CN103575798A - Method for measuring residues of ethephon, thidiazuron and diuron in cotton by using liquid chromatography tandem mass spectrometry - Google Patents
Method for measuring residues of ethephon, thidiazuron and diuron in cotton by using liquid chromatography tandem mass spectrometry Download PDFInfo
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- CN103575798A CN103575798A CN201310414972.0A CN201310414972A CN103575798A CN 103575798 A CN103575798 A CN 103575798A CN 201310414972 A CN201310414972 A CN 201310414972A CN 103575798 A CN103575798 A CN 103575798A
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Abstract
The invention relates to a method for measuring residues of ethephon, thidiazuron and diuron in cotton by using liquid chromatography tandem mass spectrometry. The method comprises the following steps: (1) processing a sample; (2) measuring; (3) judging, i.e., drawing a five-point standard working curve by taking mass concentration X as an abscissa and peak area Y as an ordinate, and quantifying the sample by using the standard working curve, wherein the response value of a medicament in the sample solution is required to be within the linear range detected by the instrument. The method is simple, convenient, quick and accurate, each item of technical index meets the requirements of domestic and international rules, and the method can be used for quantitative detection of the ethephon, the thidiazuron and the diuron in the cotton sample.
Description
Technical field
The present invention relates to a kind of method of measuring cotton Pesticide Residues, relate in particular to a kind of method that Liquid Chromatography-Tandem Mass Spectrometry is measured ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton.
Background technology
Along with improving constantly of living standard, people's consumption idea is also constantly being improved.That in dress, not only will wear is warm, also beautiful, more wants safety and health simultaneously.The different phase of Cotton Production must be used different agricultural chemicals, with pre-preventing disease and pest and weed growth, if do not add control, will affect output and the quality of cotton fiber.Although most of agricultural chemicals is removed in processing process in textile, but still have part residues of pesticides in textile, in the process contacting with human body skin, these agricultural chemicals are absorbed by the body, can produce toxic and side effect to human body, severe one can be brought out cancer, and in textile industry, the residues of pesticides in cotton can polluted water and soil in addition.
Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron can impel cotton leaf to come off, and are conducive to mechanical harvesting, and on cotton-wool without dead leaf fragment, obviously improve cotton quality.
Current Thidiazuron in high effective liquid chromatography for measuring (HPLC) mensuration cotton bibliographical information for, as Sun Jin etc., defoliant Thidiazuron detection method research in cotton. standard science, 2010,9,22～25; Flat vertical phoenix etc., in Ultra Performance Liquid Chromatography method mensuration sugarcane and soil, diuron is residual. Journal of Analytical Science, 201127(2) 235～237; Guo Yongze etc., Thidiazuron and isomeride thereof be determination of residual amount method [J] in cottonseed and soil. agricultural chemicals, and 2005,44(3): 123～124, the mensuration lower bound of 3 kinds of above-mentioned methods is 0.01～0.5mg/kg.Guo Yongze etc., the assay method [J] of diuron and metabolic product residual quantity thereof in cottonseed. Tianjin agricultural sciences, 2010,16(3): 69～71. adopt gas chromatography-nitrogen phosphorous detector (GC-NPD) to measure the residual quantity of diuron in cottonseed.Detecting of method is limited to 0.05mg/kg, and the recovery is 80.56%～94.14%.Have no the bibliographical information of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid residual quantity in cotton and textile.
In food, ethephon (CEPHA)，2-(chloroethyl) phosphonic acid residues detection generally adopts ethephon (CEPHA)，2-(chloroethyl) phosphonic acid to be heated in alkaline aqueous solution can fast decoupled to become the characteristic of ethene, in sample, add appropriate high alkali liquid, and at 70 ℃ heated at constant temperature, Headspace Gas Chromatography, as Kong Xianghong, Deng, the residual quantity of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in headspace gas chromatography Fast Measurement meat and meat products, assay office, 2010,29(4) 18～21, the method is measured lower bound 0.01mg/kg.Along with reaching its maturity of Liquid Chromatography-Tandem Mass Spectrometry technical development, the method is more and more applied to measure and confirmation textile and Pesticide Residues, above-mentioned method adopts Liquid Chromatography-Tandem Mass Spectrometry method to measure ethephon (CEPHA)，2-(chloroethyl) phosphonic acid in fruit, but do not measure Thidiazuron and diuron simultaneously, in mobile phase, adopted 20mM acetate buffer solution simultaneously, solution easily produces flocculent deposit and stops up mobile phase filter, and method poor reproducibility.Have not yet to see the report that once simultaneously detects the liquid chromatography-mass spectrography/mass spectroscopy of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron in cotton and plant sample.
