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net

ICS 59.140.30
Y 46

National Standard of the People’s Republic of China

GB/T 33392-2016

Leather and Fur - Chemical Tests -

Determination of 4-aminoazobenzene
Derived from Azo Colorants
皮革和毛皮 化学试验 禁用偶氮染料中 4-氨基偶氮苯的测定

(ISO 17234-2:2011, Leather - Chemical Tests for the Determination of Certain Azo
Colorants in Dyed Leathers - Part 2: Determination of 4-aminoazobenzene, MOD)

(English Translation)

Issue date: 2016-12-30 Implementation date: 2017-07-01

Issued by the General Administration of Quality Supervision,
Inspection and Quarantine of the People's Republic of China
the Standardization Administration of the People's Republic
of China

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Contents

Foreword ............................................................................................................................... i
1 Scope ............................................................................................................................. 1
2 Normative References ................................................................................................... 1
3 Principle.......................................................................................................................... 1
4 Reagents ........................................................................................................................ 2
5 Apparatus ....................................................................................................................... 3
6 Specimen Preparation.................................................................................................... 4
7 Analysis Procedure ........................................................................................................ 4
8 Result Calculation .......................................................................................................... 7
9 Detection Limit and Recovery Rate ............................................................................... 8
10 Result Expression ........................................................................................................ 8
11 Test Report ................................................................................................................... 8
Annex A (Informative) HPLC-DAD Chromatogram and Spectrogram ............................ 10
Annex B (Informative) GC-MS Chromatogram and Mass Spectrum ............................. 11
Annex C (Informative) Other Chromatographic Methods ............................................... 13
Annex D (Informative) Technical Differences Together with Their Reasons Between this
Standard and ISO 17234-2:2011 ....................................................................................... 16

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Foreword

ChinaStandards.net is in charge of this English translation. In case of any doubt about the
English translation, the Chinese original shall be considered authoritative.

This standard is developed in accordance with the rules given in GB/T 1.1-2009.

This standard has been redrafted and modified in relation to ISO 17234-2:2011 Leather -
Chemical Tests for the Determination of Certain Azo Colorants in Dyed Leathers - Part 2:
Determination of 4-aminoazobenzene.

This standard has structural adjustment and technical differences with respect to ISO
17234-2:2011. A list of structural changes and technical differences, together with their
reasons is given in Annex D for reference.

This standard was proposed by China National Light Industry Council.

This standard is under the jurisdiction of National Technical Committee on Leather

Industry of Standardization Administration of China (SAC/TC 252).

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Leather and Fur - Chemical Tests -

Determination of 4-aminoazobenzene Derived
from Azo Colorants

1 Scope

This standard specifies the detection method of gas chromatography-mass spectrometry

and high performance liquid chromatography for 4-aminoazobenzene (CAS No.: 60-09-3)
derived from some azo colorants and existed in free state.

This standard is applicable to various leathers, furs and their products.

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 6682-2008 Water for Analytical Laboratory Use - Specification and Test Methods
(ISO 3696:1987, MOD)
QB/T 1267 Fur - Chemical, Physical and Mechanical and Fastness Tests -
Sampling Location
QB/T 1272 Fur - Preparation of Chemical Test Samples
QB/T 2706 Leather - Chemical, Physical and Mechanical and Fastness Tests -
Sampling Location (QB/T 2706-2005, ISO 2418:2002, MOD)
QB/T 2716 Leather - Preparation of Chemical Test Samples (QB/T 2716-2005,
ISO 4044:1997, MOD)

3 Principle

After degreasing, the specimen is treated with sodium dithionite in an alkaline medium at
40℃ in a closed vessel. 4-aminoazobenzene obtained by reductive cleavage in the
process is extracted with tert-butyl methyl ether. The determination of
4-aminoazobenzene is performed using gas chromatography with a mass-selective
detector (GC-MS) or high-performance liquid chromatography with a diode array detector
(HPLC/DAD).

