CN102507802B - Extraction method for residual pyrethroid pesticides in water environment - Google Patents
Extraction method for residual pyrethroid pesticides in water environment Download PDFInfo
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- CN102507802B CN102507802B CN 201110293042 CN201110293042A CN102507802B CN 102507802 B CN102507802 B CN 102507802B CN 201110293042 CN201110293042 CN 201110293042 CN 201110293042 A CN201110293042 A CN 201110293042A CN 102507802 B CN102507802 B CN 102507802B
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Abstract
The invention relates to an extraction method for residual pyrethroid pesticides in a water environment, which is characterized by pretreating a low-density polyethylene extraction membrane bag placed into normal hexane and acetone mixture liquor; adding sodium chloride into a sample to be detected until saturated concentration and placing a saturated liquor sample in a headspace sample injection bottle; fixing the pretreated membrane bag into the headspace sample injection bottle added with the saturated liquor sample, adding extraction solvents into the membrane bag, sealing the headspace sample injection bottle and placing the headspace sample injection bottle in an oscillator to obtain extraction liquor; and transferring the extraction liquor to a small sample injection bottle and measuring the concentration of the pyrethroid pesticides in the extraction liquor by the aid of a GC-ECD (gas chromatography-electron capture detector) or a GC-MS (gas chromatography-mass spectrometer). Compared with the prior art, a membrane-assisted extraction system obtained by means of research and development can be applied to separating and purifying the residual pyrethroid pesticides such as cypermethrin, deltamethrin, fluralinate, bifenthrin, phenothrin, fenvalerate and the like in the water environment sample. Compared with common liquid-liquid extraction and solid extraction methods, the extraction method is higher in separation speed and more efficient in enrichment of the pyrethroid pesticides.
Description
Technical field
The present invention relates to analytical chemistry, water environment Pesticide Residues detection field, specifically refer to a kind of extracting process for the residual pyrethroid pesticide of water environment.
Background technology
Pyrethroid pesticide (Pyrethroid insecticides) is that a class is efficient, the wide spectrum agricultural chemicals, and therefore characteristics such as having low toxicity, drain rapidly and can be biodegradable, are usually used in killing in the fish production parasite and harmful organisms.Yet pyrethroid pesticide is larger to hydrobiont toxicity such as fish, shellfish and shell-fish, and studies show that recently, and this agricultural chemicals has certain property accumulated, and easily by the hydrobiont enrichment, and some kind has carcinogenic, teratogenesis, mutagenesis and neurotoxicity.In recent years, frequent occurrence pollutes, the aquaculture organism death incident, and the use of this type of agricultural chemicals produces water ecosystem and aquatic product quality and to have a strong impact on, and causes that the phenomenon that exceeds standard appears in such agricultural chemicals in the commercially available aquatic products, and human health is brought grave danger.Healthy for ensureing human body, various countries formulate pyrethrin pesticide residue limits standard one after another, and such as states such as China, the U.S., European Union and Japan, the environment that pyrethrin pesticide causes and food pollution have become the important means that developed country arranges the trade green barrier.Therefore, development pyrethrin pesticide retention analysis technology can be residues of pesticides monitoring, ensure that aquatic products foreign trade etc. provides technical support, significant to development green cultivation, protection food security and water area ecological environment.
