CN101718764B - Detection method of residual polychlorinated biphenyl in cosmetics with gas chromatography-mass spectrum method - Google Patents
Detection method of residual polychlorinated biphenyl in cosmetics with gas chromatography-mass spectrum method Download PDFInfo
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- CN101718764B CN101718764B CN2009101541899A CN200910154189A CN101718764B CN 101718764 B CN101718764 B CN 101718764B CN 2009101541899 A CN2009101541899 A CN 2009101541899A CN 200910154189 A CN200910154189 A CN 200910154189A CN 101718764 B CN101718764 B CN 101718764B
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Abstract
The invention relates to a detection method of residual polychlorinated biphenyl, in particular to a detection method of residual polychlorinated biphenyl in cosmetics with gas chromatography-mass spectrum method; in the method, a sample is extracted in an accelerating way by solvent, normal hexane is used as extractant, and then gel extraction and Florisil cartridge purification are carried out, and then the gas chromatography-mass spectrum method, selected ion canning detection and an external standard method are used for quantifying. The detection method has the following characteristics that: 1. in the method, the gel extraction and Florisil cartridge purification are firstly combined to measure residual polychlorinated biphenyl in cosmetics. 2. the solvent is adopted to carry out extraction in an accelerating way, and the gel extraction and Florisil cartridge purification are adopted, the gas chromatography-mass spectrum method is used for quantifying and determining the nature, and seven kinds of polychlorinated biphenyl in the matrix of the cosmetics are measured, and the method has the advantages of low detection limit and high sensitivity; the measuring low limit of PCL-180 which has the lowest response is 0.01mug.ml-1, and the linear range is set from 0,01mug.ml-1-0.10mug.ml-1.
Description
Technical field
The present invention relates to the detection method of residual polychlorinated biphenyl, relate in particular to a kind of detection method of using gas chromatography-mass spectrum to measure residual polychlorinated biphenyl in the cosmetics.
Background technology
Chlordiphenyl (english abbreviation PCBs) is a kind of organic compound of synthetic; Because good insulation performance property, heat impedance and chemical stability; This century, the '30s began; American and Britain, day etc., developed country produced in a large number, extensively was used as the insulating radiation medium of accumulator, transformer, power capacitor, and the adjuvant of product such as insulating oil, paint, ink.Polychlorinated biphenyl is a kind of low aqueous solubility, the organism of fat-solubility, and the polychlorinated biphenyl zoopery shows that PCBs has inductive effect, the interfere internal system to pathologies such as skin, liver, gastronintestinal system even canceration.Polychlorinated biphenyl is difficult to degraded, can be accumulated in for a long time in environment and the human body, and metabolism is very slow, and harmfulness is very big.In environment, animals and plants are taken in can form the biologic chain transmission; In human body, often the several years can not rehabilitation for the patient, and accumulation the toxic symptom will occur when reaching 0.5～2 gram, serious taken place acute hepatic necrosis, in addition dead.
The mensuration vapor-phase chromatography of polychlorinated biphenyl in the State Standard of the People's Republic of China GB/T 8381.8-2005 feed; This method discloses sample and has extracted with normal hexane; Extract is through concentrated acid sulfonation, and silicagel column purifies, to be furnished with the gas chromatograph for determination of electron capture detector.
Chinese invention patent (application number: the 01127140.X applying date: 2001-08-23) disclose the assay method of trace organic chlorine pesticide and residual polychlorinated biphenyl amount in the birds, beasts and eggs; This method selects suitable interior mark to be configured to interior mark annex solution as object of reference, interior mark annex solution is added in the determinand standard mixed liquor to be mixed with corresponding calibration curve working fluid then; Again the testing sample sampling is obtained chromatogram liquid to be measured behind extraction, purification, constant volume, carry out chromatographic determination with gas chromatograph at last.
Countries in the world also do not have strict residual limiting the quantity of to polychlorinated biphenyl in the cosmetics at present, and polychlorinated biphenyl is mainly brought in the cosmetics through production run, and general content is lower, the existing effective ways that also do not have to be directed against specially polychlorinated biphenyl detection in the cosmetics.
