CN103901129A - Method for detecting ten types of organophosphorus pesticides by using magnetic separation-gas chromatography - Google Patents
Method for detecting ten types of organophosphorus pesticides by using magnetic separation-gas chromatography Download PDFInfo
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Abstract
The invention relates to a method for detecting ten types of organophosphorus pesticides by using magnetic separation-gas chromatography. The method is used for quickly detecting ten types of organophosphorus pesticides (dipterex, methamidophos, acephate, omethoate, moncrotophos, dimethoate, phosphamidon, parathion-methyl, malathion and chlorpyrifos) based on combination of solid-phase extraction, magnetic separation and the gas chromatography. The method comprises the following steps: preparing a magnetic solid-phase extraction agent, establishing a combination system of the magnetic separation and the gas chromatography, and detecting the organophosphorus pesticides in objects to be detected. A method capable of quickly separating and detecting ten types of organophosphorus pesticides at high sensitivity simultaneously is established by taking prepared magnetic chitosan microspheres with high absorption performance on the ten types of organophosphorus pesticides such as dipterex and the like as adsorption functional materials and using combination of the solid-phase extraction, magnetic separation and the gas chromatography. The method is simple in experimental operation, high in detection sensitivity, low in cost and applicable to detection of residues of ten types of organophosphorus pesticides such as trace dipterex and the like in all products.
Description
Technical field
The present invention relates to a kind of ten kinds of organophosphorus pesticide methods of magnetic separation-gas chromatographic detection, belong to food safety detection technical field.
Background technology
Organophosphorus pesticide is that a class is efficient, the chemical insecticide of wide spectrum, has the advantages such as wide in variety, drug effect is high, purposes is wide, in agricultural production, is widely used, and has become one of main source of food pollution.Organophosphorus pesticide enters organism, and cholinesterase in biosome is had to inhibiting effect, suppresses cholinesterase and makes it lose the ability of decomposing acetylcholine, causes acetylcholine accumulation, causes nerve dysfunction, thereby causes the infringement to human body.The agricultural product that long-term edible organophosphorus pesticide trace exceeds standard, may cause people's slow poisoning, cause the generation of disease, more severe patient even can affect the next generation, therefore develops a kind of easy and simple to handle, highly sensitive detection technique particularly important to solving Pesticide Residue.
It is the focus of International Food Safety Control area research that pesticide multi-residues detects, and the method adopting at present mainly contains gas chromatography (GC), liquid chromatography (LC), gas chromatography-mass spectrum (GC-MS), liquid chromatography-mass spectrography (LC-MS), atomic absorption spectrum (AAS), Capillary Electrophoresis (CE) etc.Wherein chromatography mass spectrometry detection sensitivity is high but expensive.Gas chromatography rule is current the most frequently used organophosphorus pesticide detection method.Food samples Component comparison complexity, residues of pesticides content is extremely low, the process such as therefore before carrying out GC analysis, needs effectively to extract, purify, concentrate.Traditional preprocess method mainly contains Solid-Phase Extraction (SPE), liquid-liquid extraction (LLE), solid-phase microextraction (SPME), supercritical fluid extraction etc.In recent years, magnetic Solid-Phase Extraction (MSPE) technology is by the more and more pre-service for sample.MSPE only can realize and being separated by applying an external magnetic field, therefore simple to operate, save time fast, without troublesome operation such as centrifugal filtrations, avoided traditional SPE adsorbent need fill the problem consuming time such as post and sample loading.Therefore, synthetic chitosan magnetic micro-sphere Determination of Organophosphorus Pesticide to high absorption capacity, separate detection as Solid-Phase Extraction (MSPE) adsorbent and with gas chromatography coupling, operating process is simple, quick, highly sensitive, in China's food and agricultural products, organic phosphorus pesticide multi-residue will have broad application prospects in detecting.
Summary of the invention
The object of the invention is to overcome long, the defect such as cost is high, pre-treatment the is loaded down with trivial details detection time that traditional On Detection of Organophosphorus Pesticide exists, provide a kind of magnetic Solid-Phase Extraction and gas chromatography coupling the quick method that separates, detects ten kinds of organophosphorus pesticides (metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and chlopyrifos).
Existing Solid-Phase Extraction and gas chromatography also can realize the object of ten kinds of Pesticides Testing, but have sample pre-treatments complexity, the defect that detection speed is slow.The present invention, by magnetic resolution, can realize quick separation and detect.
