杨柳等;《西北林学院学报》;20061130;第21卷(第6期);第170-173页 * |
| 固相萃取-气相色谱法测定蔬菜中多种有机磷农药的残留量;李嘉静等;《安徽农学通报》;20070731;第13卷(第13期);第54-55页 * |
| 李嘉静等.固相萃取-气相色谱法测定蔬菜中多种有机磷农药的残留量.《安徽农学通报》.2007,第13卷(第13期),第54-55页. |
| 杨柳等.SPME-GC联用在鸭梨有机磷农药残留测定中的应用.《西北林学院学报》.2006,第21卷(第6期),第170-173页. |
| 气相色谱-质谱法检测蔬菜和水果中35种农药残留;赵晓萌等;《色谱》;20050531;第23卷(第3期);第328页 * |
| 赵晓萌等.气相色谱-质谱法检测蔬菜和水果中35种农药残留.《色谱》.2005,第23卷(第3期),第328页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103308630A (en) | 2013-09-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103308630B (en) | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables | |
| CN106483232A (en) | The method for quick of Multiple Pesticides residual in a kind of soil | |
| CN105675757B (en) | It is a kind of at the same determine cigarette mainstream flue gas in the peculiar N nitrosamine of tobacco and polycyclic aromatic hydrocarbon method | |
| CN103257194B (en) | GC-MS/MS (Gas chromatography - tandem mass spectrometry) method for simultaneously analyzing three polycyclic aromatic hydrocarbons and four tobacco-specific nitrosamines in main stream smoke of cigarettes | |
| CN103543221A (en) | Method for simultaneously detecting multiple mycotoxins in milk | |
| CN108072727A (en) | Method that is a kind of while measuring 23 kinds of organic chlorine agriculture chemicals residual quantities in Radix Notoginseng | |
| CN102998381A (en) | Method for measuring content of phthalic acid ester in tipping paper for cigarettes | |
| CN103278594B (en) | Universal rapid detection method for micromolecule poisonous and harmful materials in powdery food | |
| CN103776924A (en) | Method for detecting polycyclic aromatic hydrocarbon in fried food | |
| CN105158392A (en) | Method for determining special tobacco N-nitrosamine in cigarette liquid of electronic cigarette | |
| CN105203654A (en) | Method for measuring content of 11 illegally added medicaments in veterinary drug powder | |
| CN104215705B (en) | A kind of method detecting Organochlorine Pesticides Residues In Agricultural Products | |
| CN103901137A (en) | Tea pretreatment method for detecting organophosphorus pesticides and application of as well as method for detecting organophosphorus pesticides in tea | |
| CN102435681A (en) | Preprocessing method suitable for analyzing estrogen and bisphenol A in complex matrix solid sample | |
| CN104034817A (en) | Ion chromatography on-line pretreatment for measuring glyphosate in genetically modified soybean oil | |
| CN104316638B (en) | Detect the LC-MS/MS assay method of 7 kinds of invertebrate poisons in vegetables and fruit simultaneously | |
| CN104280483A (en) | Pretreatment method for detecting chloromycetin in animal product | |
| Nota et al. | Determination of cyanides and thiocyanates in water by gas chromatography | |
| CN103267820A (en) | A co-detection method for multiple estrogens in sludge | |
| Clegg et al. | Detection and quantitation of trace levels of ethyl carbamate in alcoholic beverages by selected ion monitoring | |
| CN104034835A (en) | Method for detecting multiple biotoxins in fermented wine | |
| CN102749404B (en) | Method for detecting N-methyl carbamate pesticide residues | |
| CN101655481B (en) | Gas phase chromatography-mass spectrometry detection method of polyoxyethylene nonyl phenyl ether in water | |
| CN105548382A (en) | Method for detecting benzopyrene in soil | |
| CN102680590B (en) | Two-dimensional liquid chromatogram (LC)-tandem mass spectrometry method for detecting four amine substances in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140723 Termination date: 20150510 |
|
| EXPY | Termination of patent right or utility model |