CN109061025A - The detection method of brominated flame retardant agent content in a kind of food - Google Patents
The detection method of brominated flame retardant agent content in a kind of food Download PDFInfo
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Abstract
The present invention relates to a kind of detection methods of brominated flame retardant agent content in food, and food is carried out microwave auxiliary extraction, supernatant is collected by centrifugation, and the supernatant is concentrated to get extracting solution；By the extracting solution by combined column, elutes and collect eluent；Using 8~15m of column length, 0.1~0.25mm of internal diameter, 0.10~0.25 μm of liquid film thickness of capillary column, the eluent is detected in conjunction with GC-NCI-MS choice ion pattern (SIM), the quantitative content for calculating the brominated flame-retardant is carried out using external standard method.For the present invention compared with previous method, it is simple, quick, accurate and efficient to have the characteristics that, the test result of the minimum detection of sample danger, the rate of recovery and repeatability is all satisfied the detection of a variety of BFRs residual quantities in the food such as birds, beasts and eggs.
Description
Technical field
The invention belongs to analytical chemistry, field of food safety, and in particular to the inspection of brominated flame retardant agent content in a kind of food
Survey method.
Background technique
Brominated flame-retardant (Brominated flame retardants, BFRs) is a kind of brominated organic fire-retardant, due to
The advantages that its additive amount is small, good flame retardation effect is widely used in electronic apparatus, plastics, foam, furniture, decoration and fibre
Deng.Polybrominated diphenyl ethers (PBDEs) is a kind of common addition type brominated flame-retardant, and common business product mainly have pentabromo- Biphenyl Ether
(penta-BDE), octa-BDE (octa-BDE) and decabromodiphenyl oxide (deca-BDE).Since PBDEs is lasting in the environment
Property, bioconcentration and possible bio-toxicity or even carcinogenicity, European Union and North America pentabromo- Biphenyl Ether, octa-BDE and
Decabromodiphenyl oxide business product are disabled, and China disables decabromodiphenyl oxide in January, 2018.In order to meet fire prevention and safety rule
Fixed, the substitute by decabromodiphenyl oxide ethane (DBDPE) as deca-BDE is to have relatively by force since their structures are similar
Lipophilic hydrophobicity, be easy to rich product in the high animal tissue of fat content or organ.As people are to animal-derived food demand
The increase of amount has the more detection technique for being reported in PBDEs residual quantity in the biological samples such as the flesh of fish, aquatic products in the past 10 years
And method.
Such as number of patent application discloses quantitative analysis aquatic products decabromodiphenylethane gas phase color for 201610974088.6
The method of spectrum and mass spectrometry, is with soxhlet extraction and the compound column purification United Technologies of gel permeation chromatography-aluminium oxide-silica gel
Aquatic products are handled, the crushing of one, sample drying is specifically included；Two, 250ml acetone and n-hexane (volume ratio 1:1) mixed liquor is added
Soxhlet extraction 48h, three, gel permeation chromatographic column purification；Four, aluminium oxide-silica gel composite chromatography column purification；Five, instrument analysis is molten
Agent constant volume, after film filters, GC-NCI-MS quantitative analysis.The invention sample extraction is high-efficient, but this method extraction time is long,
Increase the risk that DBDPE and BDE209 grade height bromo-derivative is decomposed.In October, 2011, marine environment science disclosed " ocean
The analysis method of polybrominated diphenyl ethers and polybrominated biphenyls in biological sample ", using ultrasonic extraction, extracting solution is through acidic silica gel, neutrality
Silica gel column chromatography column purification combine Gas Chromatography-Negative ionization the various fishes of cosmogony (NCI)/analytical reagent composition and shellfish in BDE-47,
Totally 5 kinds of polybrominated biphenyls (ether) remain by BDE-99, BDE-100, BDE-153 and BDE154, but not to high bromo BDE209 and DBDPE
It is analyzed.Above method time for sample pretreatment is long in a word or extraction is not thorough.Microwave auxiliary extraction be it is a kind of it is time saving,
Save the abstraction technique of solvent, automatic operation.Microwave auxiliary extraction has been widely used for the solid matrixs such as soil or deposit
The extraction of middle polybrominated diphenyl ethers, but it is less for the research report of the remaining microwave abstracting of PBDEs in the food such as Poultry and Eggs, therefore
The measuring method established in this respect is significant.
