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Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products - Gas chromatography and mass spectrometry
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Basic data
| Standard ID | GB/T 37639-2019 (GB/T37639-2019) |
| Description (Translated English) | Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products - Gas chromatography and mass spectrometry |
| Sector / Industry | National Standard (Recommended) |
| Classification of Chinese Standard | G31 |
| Classification of International Standard | 83.080 |
| Word Count Estimation | 10,189 |
| Date of Issue | 2019-06-04 |
| Date of Implementation | 2020-01-01 |
| Issuing agency(ies) | State Administration for Market Regulation, China National Standardization Administration |
GB/T 37639-2019: Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products - Gas chromatography and mass spectrometry
---This is a DRAFT version for illustration, not a final translation. Full copy of true-PDF in English version (including equations, symbols, images, flow-chart, tables, and figures etc.) will be manually/carefully translated upon your order.
(Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastics-Gas chromatography-mass spectrometry)
ICS 83.080
G31
National Standards of People's Republic of China
Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products
Gas chromatography-mass spectrometry
2019-06-04 release
2020-01-01 implementation
State Administration of Market Supervision
Published by China National Standardization Administration
Contents
Foreword I
1 Scope 1
2 Normative references 1
3 Principle 1
4 Reagents and materials 1
5 Instruments and equipment 2
6 Sample preparation 2
7 Analysis step 2
8 Detection limit 4
9 Precision 4
10 Recovery rate 4
11 Test report 4
Appendix A (informative) Total ion chromatographic separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB) Figure 5
Appendix B (informative) Separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB) by selective ion chromatography
Appendix C (Informative) Qualitative and quantitative selective ions of PBDEs and PBDE compounds 7
Foreword
This standard was drafted in accordance with the rules given in GB/T 1.1-2009.
This standard was proposed by the China Light Industry Federation.
This standard is under the jurisdiction of the National Plastics Standardization Technical Committee (SAC/TC48).
This standard was drafted. Beijing Technology and Business University, Suzhou Runjia Engineering Plastics Co., Ltd., Kunshan Achilles Artificial Leather Co., Ltd.,
Suzhou Aichi Bote Testing Technology Co., Ltd., National Plastic Products Quality Supervision and Inspection Center (Beijing).
The main drafters of this standard. Zhang Min, Hu Jing, Weng Yonghua, Zhao Jianming, Wang Weixin, Chen Qian.
Determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products
Gas chromatography-mass spectrometry
1 Scope
This standard specifies polybrominated biphenyls (PBBs for short, the structural formula is shown in Figure 1) and polybrominated biphenyls in plastic products.
Gas chromatography-mass spectrometry method for diphenyl ethers (polybrominated diphenylethers, PBDEs, see Figure 2).
This standard applies to the determination of polybrominated biphenyls and polybrominated diphenyl ethers in plastic products.
Figure 1 Structure of polybrominated biphenyls
Figure 2 Structure of PBDE
2 Normative references
The following documents are essential for the application of this document. For dated references, only the dated version applies to this article
Pieces. For undated references, the latest version (including all amendments) applies to this document.
GB/T 8170 Numerical rounding rules and expression and judgment of limit values
3 Principle
The sample was extracted with dichloromethane as the solvent, and the extract was purified by a silica gel column. After concentration and volume, the sample was subjected to gas chromatography-mass spectrometry.
Detection.
4 Reagents and materials
4.1 Dichloromethane. chromatographically pure.
4.2 n-hexane. chromatographically pure.
4.3 Liquid nitrogen. industrial grade.
4.4 Polybrominated biphenyls (PBBs) standard solution. The mass concentration is 10 μg/mL.
4.5 Standard solution of polybrominated diphenyl ethers (PBDEs). Mass concentration 5μg/mL.
4.6 Silica gel. particle size 0.063mm ~ 0.200mm, baked at 450 ° C for 24 hours before use, cooled during drying, stored in closed glass
In the bottle.
4.7 Acidified silica gel. prepared by mixing 2.24g of activated silica gel (4.6) with 1.76g of concentrated sulfuric acid.
4.8 toluene-methanol (volume ratio 10. 1).
