CN1563976A - Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide - Google Patents
Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide Download PDFInfo
- Publication number
- CN1563976A CN1563976A CN200410014411.2A CN200410014411A CN1563976A CN 1563976 A CN1563976 A CN 1563976A CN 200410014411 A CN200410014411 A CN 200410014411A CN 1563976 A CN1563976 A CN 1563976A
- Authority
- CN
- China
- Prior art keywords
- extraction
- extraction column
- column
- sample
- hexane
- 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.)
- Granted
Links
- 238000000605 extraction Methods 0.000 claims abstract 9
- 238000000034 method Methods 0.000 claims abstract 9
- 239000000523 sample Substances 0.000 claims abstract 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000006228 supernatant Substances 0.000 claims abstract 5
- 239000000945 filler Substances 0.000 claims abstract 4
- 239000012528 membrane Substances 0.000 claims abstract 4
- 239000003480 eluent Substances 0.000 claims abstract 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002689 soil Substances 0.000 claims abstract 3
- 238000004458 analytical method Methods 0.000 claims abstract 2
- 239000012141 concentrate Substances 0.000 claims abstract 2
- 239000012468 concentrated sample Substances 0.000 claims abstract 2
- 239000003993 organochlorine pesticide Substances 0.000 claims abstract 2
- 238000000746 purification Methods 0.000 claims abstract 2
- 230000001360 synchronised effect Effects 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000011521 glass Substances 0.000 claims 2
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical group [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims 2
- 238000002137 ultrasound extraction Methods 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000003987 organophosphate pesticide Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract 3
- 238000011084 recovery Methods 0.000 abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
本发明公开了一种用于有机氯、有机磷农药分析的同步净化提取方法。水样通过滤膜过滤后，通过固相萃取柱进行富集，再除去柱中的水分；土壤样品加入体积比为1～2∶1的正己烷－乙酸乙酯溶液15～25mL，超声提取0.5～1h，静置，移取上层萃取清液，加入无水Na2SO4干燥，将萃取液旋转蒸发至1.0～2.0ml，称取填料和无水Na2SO4至固相萃取柱，将萃取浓缩的样品溶液加入萃取柱；用正己烷和乙酸乙酯溶液淋洗水样或土壤样品的萃取柱，洗脱液浓缩至0.1～0.2mL。本方法的采用的试剂较少，安全性较高，步骤少却能分析比较多的有机氯和有机磷农药，其中有机氯农药的加标回收率大多能够达到80％以上，有机磷农药的加标回收率大多能达到70％以上。The invention discloses a synchronous purification and extraction method for the analysis of organochlorine and organophosphorus pesticides. After the water sample is filtered through the filter membrane, it is enriched by a solid-phase extraction column, and then the water in the column is removed; the soil sample is added with 15-25mL of n-hexane-ethyl acetate solution with a volume ratio of 1-2:1, and ultrasonically extracted with 0.5 ~1h, let it stand still, pipette the supernatant extract, add anhydrous Na 2 SO 4 to dry, rotate the extract to 1.0 ~ 2.0ml, weigh the filler and anhydrous Na 2 SO 4 to the solid phase extraction column, put Extract the concentrated sample solution and add it to the extraction column; rinse the extraction column of the water sample or soil sample with n-hexane and ethyl acetate solution, and concentrate the eluent to 0.1-0.2mL. The method adopts less reagents, higher safety, fewer steps but can analyze more organochlorine and organophosphorus pesticides, wherein the recovery rate of organochlorine pesticides can reach more than 80% mostly, and the addition of organophosphorus pesticides can reach more than 80%. Most of the standard recoveries can reach more than 70%.
Description
One, technical field
The present invention relates to the pre-treating method of the analysis of agricultural drugs, in particular, is a kind of synchronous purification and extraction method that is used for organochlorine, organophosphorus pesticide analysis.
