CN102890128B - Detection method for twelve kinds of pyrethroids pesticide residues in capsanthin - Google Patents
Detection method for twelve kinds of pyrethroids pesticide residues in capsanthin Download PDFInfo
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Abstract
The invention discloses a detection method for twelve kinds of pyrethroids pesticide residues in capsanthin. The detection method comprises the following steps of: ultrasonically extracting the capsanthin with an extracting solvent and then separating an extract liquor to obtain a supernatant liquor; purifying the supernatant liquor by using a gel permeation chromatography, collecting target eluant, concentrating the target eluant until dry and then making the volume constant to obtain a sample solution; and measuring the sample solution by adopting a gas chromatography-tandem mass spectrum in a selected ion monitoring mode and quantifying with an external standard method. The method is used for processing the capsanthin by adopting a GPC (gel permeation chromatography) technology, so that most of macromolecular pigment matters are moved, interference of sample matrixes on measurement is lowered greatly; and the detection method is high in accuracy and strong in applicability for the capsanthin. The detection is carried out by adopting the gas chromatography-tandem mass spectrum and selecting the ion monitoring mode, so that the method has the advantages of high sensitivity and high automation degree, is easy and fast and is capable of detecting large batches of samples easily; and generated waste liquid can be recycled and reused so as to reduce the detection cost and reduce the environmental pollution.
Description
Technical field
The present invention relates to the residual detection method of a kind of food additives middle peasant, 12 kinds of detection methods that pyrethroid agriculture is residual in especially a kind of capsanthin.
Background technology
Capsanthin is to take paprika fruit as raw material, extraction and the peony oily liquids pigment that makes is a kind of natural colorant with fortification effect, and its principal ingredient is carotenoid.Because natural colouring matter edible safety is high, and have physiologically active, capsanthin is more and more subject to people's favor.
Capsicum is the raw material that capsanthin is produced, and for ensureing and promote the normal growth of capsicum, peasant household can use all kinds of agricultural chemicals of desinsection, sterilization, kill harmful animal (or weeds), causes ubiquity residues of pesticides in capsicum.These residues of pesticides are continuous enrichment method in the extraction process of capsicum, causes the extract products such as capsanthin to have potential safety hazard.
One of main remains of pesticide in capsicum and pepper extract is pyrethroid pesticide.Pyrethroid pesticide has efficiently, wide spectrum, the relative characteristic such as low toxicity and biodegradation, have higher desinsection effect, and consumption is few than organochlorine, organophosphorus insecticide, people is poisoned little, so widespread use in the world.But show after deliberation, pyrethroid pesticide has cumulative toxicity, long-term low dose contact also can cause chronic disease.Therefore, various countries more and more pay attention to the residual monitoring in agricultural byproducts of such agricultural chemicals.In order to guarantee the edible safety of food additives capsanthin, improve China's food safety Regulation level, ensure that citizen is healthy, promote the development of capsanthin industry, study the residual detection method of pyrethroid agriculture in a kind of accurate, quick, sensitive capsanthin and be of great significance for the safety in production tool of monitoring and check capsanthin.
At present, relevant pyrethroid pesticide remained detection method is existing many, comprises High Performance Liquid Chromatography/Mass Spectrometry method, gas chromatography-mass spectrography, vapor-phase chromatography and gas chromatography-tandem mass spectrometry etc.Wherein more to research report pyrethroid pesticide remained in the food such as tobacco, tealeaves, fruits and vegetables, and there is not yet report for the research of pyrethroid pesticide remained detection in food additives capsanthin.Because contain a large amount of pigments in capsanthin, matrix is complicated, so directly use the detection method of pyrethroid in above-mentioned food, matrix interference is very large, cannot realize effective detection.Therefore,, for capsanthin characteristic, the method that special exploitation is applicable to the residual detection of multiple pyrethroid agriculture in capsanthin is very crucial.
Summary of the invention
The technical problem to be solved in the present invention is to provide 12 kinds of detection methods that pyrethroid agriculture is residual in a kind of capsanthin fast and accurately.