Larger to baseline interference in addition, contain higher protein and fat in birds, beasts and eggs, needing after purified treatment could be into
Instrument analysis, traditional purification method have the concentrated sulfuric acid to remove fat and gel permeation chromatographic column, Solid Phase Extraction column purification United Technologies,
The method fat removal amount is big, but extract, filter and conversion solvent with needing more multistep, increases the loss and experiment of object
Intensity.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide brominated flame-retardant in a kind of food
The detection limit of the detection method of content, the detection method improves, and the working strength of experimenter reduces.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
The detection method of brominated flame retardant agent content, includes the following steps: in a kind of food
(1) food is subjected to microwave auxiliary extraction, supernatant is collected by centrifugation, the supernatant is concentrated to get extraction
Liquid；
(2) extracting solution is eluted by combined column and collects eluent；
(3) 8~15m of column length, 0.1~0.25mm of internal diameter, 0.10~0.25 μm of liquid film thickness of capillary column are used, in conjunction with
GC-NCI-MS choice ion pattern detects the eluent, carries out bromo described in quantitative calculate using external standard method
The content of fire retardant.
Often generally there are the source EI and NCI with gas chromatograph-mass spectrometer about polybrominated diphenyl ethers and decabromodiphenylethane detecting instrument at present
Two kinds of source ion source, but the source NCI has higher sensitivity, can satisfy some food and vegetables etc. for the source EI
The detection of trace level in sample.Common short column length, the chromatographic column of film thickness, can effectively prevent the degradation of high-molecular compound.
A specific embodiment of the invention is utilized 15m long, 0.25mm internal diameter, the high temperature capillary column (DB-5HT) of 0.10 μm of film thickness,
Analysis time is effectively reduced, total run time is no more than 30min.
Preferably, in step (1), first the food is freeze-dried, is then ground to powder, then is carried out described
Microwave auxiliary extraction.
In the present invention, the food includes birds, beasts and eggs, salted egg, spiced egg or lime-preserved egg.
When the food is birds, beasts and eggs, birds, beasts and eggs surface is cleaned, is dried, decladding mixes yolk and egg white, first-
It is frozen into solid at 15~-25 DEG C, is subsequently placed in freeze dryer, 20~30h of vacuum freeze drying at -50~-55 DEG C, grinding
At powder, then carry out the microwave auxiliary extraction；Alternatively, accurately weighing the sample after freeze-drying, anhydrous sodium sulfate is added,
It is fully ground into powdered microwave auxiliary extraction described in carrying out.
Preferably, in step (1), the sample after the powder for taking 1~2g food to be ground into or 1~2g freeze-drying is carried out
The microwave auxiliary extraction.
Preferably, in step (1), when carrying out the microwave auxiliary extraction, the extractant used is described for organic solvent
Extractant addition volume be microwave abstracting pipe volume 0.2~0.35, Extracting temperature be 100~110 DEG C.
It is further preferred that the extractant be n-hexane and acetone that volume ratio is 1:0.85~1.25 mixing it is molten
Agent or volume ratio are the n-hexane of 1:1.25~1.75 and the mixed solvent of methylene chloride.
It is further preferred that the volume of the microwave abstracting pipe is 60~150mL.
The present invention by the optimization of extractant type, the volume of extractant, Extracting temperature to microwave auxiliary extraction so that
The preferable rate of recovery is obtained to a variety of brominated flame-retardants.
Preferably, in step (1), supernatant is collected by centrifugation, the supernatant is concentrated to get to the specific side of extracting solution
Method are as follows: 5~10min is centrifuged using 3500~4000rpm, supernatant is shifted, to avoid being adhered on microwave abstracting inside pipe wall
Residual is added n-hexane and rinses microwave abstracting inside pipe wall, and 3500~4000rpm is centrifuged 5~10min, merges supernatant, by supernatant
Liquid is concentrated into dry to the greatest extent with Rotary Evaporators, obtains the extracting solution with n-hexane weight is molten.
It is further preferred that 5~10mL n-hexane, which is added, rinses microwave abstracting inside pipe wall.
It is further preferred that molten with 1.0~2.0mL n-hexane weight.
Preferably, in step (2), absorbent cotton or mineral wool, neutrality have been sequentially filled in the combined column from bottom to top
Aluminium oxide, neutral silica gel, acidic silica gel, alkaline silica gel and anhydrous sodium sulfate, wherein the neutral alumina, it is described in
Property silica gel, the acidic silica gel, the alkaline silica gel and the anhydrous sodium sulfate filling mass ratio be 1:0.9~
1.1:1~2.5:0.9~1.1:0.4~0.6.
