CN105699526A - Method for detecting contents of brominated flame retardant and phosphorus-based flame retardant in hairs - Google Patents
Method for detecting contents of brominated flame retardant and phosphorus-based flame retardant in hairs Download PDFInfo
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Abstract
The invention provides a method for detecting the contents of a brominated flame retardant and a phosphorus-based flame retardant in hairs. According to the detection method disclosed by the invention, the brominated flame retardant and the phosphorus-based flame retardant in the hairs can be well detected, so that an effective method or measure is provided for estimation of a human body exposure risk of a novel pollutant.
Description
Technical field
The present invention relates to a kind of detection method, be specifically related in a kind of hair the detection method of bromide fire retardant and phosphorous flame-retardant agent content。
Background technology
Fire retardant (flameretardants, FRs) is the Halogen additive that a class can stop polymeric material to ignite or suppress flame to propagate, and is extensively made an addition in the products such as plastics, textile and electronic apparatus。Fire retardant application mode can be divided into addition type and response type two class。Additive flame retardant is directly and resin or sizing material mixture, easy to process, adapt to wide, is the main body of fire retardant；Reactive flame retardant is frequently as in bonding monomeis to polymer chain, on product properties impact is little and flame retardant effect is lasting。Bromide fire retardant and phosphorus flame retardant are fire retardant types the most frequently used in current commercial production, and mostly belong to additive flame retardant, it is easy to be in use gradually released in environment。PBDE (polybrominateddiphenylethers, PBDEs) once it was bromide fire retardant most important, the most widely used, but PBDE is known as by home and abroad environment educational circles in recent years is persistence organic pollutant, has the features such as environmental persistence, long-distance migration, bioconcentration, bio-toxicity。PBDE industrial goods Penta-BDE and Octa-BDE was added into " Convention of Stockholm about persistence organic pollutant " in 2009。European Union's regulation in its " using some Hazardous Substances Directive about restriction in electronic and electrical equipment " (RoHS instruction), from April, 2008, forbids that decabromodiphenyl ether product uses (http://www.cleanproduction.org/Flame.Deca.php) in electric equipment products。U.S. environment protection portion (USEPA) it is also proposed that stop producing and using the suggestion (DecaBDEPhase-outInitiative, http://www.epa.gov/) of Deca-BDE voluntarily before the end of the year 2013。While PBDE is disabled, 1, 2-double, two (2, 4, 6-tribromophenoxy) ethane (1, 2-bis (2, 4, 6-tribromophenoxy) ethane, BTBPE), TDE (decabromodiphenylethane, and phosphorus flame retardant (phosphateflameretardants DBDPE), PFRs) succedaneum being taken as PBDE produces in a large number and uses, all have the report that these substituted type fire retardants detect in the environment all over the world at present, it is likely to and there is potential bioconcentration and bio-toxicity, the Human body package risk of these environmental contaminants and the threat of health be can not be ignored。Hair is the one instruction material that man body pollution thing exposes, and indicates material relative to the pollutant such as blood, urine, has the advantage that one is that gatherer process is simple, storage and transport convenient, processing procedure risk is relatively low；Two is the Noninvasive gathered；Three is that hair does not have the biologic activity such as metabolism or excretion, and pollutant are more stable in hair, it is possible to long-time storage。On prudence, hair is used to check whether be alcohol addiction patient, or sucks the prioritizing selection material of drugs。Owing to hair has higher fat content (2%-4%), many bibliographical informations also indicate clofenotane (Dichlorodiphenyltrichloroethane with hair in recent years, and the Human Exposure via of the organic pollution such as Polychlorinated biphenyls (Polychlorinatedbiphenyls, PCBs) DDT)。But for pollutant emerging in some environment, such as phosphorus flame retardant etc., the analysis method still imperfection of hair。