For solving the problems of the technologies described above, the technical solution used in the present invention is: capsanthin is carried out ultrasonic extraction with extraction solvent, then extract separation is obtained to supernatant liquor; Described supernatant liquor adopts gel permeation chromatography to purify, and collection target eluent is concentrated into dry, then uses organic solvent constant volume, obtains sample solution; Described sample solution adopts gas chromatography-tandem mass spectrum to measure under selection ion monitoring pattern, and external standard method is quantitative.
Extraction solvent of the present invention is cyclohexane and the ethyl acetate mixed solvent of volume ratio 50:50; Described organic solvent is methylene chloride, cyclohexane, isopropyl ether, normal hexane or acetone.The mobile phase that described gel permeation chromatography purifies is that volume ratio is cyclohexane and the ethyl acetate mixed solvent of 50:50; The flow velocity of described mobile phase is 5.0mL/min, and acquisition time is 9.0～13.0min.
GC conditions of the present invention is: chromatographic column is low pole quartz capillary column, 250～300 ℃ of injector temperatures, and 250～300 ℃ of transmission line temperature, sample size is 1.0～5.0 μ L, flow rate of carrier gas is 0.5～1.2mL/min.Described low pole quartz capillary column is selected HP-5 MS quartz capillary column, HP-17 MS quartz capillary column or HP-5 DS quartz capillary column; Specification is length 30m, internal diameter 0.25mm, thickness 0.25 μ m.
The temperature programme condition of gas chromatography of the present invention is: 80 ℃ of initial temperatures, keep 1min; With 20 ℃/min speed, be warming up to 200 ℃, keep 10min; With 20 ℃/min speed, be warming up to 260 ℃ again, keep 15min.
Mass Spectrometer Method condition of the present invention is: ion source temperature is 230 ℃, and the solvent delay time is 3.0～11.0min.
Selection ion monitoring pattern of the present invention is: Biphenthrin monitoring ion is 181
*, 166,165; Fenpropathrin monitoring ion is 265
*, 208,181; Betacyfluthrin monitoring ion is 208
*, 197,181; Acrinathrin monitoring ion is 289
*, 247,208,181; Permethrin monitoring ion is 184
*, 183,165,163; Cyfloxylate monitoring ion is 226
*, 206,199,163; Cypermethrin monitoring ion is 208
*, 181,165,163; Silafluofene monitoring ion is 286
*, 258,179; Fenvalerate monitoring ion is 225
*, 181,167,152,125; S-fenvalerate monitoring ion is 225
*, 181,167,152,125; Taufluvalinate monitoring ion is 281
*, 250,181; Decis monitoring ion is 281
*, 253,209,181.
The ultrasonic extraction time of the present invention is 10～30min, and number of times is 1～3 time; Described extract adopts high speed freezing centrifuge to carry out centrifuging; High speed freezing centrifuge rotating speed is 4000～10000r/min, and centrifugation time is 5～10min; Described target eluent adopts Rotary Evaporators or automatic Nitrogen evaporator to concentrate.
Capsanthin consumption of the present invention is 0.5～1.5g, and the consumption of described extraction solvent is 10～25mL, and the constant volume of described organic solvent is 1.0～5.0mL.
Adopt the beneficial effect that technique scheme produces to be: gel permeation chromatography (GPC) is a kind ofly according to solute molecule size, to carry out separated chromatographic technique, can remove greases a large amount of in sample and pigment, there is rapidly and efficiently, save the advantages such as solvent, easy robotization.Gas chromatography-tandem mass spectrum is selected ion monitoring mode detection technology, and accuracy is high.The present invention adopts GPC purification techniques to process capsanthin sample, in conjunction with gas chromatography-tandem mass spectrum, selects ion monitoring mode detection technology, has set up a kind of method that is applicable to 12 kinds of residual detections of pyrethroid agriculture in capsanthin.