The present invention realizes by following steps:
1) preparation of chitosan magnetic:
0.1mol iron chloride and 0.2mol iron protochloride are dissolved in to the 2.0mol L of 100mL
-1in hydrochloric acid solution; Slowly drip 2.0mol L
-1ammoniacal liquor to pH value of solution be adjusted to 9.73, and vigorous stirring 2h at room temperature; Respectively wash 3-5 time with 100-150mL second alcohol and water successively, after vacuum drying, obtain γ-di-iron trioxide.
Get 70-90mL whiteruss and 3-5mL Span-80, mechanical raking 30min in 40 DEG C of water-baths, forms uniform reaction medium; It is ultrasonic mixing 15-30min in shitosan-acetic acid solution of 2% that γ-di-iron trioxide described in 0.4g is added to 20mL concentration; Potpourri is to pearl outflow under 900-1200 rev/min of high-speed stirred condition and is added drop-wise in reaction medium, continue high-speed stirred 30min; Drip again 2.5mL concentration and be 50% glutaraldehyde; Then be 1.0mol L by concentration
-1it is 9.0,60 DEG C of water-bath 2h that sodium hydroxide solution regulates pH; Leave standstill after removing oil reservoir and carry out vacuum filtration, respectively wash 3-4 time with acetone and the ethanol of 100-150mL successively, rear use 100mL distilled water washs 5 times; After vacuum drying, obtain chitosan magnetic micro-sphere.
2) foundation of magnetic separation-gas chromatography coupling system:
Take chitosan magnetic micro-sphere prepared by 50mg step 1) and join in the mixed standard solution that 100mL contains metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and ten kinds of organophosphorus pesticides of chlopyrifos, concussion extraction 1-2h.Again the mixed standard solution of the above-mentioned organophosphorus pesticide that adds chitosan magnetic micro-sphere is placed in to magnetic field chitosan magnetic micro-sphere is separated with supernatant, remove chitosan magnetic micro-sphere 0.5-1.5mL methyl alcohol/glacial acetic acid mixed solution (methyl alcohol: glacial acetic acid volume ratio=98:2) vortex concussion desorb 10-30s after supernatant; This step repetitive operation 2-3 time.Merge wash-out liquid nitrogen that above-mentioned 2-3 wash-out obtain and blow and redissolve with 0.2mL methylene chloride afterwards, after 0.22 μ m membrane filtration, get 1 μ L filtrate air inlet analysis of hplc.
3) drafting of typical curve
Accurately compound concentration is 100mg L
-1the methylene chloride standard solution mother liquor that contains metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion, chlopyrifos.Methylene chloride with 99.5% by above-mentioned methylene chloride mixed standard solution mother liquor respectively successively gradient dilution to become concentration be 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1standard solution.Taking the concentration of standard solution after above-mentioned dilution as horizontal ordinate, taking corresponding chromatographic peak area as ordinate, draw respectively ten kinds of organophosphorus pesticide typical curves.
4) in determinand organophosphorus pesticide content determine:
Get 2.0-5.0g through the sample smashed to pieces, the ultrasonic extraction of the dichloromethane solution that is 99.5% with 10-30mL concentration 3 times, merging extract is also settled to 100mL and obtains sample extracting solution.Sample extracting solution is replaced to ten kinds of organophosphorus standard solution repeating steps 2) operate, calculated the content of metrifonate in testing sample, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and/or chlopyrifos by typical curve according to the peak area of gas chromatography.
Beneficial effect of the present invention:
1. the present invention, using the chitosan magnetic that Determination of Organophosphorus Pesticide is had to high absorption property of preparation as adsorbent, has carried out effective enrichment, separation to the organophosphorus pesticide of trace in sample, has simplified sample pre-treatments step.
2. the present invention, by Solid-Phase Extraction, magnetic separation technique and gas chromatography coupling, has set up ten kinds of organophosphorus pesticides such as metrifonate, acephatemet has been had to highly sensitive detection method, has improved the sensitivity of method.
3. experimental implementation of the present invention is simple, highly sensitive, with low cost, is applicable to the fast detecting of trace organic phosphorus pesticide multi-residue in various agricultural product.
Brief description of the drawings
Fig. 1 is the chromatogram of peach sample through magnetic separation-gas chromatographic detection.As seen from the figure, detect and contain metrifonate, malathion and chlopyrifos in peach, content is respectively 0.2,0.5 and 1.0mg kg
-1.