The present invention is using aluminium oxide-silica gel composite chromatography column purification technical tie-up microwave-assisted extraction technique as PBDEs in birds, beasts and eggs
With the pre-treatment of DBDPE retention analysis, extracting solution low flow velocity loading comes into full contact with extracting solution with granular materials by the present invention,
The pollutants such as fat and macromolecular compound are effectively removed, overcome the concentrated sulfuric acid except the tedious steps of fat and commercialization pillar are net
Change halfway problem, overcomes dispersion, the hardly possible recycling volume problem of dispersed solid phase adsorbent material.This method is for trace amounts of bromine in birds, beasts and eggs
For the detection limit requirement that the preferable rate of recovery and satisfaction detection in fire retardant residue detection, can be obtained.
It is further preferred that the acidic silica gel is prepared by the neutral silica gel that mass ratio is 1:0.7~0.9 and the concentrated sulfuric acid
It forms.
It is further preferred that the alkaline silica gel by mass ratio be 1:0.4~0.5 neutral silica gel and 0.4~
0.6mol/L potassium hydroxide methanol solution after mixing evenly, is made after methanol volatilization is dry.
It is further preferred that increasing and decreasing acidic silica gel dosage according to fat content height in extracting solution, when fatty in extracting solution
When content is high, increase acidic silica gel dosage.
It is further preferred that the filling mass ratio of the absorbent cotton or mineral wool, the neutral alumina is 0.25
~0.75:1.
Preferably, the concrete operation method of step (2) are as follows: successively with methylene chloride and n-hexane to the combined column into
Row activation, it is molten with the mixing of n-hexane and methylene chloride that volume ratio is 1:0.9~1.1 then by the extracting solution loading
Agent elutes object with the flow velocity of 1~2ml/min and is collected in test tube, and nitrogen is blown to dry, is uniformly mixed so as to obtain institute with isooctane dissolution
The eluent stated.
It is further preferred that successively being lived with 8~12mL methylene chloride and 8~12mL n-hexane to the combined column
Change.
It is further preferred that the applied sample amount of the extracting solution is 1~2mL.
It is further preferred that the usage amount of the mixed solvent is 30~50mL.
It is further preferred that the usage amount of the isooctane is 90~110 μ L.
Preferably, in step (3), using Splitless injecting samples, 1.0 μ L of sample volume；Flow: 1.0~1.5mL min-1；Sample introduction
Mouth temperature is 280 DEG C；Temperature programming: 100 DEG C of initial temperature, 1min is kept, with 30 DEG C of min-1240 DEG C are warming up to, is kept
1min, then with 5 DEG C of min-1300 DEG C are warming up to, 10min is kept.
Preferably, in step (3), reaction gas is methane gas；Select ion scan mode；1100~1300v of EM voltage；
Ion source pressure is 2.04 × 10-4Torr；280~300 DEG C of interface temperature；Level four bars and ion source temperature are 150 DEG C.
It is further preferred that carrier gas is helium in step (3).
It is further preferable that purity >=99.999% of helium.
Preferably, the brominated flame-retardant includes BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-
154, BDE-183, BDE-203, BDE-206, BDE-207, BDE-208, BDE-209, DBDPE, polybrominated diphenyl ethers homologue
One of or it is a variety of.
Further, the present invention can it is convenient, fast, accurately and efficiently simultaneously detect BDE-28, BDE-47, BDE-99,
BDE-100、BDE-153、BDE-154、BDE-183、BDE-203、BDE-206、BDE-207、BDE-208、BDE-209、DBDPE
Deng the residual of 13 kinds of brominated flame-retardants, reliable, quick detection method is provided with food safety Regulation for human diet is exposed.
It is further preferred that BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183,
The scanning ion or quota ion mass-to-charge ratio (m/z) of BDE-203, BDE-206, BDE-207, BDE-208, DBDPE are 78.9 Hes
80.9；The scanning ion or quota ion mass-to-charge ratio (m/z) of BDE-209 is 78.9,80.9,486.4 and 488.4,13C-BDE-
209 scanning ion or quota ion mass-to-charge ratio (m/z) is 494 and 496.
The residual of BFRs is in trace level (only several pg/g) in birds, beasts and eggs, in order to eliminate experimental ware and use drug
Deng interference, processing to vessel used in experimentation and drug operates as follows:
After all glasswares of experimentation wash, it is residual that potential organic matter is eliminated through 450 DEG C of baking 12h of Muffle furnace
It stays, uses acetone and eluent methylene chloride using preceding.Acetone, methylene chloride and n-hexane are successively cleaned by ultrasonic before and after use.