Since the derivation of amines in very small amounts may lead to false positive results,
Annex XVII of the Regulation REACH 1907/2006 defines a limit amine value of 30mg/kg
in leather specimen. This value only applies to analytical specimen that is homogenous in
matrix, but not to a mixed sample of heterogeneous composition.

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If the detected amount of 4-aminoazobenzene is over 30mg/kg, it must be assumed that a

certain azo colorant was used. Below 30mg/kg, it is at present not possible to make a
reliable statement on the use of certain azo colorants without further information such as
the type and/or purity of the colorants used or the other raw materials used.

Note: The detection and determination of 4-aminoazobenzene is performed using high-performance

liquid chromatography with a diode array detector (HPLC/DAD) or mass selective detector (HPLC/MS),
capillary gas chromatography with a mass-selective detector (GC/MS) or capillary electrophoresis with a
diode array detector (CE/DAD), or qualitatively with thin-layer chromatography (TLC, HPTLC). Other
chromatographic methods are detailed in Annex C.

If 4-aminoazobenzene is detected by one chromatographic method, confirmation shall be made using

one or more alternative methods. Amine quantification is performed by HPLC/DAD.

4 Reagents

Unless otherwise specified, only confirmed analytical reagent and Grade 3 water specified
in GB/T 6682-2008 are used.

4.1 n-hexane.

4.2 Sodium hydroxide solution, 20g/L.

4.3 Sodium dithionite solution, 200mg/mL. Weigh sodium dithionite (Na 2S2O4
content≥85%), dissolve it with right amount of water, then place it in closed vessel. It is
prepared immediately before use.

4.4 tert-butyl methyl ether, chromatographically pure.

Note: If there is no tert-butyl methyl ether, fresh ethyl ether may be used as a substitute. Fresh ethyl ether
is prepared as follows: put 500mL of ethyl ether into a 1,000mL separating funnel, add 100mL of 5%
ferrous sulfate solution, fiercely shake out, discard the water layer and place the solution in an all-glass
device for distillation, then collect 33.5℃~34.5℃ fraction.

4.5 Sodium chloride.

4.6 Methanol, chromatographically pure.

4.7 Acetonitrile, chromatographically pure.

4.8 4-aminoazobenzene, standard, purity≥98%, CAS No.: 60-09-3.

4.9 Ammonium dihydrogen phosphate.

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4.10 Disodium hydrogen phosphate.

4.11 Anthracene-d10,internal standard, used for GC-MS analysis, purity ≥98%, CAS No.:
1719-06-8.

4.12 Standard solutions.

4.12.1 Anthracene-d10 standard solution, 2.0μg/mL, internal standard solution,

prepared by tert-butyl methyl ether (4.4).

Note: Solution of other appropriate concentrations can be prepared according to the need.

4.12.2 4-aminoazobenzene standard stock solution, 500mg/L, prepared by tert-butyl

methyl ether (4.4) or other appropriate solvent.

Note: The solution is stored in brown bottle, and a small amount of anhydrous sodium sulfate can be
added; then the solution is preserved at below -18℃ for one month.

4.12.3 4-aminoazobenzene standard working solution, 30mg/L, prepared by tert-butyl

methyl ether (4.4) or other appropriate solvent.

Note: Solution of other appropriate concentrations can be prepared according to the need.

5 Apparatus

5.1 Analytical balance, with division value of 0.1mg.

5.2 Glass reactor, which is tubular, high temperature resistant and sealable.

5.3 Ultrasonic bath, at least 160W, with temperature regulating device.

5.4 Thermostatic waterbath or appropriate heater, with accuracy of ±2℃.

5.5 Polypropylene or polyethylene syringe, 2mL.

5.6 Mechanical oscillator, with rotation speed≥300r/min.

5.7 Centrifuge, with rotation speed≥300r/min.

5.8 Rotary vacuum evaporator.

5.9 Gas chromatography - mass-selective detector (GC-MS), with electron impact (EI).

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