Embodiment
Below in conjunction with embodiment, the present invention is further described; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
The present invention has highly sensitive detection method by magnetic solid phase extraction techniques and gas chromatography coupling foundation to metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and chlopyrifos.Its specific embodiment is:
1) preparation of chitosan magnetic:
0.1mol iron chloride and 0.2mol iron protochloride are dissolved in to the 2.0mol L of 100mL
-1in hydrochloric acid solution; Slowly drip 2.0mol L
-1ammoniacal liquor to pH value of solution be adjusted to 9.73, and vigorous stirring 2h at room temperature; Use successively 100mL ethanol and water washing each 5 times, after 40 DEG C of vacuum drying, obtain γ-di-iron trioxide.
Get 70-90mL whiteruss and 3-5mL Span-80, mechanical raking 30min in 40 DEG C of water-baths, forms uniform reaction medium; It is ultrasonic mixing in 2% shitosan-acetic acid solution that 0.4g γ-di-iron trioxide is added to 20mL concentration, after ultrasonic 20min, the potpourri of γ-di-iron trioxide and shitosan-acetic acid solution is to pearl outflow under 1000 revs/min of high-speed stirred conditions and is added drop-wise in reaction medium, continue high-speed stirred 30min; The glutaraldehyde that is 50% by 2.5mL concentration is added drop-wise to reaction system, is then 1.0molL by concentration
-1it is 9.0,60 DEG C of water-bath 2h that sodium hydroxide solution regulates pH; Leave standstill after removing oil reservoir and carry out vacuum filtration, respectively wash 3 times with 150mL acetone, ethanol successively, rear with 100mL distilled water washing 5 times, must chitosan magnetic particle after 40 DEG C of vacuum drying.
2) foundation of magnetic organophosphorous pesticides coupling system:
The chitosan magnetic of preparing using step 1), as the adsorbent of magnetic Solid-Phase Extraction, with gas chromatography coupling, is set up magnetic Solid-Phase Extraction and gas chromatography coupling detection system.
A. magnetic Solid-Phase Extraction flow process:
Take 50mg chitosan magnetic particle and join in the mixed standard solution that 100mL contains ten kinds of organophosphorus pesticides (being metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and chlopyrifos), concussion extraction 1.5h.Add chitosan magnetic micro-sphere organophosphorus standard solution to be placed in magnetic field chitosan magnetic micro-sphere is separated with supernatant by above-mentioned again, remove chitosan magnetic micro-sphere 1.0mL methyl alcohol/glacial acetic acid mixed solution (methyl alcohol: glacial acetic acid volume ratio=98:2) vortex concussion desorb 20s after supernatant; Magnetic field separation, elution step repetitive operation 3 times.Merge wash-out liquid nitrogen that above-mentioned 3 wash-outs obtain and blow the rear methylene chloride that is 99.5% by 0.2mL concentration and redissolve, 0.22 μ m membrane filtration, gets 1 μ L filtrate air inlet analysis of hplc.
B. gas chromatographic detection:
GC-2010FPD detecting device; Chromatographic column: RTX-1 (the neutral capillary column of μ m × 0.1,30.0m × 250 μ m); Column temperature: 50 DEG C, keep 1.0min, with 15 DEG C of min
-1speed rising to 200 DEG C, keep 1.0min, then with 2 DEG C of min
-1speed rising to 220 DEG C, finally with 20 DEG C of min
-1speed rising to 240 DEG C, keep 5min.Injector temperature: 180 DEG C, FPD detector temperature: 270 DEG C, carrier gas is high pure nitrogen, total flow: 8.0mL min
-1, post flow: 1.0mL min
-1, purge flow rate: 3.0mL min
-1, pressure: 34.1kPa, sample size: 1 μ L, split ratio: 4:1.
3) drafting of typical curve
Accurately compound concentration is 100mg L
-1the methylene chloride standard solution mother liquor that contains metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and chlopyrifos.Methylene chloride with 99.5% successively gradient dilution to become concentration be 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1standard solution.Taking above-mentioned dilution as 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1concentration of standard solution be horizontal ordinate, taking corresponding chromatographic peak area as ordinate, draw respectively ten kinds of organophosphorus pesticide typical curves.
4) accurately take 5.0g and pass through the peach sample of smashing to pieces, the ultrasonic extraction of dichloromethane solution of use 30mL99.5% 3 times, merging extract is settled to 100mL and obtains sample extracting solution.Replace ten kinds of organophosphorus standard solution repeating steps 2 with sample extracting solution) operation, determine and in peach, contain metrifonate, malathion and chlopyrifos according to obtained gas chromatogram.According to peak area, the content that calculates metrifonate in peach, malathion and chlopyrifos by typical curve is respectively 0.2,0.5 and 1.0mg kg
-1.