Phosphorus flame retardant contains phosphide key, less stable, it is prone in acid or alkali environment and degrades, and differ bigger with bromide fire retardant physicochemical properties, in traditional hair, organic pollutant analysis method is difficult to, for detecting while multiple bromine system and phosphorus flame retardant, can only individually detect wherein some organic pollutants。And for phosphorus flame retardant, in traditional hair analysis method, many use diluted acids carry out protein denaturation process, use concentrated sulphuric acid to carry out remove impurity, it is possible to can cause the degraded of this compounds。
Summary of the invention
The weak point that it is an object of the invention to overcome prior art to exist and provide the detection method of bromide fire retardant and phosphorous flame-retardant agent content in a kind of hair。
For achieving the above object, the technical scheme taked: the detection method of bromide fire retardant content in a kind of hair, described detection method comprises the following steps:
(1a) hair to be measured is mixed with interior mark indicant, be subsequently adding the first organic solvent, with the bromide fire retardant in the first organic solvent extraction hair, after fully extracting, obtain extracting solution；
(2a) after extracting solution concentration step (1a) obtained, it is transferred on solid-phase extraction column to purify, with the second organic solvent, bromide fire retardant is eluted out from solid-phase extraction column, concentrate after collecting eluent, eluent concentrated sulphuric acid after concentration is purified further, by the eluent constant volume after purification further；
(3a) preparation is containing the bromide fire retardant standard solution of interior mark indicant described in (1a) in steps, then the solution after step (2a) constant volume and the bromide fire retardant standard solution gas chromatograph-mass spectrometer containing interior mark indicant are measured, carry out data based on internal standard method to process and after quantitative analysis, it is thus achieved that the content of bromide fire retardant in hair。
Preferably, in described step (1a), the first organic solvent is the mixture of acetone and normal hexane, and the volume ratio of described acetone and normal hexane is 1:1；Described in described step (2a), the filler of solid-phase extraction column is florisil silica, and the second organic solvent is normal hexane。Preferably, before being transferred on solid-phase extraction column by the extracting solution that step (1a) obtains, first activate described solid-phase extraction column with normal hexane。Preferably, the eluting liquid nitrogen after purification further is blown constant volume in isobutyltrimethylmethane. by described step (2a)。Preferably, described step (1a) is extracted as surname extraction。
Preferably, GC conditions in described step (3a):
Chromatographic column: DB-XLB chromatographic column (30m × 0.25mm × 0.25 μm)；
Carrier gas: high pure nitrogen；
Column flow rate is 1.0mL/min；
Injector temperature: 290 DEG C；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample；
Column temperature program: chromatographic column initial temperature is 110 DEG C, after stopping 1 minute, it is raised to 180 DEG C by the heating rate of 8 DEG C/min, keep 1 minute, then be raised to 240 DEG C with the heating rate of 2 DEG C/min, keep 5 minutes, it is raised to 280 DEG C again with the heating rate of 2 DEG C/min, keep 15 minutes, then be raised to final temperature 310 DEG C with the heating rate of 10 DEG C/min, keep 10 minutes；
Mass Spectrometry Conditions:
Ionization mode: electronics catches negative chemical ionization source；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Reaction gas is methane；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 15min。
Preferably, in in described step (1a), mark indicant is at least one in BDE118, BDE128,4-F-BDE67 and 3-F-BDE153, contains at least one in the standard substance of BDE28, BDE47, BDE66, BDE77, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE181 in described step (3a) in bromide fire retardant standard solution。
Preferably, GC conditions in described step (3a):
Chromatographic column: DB-5HT chromatographic column (15m × 0.25mm × 0.10 μm)；
Carrier gas: high pure nitrogen；
Column flow rate is 1.5mL/min；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample；