The present invention adopts GPC technical finesse capsanthin, has removed most large molecule colors, has greatly reduced the interference of sample substrate to 12 kinds of residual mensuration of pyrethroid agriculture, and detection method accuracy is high, strong to capsanthin applicability; The present invention adopts GPC technology to select ion monitoring mode detection in conjunction with gas chromatography-tandem mass spectrum, and method is highly sensitive, and whole process automation degree is high, easy, fast, is easy to realize batch samples and detects; The waste liquid producing in GPC decontamination process of the present invention can recycle, and reuses, and has reduced testing cost, has reduced environmental pollution.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is that the gas chromatography-mass spectrum of 12 kinds of pyrethroid pesticide compound standard substances of the present invention is selected ion (SIM) monitoring chromatogram.
Embodiment
In this capsanthin, 12 kinds of residual detection methods of pyrethroid agriculture adopt following equipment and test condition: Agilent 7890A GC system, and chromatographic column is selected HP-5 MS quartz capillary column, HP-17 MS quartz capillary column and HP-5 DS quartz capillary column; The triple level Four bar of Agilent 7000 GC/MS/MS Mass Spectrometer Method; Lab Tech Cleanup800 gel permeation chromatograph, joins the decontaminating column of 300mm * 25mm BIO-Beads S-X3 filler; Agents useful for same is chromatographically pure; Gas chromatography temperature programme condition is: 80 ℃ of initial temperatures, keep 1min; With 20 ℃/min speed, be warming up to 200 ℃, keep 10min; With 20 ℃/min speed, be warming up to 260 ℃ again, keep 15min; Mass Spectrometer Method, monitoring pattern is for selecting ion monitoring pattern.Computer system records chromatogram, usings peak area as signal response value, to 12 kinds of residual qualitative and quantitative analysis that carry out of pyrethroid agriculture.Wherein, Biphenthrin monitoring ion is 181
*, 166,165; Fenpropathrin monitoring ion is 265
*, 208,181; Betacyfluthrin monitoring ion is 208
*, 197,181; Acrinathrin monitoring ion is 289
*, 247,208,181; Permethrin monitoring ion is 184
*, 183,165,163; Cyfloxylate monitoring ion is 226
*, 206,199,163; Cypermethrin monitoring ion is 208
*, 181,165,163; Silafluofene monitoring ion is 286
*, 258,179; Fenvalerate monitoring ion is 225
*, 181,167,152,125; S-fenvalerate monitoring ion is 225
*, 181,167,152,125; Taufluvalinate monitoring ion is 281
*, 250,181; Decis monitoring ion is 281
*, 253,209,181.
Embodiment 1: in this capsanthin, the residual concrete implementation step of detection method of 12 kinds of pyrethroid agricultures is as described below:
(1) typical curve: it is appropriate that precision measures 12 kinds of pyrethroid agriculture residual standard storing solutions respectively, with Fisher chromatographically pure normal hexane stepwise dilution, become that mass concentration is respectively 0.01,0.05,0.1,0.2,0.5, the series standard solution of 1.0mg/L, by above-mentioned test condition sample introduction, measure, with 12 kinds of residual peak area Y of pyrethroid agriculture, its mass concentration X is mapped respectively.
(2) sample extraction: accurately take 1.0g(and be accurate to 0.0001g)
=200 capsanthin samples are in 25mL volumetric flask, and adding 12.5mL volume ratio is cyclohexane-ethyl acetate mixed solvent of 50:50, ultrasonic 15min, and number of times 2 times, is cooled to room temperature, and adding volume ratio is cyclohexane-ethyl acetate mixed solvent constant volume of 50:50.Extract is transferred in centrifuge tube, with the centrifugal 5min of rotating speed of 8000r/min, gets 0.45 μ m membrane filtration for supernatant liquor at 5 ℃, and filtrate is transferred in GPC loading bottle.
(3) GPC purified treatment: GPC detection wavelength is 254nm, and mobile phase is cyclohexane-ethyl acetate mixed solvent of volume ratio 50:50, and flow velocity is 5.0mL/min.Loading 2.0mL enters GPC purified treatment, collects the efflux of 9.0～13.0min, uses Rotary Evaporators to be concentrated in 40 ℃ dry, with acetone ultrasonic dissolution, is settled to 5.0mL, and solution is measured with sample introduction after 0.22 μ m membrane filtration.
