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This document is developed in accordance with the rules given in GB/T 1.1-2020 Directives for standardization—Part 1: Rules for the structure and drafting of standardizing documents.
This document is Part 1 of GB/T 29493 Determination of harmful substances in textile dyeing and finishing auxiliaries. The following parts of GB/T 29493 have been published:
——Part 1: Determination of the prohibited or restricted flame retardants;
——Part 2: Determination of perfluorinated compounds (PFCs);
——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 standard replaces GB/T 29493.1-2013 Determination of harmful substances in textile dyeing and finishing auxiliaries—Part 1: Determination of polybrominated biphenyl and polybrominated diphenyl ethers GC/MS method. In addition to structural adjustment and editorial changes, the following main technical changes have been made with respect to GB/T 29493.1-2013:
——The scope of the document is modified, and the number of measured target substances is increased from 20 to 32. The two test methods of gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) and their determination objects are defined (see Clause 1 hereof; Clause 1 of Edition 2013);
——The analysis steps are modified and subdivided into “qualitative analysis” and “quantitative analysis” (see 4.4.2.2, 4.4.2.3, 5.4.2.2 and 5.2.2.3 hereof; 6.2.2 of Edition 2013);
——The informative annex “Basic information of flame retardants tested in this document” is added (see Annex A hereof);
——The informative annex “Quantitative and qualitative ions by GC-MS” is added (see Annex B hereof; Table 1 of Edition 2013);
——The informative annex “Total ion chromatograms of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) by GC-MS” is modified (see Annex C hereof; Annex A of Edition 2013);
——The informative annex “Mass spectrum parameters by LC-MS/MS” is added (see Annex D hereof);
——The informative annex “Total ion chromatograms of phosphorus containing flame retardant and bromine containing flame retardant by LC-MS/MS” is added (see Annex E hereof);
——The informative annex “Standard mass spectrum of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs)” is deleted (see Annex B of Edition 2013).
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. The issuing body of this document shall not be held responsible for identifying any or all such patent rights.
This document was proposed by China Petroleum and Chemical Industry Association.
This standard is under the jurisdiction of the National Technical Committee on Dyestuff of Standardization Administration of China (SAC/TC 134).
The previous editions of this document are as follows:
——This standard was firstly issued in 2013 as GB/T 29493.1-2013;
——This edition is the first revision.
Introduction
The ecological security of textile products is an important requirement of global textile and apparel trade. For textile dyeing and finishing auxiliaries, as special chemicals for textiles, strengthening the detection and control of harmful substances from the source is conducive to reducing the risk of harmful substances in downstream textile products and ensuring personal health and safety.
At present, there are many requirements for the control of harmful substances at the consumer end of the textile industry. GB/T 29493 aims to formulate the detection method standard of main harmful substances in the textile dyeing and finishing auxiliary industry, which is composed of the following nine parts:
——Part 1: Determination of the prohibited or restricted flame retardants;
——Part 2: Determination of perfluorinated compounds (PFCs);
——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.
The nine parts of GB/T 29493 are for different harmful substances, and are relatively independent. In recent years, the types of prohibited or restricted flame retardants concerned by the upstream and downstream of the industrial chain have gradually increased. This document is revised in combination with the focus of the industry and the progress of testing technology, which improves the scientificity and applicability of the standard, realizes the source detection and control of prohibited or restricted flame retardants, and is conducive to promoting the reduction and substitution of harmful substances in the industry.
Determination of harmful substances in textile dyeing and finishing auxiliaries—
Part 1: Determination of the prohibited or restricted flame retardants
WARNING—Persons using this document shall be familiar with normal laboratory practice. This document does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of users of this standard to take appropriate measures to ensure the safety and health of personnel, and fulfill statutory and regulatory requirements for this purpose.
1 Scope
This document specifies the method for determining the content of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in textile dyeing and finishing auxiliaries by gas chromatography-mass spectrometry (GC-MS), and the method for determining the content of other prohibited or restricted phosphorus containing flame retardants and bromine containing flame retardants in textile dyeing and finishing auxiliaries by liquid chromatography tandem mass spectrometry (LC-MS/MS).