Two, background technology
Along with fast development of national economy, a large amount of uses of agriculture chemical, environmental pollution aggravates day by day, the poisoning of organochlorine, organophosphorus pesticide emerges in an endless stream, because a large amount of uses of this two classes agricultural chemicals in these years, can detect their existence in soil and the water body,, should improve from the source and detect requirement for the safety that guarantees that agricultural product are produced.
For a long time, people are often analyzing, are extracting respectively, purify with diverse ways, different chemical reagent when detecting these two kinds of agricultural chemicals, this disposal route of extracting respectively, purifying respectively of organochlorine, organophosphorus pesticide is in use to now always, and by the national standard method defined, not only time-consuming, and take reagent, expense sample.
Last 217 pages of articles " simultaneous extraction of organophosphorus, organo-chlorine pesticide, the discussion of purification " that disclose the simultaneous extraction method aspect of one piece of relevant organophosphorus, organo-chlorine pesticide of " Chinese health quarantine magazine " 1997 the 7th the 4th phase of volume, wherein Xu Shu method is with the sample acetone extract, pass through chromatographic column then, with methylene chloride-sherwood oil eluent wash-out, use acetone-second eyeball eluent wash-out more earlier.This method is many with respect to former method progress, can accomplish simultaneous extraction, but this method agents useful for same is more, and has certain toxicity mostly, can damage the experimenter.
Three, summary of the invention
1. goal of the invention: the purpose of this invention is to provide a kind of synchronous purification and extraction method that organochlorine, organophosphorus pesticide are analyzed that is used for, the organochlorine that is used to use always, organophosphorus pesticide simultaneous extraction purify.
2. technical scheme:
The principle of this programme: Gu the sample extraction before the gas chromatographic analysis and the principle that purifies institute's foundation mainly are liquid-or absorption, the desorptions of liquid-liquid.The restriction that adsorption effect is subjected to the acting in conjunction between adsorbent, sample and the eluent and adsorbs environment.Use liquid-liquid apportion design, adopt polar solvent and non-polar solvent to be made into solvent, interfering material is separated with agricultural chemicals to be measured carrying out repeated dispensing.Adopt the adsorpting column chromatography method, utilize each component in the potpourri adsorb on adsorbent-difference of desorption ability and reach the purification method of separation purpose, adsorbent commonly used has florisil silica, aluminium oxide and silica gel.Solid phase extraction techniques (SPE) is a kind of sample preparation methods based on the liquid chromatography separation mechanism.
Technical scheme of the present invention is as follows:
A kind of synchronous purification and extraction method that is used for organochlorine, organophosphorus pesticide analysis, it mainly may further comprise the steps:
(a) water sample carries out enrichment with the speed of 0.5～2L/h by solid-phase extraction column by behind the membrane filtration, before using, extraction column, dries up removing the moisture in the post through centrifugal and nitrogen more respectively with methyl alcohol and distilled water activation,
(b) take by weighing 10～15g pedotheque in glass tube, the adding volume ratio is normal hexane-ethyl acetate solution 15～25mL of 1～2: 1, puts into ultrasonic generator ultrasonic Extraction 0.5～1h after the sealing, leaves standstill, and pipettes upper strata extraction clear liquid, adds anhydrous Na
2SO
4Drying, with extract rotary evaporation to 1.0～2.0ml, by mass ratio 2～3: 1 takes by weighing filler and anhydrous Na respectively
2SO
4To solid-phase extraction column, the sample solution that extraction is concentrated adds extraction column,
(c) with 8～15mL normal hexane and ethyl acetate mass ratio be 1～9: 1 solution drip washing step (a) or (b) in extraction column, eluent is concentrated into 0.1～0.2mL.
Filter membrane is the 0.45um filter membrane.Adopt the C18 enriching column as solid-phase extraction column.General water sampling volume is 0.5～1L.Pipette that can to add volume ratio after the upper strata extraction clear liquid again in glass tube be normal hexane-ethyl acetate solution 15～25mL of 1～2: 1, put into ultrasonic generator ultrasonic Extraction 0.5～1h after the sealing, leave standstill, pipette upper strata extraction clear liquid and integrate with in the preceding extraction clear liquid.
