GB/T 29493.1-2021Determination of harmful substances in textile dyeing and finishing auxiliaries—Part 1:Determination of the prohibited or restricted flame retardants (English PDF)

4.1 Principle

After the sample is extracted with toluene by ultrasonic wave, the polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in the extract are determined by gas chromatography-mass spectrometry and quantified by external standard method.

4.2 Reagents or materials

Unless otherwise specified, only reagents confirmed as analytically pure shall be used.

4.2.3 Methanol: chromatographically pure

SN 1 to 10 in Table A.1 of Appendix A.

c) Mass spectrometer interface temperature: 340°C;

d) Injection volume: 1.0µL;

e) Injection mode: pulse non-divided flow;

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: Selected ion monitoring (SIM)/full scan (SCAN), Octabromobiphenyl (OctaBB), Nonabromobiphenyl (NonaBB), Decabromobiphenyl (DecaBB), Octabromodiphenyl ether (OctaBDE), Nonabromodiphenyl ether (NonaBDE) and Decabromodiphenyl ether (DecaBDE) use SIM; and other components use SCAN;

j) Mass scanning range: 100u~1000u;

k) Ionization source: Electron bombardment ionization source (EI);

l) Ionization energy: 70eV;

m) Quadrupole temperature: 150°C;

n) Ion source temperature: 230°C.

NOTE: Before use, adjust the parameters to completely separate the peaks of each polybrominated biphenyl (PBBs) and polybrominated diphenyl ether (PBDEs) component and the impurity peaks.

4.2.4 Polybrominated biphenyls (PBBs) standard substances

Purity >= 99% (mass fraction), see

4.2.5 Polybrominated diphenyl ethers (PBDEs) standard substances

Purity >= 99% (mass fraction), see SN 11 to 20 in Table A.1.

4.2.6 Polybrominated biphenyls (PBBs) standard stock solution

1000 mg/L: Accurately weigh 50.0 mg (accurate to 0.1 mg) of polybrominated biphenyls (PBBs) standard substance (4.2.4); place them in 50 mL volumetric flasks, respectively; dissolve them with toluene (4.2.2) and dilute to the scale; and mix well.

4.2.7 Polybrominated diphenyl ether (PBDEs) standard stock solution

1000 mg/L: Accurately weigh 50.0 mg (accurate to 0.1 mg) of polybrominated diphenyl ether (PBDEs) standard substance (4.2.5); place them in 50 mL volumetric flasks, respectively; dissolve them with toluene (4.2.2) and dilute to scale; and mix well.

4.2.8 Mixed intermediate concentration solution of PBBs and PBDEs

Mixed intermediate concentration solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs), 10 mg/L: Respectively take 1 mL of polybrominated biphenyl (PBBs) standard stock solution (4.2.6) and polybrominated diphenyl ether (PBDEs) standard stock solution (4.2.7); place them in 100 mL volumetric flasks; dilute to scale with toluene (4.2.2); and mix well.

4.2.9 Mixed standard working solution of PBBs and PBDEs

Mixed standard working solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs): Take an appropriate amount of the mixed intermediate concentration solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) (4.2.8); dilute with toluene (4.2.2); and prepare 0.1 mg/L, 0.5 mg/L, 1 mg/L, 2 mg/L and 5 mg/L mixed standard working solutions. The preparation process is shown in Table 1.

4.4.2.2 Qualitative analysis

Under the analytical conditions of 4.4.2.1 qualitative analysis is performed by comparing the retention time of the measured components in the specimen solution and the standard working solution and the relative abundance ratio of the characteristic ions in the mass spectrum (see Appendix B). If the allowable deviation of the relative ion abundance of the measured components in the specimen solution and the relative ion abundance of the measured components in the standard working solution with equivalent concentration does not exceed the provisions of Table 2, it can be judged that the corresponding analyte exists in the sample. f - dilution factor.

4.6.2 Expression of results

The calculation result is expressed by the arithmetic mean of the results of two parallel determinations, rounded-off to the unit according to the rounding value comparison method in 4.3.3 of GB/T 8170-2008.