Claims (1)
1. ten kinds of organophosphorus pesticide methods of magnetic separation-gas chromatographic detection, is characterized in that comprising the following steps:
1) preparation of chitosan magnetic:
0.1mol iron chloride and 0.2mol iron protochloride are dissolved in to the 2.0mol L of 100mL
-1in hydrochloric acid solution; Slowly drip 2.0mol L
-1ammoniacal liquor to pH value of solution be adjusted to 9.73, and vigorous stirring 2h at room temperature; Respectively wash 3-5 time with 100-150mL second alcohol and water successively, after vacuum drying, obtain γ-di-iron trioxide;
Get 70-90mL whiteruss and 3-5mL Span-80, mechanical raking 30min in 40 DEG C of water-baths, forms uniform reaction medium; It is ultrasonic mixing 15-30min in shitosan-acetic acid solution of 2% that γ-di-iron trioxide described in 0.4g is added to 20mL concentration; Potpourri is to pearl outflow under 900-1200 rev/min of high-speed stirred condition and is added drop-wise in reaction medium, continue high-speed stirred 30min; Drip again 2.5mL concentration and be 50% glutaraldehyde; Then be 1.0mol L by concentration
-1it is 9.0,60 DEG C of water-bath 2h that sodium hydroxide solution regulates pH; Leave standstill after removing oil reservoir and carry out vacuum filtration, respectively wash 3-4 time with acetone and the ethanol of 100-150mL successively, rear use 100mL distilled water washs 5 times; After vacuum drying, obtain chitosan magnetic micro-sphere;
2) foundation of magnetic separation-gas chromatography coupling system:
Take chitosan magnetic micro-sphere prepared by 50mg step 1) and join in the mixed standard solution that 100mL contains metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and ten kinds of organophosphorus pesticides of chlopyrifos, concussion extraction 1-2h; Again the mixed standard solution of the above-mentioned organophosphorus pesticide that adds chitosan magnetic micro-sphere is placed in to magnetic field chitosan magnetic micro-sphere is separated with supernatant, remove the methyl alcohol/glacial acetic acid mixed solution vortex concussion desorb 10-30s of chitosan magnetic micro-sphere 0.5-1.5mL methyl alcohol/glacial acetic acid volume ratio=98:2 after supernatant; This step repetitive operation 2-3 time; Merge wash-out liquid nitrogen that above-mentioned 2-3 wash-out obtain and blow and redissolve with 0.2mL methylene chloride afterwards, after 0.22 μ m membrane filtration, get 1 μ L filtrate air inlet analysis of hplc;
3) drafting of typical curve
Accurately compound concentration is 100mg L
-1the methylene chloride standard solution mother liquor that contains metrifonate, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion, chlopyrifos; Methylene chloride with 99.5% by above-mentioned methylene chloride mixed standard solution mother liquor respectively successively gradient dilution to become concentration be 0.1,0.25,0.5,1.5,2.5,5.0 and 10.0mg L
-1standard solution; Taking the concentration of standard solution after above-mentioned dilution as horizontal ordinate, taking corresponding chromatographic peak area as ordinate, draw respectively ten kinds of organophosphorus pesticide typical curves;
4) in determinand organophosphorus pesticide content determine:
Get 2.0-5.0g through the sample smashed to pieces, the ultrasonic extraction of the dichloromethane solution that is 99.5% with 10-30mL concentration 3 times, merging extract is also settled to 100mL and obtains sample extracting solution; Sample extracting solution is replaced to ten kinds of organophosphorus standard solution repeating steps 2) operate, calculated the content of metrifonate in testing sample, acephatemet, orthene, flolimat, Azodrin, Rogor, phosphamidon, parathion-methyl, malathion and/or chlopyrifos by typical curve according to the peak area of gas chromatography.
