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GB/T 19941.1-2025Leather and fur - Determination of formaldehyde content - Part 1: High-performance liquid chromatography method (English PDF)

皮革和毛皮 甲醛含量的测定 第 1 部分:高效液相色谱法

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Issued by

SAMR; SAC

Level / Type

National · Recommended

Issue date

December 2, 2025

Implementation date

January 1, 2027

Scope

GB/T 19941.1-2025 is the English-translated version of 皮革和毛皮 甲醛含量的测定 第 1 部分:高效液相色谱法.

This standards specifies a test method for determining the content of free and hydrolyzed formaldehyde in leather and fur using high performance liquid chromatography. This document applies to the determination of formaldehyde content in various types of leather, fur, and their products.

Document preview — GB/T 19941.1-2025

National Standard of the People's Republic of China

ICS
59.140.30
Replacing
GB/T 19941.1-2019

Issued by: State Administration for Market Regulation; Standardization Administration of the People's Republic of China.

Contents

  • Foreword3
  • Introduction6
  • 1 Scope7
  • 2 Normative references7
  • 3 Terms and definitions7
  • 4 Principle8
  • 5 Reagents and materials8
  • 6 Instruments and equipment8
  • 7 Sampling and specimen preparation9
  • 8 Test steps9
  • 9 Representation of the calculated results
  • 10 Feasibility of the method
  • 11 Test report
  • Annex A Comparison on structural numbering changes between this document and ISO
  • Annex B Technical differences between this document and ISO 17226-1:2021 and the
  • Annex C HPLC analysis conditions
  • Annex D Precision: Reliability of HPLC method

Foreword

This document was drafted 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 19941 "Leather and fur -- Determination of formaldehyde content". The following parts of GB/T 19941 have been issued:

- Part 1: High performance liquid chromatography method;

This document replaces GB/T 19941.1-2019 "Leather and fur -- Determination of formaldehyde content - Part 1: High performance liquid chromatography method". Compared with GB/T 19941.1-2019, apart from structural adjustments and editorial changes, the main technical changes are as follows:

with DNPH have been changed (see 8.2.2 of this Edition; 6.3 of Edition 2019);

formaldehyde stock solution to create a standard working curve has been modified (see 8.2.4.1 of this Edition; 6.5.1 of Edition 2019);

working curve using DNPH-formaldehyde solution has been deleted (see 6.5.2 of Edition 2019);

- "Precision" and "Recovery rate" have been added (see 10.2 and 10.3 of this Edition).

The modification of this document adopts ISO 17226-1 :2021 "Leather -- Determination of formaldehyde content -- Part 1: Method using high-performance liquid chromatography".

Compared with ISO 17226-1:2021, this document has undergone several structural adjustments. A summary table of the structural numbering changes between the two documents is provided in Annex A.

Compared with ISO 17226-1:2021, this document contains several technical differences. These differences are indicated by a vertical single line (|) in the margin outside the relevant clauses. A summary of these technical differences and their reasons is provided in Annex B.

The following editorial changes have been made to this document:

- To harmonize with existing standards, the standard name has been changed to "Leather and fur -- Determination of formaldehyde content -- Part 1: Highperformance liquid chromatography method".

17226-1:2021 and the reasons thereof" has been added.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. The issuing authority shall not be held responsible for identifying any or all such patent rights.

This document was proposed by China National Light Industry Council.

This document shall be under the jurisdiction of National Technical Committee on Leather Industry of Standardization Administration of China (SAC/TC 252).

Metrology and Quality Inspection, Sichuan University, China Leather and Footwear Research Institute Co., Ltd., Coach Trading (Shanghai) Co., Ltd., Xinji North America Leather Co., Ltd., Wenzhou Footwear and Leather Industry Research Institute, China Light Industry Inspection and Certification Co., Ltd.

Main drafters of this document: Xu Zheng, Li Chengqin, Zhou Jianfei, Sang Jun, Huang Shuya, Meng Bocun, Tang Yuling, Bu Qiaoqiao, Yang Yi, Ren Keshuai.

Versions of standard substituted by this document are:

- This is the second revision.