(4) gas chromatography-tandem mass spectrum detects: choose HP-5 MS quartz capillary column, temperature programme, 260 ℃ of injector temperatures, 260 ℃ of transmission line temperature, flow rate of carrier gas is 1.2mL/min, sample size 2.0 μ L, select ion monitoring pattern, ion source temperature is 230 ℃, solvent delay 11.0min.Gas chromatography-tandem mass spectrum detects the residual chromatogram of 12 kinds of pyrethroid agricultures as shown in Figure 1, and in Fig. 1, the peak sequence of 12 kinds of pyrethroid pesticide compounds is followed successively by: Biphenthrin, Fenpropathrin, betacyfluthrin, acrinathrin, Permethrin, cyfloxylate, cypermethrin, silafluofene, fenvalerate, S-fenvalerate, taufluvalinate, decis.
(5) replicate determination: adopt external standard method quantitative, right
=200 capsanthin samples are done 3 Duplicate Samples, and test number is A, B, C, calculate respectively 12 kinds of collimation relative standard deviations that pyrethroid agriculture is residual, and analysis result is in Table 1; To one of them sample replication five times, calculate respectively 12 kinds of precision that pyrethroid agriculture is residual, analysis result is in Table 2.
(6) recovery of standard addition: the standard solution in step (1) is joined to known pyrethroid agriculture residual content
in=200 capsanthins, according to above-mentioned steps, test, this sample is done to 10 replicate determinations continuously, average, calculate recovery of standard addition, experimental result is in Table 3.
In sum, this method is applicable to completely
12 kinds of detections that pyrethroid agriculture is residual in=200 capsanthins.
Embodiment 2: in this capsanthin, the residual concrete implementation step of detection method of 12 kinds of pyrethroid agricultures is as described below:
(1) typical curve: identical with embodiment 1.
(2) sample extraction: accurately take 0.5g(and be accurate to 0.0001g)
=50 capsanthin samples are in 10mL volumetric flask, and adding 10mL volume ratio is cyclohexane-ethyl acetate mixed solvent of 50:50, and ultrasonic 10min, is cooled to room temperature, and adding volume ratio is cyclohexane-ethyl acetate mixed solvent constant volume of 50:50.Extract is transferred in centrifuge tube, with the centrifugal 5min of rotating speed of 4000r/min, gets 0.45 μ m membrane filtration for supernatant liquor at 5 ℃, and filtrate is transferred in GPC loading bottle.
(3) GPC purified treatment: GPC detection wavelength is 254nm, and mobile phase is cyclohexane-ethyl acetate mixed solvent of volume ratio 50:50, and flow velocity is 5.0mL/min.Loading 2.0mL enters GPC purified treatment, collects the efflux of 9.0～13.0min, uses Rotary Evaporators to be concentrated in 40 ℃ dry, with isopropyl ether ultrasonic dissolution, is settled to 2.0mL, and solution is measured with sample introduction after 0.22 μ m membrane filtration.
(4) gas chromatography-tandem mass spectrum detects: choose HP-17 MS quartz capillary column, temperature programme, 250 ℃ of injector temperatures, 250 ℃ of transmission line temperature, flow rate of carrier gas is 1.0mL/min, sample size 1.0 μ L, select ion monitoring pattern, ion source temperature is 230 ℃, solvent delay 8.0min.