4.7 Determination lower limit, recovery rate, precision

4.7.1 Determination lower limit

The determination lower limit of polybrominated biphenyl (PBBs) and polybrominated diphenyl ether (PBDEs) in this Document is 5 mg/kg.

4.7.2 Recovery rate

The recovery rate of the spiked sample shall be 80%~120%.

4.7.3 Precision

The absolute difference between two independent test results obtained by the same operator using the same equipment and the same test method in the same laboratory and on the same test object independently within a short period of time shall be no greater than 10% of the arithmetic mean of the two determination values.

5.1 Principle

After the sample is extracted with tetrahydrofuran by ultrasonic wave, 11 phosphorus-containing flame retardants such as tri(aziridine-1-yl) phosphine oxide (TEPA) and bromine-containing flame retardants (see SN 21 to 31 in Table A.1) in the extract are determined by liquid chromatography-tandem mass spectrometry equipped with an electrospray ionization source (ESI). And tetrabromobisphenol A bis(dibromopropyl) ether (TBBPA-DBPE) in the extract is determined by liquid chromatography-tandem mass spectrometry equipped with an atmospheric pressure chemical ionization source (APCI), and quantified by external standard method.

5.2 Reagents or materials

Unless otherwise specified, only reagents confirmed as analytically pure and Class-1 water specified in GB/T 6682 are used.

5.2.5 Dimethyl sulfoxide, chromatographically pure

NOTE: Before use, adjust each parameter so that the mass spectrometer sensitivity meets the detection requirements. For detailed analysis conditions, see Table D.3 in Appendix D.

5.2.6 Phosphorus and bromine flame retardant standard substances

Phosphorus-containing flame retardant and bromine-containing flame retardant standard substances, purity >= 99% (mass fraction), see SN 21 to 32 in Table A.1.

5.2.7 Methanol-water solution (8+2

Volume ratio): Take 800 mL of methanol (5.2.3) and 200 mL of water and mix well.

5.2.8 Ammonium acetate stock solution

500 mmol/L: Weigh 9.635 g of ammonium acetate; add appropriate amount of water to dissolve; ultrasonicate for 30 min. Transfer to a 250 mL volumetric flask; make constant volume to the scale with water; shake well; and set aside.

5.2.9 Ammonium acetate aqueous solution

5 mmol/L: Accurately transfer 5 mL of ammonium acetate stock solution (5.2.8) to a 500 mL volumetric flask and dilute to the scale with water.

5.2.10 Ammonium acetate-acetonitrile solution

5 mmol/L: Accurately transfer 5 mL of the ammonium acetate stock solution (5.2.8) into a 500 mL volumetric flask and dilute to the scale with acetonitrile (5.2.4).

5.2.11 Tri(aziridine-1-yl) phosphine oxide (TEPA) stock solution

1000 mg/L: Accurately weigh 50.0 mg (accurate to 0.1 mg) of tri(aziridine-1-yl) phosphine oxide (TEPA) (see SN 21 in Table A.1); place in a 50 mL volumetric flask; dissolve with dimethyl sulfoxide (5.2.5); dilute to the scale; and mix well.

5.2.12 Stock solutions of the other eleven flame retardants

Other 11 phosphorus-containing flame retardant and bromine-containing flame retardant stock solutions, 1000 mg/L: Accurately weigh 50.0 mg (accurate to 0.1 mg) of 11 phosphorus-containing flame retardants and bromine-containing flame retardant standard substances such as tris(2-chloroethyl) phosphate (TCEP) (see SN 22~32 in Table A.1); respectively place in 50 mL volumetric flasks; dissolve with acetone (5.2.2); dilute to scale; and mix well.

5.2.13 Mixed intermediate concentration solution (I)

Mixed intermediate concentration solution (I) [excluding tetrabromobisphenol A bis(dibromopropyl) ether (TBBPA-DBPE)], 10 mg/L: Pipette 1 mL of standard stock solution (5.2.11~5.2.12) respectively; place in a 100 mL volumetric flask; dilute to scale with methanol (5.2.3); and mix well.