This document is applicable to the determination of 32 prohibited or restricted flame retardants in textile dyeing and finishing auxiliaries (see Annex A).
2 Normative references
The following documents contain provisions which, through reference in this text, constitute provisions 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 6682 Water for analytical laboratory use—Specification and test methods
GB/T 8170-2008 Rules of rounding off for numerical values & expression and judgment of limiting values
3 Terms and definitions
No terms and definitions are listed in this document.
4 Gas chromatography-mass spectrometry (GC-MS)
4.1 Principle
After ultrasonic extraction with toluene, polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in the extract are determined by gas chromatography-mass spectrometer and quantified by external standard method.
4.2 Reagents or materials
Unless otherwise specified, only reagents confirmed to be analytically pure shall be used.
4.2.1 Anhydrous sodium sulfate.
4.2.2 Toluene: chromatographically pure.
4.2.3 Methanol: chromatographically pure.
4.2.4 Polybrominated biphenyls (PBBs) standard substance with the purity ≥ 99% (mass fraction) (see No. 1 to 10 in Table A.1 of Annex A).
4.2.5 Polybrominated diphenyl ethers (PBDEs) standard substance with the purity ≥ 99% (mass fraction) (see No. 11 to 20 in Table A.1).
4.2.6 Polybrominated biphenyls (PBBs) standard stock solution, 1,000 mg/L: accurately weigh 50.0 mg (accurate to 0.1 mg) of polybrominated biphenyls (PBBs) standard substance (4.2.4), place in 50 mL volumetric flasks respectively, dissolve with toluene (4.2.2), dilute them to the scale, and mix well.
4.2.7 Polybrominated diphenyl ether (PBDEs) standard stock solution, 1,000 mg/L: accurately weigh 50.0 mg (accurate to 0.1 mg) of polybrominated diphenyl ether (PBDEs) standard substance (4.2.5), place in 50 mL volumetric flasks respectively, dissolve with toluene (4.2.2), dilute them to the scale, and mix well.
4.2.8 Mixed intermediate concentration solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs), 10 mg/L: pipette 1 mL standard stock solution of polybrominated biphenyls (PBBs) (4.2.6) and standard stock solution of polybrominated diphenyl ethers (PBDEs) (4.2.7) respectively into 100 mL volumetric flasks, dilute them to scale with toluene (4.2.2), and mix well.
4.2.9 Mixed standard working solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs): pipette an appropriate amount of mixed intermediate concentration solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) (4.2.8), dilute it with toluene (4.2.2), and prepare mixed standard working solutions of 0.1 mg/L, 0.5 mg/L, 1 mg/L, 2 mg/L and 5 mg/L. See Table 1 for the preparation process.
Table 1 Preparation method of mixed standard working solution of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs)
Mass concentration of mixed standard working solution/(mg/L) 0.1 0.5 1 2 5
Volume of mixed intermediate concentration solution (4.2.8) added/mL 0.1 0.5 1 2 5
Constant volume/mL 10 10 10 10 10
Note: The standard solution (4.2.6–4.2.9) is stored in a dark environment at 0°C–4°C. The validity period of the standard stock solution (4.2.6 and 4.2.7) is 12 months, that of the mixed intermediate concentration solution (4.2.8) is 3 months, and that of the mixed standard working solution (4.2.9) is 1 month.
