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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 2 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 (PAHs)—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 29493.2-2013: Determination of harmful substances in textile dyeing and finishing auxiliaries—Part 2: Determination of perfluorooctane sulfonates and perfluorooctanoicacid HPLC-MS/MS method, with respect to GB/T 29493.2-2013, the following main technical changes have been made in addition to structural adjustment and editorial changes:
——The scope is changed, and the number of measured target substances is increased from 2 to 34. The two test methods of liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-MS), and their determination objects are defined (see Clause 1 hereof; Clause 1 of Edition 2013);
——The analysis steps are changed and subdivided into “qualitative analysis” and “quantitative analysis” (see 4.4.2.2, 4.4.2.3, 5.4.2.2, 5.2.2.3 hereof; 6.2.2 of Edition 2013);
——The informative annex “Basic information of perfluorinated compounds and internal standard substance tested in this document” is added (see Annex A hereof);
——The informative annex “Mass spectrum parameters of 27 ionic perfluorinated compounds by LC-MS/MS (ESI)” is added (see Annex B hereof);
——The informative annex "Chromatogram of perfluorinated compounds" is added (see Annex C);
——The informative annex “Quantitative selective ion and qualitative ions by GC-MS” is added (see Annex D hereof);
——The informative annex "Legend of high performance liquid chromatography mass spectrometry analysis" is deleted (see Annex A 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 standard are as follows:
——This standard was firstly issued in 2013 as GB/T 29493.2-2013;
——This edition is the first revision.
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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 auxiliaries 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 (PAHs)—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 perfluorinated compounds 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 perfluorinated compounds, 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 2: Determination of perfluorinated compounds (PFCs)
WARNING — Persons using this document should 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 27 ionic perfluorinated compounds in textile dyeing and finishing auxiliaries by liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the method for determining the content of 4 fluorotelomer alcohols (FTOHs) and 3 fluorinated acrylates (FTAs) in textile dyeing and finishing auxiliaries by gas chromatography-mass spectrometry (GC-MS).
This document is applicable to the determination of 34 perfluorinated compounds in various 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.
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4 Liquid chromatography-tandem mass spectrometry (LC-MS/MS)
4.1 Principle
Using methanol as solvent, 27 ionic perfluorinated compounds in the specimen are extracted by ultrasonic. The extract is determined and confirmed by liquid chromatography-tandem mass spectrometry, and quantified by external standard method.
4.2 Reagents or materials
Unless otherwise specified, only reagents confirmed to be analytically pure and Grade 1 water specified in GB/T 6682 shall be used.
4.2.1 Methanol, chromatographically pure.
4.2.2 Acetonitrile, chromatographically pure.
4.2.3 27 ionic perfluorinated compound standard substances with the purity ≥ 95% (mass fraction) (see S.N. of 1 to 27 in Table A.1).
4.2.4 Ammonium acetate aqueous solution (5 mmol/L): accurately weigh 0.385 g of ammonium acetate into water, transfer it to a 1 mL volumetric flask and dissolve to the scale with water, and shake well.
4.2.5 Ionic perfluorinated compounds standard stock solutions (200 mg/L): accurately weigh 0.020g (accurate to 0.1 mg) of 27 ionic perfluorinated compounds standard substances (4.2.3), place them in 100 mL volumetric flasks respectively and dissolve to the scale with methanol, and shake well.
Note: Keep the ionic perfluorinated compound standard stock solution under 0°C–4°C in dark place for 12 months.
4.2.6 Ionic perfluorinated compound primary mixed standard intermediate solution (2 mg/L): accurately pipette 0.5 mL of each ionic perfluorinated compound standard stock solution (4.2.5) to a 50 mL volumetric flask, dilute to the scale with methanol (4.2.1).
Note: Keep the ionic perfluorinated compound primary mixed standard intermediate solution under 0°C–4°C in dark place for 6 months.
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4.2.7 Ionic perfluorinated compound secondary mixed standard intermediate solution (0.1 mg/L): accurately pipette 5 mL of ionic perfluorinated compound primary mixed standard intermediate solution (4.2.6) to a 100 mL volumetric flask, dilute to the scale with methanol (4.2.1).
Note: Keep the ionic perfluorinated compound secondary mixed standard intermediate solution under 0°C–4°C in dark place for 3 months.
4.2.8 Ionic perfluorinated compound mixed standard working solution: accurately pipette 40 μL, 100 μL, 200 μL, 500 μL and 1,000 μL of ionic perfluorinated compound secondary mixed standard intermediate solution (4.2.7) to a 10 mL volumetric flask respectively, dilute to the scale with methanol (4.2.1), and prepare the standard working solution with concentration of 0.4 μg/L, 1.0 μg/L, 2.0 μg/L, 5.0 μg/L and 10 μg/L respectively.
Note: Keep the ionic perfluorinated compound mixed standard working solution under 0°C–4°C in dark place for 1 month.
4.3 Apparatus
4.3.1 Liquid chromatography-tandem mass spectrometry: equipped with electrospray ionization (ESI).
4.3.2 Ultrasonic generator: with an operating frequency of 40 kHz.
4.3.3 Analytical balance: with a sensibility of 0.0001g.
4.3.4 Extractor: with dense occlusion, 50 mL–70 mL, made of hard glass.
4.3.5 Volumetric flasks: of capacity 10 mL, 50 mL and 100 mL.
4.3.6 Disposable syringe: 1 mL–5 mL.
4.3.7 Regenerated cellulose (REC) filter head: 0.45 μm.
Note: Other proven filter heads may be used.
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4.4 Test procedures
4.4.1 Preparation of specimen solution
Accurately weigh 0.2g of sample (accurate to 0.001g) into the extractor, accurately add 10.0 mL of methanol (4.2.1), and plug it tightly. Place the extractor in the ultrasonic generator to extract at normal temperature for 30 minutes, cool it to room temperature, filter the specimen solution into the sample bottle through the regenerated cellulose filter head with a disposable syringe, and analyze it after 10 times dilution with methanol (4.2.1) by LC-MS/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: C18 column, 3.5 μm, 2.1 mm × 150 mm, or equivalent;
b) flow rate: 0.3 mL/min;
c) Column temperature: 40°C;
d) Injection volume: 10 μL;
e) Ion source: electrospray ionization source; scanning polarity: negative ion scanning;
f) Scanning mode: multi-reaction monitoring (MRM);
g) Reference conditions for electrospray ion source: see Annex B;
h) Mobile phase A: ammonium acetate aqueous solution (4.2.4);
i) Mobile phase B: acetonitrile (4.2.2);
j) Gradient elution procedure: see Table 1.
Foreword i
Introduction iii
1 Scope
2 Normative references
3 Terms and definitions
4 Liquid chromatography-tandem mass spectrometry (LC-MS/MS)
5 Gas chromatography-mass spectrometry (GC-MS)
6 Test report
Annex A (Informative) Basic information of perfluorinated compounds and internal standard substance tested in this document
Annex B (Informative) Mass spectrometric parameters of 27 perfluorinated compounds by LC/MS/MSS (ESI)
Annex C (Informative) Chromatogram of perfluorinated compounds
Annex D (Information) Quantitative and qualitative ions by GC-MS