Summary of the invention
In order to solve above-mentioned technical matters, the object of this invention is to provide a kind of Liquid Chromatography-Tandem Mass Spectrometry and measure the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, the method is easy, stable, measuring lower bound is that ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron are 40 μ g/kg, Thidiazuron is 4 μ g/kg, the recovery and precision all meet retention analysis requirement, and meet the requirement of domestic and international regulations to cotton Pesticide Residues completely, and the supervision that can be imported cotton flower residues of pesticides provides technical support.
In order to realize above-mentioned object, the present invention has adopted following technical scheme:
Liquid Chromatography-Tandem Mass Spectrometry is measured the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, and the method comprises the following steps:
1) sample preparation
Take even sample 1g, be accurate to 0.01g, be placed in 50mL tool plug centrifuge tube, add the methanol-water of 20mL pH=8, the volume ratio of methanol-water is 6:4,, 20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross the organic filter membrane of 0.22mm, for Liquid Chromatography-Tandem Mass Spectrometry, measure;
2) measure
Standard operation liquid and sample solution be sample introduction under the Liquid Chromatography-Tandem Mass Spectrometry condition of table 1 and table 2 setting:
The mass spectrum parameter of table 1 ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
Wherein * represents quota ion;
2. the instrument condition parameter of Liquid Chromatography-Tandem Mass Spectrometry
Liquid chromatography:
| Chromatographic column | Agilent?ZORBAX?Eclipse?XDB-C 8Chromatographic column, 150mm * 4.6mm, 5 μ m |
| Mobile phase | Methanol-water, the volume ratio of methanol-water is 6:4 |
| Flow velocity | 0.4mL/min |
| Sample size | 20μL |
| Column temperature | Room temperature |
Mass spectrum condition:
| Ion gun | Electric spray ion source |
| Scan mode | Negative ion scanning |
| Monitoring mode | Multiple-reaction monitoring |
| Electron spray voltage (IS) | -4500V |
| Atomization gas pressure (GS1) | High pure nitrogen, 42psi |
| Gas curtain atmospheric pressure (CUR) | High pure nitrogen, 27psi |
| Assisted gas flow velocity (GS2) | High pure nitrogen, 45psi |
| Ion source temperature (TEM) | High pure nitrogen, 525 ℃ |
| Collision gas (CAD) | High pure nitrogen, 5 |
The maximum allowable offset of relative abundance of ions during qualitative confirmation:
Relative abundance of ions > 50%, relative deviation ± 20% of permission
Relative abundance of ions > 20%～50%, relative deviation ± 25% of permission
Relative abundance of ions > 10%～20%, relative deviation ± 30% of permission
Relative abundance of ions≤10%, relative deviation ± 50% of permission;
3) judgement
Take mass concentration X as horizontal ordinate, and peak area Y is ordinate, draws 5 standard working curves, with standard working curve, sample is carried out quantitatively, in the range of linearity that the response of sample solution Chinese traditional medicine should detect at instrument; Under above-mentioned chromatographic condition, in judgement sample, whether there is corresponding measured object, need to meet following condition: the mass chromatography peak retention time occurring in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, the corresponding medicine of this chromatographic peak is consistent in the relative abundance of the relative abundance of the mass spectrometry ion mixed-matrix standard operation liquid suitable with concentration, relative abundance deviation is no more than above-mentioned regulation, can determine and contain this medicine.