Filler is florisil silica or silica gel, aluminium oxide.Can adopt florisil silica as filler.Eluent concentrates and can be concentrated into about 1mL with Rotary Evaporators earlier, uses N again
2Slowly purge solvent, use the normal hexane constant volume at last.Solution behind the constant volume can be used for stratographic analysis.
3. beneficial effect: the characteristics of this method are that the reagent that adopts is less, security is higher, step but can be analyzed many organochlorines and organophosphorus pesticide less, wherein the recovery of standard addition of organo-chlorine pesticide can reach more than 80% mostly, and the big multipotency of the recovery of standard addition of organophosphorus pesticide reaches more than 70%.
Four, embodiment
Below further specify the present invention by example.
Embodiment 1:
1) filters enrichment: gather water sample 1L, behind the 0.45um membrane filtration, carry out on-the-spot enrichment by the C18 solid-phase extraction column, band meeting laboratory, freezing preservation with the speed of 1L/h.Before using, extraction column activates with 10ml methyl alcohol and 10ml distilled water.
2) drying and wash-out: hydro-extractor 3600r/min, the 3-4min rotary evaporation to slough most of moisture, then dries up with nitrogen.(10ml) as eluant, eluent, the effluent of washing pillar is received in the receiving bottle with normal hexane and ethyl acetate (4: 1).
3) concentrated and constant volume: eluent is concentrated into about 1mL with Rotary Evaporators earlier, slowly purges solvent to not enough 1ml with high pure nitrogen again, and is to be measured to 1ml with the normal hexane constant volume.
The GC/NPD operation
Condition:
60 ℃ of programmed temperature method-initial temperature are warming up to 100 ℃ with the speed of 20 ℃/min, keep 0min;
Speed with 10 ℃/min is warming up to 250 ℃, keeps 0min;
Injector temperature: 150 ℃; Temperature of vaporization chamber: 220 ℃; Detector temperature: 320 ℃;
Nitrogen flow: 4ml/min; Hydrogen flowing quantity: 4ml/min; Air mass flow: 100ml/min;
Total flow: 6.5psi
Recovery experiment
Add the standard model solution of 0.2ppm in distilled water, repeat the operating process of above sample, the organophosphorus pesticide of Huo Deing (Rogor, parathion, the malathion) recovery reaches more than 80% at last.
Embodiment 2:
Get in 8 50ml color comparison tubes, add 15 gram soil samples respectively, be numbered 1,2,3,4,5,6,7,8.Add earlier 5ml water in every part respectively, in 1, No. 2, add 20ml normal hexane-methyl alcohol (1: 1) again; 3, No. 4 20ml normal hexane-ethyl acetate (1: 1); 5, No. 6 20ml methyl alcohol-acetone (1: 1); 7, No. 8 20ml normal hexane-acetone (1: 1).Put into the ultrasonic generator ultrasonic Extraction after the sealing one hour, and left standstill, pipette upper strata extraction clear liquid, the corresponding respectively again 20ml normal hexane-methyl alcohol (1: 1) that adds; Normal hexane-ethyl acetate (1: 1); Methyl alcohol-acetone (1: 1); Normal hexane-acetone (1: 1).And ultrasonic Extraction one hour, leave standstill, pipette upper strata extraction clear liquid, be incorporated in the pyriform bottle with extract last time, add the capacity anhydrous Na
2SO
4Dry.All add the NaCl breakdown of emulsion during each ultrasonic Extraction.With extract rotary evaporation in the pyriform bottle to 2.0ml because three kinds of organophosphorus pesticide boiling points to be measured are all higher, can be suitably with the temperature raising of rotary evaporation, with pick up speed.