Summary of the invention
Polychlorinated biphenyl detects the technical barrier that exists in the existing cosmetics in order to solve, and the purpose of this invention is to provide the detection method that a kind of gas chromatography-mass spectrum is measured residual polychlorinated biphenyl in the cosmetics, and this method has low, the highly sensitive advantage of detectability.
In order to realize above-mentioned purpose, gas chromatography-mass spectrum of the present invention is measured the detection method of residual polychlorinated biphenyl in the cosmetics, and this method comprises the steps:
1. take by weighing 1.0～5.0g cosmetics solid matter; Grind into fine powder; The cosmetics that grind mix 5～10g zeyssatite, press pad, zeyssatite, mixed sample, zeyssatite, diatomaceous order dress appearance and go up accelerated solvent extraction ASE, extract solvent employing normal hexane;
2. the solution of having crossed accelerated solvent extraction goes to and concentrates bottle; Be concentrated near doing below 40 ℃,, cross film with 9mL cyclohexane/ethyl acetate mixed solution constant volume; Cross the GPC of gel purification system, above-mentioned cyclohexane/ethyl acetate mixed solution preferably adopts cyclohexane: the volume ratio of ethyl acetate is 1: 1;
3. will cross the sample concentration of the GPC of gel purification system and do 1mL normal hexane constant volume near;
4. take by weighing the florisil silica that 1～10g handles well and add 20～30mL normal hexane wet method dress post, successively use 30mL normal hexane, 30mL n-hexane/ethyl acetate mixed solution, 30mL normal hexane drip washing pillar, last kind; Discard front 10mL normal hexane leacheate, receive 30mL n-hexane/ethyl acetate mixed solution leacheate, be concentrated near doing, 0.5mL normal hexane constant volume, above-mentioned n-hexane/ethyl acetate mixed solution preferably adopts normal hexane: the volume ratio of ethyl acetate is 9: 1;
5. the solution behind the constant volume gets into into gas chromatograph-mass spectrometer (GCMS), selects ion scan to detect, and external standard method is quantitative.
As preferably, the above-mentioned step 2. flow of cyclohexane/ethyl acetate mixed solution is 5mLmin
-1, Forerun 1080s, Main run 1920s, sample introduction 5mL receives 4.5mL, and front and back concentration is constant.
As preferably, above-mentioned gas chromatography-mass spectrum condition is following:
Adopt the Agilent7890A-5975C gas chromatograph-mass spectrometer (GCMS), join electron bombardment ionization source;
Chromatographic column: HP-5 (30m * 0.25mm i.d., 0.25 μ m) capillary column;
Column temperature:
Inlet temperature: 250 ℃; carrier gas: helium, purity greater than or equal to 99.999%; flow rate, 1.0mL/min; Injection: Splitless; injection volume: 2μL;
Electron bombardment ionization source (EI): 70ev; Chromatography-mass spectroscopy interface temperature: 280 ℃; Ion source temperature: 230 ℃; The solvent delay time: 8min.
Detection mode: select ion monitoring mode (SIM).
As preferably, the retention time of every kind of compound of polychlorinated biphenyl, quota ion, qualitative ion are following:
Consolidate shape cosmetics (like emulsion) if the present invention relates to half, then consolidate the advanced freeze drying of shape cosmetics and handle, prepare the cosmetics solid matter, and then detect through above-mentioned method for half.
Sample of the present invention quickens extraction through solvent, as extraction agent, passes through gel purification, florisil silica column purification with normal hexane again, uses gas chromatography-mass spectrum, selects ion scan to detect, and external standard method is quantitative.Have following characteristics: 1, proposed to measure the method for the polychlorinated biphenyl in the cosmetics first, in conjunction with gel purification and florisil silica column purification.2, the present invention adopts solvent to quicken extraction, gel purification, florisil silica column purification, and gas chromatography-mass spectrum method qualitative and quantitative is measured 7 kinds of polychlorinated biphenyl in the cosmetic base simultaneously, has low, the highly sensitive advantage of detectability.Responding minimum PCB-180 mensuration lower bound is 0.01 μ gmL
-1The range of linearity is decided to be 0.01 μ gmL
-1～0.10 μ gmL
-1
Description of drawings
Fig. 1 be 7 kinds of polychlorinated biphenyl (PCB) total ion current figure (concentration=0.05ug/kg), wherein: 1-PCB28; 2-PCB52; 3-PCB-101; 4-PCB118; 5-PCB153; 6-PCB138; 7-PCB180.