The present invention, owing to having adopted above-mentioned technical scheme, extracts 3 plant growth regulators in cotton with methanol-water jolting, and Liquid Chromatography-Tandem Mass Spectrometry instrument is measured, negative ion scan mode, and each two pairs of ions of every kind of agricultural chemicals of multiple-reaction monitoring carry out qualitative and quantitative analysis.Ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron are at 0～10 μ g/L; Thidiazuron is related coefficient (r) all about 0.99 within the scope of 1～1 μ g/L.With each medicine LOQ, 2LOQ and 4LOQ concentration level recovery testu, recovery scope is 77.5%～109% respectively; Relative standard deviation 5.7%～11.4%; Method detects lower bound (LOQ) ethephon (CEPHA)，2-(chloroethyl) phosphonic acid and diuron is 40 μ g/kg, and Thidiazuron is 4 μ g/kg.This method is easy, quick, accurate, and all technical meets the requirement of domestic and international rules, can be used for the quantitative detection of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron in cotton sample.
Accompanying drawing explanation
Fig. 1 is the selectivity ion flow graph of blank cotton sample.
Fig. 2 is the selectivity ion flow graph of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution.
Fig. 3 is the selectivity ion flow graph that blank cotton sample adds ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution (40/4 μ g/kg).
Embodiment
1, sample preparation
Take even sample 1g (being accurate to 0.01g), be placed in 50mL tool plug centrifuge tube, add the methanol-water (6:4 of 20mL pH=8, V/V), 20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross the organic filter membrane of 0.22mm, for Liquid Chromatography-Tandem Mass Spectrometry, measure.
2, measure
Standard operation liquid and sample solution be sample introduction under the Liquid Chromatography-Tandem Mass Spectrometry condition of table 1 and table 2 setting, take mass concentration X(μ g/kg) be horizontal ordinate, peak area Y is ordinate, draw 5 standard working curves, with standard working curve, sample is carried out quantitatively, in the range of linearity that the response of sample solution Chinese traditional medicine should detect at instrument.Under above-mentioned chromatographic condition, in judgement sample, whether there is corresponding measured object, need to meet following condition: the mass chromatography peak retention time occurring in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, the relative abundance of the mixed-matrix standard operation liquid that the relative abundance of the mass spectrometry ion of the corresponding medicine of this chromatographic peak in table 2 is suitable with concentration is consistent, relative abundance deviation is no more than the regulation of table 2, can determine and contain this medicine.
Table 1 is the mass spectrum parameters such as parent ion, daughter ion and collision energy of various kinds of drug.Under the Liquid Chromatography-Tandem Mass Spectrometry condition of setting at table 2, the recovery scope of blank cotton sample interpolation recovery experiment and precision are in Table 3, and blank cotton sample, ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution, blank cotton sample add the selectivity ion flow graph of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron, diuron mixed standard solution and see Fig. 1～Fig. 3.
The mass spectrum parameter of table 1 ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
* represent quota ion
The instrument condition parameter of table 2 Liquid Chromatography-Tandem Mass Spectrometry
In table 3 cotton, ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals add the recovery and precision (n=6)
Claims (1)
1. Liquid Chromatography-Tandem Mass Spectrometry is measured the method for ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron residual quantity in cotton, it is characterized in that the method comprises the following steps:
1) sample preparation
Take even sample 1g, be accurate to 0.01g, be placed in 50mL tool plug centrifuge tube, add the methanol-water of 20mL pH=8, the volume ratio of methanol-water is 6:4,, 20min is extracted in jolting, with the centrifugal 5min of 6000r/min, get supernatant and cross the organic filter membrane of 0.22mm, for Liquid Chromatography-Tandem Mass Spectrometry, measure;
2) measure
Standard operation liquid and sample solution be sample introduction under the following Liquid Chromatography-Tandem Mass Spectrometry condition of setting:
1. the mass spectrum parameter of ethephon (CEPHA)，2-(chloroethyl) phosphonic acid, Thidiazuron and diuron agricultural chemicals
Wherein * represents quota ion;
2. the instrument condition parameter of Liquid Chromatography-Tandem Mass Spectrometry
Liquid chromatography:
Mass spectrum condition:
The maximum allowable offset of relative abundance of ions during qualitative confirmation:
Relative abundance of ions > 50%, relative deviation ± 20% of permission
Relative abundance of ions > 20%～50%, relative deviation ± 25% of permission
Relative abundance of ions > 10%～20%, relative deviation ± 30% of permission
Relative abundance of ions≤10%, relative deviation ± 50% of permission;
3) judgement
Take mass concentration X as horizontal ordinate, and peak area Y is ordinate, draws 5 standard working curves, with standard working curve, sample is carried out quantitatively, in the range of linearity that the response of sample solution Chinese traditional medicine should detect at instrument; Under above-mentioned chromatographic condition, in judgement sample, whether there is corresponding measured object, need to meet following condition: the mass chromatography peak retention time occurring in sample solution is consistent with hybrid standard working fluid, permissible variation is less than ± and 2.5%, the corresponding medicine of this chromatographic peak is consistent in the relative abundance of the relative abundance of the mass spectrometry ion mixed-matrix standard operation liquid suitable with concentration, relative abundance deviation is no more than above-mentioned regulation, can determine and contain this medicine.