At present to the more existing reports of the residual detection method of pyrethrin pesticide, but mainly be for aspects such as vegetables and tealeaves, to water environment, what especially the pyrethrin pesticide detection method was reported in the briny environment is few, mainly contains the instrument analytical methods such as GC-ECD and GC-MS.In order to eliminate the interference of complex matrices, improve detection sensitivity, before analyzing, usually need to be further purified.Therefore, various advanced persons' sample-pretreating method is developed, and traditional disposal route such as liquid-liquid extraction (Liquid-liquid extraction, LLE) need to consume a large amount of organic solvents, in enrichment of analyte, a large amount of matrix is also by enrichment, and sensitivity and the accuracy of last testing result caused interference, usually need to be further purified before analyzing.Therefore, various advanced persons' sample-pretreating method is developed, such as Solid-Phase Extraction (Solid phase extraction, SPE), matrix solid phase dispersion extraction (Matrix solid-phase dispersion, MSPD), solid-phase microextraction (Solid-phase microextraction, SPME) and Stir Bar Sorptive Extraction (Stir bar sorptive extraction, SBSE) etc.But, Solid-Phase Extraction need to consume certain organic solvent, especially before carrying out Solid-Phase Extraction, usually need to carry out first LLE object is separated from complex matrices, further increase consumption and the operation steps of organic solvent, reduced detection sensitivity.Micro-extraction technique becomes important development trend, the micro-extraction technique that grows up on the basis of solid phase extraction techniques such as SPME, have that the running time is short, sample size is few, need not the advantages such as extraction solvent, but it is expensive, the coating kind is limited, selectivity is relatively poor; SBSE is similar to the SPME adsorption mechanism, has relatively thick Polymer adsorption layer, has higher Sticking factor, but also has the shortcomings such as the coating kind is limited, expensive, and the application in pesticide residue analysis is restricted.Therefore, how to reduce the focus that the use amount of organic solvent, the extraction efficiency that improves trace materials and reduction testing cost become present detection method exploitation.
Summary of the invention
Technical matters to be solved by this invention be the present situation for prior art provide a kind of efficient, organic solvent consumption less, can realize the extracting process that is used for the residual pyrethroid pesticide of water environment of robotization, its method and further Optimized Extraction condition by setting up the film auxiliary extraction is separated fast to reach from water environment, the purpose of enrichment pyrethroid pesticide.
The present invention solves the problems of the technologies described above the technical scheme that adopts and is roughly following several step:
(1) preparation of film bag: the film that adopts character to be fit to prepares sizeable film bag;
(2) foundation of film auxiliary extraction method: further the film bag is fixed in the headspace sampling bottle, sets up the film auxiliary extraction system that can be used for residual pyrethroid pesticide in the separation and purification water environment.
(3) the film auxiliary extraction system that adopts said method of the present invention to prepare is applied to selective enrichment pyrethroid pesticide remained in the water environment, purifying.
Concrete steps are as follows:
(1) employing thickness is that the density of 0.02-0.05mm is 0.915-0.940 gram/cm
3Low density polyethylene films prepare the spe membrane bag; It is that 9: 1 normal hexane, acetone mixed solution soaks 10-15min the film bag is carried out pre-service that this film bag is put into volume ratio;
(2) add sodium chloride in the detected sample saturated to concentration, obtain the sodium chloride saturated solution sample; Get the headspace sampling bottle that 5-15ml saturated solution sample places 5-20ml;
(3) pretreated film bag is fixed in the headspace sampling bottle that has added the saturated solution sample, then in the film bag, adds the 0.2-0.8ml extraction solvent, seal the head space sample injection bottle and the headspace sampling bottle is placed oscillator; Extracting 60-180min under 25-45 ℃, 300-600rpm condition obtains extract;
(4) extract is transferred in the sample introduction bottle, measured the concentration of pyrethroid pesticide in the extract with GC-ECD or GC-MS; This concentration is the concentration of cinerins agricultural chemicals in the detected sample.
Preferably, to be selected from cyclohexane, normal hexane, volume ratio be that 9: 1 cyclohexane and mixed solution or the volume ratio of acetone are 9: 1 normal hexane and the mixed solution of acetone to described extraction solvent.
The size of described film bag is take suitable as principle with described headspace sampling bottle, and the internal diameter of film bag can be 4-6mm preferably, and length is 2-4cm.
Compared with prior art, the film auxiliary extraction system that the present invention researches and develops, can be applicable to separation, the purifying of the Determination of Pyrethroid Pesticide Residues such as cypermethrin in the environmental water sample, decis, cyfloxylate, Biphenthrin, phenothrin, fenvalerate, comparing with common liquid-liquid extraction, solid phase extraction, its velocity of separation is faster, the enrichment pyrethroid pesticide is more efficient.
Description of drawings
Fig. 1 is the GC-ECD gas chromatogram of the embodiment of the invention 1;
Fig. 2 is embodiment of the invention 2GC-MA gas chromatogram.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
Density with 0.02mm is that density is 0.915 gram/cm
3Low density polyethylene films to prepare internal diameter be that 4mm, length are the spe membrane bag of 2cm.