Florisil silica (60-100 order, 650 ℃ of calcination 5h in 130 ℃ of activation 4-6h, add 5% distilled water and take off work before using after the cooling).
(1) preparation of post accurately takes by weighing 2.4g florisil silica and 0.8g anhydrous Na
2SO
4(or 1.8g silica gel and 0.6g anhydrous Na
2SO
4) to the 6mL solid-phase extraction column, extraction column is with 10mL normal hexane drip washing twice, to remove foreign body in the post.The normal hexane post that need pressurize is to remove the bubble in the post.
(2) wash-out and the dry sample solution that concentrates that will extract are added on the extraction column top, in the time of to sample infiltration post, with the polluter that is adsorbed in 10mL n-hexane/ethyl acetate (1: 1) the solution drip washing post, and eluent are collected in the 25mL pyriform bottle.
(3) concentrate eluant is concentrated into about 1mL with Rotary Evaporators earlier, uses N again
2Slowly purge solvent, concentrate and be settled to 0.2mL with normal hexane.
With same sample extraction liquid difference Florisil silica column and silicagel column, after gas chromatographic analysis finds that the sample impurities of Florisil silica column is less and the recovery is higher.16 parts of extracts warps with gained concentrate, purify (Florisil silica column), concentrate at last, get 16 parts and treat test sample.Wherein use slightly color of sample that methyl alcohol-acetone (1: 1) makes extractant, should not carry out gas chromatographic analysis.All the other samples are through gas chromatographic analysis, relatively following result:
(1) more with sample impurities after purifying of normal hexane-methyl alcohol (1: 1) and normal hexane-acetone (1: 1) extraction, disturb the mensuration of three kinds of organophosphorus pesticides in gas chromatography, should not adopt.
(2) impure less with the sample of normal hexane-ethyl acetate (1: 1) extraction, the peak degree of separation of three kinds of organophosphorus pesticides is better and interference-free.
Embodiment 3:
Filter enrichment, dry and wash-out and the concentrated and logical embodiment 1 of three steps of constant volume, adopt GC/ECD time-and-motion study organochlorine.
The GC/ECD operating conditions:
60 ℃ of initial temperature, programmed temperature method is warming up to 170 ℃ with the speed of 25 ℃/min; 4 ℃/min is increased to 190 ℃; 10 ℃/min is increased to 220 ℃; 2 ℃/min is increased to 240 ℃; 20 ℃/min is increased to 300 ℃; Keep 5min.
Split sampling not, 250 ℃ of injection ports, sample size 1ul
Carrier gas: high-purity helium (purity 99.99%), constant voltage 28.30psi, carrier gas flux 1.6mL/min, mean flow rate 28cm/sec.
Capillary column: Model No:J﹠amp; 325 ℃ of Max DB-1 of W 122-1032 Capillary 60.0m * 250 μ m * 0.25 μ m nominal.
Detecting device: ECD, 320 ℃.N
2?60ml/min
Recovery experiment
Add the standard model solution of 10ppb in distilled water, repeat the operating process of above sample, the organo-chlorine pesticide of Huo Deing (benzene hexachloride, the D.D.T. (dichloro-diphenyl-trichloroethane) etc.) recovery reaches more than 80% at last.
Embodiment 4:
Basic operation changes in the preparation of (1) post and takes by weighing 1.8g florisil silica and 0.8g anhydrous Na with embodiment 2
2SO
4, change the polluter that is adsorbed with in 15mL n-hexane/ethyl acetate (9: 1) the solution drip washing post in (2) wash-out and the drying into.