Embodiment
Following specific embodiments of the invention is done a detailed explanation.Gas chromatography-mass spectrum of the present invention is measured the detection method of residual polychlorinated biphenyl in the cosmetics, and this method comprises the steps:
1. pre-treatment
Take by weighing 2.0g (being accurate to 0.01g) Solic cosmetic, as far as possible grind into fine powder (freeze-drying of semi-solid sample such as emulsus elder generation).Cosmetics the mixings 6g zeyssatite that grinds is adorned the last solvent acceleration of appearance in proper order by pad, zeyssatite, mixed sample zeyssatite, zeyssatite and is extracted (ASE), with normal hexane as the extraction solvent.
The solution of having crossed ASE goes to and concentrates bottle, is concentrated near doing under 40 ℃, with the 9mL cyclohexane/ethyl acetate (1: 1, v/v) constant volume is crossed film, gel purification (GPC).(1: 1, v/v) flow was 5mLmin to the solvent cyclohexane/ethyl acetate
-1, Forerun 1080s, Main run 1920s, sample introduction 5mL receives 4.5mL, and front and back concentration is constant.
The sample concentration of having crossed GPC is done 1mL normal hexane constant volume near.Take by weighing the florisil silica that 5g handles well and add 20ml normal hexane wet method dress post, successively use 30mL normal hexane, 30mL n-hexane/ethyl acetate (9: 1, v/v), 30mL normal hexane drip washing pillar, last kind.Discard front 10mL normal hexane leacheate (comprise washing and concentrate bottle), (9: 1, v/v) leacheate was concentrated into closely and does 0.5mL normal hexane constant volume, sample introduction to receive the 30mL n-hexane/ethyl acetate.
2. gas chromatography-mass spectrum is measured
The gas chromatography-mass spectrum condition:
The Agilent7890A-5975C gas chromatograph-mass spectrometer (GCMS) is joined electron bombardment ionization source;
Chromatographic column: HP-5 (30m * 0.25mm i.d., 0.25 μ m) capillary column;
Column temperature:
Inlet temperature: 250 ℃; carrier gas: helium, purity greater than or equal to 99.999%; flow rate, 1.0mL/min; Injection: Splitless; injection volume: 2μL.
Electron bombardment ionization source (EI): 70ev; Chromatography-mass spectroscopy interface temperature: 280 ℃; Ion source temperature: 230 ℃; The solvent delay time: 8min.Detection mode: select ion monitoring mode (SIM).The retention time of every kind of compound, quota ion, qualitative ion are referring to table 1.Figure is as shown in Figure 1 for 7 kinds of polychlorinated biphenyl (PCB) total ion current.
The retention time of table 1 polychlorinated biphenyl, quota ion, qualitative ion
3. result and data
Under selected gas chromatography-mass spectrum condition, the polychlorinated biphenyl hybrid standard of variable concentrations is measured.As shown in Figure 1, responding minimum PCB-180 mensuration lower bound is 0.01 μ gmL
-1The range of linearity is decided to be 0.01 μ gmL
-1～0.10 μ gmL
-1Table 2 is the linear equation and the related coefficient of polychlorinated biphenyl.