Before neutral alumina (100~200 mesh), neutral silica gel (80~100 mesh), anhydrous sodium sulfate use, dichloro is used
Methane extracts 48h, after drying for 24 hours respectively at 180 DEG C, 140 DEG C and 450 DEG C bakings.After being cooled to room temperature, 56g is taken to toast silicon
The 44g concentrated sulfuric acid is added in glue, stirs 1.0h, is made into acidic silica gel until mixing, is packed into reagent bottle of the brown with ground lid, is put into dry
It can be used after standing 6h in dry device.It takes 70g to toast silica gel, 30g 0.5mol/L potassium hydroxide methanol solution is added, stirs evenly,
Stablize for 24 hours after methanol volatilization is dry, it is spare to be made into alkaline silica gel.
Due to the implementation of above-mentioned technical proposal, the invention has the following advantages over the prior art:
For the present invention compared with previous method, it is simple, quick, accurate and efficient to have the characteristics that, the minimum detection of sample
The test result of danger, the rate of recovery and repeatability is all satisfied the detection of a variety of BFRs residual quantities in the food such as birds, beasts and eggs.
The present invention use microwave radiation exaraction, overcome traditional soxhlet type solvent usage greatly and ultrasonic extraction time
The not high problem of yield, the microwave auxiliary extraction under certain temperature and pressure mention so that solvent contacts more abundant with matrix
High extraction efficiency, reduces analysis time.
The present invention use Gas Chromatography-Negative chemical source-mass spectrometric Salbutamol Selected Ion Monitoring mode, overcome electron bombardment from
The low problem of component sensitivity, improves the detection limit of method.
Detailed description of the invention
Fig. 1 is the total ion current figure of 13 kinds of brominated flame-retardants, Detailed description of the invention 1:BDE28；2:BDE 47；3:BDE100；4:
BDE99；5:BDE154；6:BDE153；7:BDE183；8:BDE203；9:BDE208；10:BDE207；11:BDE206；12:
BDE209；13:DBDPE；The concentration of 1-7 is 2 μ g/L；The concentration of 8-11 is 10 μ g/L；BDE209 is 20 μ g/L；DBDPE is 100
μg/L。
Fig. 2 is Chromatographic Comparison's figure that the acidic silica gel in embodiment 3 using different quality is purified, wherein (A) is acid
Property silica gel dosage be 2g；It (B) be acidic silica gel dosage is 5g.
The rate of recovery effect picture of the lower 13 kinds of objects of Fig. 3 variety classes extractant.
The rate of recovery effect picture of the lower 13 kinds of objects of Fig. 4 difference extractant volume.
The rate of recovery effect picture of 13 kinds of objects at a temperature of Fig. 5 difference microwave abstracting.
Specific embodiment
Technical solution of the present invention is further described using specific embodiment below.
Neutral alumina, neutral silica gel, anhydrous sodium sulfate, acidic silica gel, alkaline silica gel in following embodiments is using such as
Lower method handles to obtain:
Neutral alumina (100~200 mesh), neutral silica gel (80~100 mesh), anhydrous sodium sulfate are extracted with methylene chloride
48h, after drying for 24 hours respectively at 180 DEG C, 140 DEG C and 450 DEG C bakings.After being cooled to room temperature, takes 56g to toast silica gel and 44g is added
The concentrated sulfuric acid stirs 1.0h, is made into acidic silica gel until mixing, is packed into reagent bottle of the brown with ground lid, is put into quiet in drier
It sets spare after 6h.It takes 70g to toast silica gel, 30g 0.5mol/L potassium hydroxide methanol solution is added, stirs evenly, methanol volatilization
Stablize for 24 hours after dry, it is spare to be made into alkaline silica gel.
Embodiment 1
The present embodiment has carried out GC-NCI-MS analysis to 13 kinds of brominated flame-retardants emphatically, it is ensured that the accuracy of qualitative, quantitative.
Step 1: mark, BDE-203, BDE- are mixed with from the PBDE8 of lark prestige scientific & technical corporation purchase model BDE-CSM
206, it is (low to be configured to PBDEs using chromatographic grade isooctane by the mono- mark of BDE-207, BDE-208 and DBDPE, concentration 1000mg/L
Bromo BDE:BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183) standard working curve concentration
For 0.5,1.0,5.0,10.0 and 50.0 μ g/L, high bromo-BDE (BDE-203, BDE-206, BDE-207, BDE-208) standard
Working curve concentration is that 1.0,5.0,10.0,50.0 and 100.0 μ g/L, BDE209 and DBDPE standard working curve concentration are
5.0, the hybrid standard working solution of 10.0,50.0,100.0 and 500.0 μ g/L.