It is that 9: 1 normal hexane, acetone mixed solution soaks 10min the film bag is carried out pre-service that the spe membrane bag is put into volume ratio.
Get the 15ml water sample, add an amount of sodium chloride saturated to solution, this saturated solution is placed 20ml headspace sampling bottle.
Above-mentioned film bag is fixed in the headspace sampling bottle, then in the film bag, adds the 0.2ml normal hexane, seal.Then the headspace sampling bottle is placed oscillator, under 25 ℃ and 300rpm condition, extract 180min.
Extraction is transferred to extraction solvent in the 2.0ml sample introduction bottle after finishing, and adopts GC-ECD to detect, and testing result is as shown in table 1, and its chromatogram as shown in Figure 1.
Pyrethroid pesticide remained GC-ECD analysis result in table 1 environmental water sample
A, the concentration of adding Biphenthrin, cyfloxylate, cypermethrin, fenvalerate, decis
B, the concentration of adding phenothrin
Embodiment 2
Density with 0.03mm is 0.920 gram/cm
3Low density polyethylene films to prepare internal diameter be that 5mm, length are the spe membrane bag of 3cm.
It is that 9: 1 normal hexane, acetone mixed solution soaks 15min the film bag is carried out pre-service that the spe membrane bag is put into volume ratio.
Get the 15ml water sample, add an amount of sodium chloride to saturated solution, place 20ml headspace sampling bottle.
Above-mentioned film bag is fixed in the headspace sampling bottle, then in the film bag, adds the 0.4ml cyclohexane, seal the apical pore sample injection bottle.
The headspace sampling bottle is placed oscillator, under 30 ℃, 450rpm condition, extract 120min.
Extraction is transferred to extraction solvent in the 2.0ml sample introduction bottle after finishing, and adopts GC-MS to detect result such as table 2 and shown in Figure 2.
Pyrethroid pesticide remained GC-MS analysis result in table 2 environmental water sample
* RSD is relative standard deviation.
Embodiment 3
Density with 0.04mm is 0.930 gram/cm
3Low density polyethylene films to prepare internal diameter be that 6mm, length are the spe membrane bag of 4cm.
It is that 9: 1 normal hexane, acetone mixed solution soaks 12min the film bag is carried out pre-service that the spe membrane bag is put into volume ratio.
Get the 15ml water sample, add an amount of sodium chloride to saturated solution, place 20ml headspace sampling bottle.
Above-mentioned film bag is fixed in the headspace sampling bottle, so adds the 0.8ml normal hexane in the film bag, seal the headspace sampling bottle.
The headspace sampling bottle is placed oscillator, under 45 ℃ and 600rpm condition, extract 60min.
Extraction is transferred to extraction solvent in the 2.0ml sample introduction bottle after finishing, and adopts GC-MS to detect, and its invention effect is similar to embodiment 2.
Embodiment 4
Density with 0.05mm is 0.940 gram/cm
3Low density polyethylene films to prepare internal diameter be that 4mm, length are the spe membrane bag of 4cm.
It is that 9: 1 normal hexane, acetone mixed solution soaks 12min the film bag is carried out pre-service that the spe membrane bag is put into volume ratio.
Get the 15ml water sample, add an amount of sodium chloride to saturated solution, place 20ml headspace sampling bottle.
Above-mentioned film bag is fixed in the headspace sampling bottle, adds the 0.6ml normal hexane: acetone (9: 1, v/v) in the film bag, seal the headspace sampling bottle.
But the headspace sampling bottle places oscillator, extracts 80min under 35 ℃ and 600rpm condition.
Extraction is transferred to extraction solvent in the 2.0ml sample introduction bottle after finishing, and adopts GC-MS to detect, and its invention effect is similar to embodiment 2.
Embodiment 5
Density with 0.03mm is 0.925 gram/cm
3Low density polyethylene films to prepare internal diameter be that 4mm, length are the spe membrane bag of 4cm.
It is that 9: 1 normal hexane, acetone mixed solution soaks 10min the film bag is carried out pre-service that the spe membrane bag is put into volume ratio.
