GB/T 29493.1-2013 English PDF (GBT29493.1-2013)

This Part of GB/T 29493 specifies using the gas chromatography-mass spectrometry (GC/MS) method for the determination of polybrominated biphenyls and polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries. This Part is applicable to the determination of polybrominated biphenyls and polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries.

GB/T 29493.1-2013
NATIONAL STANDARD OF THE
PEOPLE’S REPUBLIC OF CHINA
ICS 71.100.40
G 70
Determination of Harmful Substances in Textile
Dyeing and Finishing Auxiliaries – Part 1:
Determination of Polybrominated Biphenyl and
Polybrominated Diphenyl Ethers – GC/MS Method
ISSUED ON: FEBRUARY 07, 2013
IMPLEMENTED ON: SEPTEMBER 01, 2013
Issued by: General Administration of Quality Supervision, Inspection
and Quarantine;
Standardization Administration of PRC.
Table of Contents
Foreword ... 3
1 Scope ... 4
2 Normative References ... 4
3 Principle ... 4
4 Reagents ... 4
5 Apparatus ... 5
6 Analytical Procedures ... 5
7 Results Calculation ... 8
8 Lower Limit of Detection, Recovery Rate, and Precision ... 9
9 Test Report ... 9
Appendix A (Informative) Total Ion Current Chromatograms of PBB and PBDE Standard Substances ... 10
Appendix B (Informative) Standard Mass Spectrograms of PBBs and PBDEs
... 12
Foreword
GB/T 29493 Determination of Harmful Substances in Textile Dyeing and Finishing Auxiliaries can be divided into the following 9 parts:
--- Part 1: Determination of Polybrominated Biphenyl and Polybrominated Diphenyl Ethers – GC-MS Method;
--- Part 2: Determination of Perfluorooctane Sulfonates and Perfluuorooctanoicacid – HPLC – MS/MS Method;
--- Part 3: Determination of Organotins – GC/MS Method;
--- Part 4: Determination of Polycyclic Aromatic Hydrocarbons – GC/MS Method; --- Part 5: Determination of Free Formaldehyde in Emulsion Polymers;
--- Part 6: Determination of Isocyanate Groups in Polyurethane Prepolymers; --- Part 7: Determination of Monomeric Diisocyanates in Polyurethane Coating Agent;
--- Part 8: Determination of Residual Monomers in Polyacrylate;
--- Part 9: Determination of Acrylamide.
This Part belongs to Part 1 of GB/T 29493.
This Part was drafted as per the rules specified in GB/T 1.1-2009.
This Part was proposed by China Petroleum and Chemical Industry Federation. This Part shall be under the jurisdiction of Subcommittee on Textile Auxiliaries of Technical Committee on Dyestuff of Standardization Administration of China (SAC/TC 134/SC 1).
Drafting organizations of this Part: Hangzhou Transfer Fine Chemical Co., Ltd.; Tianjin Tianxiang Quality Technology Service Co., Ltd.; and Zhejiang University of Technology. Chief drafting staffs of this Part: Li Guangbin, Yu Tao, Wang Jianping, Zhao Ting, Zhao Mei, Wang Shengpeng, and Li Zhuguang.
Determination of Harmful Substances in Textile
Dyeing and Finishing Auxiliaries – Part 1:
Determination of Polybrominated Biphenyl and
Polybrominated Diphenyl Ethers – GC/MS Method
1 Scope
This Part of GB/T 29493 specifies using the gas chromatography-mass spectrometry (GC/MS) method for the determination of polybrominated biphenyls and
polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries. This Part is applicable to the determination of polybrominated biphenyls and polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries. 2 Normative References
The following documents are essential to the application of this document. For the dated documents, only the versions with the dates indicated are applicable to this document; for the undated documents, only the latest version (including all the amendments) are applicable to this document.
GB/T 8170-2008 Rules of Rounding off for Numerical Values and Expression and Judgement of Limiting Values
3 Principle
Take toluene as the extractant; the specimen is extracted by ultrasonic wave; the extracting solution is analyzed by gas chromatography-mass spectrometer. 4 Reagents
Unless otherwise specified, the following reagents are only the used reagents that are confirmed as analytically pure.