4.9 Toluene. chromatographically pure.
4.10 Methanol. chromatographically pure.
5 Instruments and equipment
5.1 Gas chromatography-mass spectrometry (GC-MS).
5.2 Soxhlet extraction device.
5.3 Rotary evaporator.
5.4 Crusher.
5.5 Solid phase extraction device.
5.6 Constant temperature water bath (temperature accuracy is less than 1 ℃).
5.7 Analytical balance (accurate to 0.0001g).
5.8 Sealed microwave extraction instrument.
5.9 Ultrasonic Extractor.
5.10 Organic phase filter membrane. 0.45μm filter membrane.
6 Sample preparation
According to the nature of the product, the sample is prepared by cutting, crushing or freezing and pulverizing with liquid nitrogen to obtain particles with a particle size of less than 1 mm.
7 Analysis steps
7.1 Extraction
The extraction methods include the following three methods.
a) Soxhlet extraction method. accurately weigh 0.1g sample (accurate to 1mg) on an analytical balance, put it into a filter paper tube, and add 150mL
Dichloromethane solution, control the temperature of the water bath to 60 ℃ ± 5 ℃, extract at a rate of 2 drops/s ~ 3 drops/s for more than 12h,
After cleaning, for cleaner samples, or slightly turbid, but samples that can be improved by adding methanol, spin the extract with
After the evaporator is concentrated and made up to 100 mL, the analysis is performed directly; for samples with darker colors and more impurities, the extraction solution is used.
After concentrating to a small volume with a rotary evaporator, purify it according to 7.2.
b) Microwave extraction method. accurately weigh 0.5g ~ 2g of crushed sample, accurate to 1mg, put it into the extraction tank, and accurately remove 20mL
Toluene-methanol (see 4.8), sealed in a microwave extraction apparatus (see 5.8), warmed to 115 ° C in 5 minutes, and maintained for 15 minutes
Above, cool to room temperature, completely transfer the extract, and wash the extraction tank with the extraction solvent in stages.
The extract was concentrated to 2mL ~ 3mL by an evaporator, and purified according to 7.2. For extracts that cannot be completely transferred,
In order to verify that the extraction solution is not lost during the extraction process, accurately remove 2 mL of the sample solution and purify it according to 7.2.
c) Ultrasonic extraction method. accurately weigh 0.5g (accurate to 1mg) crushed sample in glass centrifuge, add 5.0mL toluene (see
4.9). After ultrasonic extraction for 30 min, it was filtered into a 5.0 mL volumetric flask and the volume was adjusted with toluene. Pipette 100 μL of sample extract
The mobile phase was made to a constant volume of 1.0 mL, and was measured after filtration through a 0.45 μm filter. This method generally does not require purification.
Excessive, can be purified according to 7.2.
7.2 Purification
The silica gel extraction cartridge was installed on a solid-phase extraction device.First, 15 mL of a 1. 1 mixed solution of n-hexane and dichloromethane was applied to the silica gel.
The column was activated, then the concentrated sample extract was transferred to a silica gel column, and finally mixed with 120 mL of 1. 1 n-hexane and dichloromethane.
The combined solution was eluted. The eluted solution was collected, then concentrated on a rotary evaporator, and the volume was adjusted to 100 mL with the elution solvent.
7.3 GC-MS Conditions
The GC-MS conditions are as follows.
a) Chromatographic column. Quartz capillary column, 15m × 0.25mm (inner diameter) × 0.10μm, or equivalent chromatographic column;
b) Program temperature increase. keep at 100 ℃ for 1min, increase the temperature to 220 ℃ at a rate of 8 ℃/min, hold it for 0.5min, and then at 20 ℃/min
The temperature is raised to 320 ℃ for 5min;
c) Sampling method. pulse splitless, splitless time 2.0min;
d) injection volume. 1 μL;
e) inlet temperature. 280 ℃;
f) Flow rate and mode. 1.8mL/min constant flow mode;
g) Carrier gas. High-purity helium, purity ≥99.9999%;
h) Solvent delay. 1.5min;
i) Quadrupole temperature. 150 ℃;
j) Ion source temperature. 250 ° C;
k) Ionization mode. EI, energy 70eV;
l) Mass range. 100amu ~ 1000amu.