Analyze according to the GC/ECD operating conditions among the embodiment 3, the big multipotency of the recovery of standard addition of organo-chlorine pesticide reaches more than 80%.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100144112A CN1303421C (en) | 2004-03-24 | 2004-03-24 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100144112A CN1303421C (en) | 2004-03-24 | 2004-03-24 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1563976A true CN1563976A (en) | 2005-01-12 |
| CN1303421C CN1303421C (en) | 2007-03-07 |
Family
ID=34478345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100144112A Expired - Fee Related CN1303421C (en) | 2004-03-24 | 2004-03-24 | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1303421C (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332199C (en) * | 2005-04-22 | 2007-08-15 | 郑州市疾病预防控制中心 | GC/MS inner scaling detection method for simultaneous investigating residual multiple organophosphorus in food |
| CN101221102B (en) * | 2008-01-16 | 2010-08-04 | 南京大学 | A kind of simultaneous purification and extraction method of phenolic compounds |
| CN101813677A (en) * | 2010-04-29 | 2010-08-25 | 同济大学 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
| CN101126751B (en) * | 2007-09-11 | 2011-05-04 | 南京大学 | Gas phase chromatogram- ion trap tandem mass spectrometry method for detecting organochlorine pesticide |
| CN102121926A (en) * | 2010-12-20 | 2011-07-13 | 天津市农业科学院中心实验室 | Treatment method used before measurement of 2-cyanoacrylate residue-containing sample |
| CN102636603A (en) * | 2011-02-12 | 2012-08-15 | 湖北省烟草科研所 | Method for detecting organochlorine pesticide residue in soil |
| CN103105439A (en) * | 2011-11-15 | 2013-05-15 | 天津天狮生物发展有限公司 | Method for simultaneously determining residual organochlorine, pyrethroid and organophosphorus pesticides in food |
| CN103175918A (en) * | 2013-02-26 | 2013-06-26 | 福建中烟工业有限责任公司 | Method for extracting and detecting organic chloride pesticide residues in tobaccos and tobacco products by using ultrasonic solvent |
| CN103308630A (en) * | 2013-05-10 | 2013-09-18 | 浙江省林产品质量检测站 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
| CN103331037A (en) * | 2013-07-03 | 2013-10-02 | 大连海事大学 | A separation column packing and separation method for separating PCBs or OCPs in samples with high fat content |
| CN105891354A (en) * | 2016-03-31 | 2016-08-24 | 山东五洲检测有限公司 | Detection method for content of fenthion in sorghum planting soil |
| CN107576741A (en) * | 2017-09-14 | 2018-01-12 | 浙江省海洋水产研究所 | A kind of method that organophosphorus pesticide multicomponent remains in SPE gas-chromatography tandem mass spectrometry detection aquatic products |
| CN108459112A (en) * | 2018-05-18 | 2018-08-28 | 中国水产科学研究院淡水渔业研究中心 | The detection method of Organochlorine Pesticides in Eriocheir sinensis crab cream |
| CN109668991A (en) * | 2019-03-05 | 2019-04-23 | 河北大学 | A kind of method of Organochlorine Pesticide Residues in ultrasonic wave auxiliary measuring vegetables |
| WO2020000215A1 (en) * | 2018-06-26 | 2020-01-02 | 江苏宏大环保科技有限公司 | Purifying column |
| CN110763771A (en) * | 2018-07-25 | 2020-02-07 | 中国科学院大连化学物理研究所 | Pretreatment method for measuring organochlorine pesticide and polychlorinated biphenyl in aquatic product culture water body |
| CN112946141A (en) * | 2021-03-15 | 2021-06-11 | 上海国齐检测技术有限公司 | Method for detecting phosmet in soil |
| CN115184499A (en) * | 2022-07-18 | 2022-10-14 | 广东省科学院生态环境与土壤研究所 | Synergistic detection method and application of organochlorine pesticide, halogenated flame retardant and organic phosphate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273655A (en) * | 1989-10-10 | 1993-12-28 | The Regents Of The University Of California | Organic contaminant separator |