4.1 Anhydrous sodium sulfate.
4.2 Toluene: chromatographically pure.
4.3 Methanol: chromatographically pure.
4.4 Polybrominated biphenyls (PBBs) standard substance, purity is greater than 99% (mass fraction), see Table 1.
4.5 Polybrominated diphenyl ethers (PBDEs) standard substance, purity is greater than 99% (mass fraction), see Table 1.
4.6 Polybrominated biphenyls (PBBs) standard stock solution: Accurately take 10.0mg of polybrominated biphenyl standard substances (4.4); place them in 100mL volumetric flasks; dissolve with toluene (4.2), dilute to the mark and mix evenly. The concentration of this solution was 100 mg/L. Store at 4°C in the dark, and the shelf life is 1 year. 4.7 Polybrominated diphenyl ether (PBDEs) standard stock solution: Accurately take 10.0mg of polybrominated diphenyl ether standard substance (4.5); place them in 100mL volumetric flasks; dissolve with toluene (4.2); dilute to the mark and mix evenly. The concentration of this solution was 100 mg/L. Store at 4°C in the dark, the shelf life is 1 year.
4.8 Polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) mixed standard working solution: Separately pipette the appropriate amount of PBBs standard stock solution (4.6) and PBDEs standard stock solution (4.7); dilute with toluene; prepare 0.1mg/L 0.5mg/L, 1mg/L, 2mg/L and 5mg/L standard solutions. Store at 4°C in the dark, the shelf life is 1 month.
5 Apparatus
5.1 Gas chromatography-mass spectrometry (GC/MS), the highest mass-to-charge ratio is above 1000 amu.
5.2 Ultrasonic water bath, the power is no less than 500W, and the frequency is no less than 40kHz.
5.3 Screw cap test tube, 50mL.
5.4 Electronic balance, a sensitivity of 0.0001g.
6 Analytical Procedures
6.1 Preparation of sample solution
Take 0.2g of specimen, accurate to 0.001g, into a 50mL screw-cap test tube (5.3). Accurately add 10.0mL of toluene (4.2) to the test tube; tighten the test tube cap. Place the test tube in an ultrasonic water bath (5.2) and sonicate for 30 min. Let stand and add a small amount of anhydrous sodium sulfate (4.1) until the toluene layer is clear. If emulsification or non-layering occurs, centrifugation can be performed; refrigerating overnight or adding a small amount of methanol for demulsification. The toluene layer solution was removed and analyzed by GC/MS (5.1).
6.2 Determination
6.2.1 GC/MS instrument analysis conditions
Since the test results depend on the used instrument, it is impossible to give general parameters for chromatographic analysis. The set parameters shall ensure that the measured component can be effectively separated from other components during chromatographic determination. The following parameters are proved to be feasible. a) Chromatographic column: a capillary chromatographic column with a length of 15m, an inner diameter of 0.25mm and a film thickness of 0.1μm. The fixed solution is 5% phenyl-methylpolysiloxane, such as DB-5HT or equivalent; b) inlet temperature: 280°C;
c) GC/MS interface temperature: 340°C;
d) injection volume: 1.0μL;
e) Injection method: pulse split-less;
f) Carrier gas: Helium, purity ≥99.999% (volume fraction);
g) Carrier gas flow rate: 1.8mL/min;
h) Chromatographic column temperature: ;
i) Data acquisition method: Select ion detection method SIM/full SCAN (Using the SIM method for octabromobiphenyl, nonabromobiphenyl, decabromobiphenyl, octabromobiphenyl ether, nonabromobiphenyl ether and decabromobiphenyl
ether, and using the SCAN method for the other components);
j) Mass scanning range: 100~1000amu;
k) Ionization mode: EI;
l) Ionization energy: 70eV;
m) Quadrupole temperature: 150°C;
n) Ion source temperature: 230°C.
NOTE: All chromatographic conditions need to ensure complete separation between the peaks of each PBBs and PBDEs components and from the peaks of impurities. 6.2.2 Confirmation of GC/MS measurement results
Perform chromatographic analysis according to 6.2.1. Quantify according to the external standard method for the quantitatively select ion chromatographic peak area; and be qualitative according to duration and quantitative and qualitative ions in Table 1. The response values of polybrominated biphenyls and polybrominated diphenyl ethers in the standard working solution and the sample solution to be tested shall be within the linear range detected by the instrument; and the content in the sample solution to be tested shall be within the range of the standard working solution; otherwise, the sample solution shall be measured after a certain proportion of dilution. NOTE: When using the above analysis conditions, the total ion current diagram and standard mass spectra of PBBs and PBDEs are shown in Appendix A and Appendix B.
Table 1 – Quantitatively Selected Ion and Qualitatively Selected Ion of PBBs and PBDEs
6.2.3 Blank test
Perform a blank test according to the above determination procedures to ensure that no PBBs and PBDEs can be detected in each used reagent.