7.4 Determination
Prepare and initialize the gas chromatograph according to the chromatographic conditions in 7.3. After the instrument reaches the set temperature, take 1 μL of standard solutions of different concentrations.
The liquid and the sample test solution for preventive treatment were measured by a gas chromatography-mass spectrometer. Based on retention time and qualitative characteristics of individual compounds
The ions are qualitatively selected, and the peak area of the ions is selected for quantification based on the quantitative characteristics. Total ion current of PBBs and PBDEs mixed standard solution
See Appendix A and Appendix B for chromatograms and selected ion chromatograms. Qualitative and quantitative selective ions for PBBs and PBDEs
Appendix C.
7.5 Blank test
A blank test is performed with the sample.
7.6 Calculation of results
Establish polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) compounds by linear equation (1) or other suitable equations.
Calibrate the curve and determine the corresponding equation parameters a and b. The equation is shown in equation (1).
A = a × wb (1)
Where.
A --- Chromatographic peak area of each compound of polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) in the standard solution;
w --- the content (mass fraction) of each compound of polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) in the standard solution
Milligram per kilogram (mg/kg);
a --- the slope of the calibration curve of each compound in polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE);
b --- Intercept of calibration curve of each compound in polybrominated biphenyl (PB) and polybrominated diphenyl ether (PBDEB).
Calculate the content (mass fraction) of each component in the unknown sample according to formula (2).
wi = [(As-A0-b) × V]/(a × m) (2)
Where.
wi --- the content (mass fraction) of each compound of polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) in the sample, the unit is milligram
Per kilogram (mg/kg);
As --- chromatographic peak area of each compound of polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) in the sample;
A0 --- chromatographic peak area of blank sample;
V --- The final constant volume of the sample, in milliliters (mL);
m --- sample mass in grams (g).
Take the arithmetic mean of two parallel determinations and round down to the whole number according to GB/T 8170 as the measurement result.
8 detection limit
Compounds PBB-9, PBB-10, BDE-183, BDE-198, BDE-206, and BDE-209 have a detection limit of 3.3 pg (absolute injection)
Amount), the detection limit of the remaining compounds was 0.33pg.
9 Precision
In the same laboratory, the same operator uses the same equipment, uses the same test method, and measures the same object in a short time.
The absolute difference between the two independent test results obtained by the tests performed independently of each other is not greater than 10% of the arithmetic mean of the two measured values.
10 Recovery
The recovery rate of the spiked sample should be 80% ~ 120%.
11 Test report
The test report should include the following.
a) the name and number of this standard;
b) a detailed description of the sample;
c) the name of the laboratory, the location where the inspection and/or calibration was performed (if different from the laboratory's address);
d) individual test results and averages;
e) differences from the analysis steps specified in this standard;
f) abnormal phenomena during the test;
g) Test date.
Appendix A
(Informative appendix)
Total ion chromatographic separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB)
The total ion chromatogram of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB) is shown in Figure A.1.
Explanation.
1 --- PBB-1 (2-bromobiphenyl);
2 --- PBB-2 (4,4'-dibromobiphenyl);
3 --- PBB-3 (2,4,6-tribromobiphenyl);
4 --- BDE-028 (2,4,4'-tribromodiphenyl ether);
5 --- PBB-4 (2,2 ', 5,5'-tetrabromobiphenyl);
6 --- PBB-5 (2,2 ', 4,5', 6-pentabromobiphenyl);
7 --- BDE-047 (2,2 ', 4,4'-tetrabromodiphenyl ether);
8 --- BDE-100 (2,2 ', 4,4', 6-pentabromodiphenyl ether);
9 --- BDE-099 (2,2 ', 4,4', 5-pentabromodiphenyl ether);
10 --- PBB-6 (2,2 ', 4,4', 5,5'-hexabromobiphenyl);
11 --- BDE-154 (2,2 ', 4,4', 5,6'-hexabromodiphenyl ether);
12 --- BDE-153 (2,2 ', 4,4', 5,5'-hexabromodiphenyl ether);
13 --- BDE-183 (2,2 ', 3,4,4', 5 ', 6-heptabromodiphenyl ether);
14 --- BDE-198 (2,2 ', 3,3', 4 ', 5,5', 6-octabromodiphenyl ether);
15 --- BPP-9 (2,2 ', 3,3', 4,4 ', 5,5', 6-nonabromobiphenyl);
16 --- BDE-206 (2,2 ', 3,3', 4,4 ', 5,5', 6-nonabromodiphenyl ether);
17 --- PBB-10 (decabromobiphenyl);
18 --- BDE-209 (2,2 ', 3,3', 4,4 ', 5,5', 6,6'-decabromodiphenyl ether).