Step 2: setting gas chromatography-mass spectrum condition: selection DB-5HT capillary chromatographic column (15m × 0.25mm i.d.,
0.10 μm, Agilent company)；Splitless injecting samples, 1.0 μ L of sample volume；Flow: 1.0mL min-1；Injector temperature is 280 DEG C；
Temperature programming: 100 DEG C of initial temperature, 1min is kept, with 30 DEG C of min-1240 DEG C are warming up to, keeps 1min, then with 5 DEG C of min-1It rises
Temperature keeps 10min to 300 DEG C；28.67min is run altogether.Reaction gas is high-purity methane gas；High-purity helium (>=99.999%)
For carrier gas, solvent delay 5min, NCI level four bars and ion source temperature are 150 DEG C, and 280 DEG C of interface temperature；EM voltage 1200v；
Ion source pressure is 2.04 × 10-4Torr；Ion scan mode is selection ion scan (SIM)；BDE-28,BDE-47,BDE-
99, BDE-100, BDE-153, BDE-154, BDE-183, BDE-203, BDE-206, BDE-207, BDE-208 and DBDPE are scanned
Ion or quota ion mass-to-charge ratio m/z are 78.9 and 80.9, and the m/z of BDE-209 is 78.9,80.9,486.4 and 488.4,13C-
BDE-209 is 494/496.
Step 3: qualitative and quantitative analysis is carried out according to retention time and peak area.As shown in Figure 1, to 13 kinds in 28.6min
Polybrominated diphenyl ethers can be kept completely separate, and signal sensitivity is high, and peak shape is preferable.
Step 4: using the concentration of object as abscissa X, corresponding quota ion peak area is ordinate Y, is linearly returned
Return analysis.It the results are shown in Table 1, all objects have good linear relationship, phase under corresponding concentration between concentration and response
Relationship number (r) is not less than 0.99, meets the requirement of quantitative analysis.
Retention time, the range of linearity, regression equation and the correlation coefficient r of 1 object of table
| Object | Retention time/min | The range of linearity/μ g/L | Equation of linear regression | Related coefficient |
| BDE-28 | 10.46 | 0.5~50 | Y=856.7x-280.3 | 0.9998 |
| BDE-47 | 12.97 | 0.5~50 | Y=748.9x-348.2 | 0.9996 |
| BDE-100 | 14.78 | 0.5~50 | Y=761x-335.4 | 0.9996 |
| BDE-99 | 15.30 | 0.5~50 | Y=670.5x-310.8 | 0.9996 |
| BDE-154 | 16.73 | 0.5~50 | Y=589.9x-338.6 | 0.9987 |
| BDE-153 | 17.53 | 0.5~50 | Y=556.2x-333.4 | 0.9994 |
| BDE-183 | 19.41 | 0.5~50 | Y=319.8x-166.0 | 0.9993 |
| BDE-203 | 21.82 | 1-100 | Y=223.4x-1467 | 0.9954 |
| BDE-208 | 23.86 | 1~100 | Y=16.13x-50.91 | 0.9993 |
| BDE-207 | 23.98 | 1~100 | Y=26.66x-918.7 | 0.9963 |
| BDE-206 | 24.48 | 1~100 | Y=26.58x-195.1 | 0.9951 |
| BDE-209 | 26.79 | 50~5000 | Y=411.1x-584.6 | 0.9970 |
| DBDPE | 28.02 | 50~5000 | Y=11.49x-879.9 | 0.9978 |
Embodiment 2:
The present embodiment focuses on the microwave auxiliary extraction of 13 kinds of brominated flame-retardants in birds, beasts and eggs, and to the item of microwave auxiliary extraction
Part optimizes.
Step 1: egg surface being cleaned, is dried, decladding, and yolk and egg white are mixed, and is first frozen at -20 DEG C solid
Body is subsequently placed in freeze dryer, and for 24 hours, 1.0g eggs sample is added 5.0g to vacuum freeze drying by grind into powder at -55 DEG C
Anhydrous sodium sulfate mixes, and is completely transferred to 100ml polytetrafluoroethylene (PTFE) extraction tube, adds 13 kinds of determinand standard samples (50ng/g),
Concussion mixes, and balances 3h.
