Determination of harmful substances in textile dyeing and finishing auxiliaries—Part 1:Determination of polybrominated biphenyl and polybrominated diphenyl ethers—GC/MS method
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GB/T 29493 consists of the following nine parts under the general title Determination of Harmful Substances in Textile Dyeing and Finishing Auxiliaries:
——Part 1: Determination of Polybrominated Biphenyl and Polybrominated Diphenyl Ethers - GC/MS Method;
——Part 2: Determination of Perfluorooctane Sulfonates and Perfluorooctanoic Acid - 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 is Part 1 of GB/T 29493.
This part is developed in accordance with the rules given in GB/T 1.1-2009.
This part was proposed by China Petroleum and Chemical Industry Association.
This part is under the jurisdiction of SAC/TC 134/SC 1 the Subcommittee on Textile Auxiliaries of National Technical Committee on Dyestuffs of the Standardization Administration of China.
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 the method for determining polybrominated biphenyl and polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries with GC/MS method.
This part is applicable to the determination of polybrominated biphenyl and polybrominated diphenyl ethers in textile dyeing and finishing auxiliaries.
2 Normative References
The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.
GB/T 8170-2008 Rules of Rounding Off for Numerical Values & Expression and Judgment of Limiting Values
3 Theory
Subject the specimen to ultrasonic extraction by taking toluene as an extracting agent, and then analyze the extract with a gas chromatography-mass spectrometer.
4 Reagents
Unless otherwise specified, only recognized analytical reagent shall be used.
4.1 Anhydrous sodium sulfate.
4.2 Toluene: chromatographically pure.
4.3 Methanol: chromatographically pure.
4.4 Polybrominated biphenyls (PBBs) standard substance, with a purity greater than 99% (mass fraction), see Table 1.
4.5 Polybrominated diphenyl ethers (PBDEs) standard substance, with a purity greater than 99% (mass fraction), see Table 1.
4.6 Polybrominated biphenyls (PBBs) standard stock solution: accurately weigh 10.0 mg of polybrominated biphenyls (PBBs) standard substance (4.4) and put it into a 100-mL volumetric flask, then dissolve it with toluene (4.2), after that, dilute it to scale and mix it well. The concentration of the solution shall be 100 mg/L. The solution, with a shelf life of 1 year, shall be stored at 4℃ in dark place.
4.7 Polybrominated diphenyl ethers (PBDEs) standard stock solution: accurately weigh 10.0 mg of polybrominated diphenyl ethers standard substance (4.5) and put it into a 100-mL volumetric flask, then dissolve it with toluene (4.2), after that, dilute it to scale and mix it well. The concentration of the solution shall be 100 mg/L. The solution, with a shelf life of 1 year, shall be stored at 4 ℃ in dark place.
4.8 Mixed standard working solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs): take appropriate amount of PBBs standard stock solution (4.6) and PBDEs standard stock solution (4.7) respectively and dilute them with toluene to prepare standard solutions of 0.1 mg/L, 0.5 mg/L, 1 mg/L, 2 mg/L and 5 mg/L respectively. The solutions, with a shelf life of 1 month, shall be stored at 4 ℃ in dark place.
5 Instruments and Apparatus
5.1 Gas chromatograph-mass spectrometer (GC/MS), with a maximum mass-to-charge ratio of over 1,000 amu.
5.2 Ultrasonic water bath, with a power of no less than 500 W and a frequency of no less than 40 kHz.
5.3 50-mL screw cap test tube.
5.4 Electronic balance, with a sensitivity of 0. 0001 g.
6 Analytical Procedures
6.1 Preparation of sample solution
Weigh 0.2 g of specimen and put it in the 50-mL screw cap test tube (5.3), accurate to 0.001 g. Accurately add 10.0 mL of toluene (4.2) into the test tube and tighten the cap. And then put the test tube in the ultrasonic water bath (5.2) to subject it to ultrasonic treatment for 30 min. After that, leave it stand and add a small amount of anhydrous sodium sulfate (4.1) to it until the toluene layer is clear. If the solution is emulsified or does not stratify, it can be demulsified via centrifugation, overnight refrigeration or by adding a small amount of methanol. Take the solution of toluene layer and analyze it with GC/MS (5.1).