Introduction

In the processing of leather and fur, formaldehyde or chemicals with formaldehyde as a precursor are frequently used for sterilization, tanning, retanning, and finishing, which may introduce formaldehyde into the leather, fur, and their products. This formaldehyde slowly hydrolyzes and releases during product use, posing a threat to human health. As a highly toxic protoplasmic poison, formaldehyde can cause irreversible coagulation of proteins in cell protoplasm, resulting in significant health hazards. These hazards manifest as sensitization, genotoxicity, induction of dermatitis and asthma, and potential carcinogenicity. Therefore, the determination of formaldehyde content in leather and fur is a crucial step in assessing the quality of leather, fur, and their products. It is of great significance for identifying the quality of leather and fur products, directly impacting product inspection and the normal operation of daily trade. GB/T 19941 aims to provide a basis for the determination of formaldehyde content in leather and fur. It consists of three parts.

- Part 1: High-performance liquid chromatography method. The purpose is to establish a test method for determining the formaldehyde content in leather and fur using high performance liquid chromatography.

- Part 2: Colorimetric method. The purpose is to establish a spectrophotometric method for determining formaldehyde content in leather and fur. This method is widely used in the industry.

- Part 3: Formaldehyde emissions. The purpose is to establish a test method for formaldehyde release from leather and fur, which is particularly applicable to leather and fur products used in furniture and automobiles.

1 Scope

This document specifies a test method for determining the content of free and hydrolyzed formaldehyde in leather and fur using high performance liquid chromatography.

This document applies to the determination of formaldehyde content in various types of leather, fur, and their products.

making it particularly suitable for the precise quantification of formaldehyde content.

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.

3 Terms and definitions

This document does not contain any terms or definitions that need to be defined.

4 Principle

Leather or fur specimens are extracted under specified conditions. The extract is mixed with 2,4-dinitrophenyl ether. Different types of aldehydes and ketones react with the extract to form their respective hydrazones. After separation, the samples are determined by high-performance liquid chromatography (HPLC) with a UV detector or a diode array detector (DAD).

from leather and fur under standard conditions.

5 Reagents and materials

5.1 Unless otherwise specified, all reagents used are analytically pure. The water used in the tests shall meet the requirements for Grade III water in GB/T 6682, and all solutions used shall be aqueous solutions.

5.2 Formaldehyde solution: the mass fraction is approximately 37%.

available. If using commercially available solutions, procedure 8.1 is unnecessary.

5.3 Iodine solution: 0.05 mol/L, which means it contains 12.68 g of iodine per liter.

5.5 Sulfuric acid (H2SO4) solution: 2.0 mol/L.

5.6 Sodium thiosulfate (Na2S2O3) solution: 0.1 mol/L.

5.7 Starch solution: 1% by mass, that is, 1 g of starch are dissolved in 100 mL of water.

5.8 Acetonitrile: chromatographically pure.

5.9 Extraction solution: 0.1% by mass, i.e., 1 g of sodium dodecyl sulfonate or sodium dodecyl sulfate are dissolved in 1000 mL of water.

5.10 2,4-Dinitrophenylhydrazine (DNPH) solution: dissolve 0.3 g of DNPH (2,4dinitrophenylhydrazine) in 100 mL of acetonitrile (5.8).

6 Instruments and equipment

6.2 Erlenmeyer flasks: with stoppers or screw caps, 100 mL and 250 mL.

6.3 Glass fiber filter: GF8 (or glass filter G3, diameter is 70 mm~100 mm).

6.6 High performance liquid chromatograph: equipped with a UV detector or diode array detector.

6.7 Membrane filters: such as polyamide membranes, with a pore size of 0.45µm.

6.8 Analytical balance: scale division value is 0.1 mg.

7 Sampling and specimen preparation

7.1 Sampling

The leather is manufactured in accordance with GB/T 39364. The sampling of fur shall be conducted in accordance with the provisions of QB/T 1267. During the sampling process, care shall be taken to avoid damage to the fur and to keep the fur intact. […]

7.2 Specimen preparation

The leather shall be manufactured in accordance with the provisions of QB/T 2716.