Step 2: it is mixed that 30ml n-hexane/acetone (1/1, v/v) is added into the polytetrafluoroethylene (PTFE) extraction tube of step 1 respectively
Close liquid, n-hexane: acetone (volume ratio, 2:3) mixed liquor, n-hexane: acetone (volume ratio, 3:2) mixed liquor, n-hexane: dichloro
Methane (volume ratio, 2:3) mixed liquor and n-hexane: water (volume ratio, 2:3) mixed liquor, it is cooling in 110 DEG C of Microwave Extraction 20min
To room temperature, 4000rpm is centrifuged 5min, shifts supernatant, is rinsed with 5ml n-hexane and extracts inside pipe wall, and 4000rpm is centrifuged 5min,
Merge supernatant, be concentrated to dryness with Rotary Evaporators, with molten, the subsequent purification of 1.5ml n-hexane weight.
Step 3: respectively into the polytetrafluoroethylene (PTFE) extraction tube of step 1 be added 30ml, 10ml, 20ml and 40ml just oneself
Alkane/acetone (1/1, v/v) mixed liquor is cooled to room temperature in 110 DEG C of Microwave Extraction 20min, 4000rpm centrifugation 5min, in transfer
Clear liquid is rinsed with 5ml n-hexane and extracts inside pipe wall, and 4000rpm is centrifuged 5min, is merged supernatant, is concentrated into Rotary Evaporators
It is dry, with molten, the subsequent purification of 1.5ml n-hexane weight.
Step 4: 30ml n-hexane/acetone (1/1, v/v) mixing is added into the polytetrafluoroethylene (PTFE) extraction tube of step 1
Liquid is cooled to room temperature respectively at 110 DEG C, 80 DEG C, 90 DEG C, 100 DEG C and 120 DEG C Microwave Extraction 20min, 4000rpm centrifugation
5min shifts supernatant, is rinsed with 5ml n-hexane and extracts inside pipe wall, and 4000rpm is centrifuged 5min, merges supernatant, is steamed with rotation
Hair instrument is concentrated to dryness, with molten, the subsequent purification of 1.5ml n-hexane weight.
Step 5: respectively will be Step 2: Step 3: the extract liquor of step 4 is centrifuged 5min, transfer supernatant using 4000rpm
Liquid is added 5mL n-hexane and rinses microwave abstracting inside pipe wall, 4000rpm to avoid the residual being adhered on microwave abstracting inside pipe wall
Be centrifuged 5min, merge supernatant, supernatant is concentrated into Rotary Evaporators it is dry to the greatest extent, it is molten with 1.0mL n-hexane weight, it is subsequent net
Change.
Step 6: it is sequentially filled 1g absorbent cotton or glass from bottom to top in the glass chromatography column (10mm i.d.) of 100mm long
Glass cotton, 2g neutral alumina, 2g neutral silica gel, 2g acidic silica gel, 2g alkaline silica gel and 1g anhydrous sodium sulfate.Successively use 10ml bis-
Chloromethanes and the activation of 10ml n-hexane, extracting solution (about 1.5ml) loading that step 5 is handled, with 30ml n-hexane/dichloro
Methane (1:1v/v) elutes object with the flow velocity of 1.0ml/min and is collected in test tube, nitrogen evaporator nitrogen be blown to it is dry, with 100 μ L
Isooctane constant volume adds interpolation pipe, bottles to be analyzed.
The above microwave abstracting optimum results are shown in Fig. 3-Fig. 5, wherein Fig. 3 is step 2 treated result figure；Fig. 4 is step
Rapid three treated result figures；Fig. 5 is step 4 treated result figure.N-hexane: methylene chloride also has higher recovery,
But it considers the toxicity of methylene chloride, selects n-hexane and acetone (volume ratio 1:1) mixed liquor；Volume is extracted as 40mL microwave extraction
During taking, high temperature and high pressure can allow extract liquor to have liquid to be changed into gaseous state, and remaining space is less, can make gas in extracting tube
It presses through greatly, causes to reveal, therefore select 30mL for optimum；Extraction temperature some high bromo-BDEs generating units when being 120 DEG C
Divide degradation, therefore selects at 110 DEG C to be best extraction temperature.
Embodiment 3
The present embodiment focuses on 13 kinds of brominated flame-retardant pretreatment technologies in birds, beasts and eggs, is selected according to actual sample fat content
The ratio of acidic silica gel.Since the fat content of duck's egg is relatively higher than egg, clean-up effect is improved, increases acidic silica gel dosage.