Get the 15ml water sample, add an amount of sodium chloride to saturated solution, place 20ml headspace sampling bottle.
Above-mentioned film bag is fixed in the apical pore sample injection bottle, further adds the 0.2ml cyclohexane: acetone (9: 1, v/v) in the film bag, seal the apical pore sample injection bottle.
Then the apical pore sample injection bottle is placed oscillator, under 25 ℃ and 300rpm condition, extract 180min.
Extraction is transferred to extraction solvent in the 2.0ml sample introduction bottle after finishing, and adopts GC-ECD to detect, and its invention effect is similar to embodiment 1.
Claims (3)
1. extracting process that is used for the residual pyrethroid pesticide of water environment is characterized in that may further comprise the steps:
(1) adopting thickness is that the density of 0.02-0.05mm is that the low density polyethylene films of 0.915-0.940 gram/cm3 prepares the spe membrane bag; It is that 9: 1 normal hexane, acetone mixed solution soaks 10-15min the film bag is carried out pre-service that this film bag is put into volume ratio;
(2) add sodium chloride in the detected sample saturated to concentration, obtain the sodium chloride saturated solution sample; Get the headspace sampling bottle that 5-15ml saturated solution sample places 5-20ml;
(3) pretreated film bag is fixed in the headspace sampling bottle that has added the saturated solution sample, then in the film bag, adds the 0.2-0.8ml extraction solvent, seal the head space sample injection bottle and the headspace sampling bottle is placed oscillator; Extracting 60-180min under 25-45 ℃, 300-600rpm condition obtains extract;
(4) adopt GC-ECD or GC-MS to measure the concentration of pyrethroid pesticide in the extract.
2. the extracting process for the residual pyrethroid pesticide of water environment according to claim 1 is characterized in that it is that 9: 1 cyclohexane and mixed solution or the volume ratio of acetone are 9: 1 normal hexane and the mixed solution of acetone that described extraction solvent is selected from cyclohexane, normal hexane, volume ratio.
3. the extracting process for the residual pyrethroid pesticide of water environment according to claim 1 and 2, the internal diameter that it is characterized in that described film bag is 4-6mm, length is 2-4cm.
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| CN103558299B (en) * | 2013-08-07 | 2015-07-01 | 公安部物证鉴定中心 | Pyrethroid pesticide inspection method for treating biological detection material by using gel permeation chromatography |
| CN103472151A (en) * | 2013-09-08 | 2013-12-25 | 邬金飞 | Gas chromatographic method for detecting pesticide residue of beta-cypermethrin in farmland surface water |
| CN103499660A (en) * | 2013-09-23 | 2014-01-08 | 邬金飞 | Gas chromatographic method for detecting residues of seven pyrethroid pesticides in surface water of farmland |
| CN104297043B (en) * | 2014-09-29 | 2017-07-04 | 宁波大学 | The membrane extraction method of pyrethroid pesticide is remained in a kind of complex sample |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101393183A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring pesticide residue of six kinds of dinitroaniline in tobacco and tobacco products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101393183A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring pesticide residue of six kinds of dinitroaniline in tobacco and tobacco products |
Non-Patent Citations (5)
| Title |
|---|
| Analyses of pesticides and their metabolites in foods and drinks;Farid E. Ahmed;《trends in analytical chemistry》;20011231;第20卷(第11期);649-661 * |
| Farid E. Ahmed.Analyses of pesticides and their metabolites in foods and drinks.《trends in analytical chemistry》.2001,第20卷(第11期),649-661. |
| 吴志华 等.饲料中拟除虫菊醋类农药的多残留分析技术.《湖南农业大学学报（自然科学版）》.2006,第32卷(第1期),77-80. * |
| 微波辅助液液微萃取-气相色谱-质谱分析蔬菜、水果中的多种拟除虫菊酯残留;郑孝华;《分析化学》;20040229;第32卷(第2期);225-228 * |
| 郑孝华.微波辅助液液微萃取-气相色谱-质谱分析蔬菜、水果中的多种拟除虫菊酯残留.《分析化学》.2004,第32卷(第2期),225-228. |
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