6.2 Determination
6.2.1 GC/MS instrument analysis conditions
As the test result depends on the instrument used, it is hard to provide general parameters for the chromatographic analysis. However, it shall ensure that, with the parameters set, the components under test can be effectively separated from other components during chromatographic determination. The following parameters have been proved to be feasible for the test.
a) chromatographic column: capillary chromatographic column with a length of 15 m, an inner diameter of 0.25 mm and a film thickness of 0.1 μm. The fixing solution shall be 5% phenyl-methyl polysiloxane, such as DB-5HT or equivalent;
b) injection temperature: 280 ℃;
c) chromatography-mass spectrometry interface temperature: 340 ℃;
d) injection volume: 1.0 μL;
e) injection mode: pulse splitless injection;
f) carrier gas: helium, with a purity of ≥ 99.999% (volume fraction);
g) flow rate of carrier gas: 1.8 mL/min;
h) chromatographic column temperature: 90 ℃ (1 min) 340 ℃ (3 min);
i) data collection mode: selected ion monitoring (SIM) (for octabromobiphenyl, nonabromobiphenyl, decabromobiphenyl, octabromodiphenyl ether, nonabromodiphenyl ether and decabromodiphenyl ether) /full scan (SCAN) mode (for other components);
j) mass scan range: 100~1,000 amu;
k) ionization mode: EI;
l) ionization energy: 70 eV;
m) temperature of quadrupole: 150 ℃;
n) temperature of ion source: 230 ℃.
Note: it shall ensure that, with all the chromatographic conditions, peaks of various polybrominated biphenyl and polybrominated diphenyl ether components as well as that of the impurity components can be completely separated.
6.2.2 Confirmation of GC/MS determination result
Perform chromatographic analysis in accordance with those specified in 6.2.1. Select ion chromatographic peak area on the basis of ration and perform quantitative analysis with external standard method; perform qualitative analysis on the basis of retention time as well as the quantitative and qualitative ions specified in Table 1. The response values of polybrominated biphenyl and polybrominated diphenyl ether in the standard working solution and the sample solution to be tested shall be within the linear range of the instrument detection, and the content of polybrominated biphenyl and polybrominated diphenyl ether in the sample solution to be tested shall be within the content range of the standard working solution, otherwise, it shall be diluted in a certain ratio and then determined.
Note: see Annexes A and B for the total ion chromatograms and standard mass spectrograms of polybrominated biphenyls and polybrominated diphenyl ethers tested under the above-mentioned analysis conditions.
Table 1 Quantitative Selection Ions and Qualitative Ions of Polybrominated Biphenyls and Polybrominated Diphenyl Ethers
Chemical name Quantitative selection ion Qualitative ion
Monobromobiphenyl 232 234, 232, 152
Dibromobiphenyl 312 310, 314, 312
Tribromobiphenyl 390 388, 392, 390
Tetrabromobiphenyl 310 308, 468, 310
Pentabromobiphenyl 388 546, 386, 388
Hexabromobiphenyl 468 628, 466, 468
Heptabromobiphenyl 546 544, 705, 546
Octabromobiphenyl 626 624, 628, 785
Nonabromobiphenyl 703 701, 706, 864
Decabromobiphenyl 783 782, 785, 943
Monobromodiphenyl ether 248 250, 168, 248
Dibromodiphenyl ether 328 330, 326, 328
Tribromodiphenyl ether 406 408, 404, 406
Tetrabromodiphenyl ether 326 484, 324, 326
Pentabromodiphenyl ether 404 562, 402, 404
Hexabromodiphenyl ether 484 644, 482, 484
Heptabromodiphenyl ether 562 721, 560, 562
Octabromodiphenyl ether 642 644, 804, 321
Nonabromobiphenyl ether 720 722, 880, 360
Decabromodiphenyl ether 800 960, 720, 400
6.2.3 Blank test
Perform blank test according to the above-mentioned test procedures and ensure that no polybrominated biphenyl and polybrominated diphenyl ether are detected in all the reagents used.
Foreword i
1 Scope
2 Normative References
3 Theory
4 Reagents
5 Instruments and Apparatus
6 Analytical Procedures
7 Result Calculation
8 Determination Lower Limit, Recovery Rate and Precision
9 Test Report
Annex A (Informative) Total Ion Chromatogram of Polybrominated Biphenyl and Polybrominated Diphenyl Ether Standards
Annex B (Informative) Standard Mass Spectrograms of Polybrominated Biphenyls and Polybrominated Diphenyl Ethers