(5) replicate determination: adopt external standard method quantitative, right
=50 capsanthin samples are done 3 Duplicate Samples, test number is A, B, C, calculate respectively 12 kinds of collimation relative standard deviations that pyrethroid agriculture is residual, obtain Biphenthrin 1.1%, Fenpropathrin 2.6%, betacyfluthrin 1.7%, acrinathrin 5.7%, Permethrin 4.2%, cyfloxylate 3.9%, cypermethrin 5.2%, silafluofene 7.9%, fenvalerate 3.4%, S-fenvalerate 1.2%, taufluvalinate 5.0%, decis 4.6%.To one of them sample replication five times, calculate respectively 12 kinds of precision that pyrethroid agriculture is residual, obtain Biphenthrin 1.3%, Fenpropathrin 2.1%, betacyfluthrin 1.9%, acrinathrin 5.1%, Permethrin 2.3%, cyfloxylate 4.4%, cypermethrin 5.4%, silafluofene 1.8%, fenvalerate 8.3%, S-fenvalerate 2.8%, taufluvalinate 6.0% and decis 6.2%.
(6) recovery of standard addition: the standard solution in step (1) is joined to known 12 kinds of residual content of pyrethroid agriculture
in=50 capsanthins, according to above-mentioned steps, test, this sample is done to 10 replicate determinations continuously, average, calculate recovery of standard addition, obtain Biphenthrin 85～105%, Fenpropathrin 80～96%, betacyfluthrin 90～110%, acrinathrin 80～100%, Permethrin 89～106%, cyfloxylate 92～110%, cypermethrin 79～103%, silafluofene 94～106%, fenvalerate 83～110%, S-fenvalerate 80～105%, taufluvalinate 86～110% and decis 85～95%.
To sum up, this method is applicable to
12 kinds of detections that pyrethroid agriculture is residual in=50 capsanthins.
Embodiment 3: in this capsanthin, the residual concrete implementation step of detection method of 12 kinds of pyrethroid agricultures is as described below:
(1) typical curve: identical with embodiment 1.
(2) sample extraction: accurately take 1.5g(and be accurate to 0.0001g)
=50 capsanthin samples are in 25mL volumetric flask, and adding 25mL volume ratio is cyclohexane-ethyl acetate mixed solvent of 50:50, ultrasonic 30min, and number of times 3 times, is cooled to room temperature, and adding volume ratio is cyclohexane-ethyl acetate mixed solvent constant volume of 50:50.Extract is transferred in centrifuge tube, with the centrifugal 10min of rotating speed of 10000r/min, gets 0.45 μ m membrane filtration for supernatant liquor at 5 ℃, and filtrate is transferred in GPC loading bottle.
(3) GPC purified treatment: GPC detection wavelength is 254nm, and mobile phase is cyclohexane-ethyl acetate mixed solvent of volume ratio 50:50, and flow velocity is 5.0mL/min.Loading 2.0mL enters GPC purified treatment, collects the efflux of 9.0～13.0min, uses Rotary Evaporators to be concentrated in 40 ℃ dry, with normal hexane ultrasonic dissolution, is settled to 1.0mL, and solution is measured with sample introduction after 0.22 μ m membrane filtration.
(4) gas chromatography-tandem mass spectrum detects: choose HP-5 DS quartz capillary column, temperature programme, 300 ℃ of injector temperatures, 300 ℃ of transmission line temperature, flow rate of carrier gas is 0.5mL/min, sample size 5.0 μ L, select ion monitoring pattern, ion source temperature is 230 ℃, solvent delay 3.0min.
(5) replicate determination: adopt external standard method quantitative, right
=50 capsanthin samples are done 3 Duplicate Samples, test number is A, B, C, calculate respectively 12 kinds of collimation relative standard deviations that pyrethroid agriculture is residual, obtain Biphenthrin 1.1%, Fenpropathrin 2.3%, betacyfluthrin 1.2%, acrinathrin 5.8%, Permethrin 4.6%, cyfloxylate 3.0%, cypermethrin 6.0%, silafluofene 6.2%, fenvalerate 3.2%, S-fenvalerate 1.3%, taufluvalinate 5.7% and decis 1.0%.To one of them sample replication five times, calculate respectively 12 kinds of residual precision of chrysanthemum ester class agriculture, obtain Biphenthrin 1.5%, Fenpropathrin 2.8%, betacyfluthrin 1.2%, acrinathrin 5.7%, Permethrin 2.4%, cyfloxylate 4.8%, cypermethrin 5.1%, silafluofene 1.2%, fenvalerate 8.5%, S-fenvalerate 2.1%, taufluvalinate 2.6% and decis 6.6%.