Step 1: from man of certain electronics dismantling concentration zones peasant household, domestic duck's egg is bought, laboratory is taken back after being put into ice chest, goes
Eggshell is put into stainless steel bowl and is stirred evenly albumen and yolk with glass bar, and -20 DEG C are frozen into solid-state, are freezed using freeze dryer
It is dry, 2.0g sample is accurately weighed, appropriate anhydrous sodium sulfate is added, grinding is uniform.It is transferred to microwave abstracting pipe completely, is adding 30ml just
Hexane/acetone (50/50, v/v) mixed liquor is cooled to room temperature in 110 DEG C of microwave abstracting 20min, is centrifuged in 4000r/min
5min, supernatant are transferred to 250ml round-bottomed flask, 35 ± 2 DEG C at a temperature of rotary evaporation to 1.0ml.
Step 2: by 1g absorbent cotton, 2g neutral alumina, 2g neutral silica gel, 5g acidic silica gel, 2g alkaline silica gel and 1g without
Aqueous sodium persulfate is successively activated with 10ml methylene chloride and 10ml n-hexane according to sequentially installing from bottom to up.It is flowed with 0.5ml/min
Fast loading is eluted with 30ml n-hexane/methylene chloride (50/50, v/v), collects eluent, at a temperature of 35 ± 2 DEG C, nitrogen is blown
It is extremely dry.Add internal standard, with 100 μ l isooctane constant volumes, crosses 0.22 μm of filter membrane.
Step 3: absorbent cotton, 2g neutral alumina, 2g neutral silica gel, 2g acidic silica gel, 2g alkaline silica gel and 1g is anhydrous
Sodium sulphate is successively activated with 10ml methylene chloride and 10ml n-hexane according to sequentially installing from bottom to up.With 0.5ml/min flow velocity
Loading.With 30ml n-hexane/methylene chloride (volume ratio 1:1) mixed liquor elution, eluent is collected, at a temperature of 35 ± 2 DEG C,
Nitrogen is blown to dry.The concussion dissolution of 100 μ l isooctane is added, crosses 0.22 μm of organic filter membrane, adds sample internal standard.
Fig. 2 is seen using 2.0g (A) and the purified chromatogram of 5.0g (B) acidic silica gel.
Embodiment 4
The present embodiment focuses on the accuracy and precision of this method.
Step 1: buying fresh grass egg from certain food market, is put into ice chest and takes back laboratory, decladding, by yolk and albumen
It mixes, -20 DEG C are frozen into solid-state, are freeze-dried using freeze dryer, after sample grinding uniformly, utilize n-hexane and acetone mixture
(volume ratio 1:1) repeatedly extracts egg sample, until detecting in extracting solution without object, egg sample conduct at this time
Bare substrate (is not detected, residual quantity is respectively less than LOD).
Step 2: be added 7 kinds of low bromine PBDEs (BD-28, BDE-47, BDE-100, BDE-99, BDE-154, BDE-153 and
BDE-183) concentration is respectively 50,100 and 200ng/g；Bromine PBDEs (BDE-203, BDE-208, BDE-207, BDE- 4 kinds high
206) concentration is respectively 100,200 and 400ng/g；The concentration of BDE-209 and DBDPE is respectively 500,1000 and 2000ng/g
(every gram of egg (dry weight)) balances 3h, does matrix recovery testu, every group is done 6 times in parallel.
Step 3: subsequent step is analyzed according to embodiment 1 and 2 optimal conditions of embodiment.
Measured value, recovery of standard addition, standard deviation and the detection limit of blank sample are shown in Table 2, have in blank sample a small amount of
BDE-47, BDE-99 and BDE-209 detection, but its content is below 3%, PBDEs and the DBDPE average recovery rate of sample and exists
Between 84.3%~121.5% and between 72.8%~86.8%.It is measured in parallel 6 times, the relative standard deviation of object
(RSD) it is respectively less than 20%.Method quantitative limit MLOQ be defined as target peak signal and 10 times of noise ratio, this is that signal is corresponding
Cmin, method detection limit MLOD are defined as corresponding concentration when 3 times of signal-to-noise ratio.
With dry weight 1.0g eggs sample in the present invention, 100 μ L of constant volume meter calculates the method detection limit of object.12
The method detection limit of kind PBDEs and DBDPE is between 0.01~0.38ng/g.The rate of recovery of objectives compound, opposite mark
Quasi- deviation and detection limit are shown in Table 2.