Column temperature program: chromatographic column initial temperature is 110 DEG C, after stopping 5 minutes, is raised to 200 DEG C by the heating rate of 20 DEG C/min, keeps 4.5 minutes, then is raised to 310 DEG C with 10 DEG C/min, keeps 15 minutes；
Mass Spectrometry Conditions:
Ionization mode: electronics catches negative chemical ionization source；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Reaction gas is methane；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 5min。
Preferably, in in described step (1a), mark indicant is at least one in 4-F-BDE67 and 3-F-BDE153, contains at least one in the standard substance of BDE196, BDE197, BDE202, BDE203, BDE205, BDE206, BDE207, BDE208, BDE209, BTBPE and DBDPE in described step (3a) in bromide fire retardant standard solution。
The invention provides the detection method of phosphorous flame-retardant agent content in a kind of hair, described detection method comprises the following steps:
(1b) hair to be measured is mixed with interior mark indicant, be subsequently adding the first organic solvent, with the phosphorus flame retardant in the first organic solvent extraction hair, after fully extracting, obtain extracting solution；
(2b) after extracting solution concentration step (1b) obtained, it is transferred on solid-phase extraction column to purify, with the second organic solvent, phosphorus flame retardant is eluted out from solid-phase extraction column, concentrates after collecting eluent, by the eluent constant volume after concentration；
(3b) preparation is containing the phosphorus flame retardant standard solution of interior mark indicant described in (1b) in steps, then the solution after step (2b) constant volume and the phosphorus flame retardant standard solution gas chromatograph-mass spectrometer containing interior mark indicant are measured, carry out data based on internal standard method to process and after quantitative analysis, it is thus achieved that the content of phosphorus flame retardant in hair。
Preferably, in described step (1b), the first organic solvent is the mixture of acetone and normal hexane, and the volume ratio of described acetone and normal hexane is 1:1；Described in described step (2b), the filler of solid-phase extraction column is florisil silica, and the second organic solvent is ethyl acetate。Preferably, before being transferred on solid-phase extraction column by the extracting solution that step (1b) obtains, first activate described solid-phase extraction column by ethyl acetate。Preferably, the eluting liquid nitrogen after purification further is blown constant volume in isobutyltrimethylmethane. by described step (2b)。Preferably, described step (1a) is extracted as surname extraction。
Preferably, GC conditions in described step (3b):
Chromatographic column: DB-5MS chromatographic column (30m × 0.25mm × 0.25 μm)；
Carrier gas: helium；
Column flow rate is；1.5mL/min；
Injector temperature: 290 DEG C；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample
Column temperature program: chromatographic column initial temperature is 70 DEG C, after stopping 2 minutes, rises to 300 DEG C with the heating rate of 15 DEG C/min, keeps 10 minutes；
Mass Spectrometry Conditions:
Ionization mode: electron bombardment ion；
Ionizing energy: 70eV；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 4min。
Preferably, in described step (1b), mark indicant is d27-TnBP, contains at least one in the standard substance of TEP, TnPP, TiPP, TnBP, TCEP, TCPP-1, TCPP-2, TBOEP, TDCPP, TPhP, EHDPP, TEHP and TCP in phosphorus flame retardant standard solution in described step (3b)。
The beneficial effects of the present invention is: the invention provides the detection method of bromide fire retardant and phosphorous flame-retardant agent content in a kind of hair, by detection method of the present invention, can detecting bromide fire retardant and phosphorus flame retardant in hair well, the Human body package risk assessment for emerging pollutant provides effective Method means。
Accompanying drawing explanation
Fig. 1 is low bromo PBDEs sample introduction chromatogram in the embodiment of the present invention 1；
Fig. 2 is high bromo PBDEs, BTBPE and DBDPE sample introduction chromatogram in the embodiment of the present invention 1；
Fig. 3 is phosphorus flame retardant sample introduction chromatogram in the embodiment of the present invention 1。
Detailed description of the invention