| US5576217A (en) * | 1995-02-28 | 1996-11-19 | Mallinckrodt Baker, Inc. | Solid phase microextraction of trace amounts of organic analytes |
| CN1168982C (en) * | 1999-03-12 | 2004-09-29 | 汪土新 | Reagent for speedily detecting residual agricultural organophosphorus chemicals |
| CN1430060A (en) * | 2001-12-30 | 2003-07-16 | 张志明 | Pesticide residue chemical agent detecting tube and its preparation method |
| EP3862109A2 (en) * | 2018-09-26 | 2021-08-11 | Nanogap Sub NM Powder, S.A. | Therapeutic uses of atomic quantum clusters |
-
2004
- 2004-03-24 CN CNB2004100144112A patent/CN1303421C/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332199C (en) * | 2005-04-22 | 2007-08-15 | 郑州市疾病预防控制中心 | GC/MS inner scaling detection method for simultaneous investigating residual multiple organophosphorus in food |
| CN101126751B (en) * | 2007-09-11 | 2011-05-04 | 南京大学 | Gas phase chromatogram- ion trap tandem mass spectrometry method for detecting organochlorine pesticide |
| CN101221102B (en) * | 2008-01-16 | 2010-08-04 | 南京大学 | A kind of simultaneous purification and extraction method of phenolic compounds |
| CN101813677B (en) * | 2010-04-29 | 2013-06-05 | 同济大学 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
| CN101813677A (en) * | 2010-04-29 | 2010-08-25 | 同济大学 | Method for analyzing and determining organics persistently containing chlorine in aquatic product |
| CN102121926A (en) * | 2010-12-20 | 2011-07-13 | 天津市农业科学院中心实验室 | Treatment method used before measurement of 2-cyanoacrylate residue-containing sample |
| CN102121926B (en) * | 2010-12-20 | 2012-09-26 | 天津市农业科学院中心实验室 | Treatment method used before measurement of 2-cyanoacrylate residue-containing sample |
| CN102636603B (en) * | 2011-02-12 | 2014-05-07 | 湖北省烟草科研所 | Method for detecting organochlorine pesticide residue in soil |
| CN102636603A (en) * | 2011-02-12 | 2012-08-15 | 湖北省烟草科研所 | Method for detecting organochlorine pesticide residue in soil |
| CN103105439A (en) * | 2011-11-15 | 2013-05-15 | 天津天狮生物发展有限公司 | Method for simultaneously determining residual organochlorine, pyrethroid and organophosphorus pesticides in food |
| CN103175918A (en) * | 2013-02-26 | 2013-06-26 | 福建中烟工业有限责任公司 | Method for extracting and detecting organic chloride pesticide residues in tobaccos and tobacco products by using ultrasonic solvent |
| CN103308630A (en) * | 2013-05-10 | 2013-09-18 | 浙江省林产品质量检测站 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
| CN103308630B (en) * | 2013-05-10 | 2014-07-23 | 浙江省林产品质量检测站 | Extraction and purification method for determining organophosphorus pesticide residues in fruits and vegetables |
| CN103331037A (en) * | 2013-07-03 | 2013-10-02 | 大连海事大学 | A separation column packing and separation method for separating PCBs or OCPs in samples with high fat content |
| CN105891354B (en) * | 2016-03-31 | 2018-03-09 | 山东五洲检测有限公司 | The detection method of content of fenthion in a kind of sorghum planting soil |
| CN105891354A (en) * | 2016-03-31 | 2016-08-24 | 山东五洲检测有限公司 | Detection method for content of fenthion in sorghum planting soil |
| CN107576741A (en) * | 2017-09-14 | 2018-01-12 | 浙江省海洋水产研究所 | A kind of method that organophosphorus pesticide multicomponent remains in SPE gas-chromatography tandem mass spectrometry detection aquatic products |
| CN108459112A (en) * | 2018-05-18 | 2018-08-28 | 中国水产科学研究院淡水渔业研究中心 | The detection method of Organochlorine Pesticides in Eriocheir sinensis crab cream |
| CN108459112B (en) * | 2018-05-18 | 2020-12-29 | 中国水产科学研究院淡水渔业研究中心 | Method for detecting content of organochlorine pesticide in crab cream of Eriocheir sinensis |
| WO2020000215A1 (en) * | 2018-06-26 | 2020-01-02 | 江苏宏大环保科技有限公司 | Purifying column |