Recovery of standard addition, standard deviation and the detection limit (n=6) of 2 object of table
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this
The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, and the present invention is not limited to above-mentioned implementations
, equivalent change or modification made by all Spirit Essences according to the present invention should be covered by the protection scope of the present invention.
Claims (10)
1. the detection method of brominated flame retardant agent content in a kind of food, characterized by the following steps:
(1) food is subjected to microwave auxiliary extraction, supernatant is collected by centrifugation, the supernatant is concentrated to get extracting solution；
(2) extracting solution is eluted by combined column and collects eluent；
(3) 8~15m of column length, 0.1~0.25mm of internal diameter, 0.10~0.25 μm of liquid film thickness of capillary column are used, in conjunction with GC-
NCI-MS choice ion pattern detects the eluent, carries out brominated flame retardant described in quantitative calculate using external standard method
The content of agent.
2. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (1),
First the food is freeze-dried, is then ground to powder, then carries out the microwave auxiliary extraction.
3. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (1),
When carrying out the microwave auxiliary extraction, for the extractant used for organic solvent, the addition volume of the extractant is microwave
The 0.2~0.35 of pipe volume is extracted, Extracting temperature is 100~110 DEG C.
4. the detection method of brominated flame retardant agent content in food according to claim 3, it is characterised in that: the extraction
Agent be the n-hexane that volume ratio is 1:0.85~1.25 and acetone mixed solvent or volume ratio be 1:1.25~1.75 just
The mixed solvent of hexane and methylene chloride.
5. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (1),
Supernatant is collected by centrifugation, the supernatant is concentrated to get extracting solution method particularly includes: is centrifuged using 3500~4000rpm
5~10min shifts supernatant, and n-hexane is added and rinses microwave abstracting inside pipe wall, and 3500~4000rpm is centrifuged 5~10min, closes
And supernatant, supernatant is concentrated into Rotary Evaporators dry to the greatest extent, obtains the extracting solution with n-hexane weight is molten.
6. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (2),
Be sequentially filled from bottom to top in the combined column absorbent cotton or mineral wool, neutral alumina, neutral silica gel, acidic silica gel,
Alkaline silica gel and anhydrous sodium sulfate, wherein the neutral alumina, the neutral silica gel, the acidic silica gel, described
Alkaline silica gel and the anhydrous sodium sulfate filling mass ratio be 1:0.9~1.1:1~2.5:0.9~1.1:0.4~
0.6。
7. the detection method of brominated flame retardant agent content in food according to claim 1 or 6, it is characterised in that: step (2)
Concrete operation method are as follows: successively the combined column is activated with methylene chloride and n-hexane, then mentions described
Liquid loading is taken, is washed with the mixed solvent of n-hexane and methylene chloride that volume ratio is 1:0.9~1.1 with the flow velocity of 1~2ml/min
De- object is simultaneously collected in test tube, and nitrogen is blown to dry, is uniformly mixed so as to obtain the eluent with isooctane dissolution.
8. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (3),
Using Splitless injecting samples, 1.0 μ L of sample volume；Flow: 1.0~1.5mL min-1；Injector temperature is 280 DEG C；Temperature programming: just
100 DEG C of beginning temperature, 1min is kept, with 30 DEG C of min-1240 DEG C are warming up to, keeps 1min, then with 5 DEG C of min-1300 DEG C are warming up to,
Keep 10min.
9. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: in step (3),
Reaction gas is methane gas；Select ion scan mode；1100~1300v of EM voltage；Ion source pressure is 2.04 × 10- 4Torr；280~300 DEG C of interface temperature；Level four bars and ion source temperature are 150 DEG C.
10. the detection method of brominated flame retardant agent content in food according to claim 1, it is characterised in that: the food
Product include birds, beasts and eggs, salted egg, spiced egg or lime-preserved egg；The brominated flame-retardant includes BDE-28, BDE-47, BDE-99, BDE-
100, BDE-153, BDE-154, BDE-183, BDE-203, BDE-206, BDE-207, BDE-208, BDE-209, DBDPE, more
One of homologue of bromo biphenyl ether is a variety of；Wherein, BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-
154, the scanning ion of BDE-183, BDE-203, BDE-206, BDE-207, BDE-208, DBDPE or quota ion mass-to-charge ratio are
78.9 with 80.9；The scanning ion or quota ion mass-to-charge ratio of BDE-209 is 78.9,80.9,486.4 and 488.4,13C-BDE-
209 scanning ion or quota ion mass-to-charge ratio is 494 and 496.
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