(6) recovery of standard addition: the standard solution in step (1) is joined to known 12 kinds of residual content of pyrethroid agriculture
in=50 capsanthins, according to above-mentioned steps, test, this sample is done to 10 replicate determinations continuously, average, calculate recovery of standard addition, obtain Biphenthrin 82～106%, Fenpropathrin 80～101%, betacyfluthrin 87～105%, acrinathrin 80～106%, Permethrin 85～110%, cyfloxylate 84～110%, cypermethrin 86～105%, silafluofene 92～107%, fenvalerate 81～111%, S-fenvalerate 85～102%, taufluvalinate 91～112% and decis 90～105%.
Methylene chloride, cyclohexane, isopropyl ether, normal hexane and acetone for constant volume in this detection method all can dissolve 12 kinds of pyrethroid pesticides, therefore above-mentioned solvent all can be used for constant volume to obtain sample solution, and does not affect gas chromatography-tandem mass spectrum in the mensuration of selecting under ion monitoring pattern.
Claims (5)
1. 12 kinds of detection methods that pyrethroid agriculture is residual in capsanthin, is characterized in that: capsanthin is carried out ultrasonic extraction with extraction solvent, then extract separation are obtained to supernatant liquor; Described supernatant liquor adopts gel permeation chromatography to purify, and collection target eluent is concentrated into dry, then uses organic solvent constant volume, obtains sample solution; Described sample solution adopts gas chromatography-tandem mass spectrum to measure under selection ion monitoring pattern, and external standard method is quantitative;
Described extraction solvent is cyclohexane and the ethyl acetate mixed solvent of volume ratio 50:50; Described organic solvent is methylene chloride, cyclohexane, isopropyl ether, normal hexane or acetone;
Described selection ion monitoring pattern is: Biphenthrin monitoring ion is 181
*, 166,165; Fenpropathrin monitoring ion is 265
*, 208,181; Betacyfluthrin monitoring ion is 208
*, 197,181; Acrinathrin monitoring ion is 289
*, 247,208,181; Permethrin monitoring ion is 184
*, 183,165,163; Cyfloxylate monitoring ion is 226
*, 206,199,163; Cypermethrin monitoring ion is 208
*, 181,165,163; Silafluofene monitoring ion is 286
*, 258,179; Fenvalerate monitoring ion is 225
*, 181,167,152,125; S-fenvalerate monitoring ion is 225
*, 181,167,152,125; Taufluvalinate monitoring ion is 281
*, 250,181; Decis monitoring ion is 281
*, 253,209,181;
Described capsanthin consumption is 0.5～1.5g, and the consumption of described extraction solvent is 10～25mL, and the constant volume of described organic solvent is 1.0～5.0mL; The mobile phase that described gel permeation chromatography purifies is that volume ratio is cyclohexane and the ethyl acetate mixed solvent of 50:50; The flow velocity of described mobile phase is 5.0mL/min, and acquisition time is 9.0～13.0min; Described GC conditions is: chromatographic column is low pole quartz capillary column, 250～300 ℃ of injector temperatures, and 250～300 ℃ of transmission line temperature, sample size is 1.0～5.0 μ L, flow rate of carrier gas is 0.5～1.2mL/min.
2. 12 kinds of detection methods that pyrethroid agriculture is residual in capsanthin according to claim 1, is characterized in that: described low pole quartz capillary column is selected HP-5 MS quartz capillary column, HP-17 MS quartz capillary column or HP-5 DS quartz capillary column; Specification is length 30m, internal diameter 0.25mm, thickness 0.25 μ m.
3. 12 kinds of detection methods that pyrethroid agriculture is residual in capsanthin according to claim 1, is characterized in that, the temperature programme condition of described gas chromatography is: 80 ℃ of initial temperatures, keep 1min; With 20 ℃/min speed, be warming up to 200 ℃, keep 10min; With 20 ℃/min speed, be warming up to 260 ℃ again, keep 15min.