7 Results Calculation
The content of PBBs and PBDEs in the sample is expressed as, w; and the value is expressed in milligrams per kilogram (mg/kg), which is calculated according to Formula (1):
Where:
A – peak areas of PBBs and PBDEs in sample solution;
Chemical name Quantitatively selected ion Qualitative selected ion
Monobromobiphenyl
Dibromobiphenyl
Tribromobiphenyl
Tetrabromobiphenyl
Pentabromobiphenyl
Hexabromobiphenyl
Heptabromobiphenyl
Octabromobiphenyl
Nonabromobiphenyl
Decabromobiphenyl
Monobromobiphenyl ether
Dibromobiphenyl ether
Tribromobiphenyl ether
Tetrabiphenyl ether
Pentabromobiphenyl ether
Hexabromobiphenyl ether
Heptabromobiphenyl ether
Octabromobiphenyl ether
Nonabromobiphenyl ether
Decabromobiphenyl ether
As – peak areas of PBBs and PBDEs in the standard working solution;
ρ – concentrations of PBBs and PBDEs in the standard working solution, in µg/mL; V – extractant volume, in mL;
m – the amount of specimen represented by the final sample solution, in g; F – dilution factor.
Take the arithmetic mean of two parallel determinations and round off to integer according to GB/T 8170-2008 for the measurement result.
8 Lower Limit of Detection, Recovery Rate, and
Precision
8.1 Lower limit of detection
The lower limit of detection is 5 mg/kg.
8.2 Recovery rate
The recovery rate of standard addition of sample shall be 80%~120%.
8.3 Precision
In the same laboratory, the absolute difference between the two independent test results obtained by the same operator using the same equipment, according to the same test method, and within a short period of time for the same test object shall be no greater than 10% of the arithmetic mean of the two measured values.
9 Test Report
The test report should give at least the following contents:
a) A description of the specimen;
b) The number of this Part;
c) Test results;
d) differences from this Part;
e) Test date.
Appendix A
(Informative)
Total Ion Current Chromatograms of PBB and PBDE Standard
Substances
The total ion current chromatograms of PBB and PBDE standard substances are shown in Figure A.1.
Key:
Figure A.1 -- Total Ion Current Chromatograms of PBB Standard Substances Time / min
Key:
Figure A.2 -- Total Ion Current Chromatograms of PBDE Standard Substances (1-7PBDEs)
Key:
Figure A.3 -- Total Ion Current Chromatograms of PBDE Standard Substances (8-10PBDEs)
Appendix B
(Informative)
Standard Mass Spectrograms of PBBs and PBDEs
The standard mass spectrograms of PBBs and PBDEs can refer to Figures B.1~B.20. Figure B.1 -- 2-Bromobiphenyl Standard Mass Spectrogram
Figure B.2 -- 2,5-Dibromobiphenyl Standard Mass Spectrogram
Figure B.3 -- 2,4,6-Tribromobiphenyl Standard Mass Spectrogram
Figure B.4 -- 2,2’,5,5’-Tetrabromobiphenyl Standard Mass Spectrogram
Figure B.5 -- 2,2’,4,5’,6-Pentabromobiphenyl Standard Mass Spectrogram
Figure B.6 -- 2,2’,4,4’,6,6’-Hexabromobiphenyl Standard Mass Spectrogram Figure B.7 -- 2,2’,3,4,4’,5,5’-Heptabromobiphenyl Standard Mass Spectrogram Figure B.8 – Octabromobiphenyl Standard Mass Spectrogram
Figure B.9 – Nonabromobiphenyl Standard Mass Spectrogram
Figure B.10 – Decabromobiphenyl Standard Mass Spectrogram
Figure B.11 -- 4-Bromobiphenyl Ether Standard Mass Spectrogram
Figure B.12 -- 4,4’-Dibromobiphenyl Ether Standard Mass Spectrogram
Figure B.13 -- 3,3’,4-Tribromobiphenyl Ether Standard Mass Spectrogram
Figure B.14 -- 3,3’,4,4’-Tetrabiphenyl Ether Standard Mass Spectrogram
Figure B.15 -- 2,2’,3,4,4’-Pentabromobiphenyl Ether Standard Mass
Spectrogram
Figure B.16 -- 2,2’,3,3’,4,4’-Hexabromobiphenyl Ether Standard Mass
Spectrogram
Figure B.17 -- 2,3,3’,4,4’,5,6-Heptabromobiphenyl Ether Standard Mass
Spectrogram
Figure B.18 – Octabromobiphenyl Ether Standard Mass Spectrogram
Figure B.19 – Noanbromobiphenyl Ether Standard Mass Spectrogram
Figure B.20 – Decabromobiphenyl Ether Standard Mass Spectrogram
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