SIST ISO 17734-2:2013

INTERNATIONAL ISO
STANDARD 17734-2
First edition
2006-03-01
Determination of organonitrogen
compounds in air using liquid
chromatography and mass
spectrometry —
Part 2:
Amines and aminoisocyanates using
dibutylamine and ethyl chloroformate
derivatives
Détermination des composés organiques azotés dans l'air par
chromatographie liquide et spectrométrie de masse —
Partie 2: Amines et aminoisocyanates par les dérivés de la dibutylamine
et du chloroformate d'éthyle
Reference number
©
ISO 2006
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ii © ISO 2006 – All rights reserved

Contents Page
Foreword. iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Principle. 1
4 Reagents and materials . 3
5 Standard solutions . 3
5.1 Reference compounds . 3
5.2 Preparation of amine and deuterium-labelled amine derivatives . 4
5.3 Aminoisocyanate derivatives . 4
5.4 Thermal decomposition products of polyurethane (PUR). 4
5.5 Stability of the amine and aminoisocyanate derivatives. 4
6 Apparatus . 5
7 Air sampling . 6
7.1 Pre-sampling laboratory preparation. 6
7.2 Pre-sampling field preparations. 7
7.3 Collection of air samples . 7
7.4 Blanks . 7
7.5 Raw material. 7
7.6 Shipment of samples. 7
8 Laboratory sample preparation. 8
8.1 Sample sequence. 8
8.2 Work-up procedure. 8
9 Instrumental settings. 9
9.1 HPLC program (LC-MS). 9
9.2 HPLC program (LC-chemiluminescent nitrogen detector) (LC-CLND) . 9
9.3 Mass spectrometer . 9
10 Data handling . 10
10.1 Identification. 10
10.2 Calibration curves. 10
10.3 Quantification. 10
11 Determination of performance characteristics. 10
11.1 Introduction . 10
11.2 Relevant uncertainty contributions and criteria. 11
11.3 Assessment of performance characteristics, following the detailed approach in
Reference [12] . 11
Annex A (informative) Performance characteristics. 19
Annex B (informative) Examples . 21
Bibliography . 27

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 17734-2 was prepared by Technical Committee ISO/TC 146, Air Quality, Subcommittee SC 2, Workplace
Atmospheres.
ISO 17734 consists of the following parts, under the general title Determination of organonitrogen compounds
in air using liquid chromatography and mass spectrometry:
⎯ Part 1: Isocyanates using dibutylamine derivatives
⎯ Part 2: Amines and aminoisocyanates using dibutylamine and ethyl chloroformate derivatives
iv © ISO 2006 – All rights reserved

Introduction
In many applications, when considering isocyanates as a workplace contaminant, there is also a need to
investigate the presence of aminoisocyanates and amines. During thermal decomposition of polyurethane
[1], [2], [3], [4], [5], [6]
(PUR), not only isocyanates, but also amines and aminoisocyanates, are formed .
The determination of isocyanates in the work environment using DBA as a reagent has been demonstrated to
be a robust method (ISO 17734-1). Using the DBA-method and derivatization with ethyl chloroformate in the
following work-up procedure makes simultaneous determination of amines, aminoisocyanates and
[6], [7]
isocyanates possible .
For quantification of amine and aminoisocyanate derivatives, reference compounds are necessary, but are
only available for a few diamines. Aminoisocyanates can not be analysed directly because they react with
themselves. In this method, a nitrogen-specific detector has been used for quantification of amine and
aminoisocyanate derivatives in reference solutions. This technique has been demonstrated to be a useful tool,
[6]
together with MS characterization, in greatly facilitating the production of reference solutions .
INTERNATIONAL STANDARD ISO 17734-2:2006(E)

Determination of organonitrogen compounds in air using liquid
chromatography and mass spectrometry —
Part 2:
Amines and aminoisocyanates using dibutylamine and ethyl
chloroformate derivatives
1 Scope
This part of ISO 17734 gives general guidance for the sampling and analysis of airborne amines and
aminoisocyanates in workplace air. It is strongly recommended that the determination of amines and
aminoisocyanates is made together with the determination of isocyanates in air, using DBA as a reagent
(ISO 17734-1).
The method can be used for simultaneous determinations of amines, 4,4'-methylenediphenyldiamine
(4,4'-MDA), 2,4- and 2,6-toluenediamine (2,4-, 2,6-TDA) and 1,6-hexamethylenediamine (1,6-HDA), and
compounds containing both isocyanate and amine groups, 4,4'-methylenediphenyl aminoisocyanate
(4,4'-MAI), 2,4-, 4,2- and 2,6-toluene aminoisocyanate (2,4, 4,2, 2,6-TAI), 1,6-hexamethylene
aminoisocyanate (1,6-HAI). The method is suitable for collecting amines and aminoisocyanates in both the
gas and particle phases. The instrumental detection limit for the amines is about 50 fmol and for the
–3
aminoisocyanate, it is about 3 fmol. For a 15-l air sample, this corresponds to 0,4 ng⋅m for TDA and
–3
0,03 ng⋅m for TAI.
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.
ISO 16200-1:2001, Workplace air quality — Sampling and analysis of volatile organic compounds by solvent
desorption/gas chromatography — Part 1: Pumped sampling method
ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic
method for the determination of repeatability and reproducibility of a standard measurement method (including
Technical Corrigendum 1:2002)
3 Principle
The method permits the simultaneous sampling and analysis of amines, aminoisocyanates and isocyanates.
Only amines and aminoisocyanates are discussed in this part, because isocyanates are considered in
ISO 17734-1.
Samples are collected by drawing a known volume of air through a midget impinger flask followed by a filter.
–1
The impinger contains 10 ml of 0,01 mol⋅l of di-n-butylamine (DBA) in toluene, and the filter is a glass fibre
filter with no binder. After sampling, deuterium-labelled amine-ethyl chloroformate (ET) and isocyanate-DBA
derivatives (used as internal standard) are added to the sample solutions. The excess reagent and solvent are
evaporated, and the samples are dissolved in acetonitrile. The samples are analysed using reversed-phase
liquid chromatography (LC) and electrospray (ESP) mass spectrometric (MS) detection, monitoring positive
ions. Quantification is made by monitoring selected ions.
Quantification and qualitative determinations can be performed using different LC-MS techniques. LC-CLND
(chemiluminescent nitrogen detection) or for aromatic isocyanates, aminoisocyanates and amines LC-UV
(ultraviolet detection) can be used for the determination of higher concentrations. Reference materials can be
characterized using LC-MS/CLND. For characterization of volatile compounds, a GC-thermoionic specific
detector (TSD) can also be used.

Figure 1 — Principle of the described method
2 © ISO 2006 – All rights reserved

4 Reagents and materials
4.1 DBA reagent.
Analytical grade di-n-butylamine is commercially available.
4.2 Ethyl chloroformate reagent.
Analytical grade ethy
...