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Cited By (6)
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| CN103969363A (en) * | 2014-04-09 | 2014-08-06 | 温州市质量技术监督检测院 | Detection method for plant growth regulator residues in fruits |
| CN105203652A (en) * | 2015-08-21 | 2015-12-30 | 河南省农业科学院农业质量标准与检测技术研究所 | Method for detecting regulating-agent thidiazuron residues and regulating-agent diuron residues |
| CN108760949A (en) * | 2018-04-20 | 2018-11-06 | 公安部物证鉴定中心 | The detection method of plant growth regulator ethephon (CEPHA),2-(chloroethyl) phosphonic acid in biological fluid |
| CN108828101A (en) * | 2018-08-08 | 2018-11-16 | 广西科技师范学院 | The remaining method of diuron in measurement sugarcane based on 3,4- dichloroaniline |
| CN110470759A (en) * | 2019-08-16 | 2019-11-19 | 谱尼测试集团吉林有限公司 | A kind of method of ethephon (CEPHA),2-(chloroethyl) phosphonic acid residual quantity in measurement fruits and vegetables |
| CN115452999A (en) * | 2022-09-28 | 2022-12-09 | 普研（上海）标准技术服务有限公司 | Method for measuring residual quantity of diuron in beef |
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| CN101943685A (en) * | 2009-12-02 | 2011-01-12 | 天津市农业科学院中心实验室 | Method for measuring residual quantity of thidiazuron and diuron as well as metabolites thereof in cotton |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969363A (en) * | 2014-04-09 | 2014-08-06 | 温州市质量技术监督检测院 | Detection method for plant growth regulator residues in fruits |
| CN105203652A (en) * | 2015-08-21 | 2015-12-30 | 河南省农业科学院农业质量标准与检测技术研究所 | Method for detecting regulating-agent thidiazuron residues and regulating-agent diuron residues |
| CN108760949A (en) * | 2018-04-20 | 2018-11-06 | 公安部物证鉴定中心 | The detection method of plant growth regulator ethephon (CEPHA),2-(chloroethyl) phosphonic acid in biological fluid |
| CN108828101A (en) * | 2018-08-08 | 2018-11-16 | 广西科技师范学院 | The remaining method of diuron in measurement sugarcane based on 3,4- dichloroaniline |
| CN108828101B (en) * | 2018-08-08 | 2021-05-07 | 广西科技师范学院 | Method for determining diuron residues in sugarcane based on 3, 4-dichloroaniline |
| CN110470759A (en) * | 2019-08-16 | 2019-11-19 | 谱尼测试集团吉林有限公司 | A kind of method of ethephon (CEPHA),2-(chloroethyl) phosphonic acid residual quantity in measurement fruits and vegetables |
| CN115452999A (en) * | 2022-09-28 | 2022-12-09 | 普研（上海）标准技术服务有限公司 | Method for measuring residual quantity of diuron in beef |
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