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Cited By (11)
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| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN104475030A (en) * | 2014-11-20 | 2015-04-01 | 杭州电子科技大学 | Preparation method of magnetic metal organic framework material and application of magnetic metal organic framework material |
| CN106732437A (en) * | 2017-03-10 | 2017-05-31 | 深圳市瑞赛生物技术有限公司 | A kind of affine magnetic microsphere and its preparation and application for purifying and detecting carbamate and organophosphorus pesticide |
| CN107957465A (en) * | 2017-12-28 | 2018-04-24 | 广东集菜送食品科技有限公司 | Practice for Pesticide Residue in Agricultural Products accurate detecting method |
| CN108956918A (en) * | 2018-06-11 | 2018-12-07 | 安徽省佳逸环保科技有限公司 | It is a kind of for being enriched with the concentration detection method of the preparation method of the magnetic film materials of organophosphorus pesticide and organophosphorus pesticide in water body |
| CN109142571A (en) * | 2018-08-20 | 2019-01-04 | 浙江工业大学 | Method for measuring content of anthraquinone components |
| CN109655365A (en) * | 2018-12-29 | 2019-04-19 | 江苏微谱检测技术有限公司 | The detection method of organic agricultural chemicals in a kind of soil |
| CN110694601A (en) * | 2019-11-12 | 2020-01-17 | 红河学院 | Solid phase micro-extraction head and preparation method and application thereof |
| CN114544836A (en) * | 2022-03-11 | 2022-05-27 | 天津国科医工科技发展有限公司 | Pretreatment method and detection method for detecting trace estrogen, 17-hydroxypregnanolone, aldosterone and dehydroepiandrosterone sulfate |
| CN114689744A (en) * | 2022-03-21 | 2022-07-01 | 江南大学 | Application of functionalized three-dimensional covalent organic framework in detection of organophosphorus pesticide residues |
| CN115812700A (en) * | 2021-12-31 | 2023-03-21 | 中山大学 | Nano pesticide and preparation method thereof |
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| CN104475030A (en) * | 2014-11-20 | 2015-04-01 | 杭州电子科技大学 | Preparation method of magnetic metal organic framework material and application of magnetic metal organic framework material |
| CN104475030B (en) * | 2014-11-20 | 2017-01-04 | 杭州电子科技大学 | A kind of preparation method and applications of magnetic metal organic framework material |
| CN104360000A (en) * | 2014-11-20 | 2015-02-18 | 山东农业大学 | Method for simultaneously detecting three organophosphorus pesticides |
| CN106732437A (en) * | 2017-03-10 | 2017-05-31 | 深圳市瑞赛生物技术有限公司 | A kind of affine magnetic microsphere and its preparation and application for purifying and detecting carbamate and organophosphorus pesticide |
| CN107957465B (en) * | 2017-12-28 | 2020-11-03 | 广东集菜送食品科技有限公司 | Method for accurately detecting pesticide residue of agricultural products |
| CN107957465A (en) * | 2017-12-28 | 2018-04-24 | 广东集菜送食品科技有限公司 | Practice for Pesticide Residue in Agricultural Products accurate detecting method |
| CN108956918B (en) * | 2018-06-11 | 2022-01-11 | 安徽省佳逸环保科技有限公司 | Preparation method of magnetic film material for enriching organophosphorus pesticide in water body and concentration detection method of organophosphorus pesticide |
| CN108956918A (en) * | 2018-06-11 | 2018-12-07 | 安徽省佳逸环保科技有限公司 | It is a kind of for being enriched with the concentration detection method of the preparation method of the magnetic film materials of organophosphorus pesticide and organophosphorus pesticide in water body |
| CN109142571A (en) * | 2018-08-20 | 2019-01-04 | 浙江工业大学 | Method for measuring content of anthraquinone components |
| CN109142571B (en) * | 2018-08-20 | 2021-02-02 | 浙江工业大学 | Method for measuring content of anthraquinone components |
| CN109655365A (en) * | 2018-12-29 | 2019-04-19 | 江苏微谱检测技术有限公司 | The detection method of organic agricultural chemicals in a kind of soil |
| CN109655365B (en) * | 2018-12-29 | 2021-03-12 | 江苏微谱检测技术有限公司 | Method for detecting organic pesticide in soil |
| CN110694601A (en) * | 2019-11-12 | 2020-01-17 | 红河学院 | Solid phase micro-extraction head and preparation method and application thereof |
| CN110694601B (en) * | 2019-11-12 | 2022-04-15 | 红河学院 | Solid phase micro-extraction head and preparation method and application thereof |
| CN115812700A (en) * | 2021-12-31 | 2023-03-21 | 中山大学 | Nano pesticide and preparation method thereof |
| CN114544836A (en) * | 2022-03-11 | 2022-05-27 | 天津国科医工科技发展有限公司 | Pretreatment method and detection method for detecting trace estrogen, 17-hydroxypregnanolone, aldosterone and dehydroepiandrosterone sulfate |
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Application publication date: 20140702 |