For better illustrating the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment, the invention will be further described。
Embodiment 1
This experiment establishes the method for soxhlet type-organophosphorous pesticides/mass spectrometry and measures 18 kinds of PBDEs monomers in hair sample, BTBPE, DBDPE and 13 kinds of PFRs monomers (Chinese and English full name and CAS number in Table 1), the Human body package risk assessment for emerging pollutant provides effective Method means。
Bromine system and phosphorus flame retardant Chinese and English full name in the research of 1, table
1 experiment material
Consumptive material:
Glass drying oven: all glass drying ovens use front and back to soak through suds successively, and clear water rinses, and dry, potassium dichromate/sulfuric acid lotion washing, tap water, then with distilled water flushing, dry 450 DEG C of roasting 4h of rearmounted Muffle furnace。As using acetone, dichloromethane, normal hexane drip washing before sample analysis more successively；
Filter paper: the filter paper that extracting ladle sample uses dries standby after dichloromethane extracting 72h。
(3) absorbent cotton: dichloromethane extracting 72h used before use by the absorbent cotton used in chromatographic column, and period changes single extraction liquid, seals preservation stand-by。Then through acetone, dichloromethane and normal hexane successively drip washing before using；
(4) solid-phase extraction column: filler is the solid-phase extraction column (ENVI-Florisil, 500mg, 3mL, Supleco company) of Fo Luoli tripoli (500mg)；
Reagent:
Acetone, normal hexane, ethyl acetate and isobutyltrimethylmethane. are chromatographically pure (HPLC)；The water of all research uses is all Milli-Q ultra-pure water；Concentrated sulphuric acid is analytical pure (AR)；
Standard substance:
Isotope-labeled standard substance (13C-BDE209,d27-TnBP) it is purchased from CambridgeIsotopeLaboratories company, other standard specimens (BDE28, BDE47, BDE66, BDE77, BDE85, BDE99, BDE100, BDE118, BDE128, BDE138, BDE153, BDE154, BDE183, BDE181, BDE196, BDE197, BDE202, BDE203, BDE205, BDE206, BDE207, BDE208, BDE209,4-F-BDE67,3-F-BDE153, BTBPE, DBDPE, TEP, TnPP, TiPP, TnBP, TCEP, TCPP-1, TCPP-2, TBOEP, TDCPP, TPhP, EHDPP, TEHP, TCP) all it is purchased from AccuStandard (USA) company。
2 instruments
Bromide fire retardant (PBDEs, BTBPE and DBDPE) content analysis adopts gas chromatograph-mass spectrometer (GC-MS) (Agilent6890GC/5975MS), completes under the Salbutamol Selected Ion Monitoring pattern (SIM) that electronics catches negative chemical ionization (ECNI)。Carrier gas is high pure nitrogen, and reaction gas is methane。Ion source pressure is 2.5 × 10-3Pa, ion source temperature is 250 DEG C, level Four bar temperature: 150 DEG C；Interface (gas chromatography-mass spectrum connecting line) temperature 280 DEG C。Adopting Splitless injecting-Sample, sample size is 1 μ L, injector temperature 290 DEG C。
Phosphorus flame retardant content analysis adopts gas chromatograph-mass spectrometer (GC-MS) (ShimadzuQP2010GC-MS), completes under the Salbutamol Selected Ion Monitoring pattern (SIM) of electron impact ion source (EI)。Carrier gas is helium。Ion source pressure is 2.5 × 10-3Pa, ion source temperature is 200 DEG C, interface (gas chromatography-mass spectrum connecting line) temperature 290 DEG C。Adopting Splitless injecting-Sample, sample size is 1 μ L, injector temperature 300 DEG C。
3 experimental techniques and result
3.1 soxhlet type
Being respectively put in conical flask by each hair sample, add the Milli-Q ultra-pure water of q.s, vibration washing 1h in shaking table, in shaking table, temperature is maintained at 40 DEG C, and rotating speed is 300 turns/min。Repeat twice。-20 DEG C of lyophilization 48h of hair sample that will clean up, fully mix hair scissors thin (2-3mm) with rustless steel shears (with successively with acetone, dichloromethane and normal hexane ultrasonic cleaning before using)。Weigh the hair of about 2g, in acetone/normal hexane mixed solvent (1:1, V/V) soxhlet type 48h in, mark indicant in adding before extracting, when detecting low bromo PBDEs, select mixture (BDE118, the BDE128 of BDE118, BDE128,4-F-BDE67 and 3-F-BDE153, the each 10ng of 4-F-BDE67,3-F-BDE153) as interior mark indicant；As detection high bromo PBDEs, BTBPE and DBDPE, select the mixture (each 10ng of 4-F-BDE67,3-F-BDE153) of 4-F-BDE67 and 3-F-BDE153 as interior mark indicant；When detection phosphorus flame retardant, select d27-TnBP (10ng) is as interior mark indicant。It is 2mL normal hexane by extract concentration conversion solvent。
3.2 Solid-Phase Extraction
First activating florisil silica solid-phase extraction column successively with 8mL ethyl acetate and 6mL normal hexane, elute the first component with 10mL normal hexane after application of sample, 8mL ethyl acetate elutes second component。First component is concentrated into 2mL and uses concentrated sulphuric acid to purify further, and eluting liquid nitrogen blows constant volume in 50 μ L isobutyltrimethylmethane .s, wherein contains PBDEs, BTBPE and DBDPE, adopts GC-MS-ECNI source to analyze；Second component concentration nitrogen blows constant volume in 50 μ L isobutyltrimethylmethane .s, wherein contains PFRs, adopts GC-MS-EI source to analyze；
The optimization of 3.3GC-MS testing conditions
First by each standard substance list mark, sample introduction under full scan pattern, it is determined that the fragment ion that abundance is the highest is qualitative and quota ion。Then under Salbutamol Selected Ion Monitoring pattern, following heating schedule sample introduction is adopted: initial temperature is 110 DEG C and is warming up to 310 DEG C with 10 DEG C/min, on this basis Optimum Temperature Raising interval and heating rate, to obtain best target compound peak shape and separating degree。Finally determine that instrument parameter is as follows:
Bromide fire retardant (PBDEs, BTBPE, DBDPE): low bromo PBDEs (BDE28, BDE47, BDE66, BDE77, BDE85, BDE99, BDE100, BDE118, BDE128, BDE138, BDE153, BDE154, BDE183, BDE181,4-F-BDE67,3-F-BDE153) detection adopt DB-XLB chromatographic column (30m × 0.25mm × 0.25 μm, Agilent) separating, column flow rate is 1.0mL/min, solvent delay time: 15min。Chromatographic column initial temperature is 110 DEG C, after stopping 1 minute, it is raised to 180 DEG C by the heating rate of 8 DEG C/min, keep 1 minute, then be raised to 240 DEG C with the heating rate of 2 DEG C/min, keep 5 minutes, it is raised to 280 DEG C again with the heating rate of 2 DEG C/min, keep 15 minutes, then be raised to final temperature 310 DEG C with the heating rate of 10 DEG C/min, keep 10 minutes。Related color spectrogram is shown in Fig. 1。
High bromo PBDEs (BDE196, BDE197, BDE202, BDE203, BDE205, BDE206, BDE207, BDE208, BDE209,4-F-BDE67,3-F-BDE153), BTBPE and DBDPE uses DB-5HT chromatographic column (15m × 0.25mm × 0.10 μm, Agilent) to be easily separated, column flow rate is 1.50mL/min, solvent delay time: 5min。Chromatographic column initial temperature is 110 DEG C, after stopping 5 minutes, is raised to 200 DEG C by the heating rate of 20 DEG C/min, keeps 4.5 minutes, then is raised to 310 DEG C with 10 DEG C/min, keeps 15 minutes。Scanning ion charge-mass ratio (m/z): PBDEs (except BDE209) and DBDPE is 79 and 81；BDE209 is 486.7 and 488.7；13C-BDE209 is 494.7 and 496.7。Wherein front one scan ion is as quantitative use。Relevant spectrogram is shown in Fig. 2。
Phosphorus flame retardant: adopting DB-5MS chromatographic column (30m × 0.25mm × 0.25um, J&WScientific), column flow rate is 1.50mL/min, solvent delay time: 4min。Chromatographic column initial temperature is 70 DEG C, after stopping 2 minutes, rises to 300 DEG C with the heating rate of 15 DEG C/min, keeps 10 minutes。Relevant spectrogram is shown in Fig. 3。Qualitatively and quantitatively scanning ion is as follows: TEP:155 and 127；TnPP:125 and 183；TiPP:183 and 123；D27-TnBP:103 and 231；TnBP:211 and 155；TCEP:249 and 251；TCPP-1/TCPP-2:277 and 279；TDCPP:381 and 379；TBOEP:299 and 199；TPhP:326 and 325；EHDPP:251 and 362；TEHP:99 and 113；TCP:368 and 367。
The foundation of 3.4 quantitation curves and detection limit
In this research, all compounds quantitatively adopts inner mark method ration。Wherein the Concentraton gradient of low bromo PBDEs monomer is 0.2-200ng/mL, the Concentraton gradient of high bromo PBDEs monomer (except BDE209) is 20-500ng/mL, the Concentraton gradient of BDE209 is 20-5000ng/mL, the concentration range 10-2000ng/mL of concentration range 50-3000ng/mL, the PFRs of BTBPE and DBDPE。The R2 value of standard curve is all higher than 0.99。
For there being the compound of detection in blank sample, method is quantitatively limited in blank+3 times of standard deviations of target compound meansigma methods。Not having the compound of detection in blank sample, method is quantitatively limited to the instrument signal to noise ratio of 10 times。Method detection is limited to 3 times of instrument signal to noise ratio。In this research, the detection limit of all target compounds and quantitative limit are in Table 2。
The detection limit of table 2 bromine system and phosphorus flame retardant and quantitative limit
3.5 instrument precision tests
Configuration target compound standard substance mixed sample (100ppb), every day sample introduction 1-2 time, determining instrument precision, quantitative Analysis deviation RSD is less than 10%。Show that the method precision is good。
3.6 Quality Assurance/Quality Control systems
3 blank samples are set, 5 blank mark-ons, 5 substrate mark-ons (hair sample taking extracting adds target compound mixed sample (every kind of each 5ng of monomer)), by above-mentioned experimental procedure and instrument detection method gained target compound response rate result in Table 3。
The response rate of table 3 target compound and standard deviation
3.7 hair sample assays
The hair sample sample introduction acquiring 10 volunteers measures bromine system and phosphorous flame-retardant agent content, and experimental result is in Table 4。Except the outer all bromide fire retardants of BDE66, BDE154, BDE183 and all phosphorus flame retardants except TCP have detection, illustrate that this method can measure the concentration of multiple bromine system and phosphorus flame retardant in hair effectively simultaneously。
Bromine system and phosphorous flame-retardant agent content in table 4 hair sample
Finally be should be noted that; above example is only in order to illustrate technical scheme but not limiting the scope of the invention; although the present invention being explained in detail with reference to preferred embodiment; it will be understood by those within the art that; technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention。
Claims (10)
1. the detection method of bromide fire retardant content in a hair, it is characterised in that described detection method comprises the following steps:
(1a) hair to be measured is mixed with interior mark indicant, be subsequently adding the first organic solvent, with the bromide fire retardant in the first organic solvent extraction hair, after fully extracting, obtain extracting solution；
(2a) after extracting solution concentration step (1a) obtained, it is transferred on solid-phase extraction column to purify, with the second organic solvent, bromide fire retardant is eluted out from solid-phase extraction column, concentrate after collecting eluent, eluent concentrated sulphuric acid after concentration is purified further, by the eluent constant volume after purification further；
(3a) preparation is containing the bromide fire retardant standard solution of interior mark indicant described in (1a) in steps, then the solution after step (2a) constant volume and the bromide fire retardant standard solution gas chromatograph-mass spectrometer containing interior mark indicant are measured, carry out data based on internal standard method to process and after quantitative analysis, it is thus achieved that the content of bromide fire retardant in hair。
2. detection method according to claim 1, it is characterised in that in described step (1a), the first organic solvent is the mixture of acetone and normal hexane, and the volume ratio of described acetone and normal hexane is 1:1；Described in described step (2a), the filler of solid-phase extraction column is florisil silica, and the second organic solvent is normal hexane。
3. detection method according to claim 1, it is characterised in that GC conditions in described step (3a):
Chromatographic column: DB-XLB chromatographic column (30m × 0.25mm × 0.25 μm)；
Carrier gas: high pure nitrogen；
Column flow rate is 1.0mL/min；
Injector temperature: 290 DEG C；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample；
Column temperature program: chromatographic column initial temperature is 110 DEG C, after stopping 1 minute, it is raised to 180 DEG C by the heating rate of 8 DEG C/min, keep 1 minute, then be raised to 240 DEG C with the heating rate of 2 DEG C/min, keep 5 minutes, it is raised to 280 DEG C again with the heating rate of 2 DEG C/min, keep 15 minutes, then be raised to final temperature 310 DEG C with the heating rate of 10 DEG C/min, keep 10 minutes；
Mass Spectrometry Conditions:
Ionization mode: electronics catches negative chemical ionization source；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Reaction gas is methane；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 15min。
4. detection method according to claim 3, it is characterized in that, in in described step (1a), mark indicant is at least one in BDE118, BDE128,4-F-BDE67 and 3-F-BDE153, contains at least one in the standard substance of BDE28, BDE47, BDE66, BDE77, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE181 in described step (3a) in bromide fire retardant standard solution。
5. detection method according to claim 1, it is characterised in that GC conditions in described step (3a):
Chromatographic column: DB-5HT chromatographic column (15m × 0.25mm × 0.10 μm)；
Carrier gas: high pure nitrogen；
Column flow rate is 1.5mL/min；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample；
Column temperature program: chromatographic column initial temperature is 110 DEG C, after stopping 5 minutes, is raised to 200 DEG C by the heating rate of 20 DEG C/min, keeps 4.5 minutes, then is raised to 310 DEG C with 10 DEG C/min, keeps 15 minutes；
Mass Spectrometry Conditions:
Ionization mode: electronics catches negative chemical ionization source；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Reaction gas is methane；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 5min。
6. detection method according to claim 5, it is characterized in that, in in described step (1a), mark indicant is at least one in 4-F-BDE67 and 3-F-BDE153, contains at least one in the standard substance of BDE196, BDE197, BDE202, BDE203, BDE205, BDE206, BDE207, BDE208, BDE209, BTBPE and DBDPE in described step (3a) in bromide fire retardant standard solution。
7. the detection method of phosphorous flame-retardant agent content in a hair, it is characterised in that described detection method comprises the following steps:
(1b) hair to be measured is mixed with interior mark indicant, be subsequently adding the first organic solvent, with the phosphorus flame retardant in the first organic solvent extraction hair, after fully extracting, obtain extracting solution；
(2b) after extracting solution concentration step (1b) obtained, it is transferred on solid-phase extraction column to purify, with the second organic solvent, phosphorus flame retardant is eluted out from solid-phase extraction column, concentrates after collecting eluent, by the eluent constant volume after concentration；
(3b) preparation is containing the phosphorus flame retardant standard solution of interior mark indicant described in (1b) in steps, then the solution after step (2b) constant volume and the phosphorus flame retardant standard solution gas chromatograph-mass spectrometer containing interior mark indicant are measured, carry out data based on internal standard method to process and after quantitative analysis, it is thus achieved that the content of phosphorus flame retardant in hair。
8. detection method according to claim 7, it is characterised in that in described step (1b), the first organic solvent is the mixture of acetone and normal hexane, and the volume ratio of described acetone and normal hexane is 1:1；Described in described step (2b), the filler of solid-phase extraction column is florisil silica, and the second organic solvent is ethyl acetate。
9. detection method according to claim 7, it is characterised in that GC conditions in described step (3b):
Chromatographic column: DB-5MS chromatographic column (30m × 0.25mm × 0.25 μm)；
Carrier gas: helium；
Column flow rate is；1.5mL/min；
Injector temperature: 290 DEG C；
Sample size: 1 μ L；
Input mode: Splitless injecting-Sample；
Column temperature program: chromatographic column initial temperature is 70 DEG C, after stopping 2 minutes, rises to 300 DEG C with the heating rate of 15 DEG C/min, keeps 10 minutes；
Mass Spectrometry Conditions:
Ionization mode: electron bombardment ion；
Ionizing energy: 70eV；
Ion source temperature: 250 DEG C；
Ion source pressure: 2.5 × 10-3Pa；
Level Four bar temperature: 150 DEG C；
Gas chromatography-mass spectrum connecting line temperature: 280 DEG C；
Monitoring mode: Salbutamol Selected Ion Monitoring pattern；
Solvent delay time: 4min。
10. detection method according to claim 7, it is characterised in that in described step (1b), mark indicant is d27-TnBP, contains at least one in the standard substance of TEP, TnPP, TiPP, TnBP, TCEP, TCPP-1, TCPP-2, TBOEP, TDCPP, TPhP, EHDPP, TEHP and TCP in phosphorus flame retardant standard solution in described step (3b)。
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