Figure A.1 Chromatographic separation of total bromine diphenyl ether (PBDE) and polybrominated biphenyl (PBB)
Appendix B
(Informative appendix)
Separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB) by selective ion chromatography
Selective ion chromatographic separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB) is shown in Figure B.1.
Explanation.
1 --- PBB-1 (2-bromobiphenyl);
2 --- PBB-2 (4,4'-dibromobiphenyl);
3 --- PBB-3 (2,4,6-tribromobiphenyl);
4 --- BDE-028 (2,4,4'-tribromodiphenyl ether);
5 --- PBB-4 (2,2 ', 5,5'-tetrabromobiphenyl);
6 --- PBB-5 (2,2 ', 4,5', 6-pentabromobiphenyl);
7 --- BDE-047 (2,2 ', 4,4'-tetrabromodiphenyl ether);
8 --- BDE-100 (2,2 ', 4,4', 6-pentabromodiphenyl ether);
9 --- BDE-099 (2,2 ', 4,4', 5-pentabromodiphenyl ether);
10 --- PBB-6 (2,2 ', 4,4', 5,5'-hexabromobiphenyl);
11 --- BDE-154 (2,2 ', 4,4', 5,6'-hexabromodiphenyl ether);
12 --- BDE-153 (2,2 ', 4,4', 5,5'-hexabromodiphenyl ether);
13 --- BDE-183 (2,2 ', 3,4,4', 5 ', 6-heptabromodiphenyl ether);
14 --- BDE-198 (2,2 ', 3,3', 4 ', 5,5', 6-octabromodiphenyl ether);
15 --- BPP-9 (2,2 ', 3,3', 4,4 ', 5,5', 6-nonabromobiphenyl);
16 --- BDE-206 (2,2 ', 3,3', 4,4 ', 5,5', 6-nonabromodiphenyl ether);
17 --- PBB-10 (decabromobiphenyl);
18 --- BDE-209 (2,2 ', 3,3', 4,4 ', 5,5', 6,6'-decabromodiphenyl ether).
Figure B.1 Selective ion chromatographic separation of polybrominated diphenyl ether (PBDE) and polybrominated biphenyl (PBB)
Appendix C
(Informative appendix)
Qualitative and quantitative selective ions of polybrominated biphenyls and polybrominated diphenyl ether compounds
Qualitative and quantitative selective ions of PBDEs and PBDE compounds are shown in Table C.1.
Table C.1 Qualitative and quantitative selective ions of PBDEs and PBDE compounds
Compound name retention time/min Qualitative characteristic ion Quantitative characteristic ion
PBB-1 3.31 232.0 232.0
PBB-2 7.24 311.9 311.9
PBB-3 7.65 389.8 389.8
PBB-4 10.46 3.9.9/388.8/469.7 469.7
PBB-5 12.26 468.7/547.6 547.6
PBB-6 15.60 467.6/546.5/627.5 627.5
PBB-9 17.49 748.6/863.9 863.9
PBB-10 17.90 623.4/944.3 944.3
BDE-028 9.83 248.0/405.8 405.8
BDE-047 12.29 325.9/485.6 485.6
BDE-099 14.60 403.8/563.6 563.6
BDE-100 14.06 403.8/563.6 563.6
BDE-153 15.91 241.9/483.6/643.5 643.5
BDE-154 15.64 241.9/483.6/643.5 643.5
BDE-183 16.49 281.9/561.5/721.5 721.5
BDE-198 17.09 320.8/641.5/801.7 801.7
BDE-206 17.75 360.7/719.5/880.0 880.0
BDE-209 18.51 399.7/799.7/960.5 960.5
...