The linear equation of table 2 polychlorinated biphenyl and related coefficient
Claims (7)
1. gas chromatography-mass spectrum is measured the detection method of residual polychlorinated biphenyl in the cosmetics, it is characterized in that this method comprises the steps:
1. take by weighing 1.0～5.0g cosmetics solid matter, grind into fine powder, the cosmetics of grinding mix 5～10g zeyssatite, press upward accelerated solvent extraction ASE of pad, zeyssatite, mixed sample zeyssatite, diatomaceous order dress appearance, extract solvent and adopt normal hexane;
2. the solution of having crossed accelerated solvent extraction goes to and concentrates bottle, is concentrated near doing below 40 ℃, with 9mL cyclohexane/ethyl acetate mixed solution constant volume, crosses film, crosses the gel purification GPC of system;
3. will cross the sample concentration of the GPC of gel purification system and do 1mL normal hexane constant volume near;
4. take by weighing the florisil silica that 1～10g handles well and add 20～30ml normal hexane wet method dress post, successively use 30mL normal hexane, 30mL n-hexane/ethyl acetate mixed solution, 30mL normal hexane drip washing pillar, last kind; Discard front 10mL normal hexane leacheate, receive 30mL n-hexane/ethyl acetate mixed solution leacheate, be concentrated into closely and do 0.5mL normal hexane constant volume;
5. the solution behind the constant volume gets into into gas chromatograph-mass spectrometer (GCMS), selects ion scan to detect, and external standard method is quantitative.
2. gas chromatography-mass spectrum according to claim 1 is measured the detection method of residual polychlorinated biphenyl in the cosmetics, it is characterized in that: the cyclohexane/ethyl acetate mixed solution adopts cyclohexane: the volume ratio of ethyl acetate is 1: 1.
3. gas chromatography-mass spectrum according to claim 1 is measured the detection method of residual polychlorinated biphenyl in the cosmetics, it is characterized in that: the n-hexane/ethyl acetate mixed solution adopts normal hexane: the volume ratio of ethyl acetate is 9: 1.
4. gas chromatography-mass spectrum according to claim 1 is measured the detection method of residual polychlorinated biphenyl in the cosmetics, and it is characterized in that: the step 2. flow of cyclohexane/ethyl acetate mixed solution is 5mLmin
-1, it is 1080s that impurity abandons the time, and main acquisition time is 1920s, and sample introduction 5mL receives 4.5mL, and front and back concentration is constant.
5. gas chromatography-mass spectrum according to claim 1 is measured the detection method of residual polychlorinated biphenyl in the cosmetics, it is characterized in that the gas chromatography-mass spectrum condition is following:
Adopt the Agilent7890A-5975C gas chromatograph-mass spectrometer (GCMS), join electron bombardment ionization source;
Chromatographic column: HP-5 capillary column;
Chromatogram column temperature: 70 ℃, kept 0 minute, 20 ℃/min is warming up to 200 ℃, keeps 0 minute, and 5 ℃/min is warming up to 300 ℃, keeps 10 minutes; Injector temperature: 250 ℃; Carrier gas: helium, purity is more than or equal to 99.999%;
Flow velocity, 1.0mL/min; Input mode: split sampling not; Sample size: 2 μ L;
Electron bombardment ionization source: 70ev; Chromatography-mass spectroscopy interface temperature: 280 ℃; Ion source temperature: 230 ℃; The solvent delay time: 8min;
Detection mode: select the ion monitoring mode.
6. gas chromatography-mass spectrum according to claim 5 is measured the detection method of residual polychlorinated biphenyl in the cosmetics, it is characterized in that retention time, quota ion, the qualitative ion of every kind of compound is following:
7. measure the detection method of residual polychlorinated biphenyl in the cosmetics according to the described gas chromatography-mass spectrum of any claim of claim 1～6, it is characterized in that consolidating the shape cosmetics for half carries out the freeze drying processing earlier, preparation cosmetics solid matter.
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| CN105699527A (en) * | 2016-02-02 | 2016-06-22 | 环境保护部华南环境科学研究所 | Detection method of content of brominated flame retardant and phosphorus-based flame retardant in blood serum |
| CN107478740B (en) * | 2017-08-07 | 2020-08-14 | 中山出入境检验检疫局检验检疫技术中心 | Method for measuring polychlorinated biphenyl in aquatic vegetables |
| CN112946152B (en) * | 2019-12-11 | 2024-02-02 | 中国科学院大连化学物理研究所 | HRGC-HRMS detection method for 209 polychlorinated biphenyl homologs in animal-derived food |
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