5.2.14 Mixed intermediate concentration solution (II)

Mixed intermediate concentration solution (II) [excluding tetrabromobisphenol A bis(dibromopropyl) ether (TBBPA-DBPE)], 1 mg/L: Pipette 1 mL of mixed intermediate concentration solution (I) (5.2.13); place in a 10 mL volumetric flask; dilute to scale with methanol (5.2.3); mix well; and prepare for use immediately. fraction).

5.4.2.3 Qualitative analysis

Under the analytical conditions of 5.4.2.1 and 5.4.2.2, qualitative analysis is performed by comparing the retention time of the measured components in the specimen solution and the standard working solution (see Appendix D) and comparing the relative abundance of each monitoring ion pair in the mass spectrometer. If the allowable deviation of relative abundance of the measured component ion pair in the specimen solution and the relative abundance of the measured component ion pair in the standard working solution with equivalent concentration are within the provisions specified in Table 2, it can be determined that the corresponding analyte exists in the sample.

5.4.2.4 Quantitative analysis

Based on the content of the analyte in the specimen, select a standard working solution with a similar response value for analysis. A standard working curve is drawn with the peak area of the target compound as the ordinate and its concentration as the abscissa; and quantification is performed by the external standard method. The response value of the target compound in the specimen solution shall be within the linear range of the instrument detection. If the content exceeds the range of the standard working curve, the specimen solution shall be diluted to an appropriate concentration before analysis. The total ion flow diagram of 11 phosphorus-containing flame retardants and bromine-containing flame retardants such as tri(aziridine-1-yl) phosphine oxide (TEPA) are shown in Figures E.1 and E.2 in Appendix E; and the total ion flow diagram of tetrabromobisphenol A bis(dibromopropyl) ether (TBBPA-DBPE) is shown in Figure E.3 in Appendix E.

NOTE 1: If tris-o-cresyl phosphine (TOCP) is detected in the specimen, its single standard working curve is used for re-quantitative analysis.

NOTE 2: The working curve of tri(aziridine-1-yl) phosphine oxide (TEPA) is corrected in content through the working curve drawn by the peak area and concentration after the sum of two retention times.

5.5 Blank test

Except for not adding samples, follow the procedures in 5.4.

5.6 Test data processing

5.6.1 Calculation of results

The test results are respectively expressed by the test results of phosphorus-containing flame retardant and bromine-containing flame retardant.

The content of phosphorus-containing flame retardant and bromine-containing flame retardant in the sample is expressed by mass fraction wi, and the value is expressed in milligrams per kilogram (mg/kg), calculated according to Formula (2):

Where:

Ai - value of the peak area of the target compound in the specimen solution;

rhoi - value of the concentration of the target compound in the standard working solution, in mg/L;

V - value of the volume of the extraction solution, in mL;

Asi - value of the peak area of the target compound in the standard working solution; m - value of the specimen mass, in g; f - dilution factor.

5.6.2 Expression of results

The calculation result is expressed by the arithmetic mean of the results of two parallel determinations, rounded-off to the unit according to the rounding value comparison method in 4.3.3 of GB/T 8170-2008.

5.7 Determination lower limit, recovery rate and precision

5.7.1 Determination lower limit

The determination lower limit for 11 phosphorus-containing flame retardants and bromine-containing flame retardants (see SN 21 to 31 in Table A.1) such as tri(aziridine-1-yl) phosphine oxide (TEPA) in this document is 5 mg/kg; and the determination lower limit for tetrabromobisphenol A bis(dibromopropyl) ether (TBBPA-DBPE) is 25 mg/kg.

5.7.2 Recovery rate

The recovery rate of the spiked sample shall be 80% to 120%.

5.7.3 Precision

The absolute difference between two independent test results obtained by the same operator using the same equipment and the same test method in the same laboratory and on the same test object within a short period of time and independently of each other shall be no greater than 10% of the arithmetic mean of the two determination values.