4. 12 kinds of detection methods that pyrethroid agriculture is residual in capsanthin according to claim 1, is characterized in that, described Mass Spectrometer Method condition is: ion source temperature is 230 ℃, and the solvent delay time is 3.0～11.0min.
5. according to 12 kinds of detection methods that pyrethroid agriculture is residual in the capsanthin described in claim 1-4 any one, it is characterized in that: the described ultrasonic extraction time is 10～30min, number of times is 1～3 time; Described extract adopts high speed freezing centrifuge to carry out centrifuging; High speed freezing centrifuge rotating speed is 4000～10000r/min, and centrifugation time is 5～10min; Described target eluent adopts Rotary Evaporators or automatic Nitrogen evaporator to concentrate.
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| CN113466371B (en) * | 2021-06-30 | 2023-09-08 | 黔西县黔希煤化工投资有限责任公司 | Method for determining trace diisopropyl ether in phenolic water |
| CN114441700A (en) * | 2021-12-24 | 2022-05-06 | 江苏赫尔斯检测技术有限公司 | Method for determining deltamethrin in water based on gas-mass linkage method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101498692A (en) * | 2008-08-18 | 2009-08-05 | 通标标准技术服务（天津）有限公司 | Method for measuring pesticide residue quantity in leather |
| JP2009186435A (en) * | 2008-02-08 | 2009-08-20 | Tsumura & Co | Method of purifying residual agricultural chemicals in herbal medicine sample |
| CN101598707A (en) * | 2009-05-19 | 2009-12-09 | 烟台杰科检测服务有限公司 | The residual detection method of Multiple Pesticides in a kind of oil-containing food |
| CN101915809A (en) * | 2010-07-01 | 2010-12-15 | 王冬群 | Detection method of pyrethroid pesticide remained in rice |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5286393A (en) * | 1976-01-12 | 1977-07-18 | Sumitomo Chemical Co | Gas chromatography for optical isomer in pyrethroid insecticide |
| JP5045282B2 (en) * | 2007-07-11 | 2012-10-10 | 株式会社ツムラ | Purification method of pesticide residues in crude drug samples |
-
2012
- 2012-09-21 CN CN201210354090.5A patent/CN102890128B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009186435A (en) * | 2008-02-08 | 2009-08-20 | Tsumura & Co | Method of purifying residual agricultural chemicals in herbal medicine sample |
| CN101498692A (en) * | 2008-08-18 | 2009-08-05 | 通标标准技术服务（天津）有限公司 | Method for measuring pesticide residue quantity in leather |
| CN101598707A (en) * | 2009-05-19 | 2009-12-09 | 烟台杰科检测服务有限公司 | The residual detection method of Multiple Pesticides in a kind of oil-containing food |
| CN101915809A (en) * | 2010-07-01 | 2010-12-15 | 王冬群 | Detection method of pyrethroid pesticide remained in rice |
Non-Patent Citations (6)
| Title |
|---|
| GPC-GC 法测定辣椒粉中乙草胺农药残留;吕庆 等;《农药研究与应用》;20110228;第15卷(第1期);摘要 * |
| GPC净化处理在测定拟除虫菊酯残留量中的应用;王明泰 等;《印染》;20071231(第6期);摘要和试验部分 * |
| 凝胶渗透色谱净化-气相色谱法测定茶叶中30种有机氯及菊酯类农药残留量;杨晓凤 等;《理化检验—化学分册》;20110630;第47卷(第6期);全文 * |
| 吕庆 等.GPC-GC 法测定辣椒粉中乙草胺农药残留.《农药研究与应用》.2011,第15卷(第1期),24-26. |
| 杨晓凤 等.凝胶渗透色谱净化-气相色谱法测定茶叶中30种有机氯及菊酯类农药残留量.《理化检验—化学分册》.2011,第47卷(第6期),698-700. |
| 王明泰 等.GPC净化处理在测定拟除虫菊酯残留量中的应用.《印染》.2007,(第6期),37-40. |
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