The fur shall be tested in accordance with the provisions of QB/T 1272. The test specimen shall be tested together with the fur.

If the test results are based on the oven-dry weight of the specimen, the volatile content of another leather or fur specimen shall be determined in accordance with the provisions of QB/T 2717 or QB/T 1273.

8 Test steps

8.1 Determination of formaldehyde content in stock solution

8.1.1 Preparation of formaldehyde stock solution

Transfer 5 mL of formaldehyde solution (5.2) to a 1000 mL volumetric flask (6.1) containing approximately 100 mL of water. Then dilute to volume with water. The resulting solution is the formaldehyde stock solution.

8.1.2 Determination

Transfer 10 mL of formaldehyde stock solution to a 250 mL Erlenmeyer flask (6.2). Add 50 mL of iodine solution (5.3). Mix well. Slowly add NaOH solution (5.4) until the solution turns yellow. Incubate the reaction at room temperature (18°C~26°C) for 15 ± 1 min. Then add 15 mL of H₂SO₄ solution (5.5). Shake. Subsequently add 2 mL of starch solution (5.7). Titrate the excess iodine with Na₂S₂O₃ solution (5.6) until the color changes. Perform the determination in triplicate.

Titrate the blank solution at least twice in the same manner.

8.2 Determination of formaldehyde content in samples

8.2.2 Reaction with DNPH

Transfer 4.0 mL of acetonitrile (5.8), 5.0 mL of filtered extract (8.2.1), and 0.5 mL of DNPH solution (5.10) into a 10 mL volumetric flask (6.1). Place the volumetric flask in a water bath or oven preheated to (50 ± 2)°C for (180 ± 5) min. Cool the volumetric flask to room temperature (18°C~26°C) and then dilute to volume with water. […]

8.2.4 Preparation of standard working curves

9 Representation of the calculated results

9.1 Calculated results

The formaldehyde content in the specimen is calculated according to formula (3), accurate to 0.1 mg/kg:

wF - Formaldehyde content in the specimen, in milligrams per kilogram (mg/kg);

ρS - Formaldehyde concentration obtained from the standard working curve, in micrograms per milliliter (µg/mL);

V - Volume of the extract (8.2.1), in milliliters (mL), usually 50 mL;

F - Dilution factor, which is 2 under standard conditions (8.2.2);

m - Specimen mass, in grams (g).

wF-dry - Formaldehyde content in the specimen (based on oven-dry mass), in milligrams per kilogram (mg/kg);

wF - Formaldehyde content in the specimen [calculated by formula (3)], in milligrams per kilogram (mg/kg);

w - Moisture and volatile matter content measured according to QB/T 2717 or QB/T 1273, %.

9.2 Results representation

The test results are taken as the arithmetic mean of two parallel experiments. The results are accurate to 0.1 mg/kg.

The test results of the methods specified in this document shall have a similar trend to the test results of GB/T 19941.2, but the results are not necessarily identical. In case of dispute, the test results of the methods specified in this document shall prevail.

10 Feasibility of the method

10.1 Limit of quantification

The limit of quantitation for the method specified in this document is 5.0 mg/kg.

10.2 Precision

The difference between two parallel test results shall be less than 20% of the average. Annex D provides data on the consistency of test results between laboratories.

11 Test report

The test report shall include the following:

b) Detailed sample information, including any discrepancies between the sampling c) Formaldehyde content, in milligrams per kilogram (mg/kg);

d) If the test results are based on oven-dry mass, indicate this in the test report;

e) Any deviations from the specifications in this document.

Annex A Comparison on structural numbering changes between this document and ISO

A table comparing the structural designations in this document with those in ISO 17226- 1:2021 is shown in Table A.1.

Remaining clauses in the full document

  • Annex B Technical differences between this document and ISO 17226-1:2021 and the
  • Annex C HPLC analysis conditions
  • Annex D Precision: Reliability of HPLC method

......
This preview omits tables, figures, formulas and parts of the technical clauses. The complete document — 18 pages — is available in the English PDF.

Referenced standards

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