| CN110763771A (en) * | 2018-07-25 | 2020-02-07 | 中国科学院大连化学物理研究所 | Pretreatment method for measuring organochlorine pesticide and polychlorinated biphenyl in aquatic product culture water body |
| CN109668991A (en) * | 2019-03-05 | 2019-04-23 | 河北大学 | A kind of method of Organochlorine Pesticide Residues in ultrasonic wave auxiliary measuring vegetables |
| CN112946141A (en) * | 2021-03-15 | 2021-06-11 | 上海国齐检测技术有限公司 | Method for detecting phosmet in soil |
| CN115184499A (en) * | 2022-07-18 | 2022-10-14 | 广东省科学院生态环境与土壤研究所 | Synergistic detection method and application of organochlorine pesticide, halogenated flame retardant and organic phosphate |
| CN115184499B (en) * | 2022-07-18 | 2024-03-05 | 广东省科学院生态环境与土壤研究所 | Synergistic detection method of organic chlorine pesticide, halogenated flame retardant and organic phosphate and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1303421C (en) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1303421C (en) | Synchronous purifying and extracting process for analysis of organic chlorine and organic phosphorus pesticide | |
| Ahling et al. | Reversed liquid-liquid partition in determination of polychlorinated biphenyl (PCB) and chlorinated pesticides in water | |
| JP3656527B2 (en) | Analytical pretreatment method for chromatographic column and dioxin extract | |
| CN101871920B (en) | Multistage improvement column for quickly pre-processing and purifying polychlorinated biphenyl in biological sample | |
| CN103776924B (en) | A method for detecting polycyclic aromatic hydrocarbons in fried food | |
| CN104324521B (en) | The sample-pretreating method of Chinese herbal medicine solid-phase extraction column and detection pesticide made of Chinese medicinal herbs residue | |
| CN101881758A (en) | A method for measuring phthalates in atmospheric particles | |
| CN102520101A (en) | Pre-treatment and analysis methods of organochlorine pesticides in soil | |
| CN101995353A (en) | Ultrafiltration membrane-solid phase extraction combined device for sample pretreatment and application thereof | |
| CN101865898B (en) | Method for determining phthalate ester in soil | |
| JP2007225283A (en) | Analytical method for dioxins | |
| CN102507808A (en) | Method for enriching and separating trace amount of polychlorinated biphenyls (PCBs) | |
| David et al. | Analytical methods review | |
| CN113237978A (en) | Detection method of adamantanamine and rimantadine in tomatoes | |
| CN107607656B (en) | Method for detecting cyantraniliprole and metabolite J9Z38 in fish | |
| CN104678033A (en) | Filling method of double-layer solid-phase extraction small column and solid-phase extraction small column | |
| CN113419013A (en) | Method for analyzing perfluoroalkyl acid pollutants in environmental water sample and application | |
| CN110672763B (en) | Application of porous imine chain covalent organic framework material in estrogen detection | |
| CN1161607C (en) | A method for separating and analyzing niobium, tantalum, zirconium and hafnium | |
| CN103772472B (en) | A kind of method utilizing high-speed countercurrent chromatography separation and purification peimisine from the bulb of fritillary | |
| JP3692886B2 (en) | Gas chromatography-mass spectrometry method for PCDD, PCDF and co-PCB | |
| CN1298712C (en) | Method for elementary separating 10-noracetyl Baccatins III from branches and leaves of yew | |
| CN1394673A (en) | Application of beta-cyclodextrin bonded silicone gel as solid phase extraction adsorption medium | |
| CN1172186C (en) | Separation and preparation method of set ginsenoside standard reference substance | |
| CN102452892A (en) | Method for purifying pesticide residue grade dichloromethane for extraction |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |