CN104897824B - The gel chromatographic columns of a kind of gas chromatography mass spectrometry detection PBDE and metabolite thereof and detection method thereof - Google Patents
The gel chromatographic columns of a kind of gas chromatography mass spectrometry detection PBDE and metabolite thereof and detection method thereof Download PDFInfo
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Abstract
The invention provides the gel chromatographic columns of a kind of gas chromatography mass spectrometry detection PBDE and metabolite thereof, described gel chromatographic columns is adopted and is prepared with the following method: weigh gel and solvent, is mixed in solvent by gel, shakes up swelling；Take the chromatographic column of a dried and clean, in chromatographic column, then add solvent, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space；Gel suspension is poured in chromatographic column, on gel layer, add sea sand, namely prepare described gel chromatographic columns.This gel chromatography column preparation method is simple, it is possible to effectively overcoming the matrix effect of complexity, being easily separated containing the plurality of impurities in organic pollution matrix, thus effectively removing plurality of impurities, it is to avoid interference to follow-up organic contamination analyte detection.The present invention additionally provides the method detecting PBDE and metabolite thereof based on above-mentioned gel chromatographic columns simultaneously, the advantage that the method has simple to operate, favorable reproducibility, highly sensitive and accuracy is high.
Description
Technical field
The preparation method that the present invention relates to the gel chromatographic columns of a kind of gas chromatography mass spectrometry detection PBDE and metabolite, and the detection method of this gel chromatographic columns detection PBDE and metabolite thereof, belong to environment or technical field of food detection.
Background technology
At present, organic pollutant category in environment and food gets more and more, such as PBDE and metabolite, it is the organic brominated flame retardant of a class halo (BFRs), due to good anti-flammability, it is used in various commercial product at industrial circle by substantial amounts of, for instance electric equipment products and textile.The PBBs ether product of business mainly includes pentabromo-, eight bromines and decabromodiphenyl oxide.Due to their physicochemical property and biological accumulation feature, as environmental persistence and high hydrophobicity result in this series products in natural environment widely distributed.Methoxyl polybrominated diphenyl ethers (MeO-PBDEs) is the compound that a class is similar with PBBs ether structure, and they are considered as the compound of synthetic.Toxicologic study shows, the liver of human body, thyroid and genitals and nervous system are produced specific toxicological effect by this two compounds.And matrix residing for this kind of organic pollution is generally sufficiently complex, content is also very micro-, often in μ g/kg.At present, the detection method measuring PBDE and metabolite comparative maturity is GC-MS, but the accuracy of its result is largely limited by the impurity content of sample.If these impurity are not treated, then the testing result of follow-up organic pollution can be produced larger interference, the result of impact detection.
Summary of the invention
The invention solves the deficiency in background technology, provide the gel chromatographic columns of a kind of gas chromatography mass spectrometry detection PBDE and metabolite thereof, this gel chromatography column preparation method is simple, can effectively overcome the matrix effect of complexity, can be easily separated containing the plurality of impurities in organic pollution matrix, thus effectively removing plurality of impurities, it is to avoid interference to follow-up organic contamination analyte detection.
Realizing the technical scheme that above-mentioned purpose of the present invention adopts is:
A kind of gel chromatographic columns of gas chromatography mass spectrometry detection PBDE and metabolite thereof, described gel chromatographic columns is adopted and is prepared with the following method: (1), weigh polystyrene gel and solvent, wherein every 1 gram of polystyrene correspondence measures 5～8 milliliters of solvents, described solvent is the mixed solution of hexamethylene and ethyl acetate, polystyrene gel is mixed in solvent, shake up, then carry out swelling, swelling time was more than 24 hours, after swelling equilibrium, pour out supernatant and particle impurity, standby；
(2) chromatographic column of a dried and clean and a silica gel hose, are taken, silica gel hose is connected to the exit, lower end of chromatographic column, then in chromatographic column, add the solvent accounting for column volume 20～30%, stand, until bubble-free is overflowed in the glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, be then shut off piston；
(3), polystyrene gel after swelling and solvent are poured in beaker, it is sufficiently stirred for until polystyrene gel suspends in a solvent uniformly, prepare gel suspension, then gel suspension is poured slowly in chromatographic column by the top of chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom deposits to 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2～3mL/min, then proceed to pour gel suspension into column volume 5/6 place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand of 1/12 column volume is added on gel layer, pave, namely described gel chromatographic columns is prepared.
Solvent cyclohexane and the volume ratio of ethyl acetate described in step (1) are 1:1.
The draw ratio of the chromatographic column described in step (2) is 8～10:1.
The present invention additionally provides the method detecting PBDE and metabolite thereof based on above-mentioned gel chromatographic columns simultaneously, the advantage that the method has simple to operate, favorable reproducibility, highly sensitive and accuracy is high.The method comprises the following steps: (1), mixed according to the volume ratio of 1:8～10 with kieselguhr by testing sample, eluting is carried out according to the mixed solution of the volume ratio of 1:1 again with dichloromethane and normal hexane, collect and concentrate testing sample eluent, prepare concentrated solution A；
null(2)、Mark PBDEs28 in mark carbon 13 labelling in adding in concentrated solution A,47,99,100,154,153 and 183，Concentration is 100ng/mL，And BDE17,BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The mixed standard solution of 4 '-MeO-BDE101 and 4 '-MeO-BDE103，Concentration is 100ng/mL；Above material is added in concentrated solution and mix homogeneously, then concentrated solution is injected in chromatographic column, until the liquid level of concentrated solution is concordant with sea sand face；
(3), the solvent of 1.2～1.4 times of column volumes is adopted to carry out eluting, elution flow rate is 1.00～1.50mL/min, discard the eluent of front 50～60% column volumes, collect the eluent of remainder in evaporative flask, follow-up rotated evaporation and nitrogen blow and are concentrated into 0.9～1.1mL, prepare concentrated solution B, detect for GC-MS；
(4), injecting in GC-MS by concentrated solution B, adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0～3.0 μ L, not shunt mode sample introductions, and using helium as carrier gas, flow rate of carrier gas is 0.8～1.2mL/min.Injector temperature is 270～280 DEG C, bushing pipe adopts deactivation bushing pipe, transmission line temperature is 315 DEG C～325 DEG C, ion source temperature 245 DEG C～255 DEG C, the EI adopting 70ev ionizes mode, scan mode is SIM, and column oven temperature programming condition is: 95 DEG C～105 DEG C keep 0.8～1.2min → 195 DEG C～205 DEG C, and programming rate is 18 DEG C/min～22 DEG C/min；195 DEG C～205 DEG C → 275 DEG C～285 DEG C, programming rate is 2.4 DEG C/min～2.6 DEG C/min；275 DEG C～285 DEG C → 315 DEG C～325 DEG C, programming rate is 4.5 DEG C/min～5.5 DEG C/min, and 315 DEG C～325 DEG C keep 9～11min；
null(5)、Adopt Isotope internal standard dilution standard measure，Namely with testing concentration for abscissa，Determinand peak area is vertical coordinate with corresponding isotopic peak area ratio，Obtain working curve，Thus BDE17 in testing sample in calculating，BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The content of 4 '-MeO-BDE101 and 4 '-MeO-BDE103.
It is a kind of very effective processing method that gel separates, when in matrix, the mixture of different molecular size flows through gel chromatography column, the molecule bigger than gel mesh can not enter the network structure in microgel particle, and by outside exclusion Gel microgranule, along with solvent hole between microgel particle flows downward and flows out at first outside post；The molecule less than mesh can the microgel particle that freely comes in and goes out in various degree cancellated inside and outside, holdup time in the chromatography column is longer, so separated owing to the distance of different size of molecule institute warp is different, macromolecular substances is first eluted out, such as protein, small-molecule substance by after be eluted out, such as PBDE and metabolite.Therefore, sample, after gel chromatography separation purifies, can be removed major part impurity, the accuracy measuring PBDE and metabolite is had facilitation.Then sample solution is concentrated, measure for GC-MS.
First have to expect good separating effect, gel must carry out swelling treatment, after swelling, gel volume expands, solvent penetration is among gel, and the network structure of microgel particle just can be fully extended, and such macromolecular substances could by exclusion, small-molecule substance can freely come in and go out, thus reaching good isolation of purified effect.
Secondly dress post must be wanted uniformly, smooth, it is impossible to have bubble.Bubble is typically derived among the space below glass core filter plate, adopts the mode of silica gel hose aerofluxus bubble, it is possible to make solvent be full of the dead volume below glass core filter plate and between piston, thus suppressing the generation of bubble.In dress post process, the homogeneity of gel is also extremely important, gel dress namely can not cross pine can not tension, if dress is too loose, in chromatography process, gel layer height can decline, the tension of dress, then eluting resistance is too big, extends analysis time.And adopting the dress column method of the present invention, the tightness of gel is just right.
The present invention employs sea sand at the top layer of chromatographic column, sea sand is mainly composed of silicon dioxide, stable in properties, do not react with other compounds, gel compacting can be flattened by sea sand in the filling process, and then in loading and elution process, due to sea sand cushioning effect, gel will not be kicked up because of impulsive force.
Present invention agents useful for same in purification process is that environmentally friendly reagent, hexamethylene and ethyl acetate are little compared with dichloromethane toxicity, and the pollution of environment is also little.The present invention can avoid the dichloromethane solvent that operator's contact toxicity is stronger, reduces the hazardness to human body and environment.
Chromatography of gases Mass Spectrometry Conditions is also optimized by the present invention, injector temperature is set to 270～280 DEG C, ensure that the gasification cmpletely of institute's analysis of compounds, bushing pipe adopts deactivation bushing pipe, the active site adsorption sample component on injection port bushing pipe can be avoided and cause that tailing peak occurs, in particular for some high boiling substances in PBBs ether compound.Transmission line temperature is set to 315 DEG C～325 DEG C, it is ensured that determinand enters the process of mass detector from gas chromatogram and condensation effect does not occur.
The present invention is from analyzing methodology, Isotope internal standard dilution method has been selected to come quantitatively, this method quantitatively on more accurate science, can getting rid of the error that the interference due to sample mesostroma (ion suppression etc) causes, in adding before sample purification, mark compound can also investigate the damaed cordition in whole experimentation to target compound simultaneously.
Compared with prior art, its beneficial effect and advantage are in that the present invention:
In the present invention preparation gelling performance superior, and in the method the padding of gel describe careful specifically, with strong points, thus strengthening operability.Therefore, gel purification chromatographic column prepared by the method can overcome the matrix effect of complexity, can remove containing the plurality of impurities in polybrominated biphenyl and metabolite matrix thereof, eliminates and follow-up PBBs and metabolite thereof are detected the interference produced；Follow-up detection method give also the suitableeest parameter of instrument, makes the result of analysis more accurately and reliably.The more important thing is, solidifying purification chromatographic column prepared by the method is simple to operate, the results showed, use the method detection organic pollution such as PBBs compounds have highly sensitive, accuracy is high, favorable reproducibility and the high advantage of the response rate.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention done detailed specific description, but protection scope of the present invention is not limited to following example.
For checking gas chromatography mass spectrometry provided by the invention detection PBDE and the gel chromatographic columns of metabolite and the feasibility of detection method thereof and superiority, present inventor specially adds mixed standard solution and the inner mark solution of PBDE and metabolite thereof in milk product, adopt the preparation of gel purification chromatographic column provided by the invention and fill method to be easily separated the milk product of mark-on solution, detect according to instrument parameter provided by the invention.Measure the PBDE of the milk product after gel purification chromatographic column separates and the content of metabolite thereof, difference according to the result concentration detected and known organic concentration, feasibility and the superiority of the separation of gel purification chromatographic column prepared by the method and instrument detection are estimated.
Embodiment 1
Taking 100g polystyrene gel, be immersed in the hexamethylene of 500mL: in ethyl acetate (1:1), shake up, then carry out swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and particle impurity, standby.Take a clean chromatographic column (ID:2.5cm × L:20cm), add the hexamethylene of about 5cm: ethyl acetate (1:1), stand, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extrude silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, be then shut off piston.Polystyrene gel after swelling and solvent are poured in beaker, it is sufficiently stirred for until polystyrene gel suspends in a solvent uniformly, prepare gel suspension, then gel suspension is poured slowly in chromatographic column by the top of chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom deposits to 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2～3mL/min, then proceed to pour gel suspension into 17cm place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the high sea sand of 1.6cm is added on gel layer, pave, namely described gel chromatographic columns is prepared.
Weigh the 2g milk powder processed in advance, mix with the kieselguhr of 16g, with the dichloromethane of 150mL: normal hexane (1:1) carries out eluting extraction, collect extract, be concentrated into 1mL, prepare concentrated solution A.nullMark PBDEs28 in mark carbon 13 labelling in adding in concentrated solution A,47,99,100,154,153 and 183，Concentration is 100ng/mL，And BDE17,BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The mixed standard solution of 4 '-MeO-BDE101 and 4 '-MeO-BDE103，Concentration is 100ng/mL；Above material is added in concentrated solution and mix homogeneously, then concentrated solution is injected in chromatographic column, until the liquid level of concentrated solution is concordant with sea sand face.
Carrying out eluting with 120mL solvent (hexamethylene: ethyl acetate 1:1), discard front 60mL eluent, elution flow rate is 1mL/min.60mL eluent after collection, eluent is evaporated to 1.0mL, prepares concentrated solution B, detects for GC-MS.
Being injected by concentrated solution B in GC-MS, adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0 μ L.Not shunt mode sample introduction.Helium is as carrier gas.Flow rate of carrier gas is 0.8mL/min.Injector temperature is 270 DEG C, and bushing pipe adopts deactivation bushing pipe.Transmission line temperature is 315 DEG C, and ion source temperature is 245 DEG C.The EI adopting 70ev ionizes mode, and scan mode is SIM.
Column oven temperature programming condition is: 95 DEG C (keeping 0.8min) → 195 DEG C, 18 DEG C/min；195 DEG C → 275 DEG C, 2.4 DEG C/min；275 DEG C → 315 DEG C, 4.5 DEG C/min (keeping 9min).
By Isotope internal standard dilution method, sample is carried out quantitatively, and calculate the response rate, record BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68, the response rate of 5 '-MeO-BDE99,5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103 is 70%～110%.
The result of the above-mentioned response rate meets the related request in european union directive (EuropeanUniondocument2002/657/EC).Namely during P < 1 μ g/L, the response rate need in 50%～120% scope, and P refers to the concentration of determinand.
Embodiment 2
Taking 100g polystyrene gel, be immersed in the hexamethylene of 800mL: in ethyl acetate (1:1), shake up, then carry out swelling, swelling time is one day, after swelling equilibrium, pours out supernatant and particle impurity, standby.Take a clean chromatographic column (ID:3cm × L:30cm), add the hexamethylene of about 7.5cm: ethyl acetate (1:1), stand, until bubble-free is overflowed in glass core filter plate in chromatographic column, then open piston, extrude silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, be then shut off piston.Polystyrene gel after swelling and solvent are poured in beaker, it is sufficiently stirred for until polystyrene gel suspends in a solvent uniformly, prepare gel suspension, then gel suspension is poured slowly in chromatographic column by the top of chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom deposits to 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2～3mL/min, then proceed to pour into gel suspension to 25cm At The Height, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the high sea sand of 2.5cm is added on gel layer, pave, namely described gel chromatographic columns is prepared.
Weigh the 3g milk powder processed in advance, mix with the kieselguhr of 30g, with the dichloromethane of 250mL: normal hexane (1:1) carries out eluting extraction, collect extract, be concentrated into 1mL, prepare concentrated solution A.nullMark PBDEs28 in mark carbon 13 labelling in adding in concentrated solution A,47,99,100,154,153 and 183，Concentration is 100ng/mL，And BDE17,BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The mixed standard solution of 4 '-MeO-BDE101 and 4 '-MeO-BDE103，Concentration is 100ng/mL；Above material is added in concentrated solution and mix homogeneously, then concentrated solution is injected in chromatographic column, until the liquid level of concentrated solution is concordant with sea sand face.
Carrying out eluting with 250mL solvent (hexamethylene: ethyl acetate 1:1), discard front 150mL eluent, elution flow rate is 1.5mL/min.100mL eluent after collection, eluent is evaporated to 1.0mL, prepares concentrated solution B, detects for GC-MS.
Being injected by concentrated solution B in GC-MS, adopt Elite-5MS capillary chromatographic column, sampling volume is 3.0 μ L.Not shunt mode sample introduction.Helium is as carrier gas.Flow rate of carrier gas is 1.2mL/min.Injector temperature is 280 DEG C, and bushing pipe adopts deactivation bushing pipe.Transmission line temperature is 385 DEG C, and ion source temperature is 255 DEG C.The EI adopting 70ev ionizes mode, and scan mode is SIM.
Column oven temperature programming condition is: 105 DEG C (keeping 1.2min) → 205 DEG C, 2.2 DEG C/min；205 DEG C → 285 DEG C, 2.6 DEG C/min；285 DEG C → 325 DEG C, 5.5 DEG C/min (keeping 11min).
By Isotope internal standard dilution method, sample is carried out quantitatively, and calculate the response rate, record BDE17, BDE28, BDE47, BDE66, BDE71, BDE85, BDE99, BDE100, BDE138, BDE153, BDE154, BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4 '-MeO-BDE49,2 '-MeO-BDE68, the response rate of 5 '-MeO-BDE99,5 '-MeO-BDE100,4 '-MeO-BDE101 and 4 '-MeO-BDE103 is 70%～110%.
The result of the above-mentioned response rate meets the related request in european union directive (EuropeanUniondocument2002/657/EC).Namely during P < 1 μ g/L, the response rate need in 50%～120% scope, and P refers to the concentration of determinand.
Claims (1)
1. the method adopting gas chromatography mass spectrometry gel chromatographic columns detection PBDE and metabolite thereof, described gel chromatographic columns is adopted and is prepared with the following method: (1), weigh polystyrene gel and solvent, wherein every 1 gram of polystyrene correspondence measures 5～8 milliliters of solvents, described solvent is the mixed solution of hexamethylene and ethyl acetate, the volume ratio of hexamethylene and ethyl acetate is 1:1, polystyrene gel is mixed in solvent, shake up, then carry out swelling, swelling time was more than 24 hours, after swelling equilibrium, pour out supernatant and particle impurity, standby；
(2) chromatographic column of a dried and clean and a silica gel hose, are taken, silica gel hose is connected to the exit, lower end of chromatographic column, then in chromatographic column, add the solvent accounting for column volume 20～30%, stand, until bubble-free is overflowed in the glass core filter plate in chromatographic column, then open piston, extruding silica gel hose, discharge the bubble below glass core filter plate and between piston, make solvent be full of this segment space, be then shut off piston；
(3), polystyrene gel after swelling and solvent are poured in beaker, it is sufficiently stirred for until polystyrene gel suspends in a solvent uniformly, prepare gel suspension, then gel suspension is poured in chromatographic column by the top of chromatographic column, make gel suspension natural subsidence, when the gel suspension of column bottom deposits to 1/5 column volume, open chromatographic column lower end piston, and regulate flow velocity to 2～3mL/min, then proceed to pour gel suspension into column volume 5/6 place, and keep gel to soak all the time in a solvent, after the complete Equalsettlement of gel, the sea sand of 1/12 column volume is added on gel layer, pave, namely described gel chromatographic columns is prepared；
It is characterized in that detection method comprises the following steps: (1), mixed according to the volume ratio of 1:8～10 by testing sample with kieselguhr, eluting is carried out according to the mixed solution of the volume ratio of 1:1 again with dichloromethane and normal hexane, collect and concentrate testing sample eluent, prepare concentrated solution A；
null(2)、Mark PBDEs28 in mark carbon 13 labelling in adding in concentrated solution A,47,99,100,154,153 and 183，Concentration is 100ng/mL，And BDE17,BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The mixed standard solution of 4 '-MeO-BDE101 and 4 '-MeO-BDE103，Concentration is 100ng/mL；Above material is added in concentrated solution and mix homogeneously, then concentrated solution is injected in chromatographic column, until the liquid level of concentrated solution is concordant with sea sand face；
(3), the solvent of 1.2～1.4 times of column volumes is adopted to carry out eluting, elution flow rate is 1.00～1.50mL/min, discard the eluent of front 50～60% column volumes, collect the eluent of remainder in evaporative flask, follow-up rotated evaporation and nitrogen blow and are concentrated into 0.9～1.1mL, prepare concentrated solution B, detect for GC-MS；
(4), concentrated solution B is injected in GC-MS, adopt Elite-5MS capillary chromatographic column, sampling volume is 2.0～3.0 μ L, not shunt mode sample introduction, using helium as carrier gas, flow rate of carrier gas is 0.8～1.2mL/min, injector temperature is 270～280 DEG C, bushing pipe adopts deactivation bushing pipe, transmission line temperature is 315 DEG C～325 DEG C, ion source temperature 245 DEG C～255 DEG C, the EI adopting 70ev ionizes mode, scan mode is SIM, column oven temperature programming condition is: 95 DEG C～105 DEG C keep 0.8～1.2min → 195 DEG C～205 DEG C, programming rate is 18 DEG C/min～22 DEG C/min；195 DEG C～205 DEG C → 275 DEG C～285 DEG C, programming rate is 2.4 DEG C/min～2.6 DEG C/min；275 DEG C～285 DEG C → 315 DEG C～325 DEG C, programming rate is 4.5 DEG C/min～5.5 DEG C/min, and 315 DEG C～325 DEG C keep 9～11min；
null(5)、Adopt Isotope internal standard dilution standard measure，Namely with testing concentration for abscissa，Determinand peak area is vertical coordinate with corresponding isotopic peak area ratio，Obtain working curve，Thus BDE17 in testing sample in calculating,BDE28,BDE47,BDE66,BDE71,BDE85,BDE99,BDE100,BDE138,BDE153,BDE154,BDE183 and BDE190 and metabolite 5-MeO-BDE47,6-MeO-BDE47,4′-MeO-BDE49,2′-MeO-BDE68,5′-MeO-BDE99,5′-MeO-BDE100,The content of 4 '-MeO-BDE101 and 4 '-MeO-BDE103.
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| CN106248815A (en) * | 2016-07-11 | 2016-12-21 | 环境保护部华南环境科学研究所 | The monomer stabilization carbon isotope analysis method of PBDE in fish body |
| CN110068634B (en) * | 2019-06-06 | 2020-07-17 | 华东师范大学 | Method for detecting twelve polybrominated diphenyl ethers in soil |
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