4.3 Apparatus
4.3.1 Gas chromatograph-mass spectrometer: the highest mass number is more than 1,000u.
4.3.2 Ultrasonic water bath: power ≥ 500W, frequency ≥ 40 kHz.
4.3.3 Test tube with screw cap: 50 mL.
4.3.4 Analytical balance: with a sensibility of 0.0001g.
4.4 Test procedures
4.4.1 Preparation of specimen solution
Weigh 0.2g of sample (accurate to 0.0001g) in the test tube with screw cap. Accurately add 10 mL of toluene (4.2.2) and tighten the tube cover. Place the test tube in ultrasonic water bath for 30 min at room temperature. Stand it and add a small amount of anhydrous sodium sulfate (4.2.1) until the toluene layer is clear. If emulsification or non stratification occurs, demulsification may be carried out by centrifugation, refrigeration overnight or adding a small amount of methanol (4.2.3). Pipette the toluene layer solution and analyze it by GC-MS.
4.4.2 Analysis method
4.4.2.1 Analysis conditions
As the test result depends on the instrument used, it is impossible to provide the general parameters of chromatographic analysis. The set parameters shall be able to ensure the effective separation between the measured components and other components during chromatographic determination; the following parameters are proved to be feasible:
a) Chromatographic column: DB-5HT, 0.1 μm, 0.25 mm × 15m, or equivalent;
b) Temperature at injection port: 280°C;
c) Mass spectrometry interface temperature: 340°C;
d) Injection volume: 1.0 μL;
e) Injection mode: pulse splitless;
f) Carrier gas: helium, with the purity ≥ 99.999% (volume fraction);
g) Flow rate of carrier gas: 1.8 mL/min;
h) Chromatographic column temperature: ;
i) Data acquisition method: Selected ion Monitor (SIM)/SCAN. For octabromobiphenyls (OctaBB), nonabromobiphenyls (NonaBB), decabromobiphenyl (DecaBB), octabromodiphenyl ethers (OctaBDE), nonabromodiphenyl ethers (NonaBDE), and decabromodiphenyl ether (DecaBDE), SIM mode is adopted; for other components, SCAN mode is adopted;
j) Quality scanning range: 100u–1,000u;
k) Ionization source: electron impact ionization source (EI);
l) Ionization energy: 70 eV;
m) Quadrupole temperature: 150°C;
n) Temperature of ion source: 230°C.
Note: Before use, adjust the parameters so that the peaks of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) components and impurity peaks are completely separated.
4.4.2.2 Qualitative analysis
Under the analysis conditions of 4.4.2.1, qualitative analysis is carried out by comparing the retention time of the measured components in the specimen solution with that of the measured components in the standard working solution and the relative abundance ratio of characteristic ions in the mass spectrum (see Annex 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 the same concentration does not exceed those specified in Table 2, it can be judged that there are corresponding measured substances in the sample.
Table 2 Maximum allowable deviation of relative ion abundance in qualitative analysis
Relative ion abundance/% > 50 > 20–50 > 10–20 ≤ 10
Allowable relative deviation/% ±20 ±25 ±30 ±50
4.4.2.3 Quantitative analysis
According to the content of the measured substance in the specimen, select the standard working solution with similar response value for analysis. Plot the standard working curve taking the peak area of the target compound as the Y-coordinate and its concentration as the X-coordinate, and external standard method shall be used for quantification. The response value of the target substance in the specimen solution shall be within the linear range detected by the instrument. If the content exceeds the standard working curve range, the specimen solution shall be diluted to an appropriate concentration before analysis. See Figure C.1 in Annex C for the total ion chromatogram of polybrominated biphenyls (PBBs), and Figures C.2 and C.3 for the total ion chromatogram of polybrominated diphenyl ethers (PBDEs).
Foreword i
Introduction iii
1 Scope
2 Normative references
3 Terms and definitions
4 Gas chromatography-mass spectrometry (GC-MS)
5 Liquid chromatography-tandem mass spectrometry (LC-MS/MS)
6 Test report
Annex A (Informative) Basic information of flame retardants tested in this document
Annex B (Informative) Quantitative and qualitative ions by GC-MS
Annex C (Informative) Total ion chromatograms of polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) by GC-MS
Annex D (Informative) Mass spectrum parameters by LC-MS/MS
Annex E (Informative) Total ion flow chromatograms of phosphorus containing flame retardant and bromine containing flame retardant by LC-MS/MS
