SIST ISO 17734-2:2015

INTERNATIONAL ISO
STANDARD 17734-2
Second edition
2013-12-01
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 2013
© ISO 2013
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2013 – All rights reserved

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents and materials . 2
5 Standard solutions. 3
5.1 Reference compounds . 3
5.2 Amine and deuterium-labelled amine derivatives . 3
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 . 7
7.1 Pre-sampling laboratory preparation . 7
7.2 Pre-sampling field preparations . 7
7.3 Collection of air samples . 7
7.4 Blanks . . 8
7.5 Raw material . 8
7.6 Shipment of samples . 8
8 Laboratory sample preparation . 9
8.1 Sample sequence . 9
8.2 Work-up procedure .10
9 Instrumental settings .10
9.1 HPLC program (LC-MS) .10
9.2 HPLC program [LC-chemiluminescent nitrogen detector (LC-CLND)] .10
9.3 Mass spectrometer .10
10 Data handling .11
10.1 Identification .11
10.2 Calibration curves .11
10.3 Quantification .11
11 Determination of performance characteristics.11
11.1 General .11
11.2 Relevant uncertainty contributions and criteria .12
11.3 Assessment of performance characteristics (following the detailed approach in Reference
[12]) .12
Annex A (informative) Performance characteristics
........................................................................................................................20
Annex B (informative) Examples .22
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.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
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. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 2,
Workplace atmospheres.
This second edition of ISO 17734-2 cancels and replaces ISO 17734-2:2006, which has been
technically revised.
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 2013 – 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 (see ISO 17734-1). Using the DBA method and derivatization with
ethyl chloroformate in the following work-up procedure makes simultaneous determination of amines,
[6][7]
aminoisocyanates, and isocyanates possible.
For quantification of amine and aminoisocyanate derivatives, reference compounds are necessary,
but are only available for a few diamines. Aminoisocyanates cannot 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, together with MS characterization, in greatly facilitating the production of reference
[6]
solutions.
INTERNATIONAL STANDARD ISO 17734-2:2013(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
(see ISO 17734-1).
The method can be used for simultaneous determinations of amines, such as 4,4’-methylenediphenyldiamine
(4,4’-MDA), 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), and 1,6-hexamethylenediamine (1,6-
HDA), and compounds containing both isocyanate and amine groups, such as 4,4’-methylenediphenyl
aminoisocyanate (4,4’-MAI), 2,4-, 4,2-, and 2,6-toluene aminoisocyanate (2,4-, 4,2-, and 2,6-TAI), and
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 5 nmol/sample and for the aminoisocyanate, it is about 0,3 nmol/sample. For a 15 l air sample,
–3 –3
this corresponds to 0,4 ng⋅m for TDA and 0,03 ng⋅m for TAI.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. 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, Workplace air quality — Sampling and analysis of volatile organic compounds by solvent
desorption/gas chromatography — Part 1: Pumped sampling method
ISO 5725-2, 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
3 Principle
The method permits the simultaneous sampling and analysis of amines, aminoisocyanates, and
isocyanates. Only amines and aminoisocyanates ar
...

INTERNATIONAL ISO
STANDARD 17734-2
Second edition
2013-12-01
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 2013
© ISO 2013
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2013 – All rights reserved

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents and materials . 2
5 Standard solutions. 3
5.1 Reference compounds . 3
5.2 Amine and deuterium-labelled amine derivatives . 3
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 . 7
7.1 Pre-sampling laboratory preparation . 7
7.2 Pre-sampling field preparations . 7
7.3 Collection of air samples . 7
7.4 Blanks . . 8
7.5 Raw material . 8
7.6 Shipment of samples . 8
8 Laboratory sample preparation . 9
8.1 Sample sequence . 9
8.2 Work-up procedure .10
9 Instrumental settings .10
9.1 HPLC program (LC-MS) .10
9.2 HPLC program [LC-chemiluminescent nitrogen detector (LC-CLND)] .10
9.3 Mass spectrometer .10
10 Data handling .11
10.1 Identification .11
10.2 Calibration curves .11
10.3 Quantification .11
11 Determination of performance characteristics.11
11.1 General .11
11.2 Relevant uncertainty contributions and criteria .12
11.3 Assessment of performance characteristics (following the detailed approach in Reference
[12]) .12
Annex A (informative) Performance characteristics
........................................................................................................................20
Annex B (informative) Examples .22
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.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
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. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 2,
Workplace atmospheres.
This second edition of ISO 17734-2 cancels and replaces ISO 17734-2:2006, which has been
technically revised.
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 2013 – 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 (see ISO 17734-1). Using the DBA method and derivatization with
ethyl chloroformate in the following work-up procedure makes simultaneous determination of amines,
[6][7]
aminoisocyanates, and isocyanates possible.
For quantification of amine and aminoisocyanate derivatives, reference compounds are necessary,
but are only available for a few diamines. Aminoisocyanates cannot 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, together with MS characterization, in greatly facilitating the production of reference
[6]
solutions.
INTERNATIONAL STANDARD ISO 17734-2:2013(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
(see ISO 17734-1).
The method can be used for simultaneous determinations of amines, such as 4,4’-methylenediphenyldiamine
(4,4’-MDA), 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), and 1,6-hexamethylenediamine (1,6-
HDA), and compounds containing both isocyanate and amine groups, such as 4,4’-methylenediphenyl
aminoisocyanate (4,4’-MAI), 2,4-, 4,2-, and 2,6-toluene aminoisocyanate (2,4-, 4,2-, and 2,6-TAI), and
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 5 nmol/sample and for the aminoisocyanate, it is about 0,3 nmol/sample. For a 15 l air sample,
–3 –3
this corresponds to 0,4 ng⋅m for TDA and 0,03 ng⋅m for TAI.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. 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, Workplace air quality — Sampling and analysis of volatile organic compounds by solvent
desorption/gas chromatography — Part 1: Pumped sampling method
ISO 5725-2, 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
3 Principle
The method permits the simultaneous sampling and analysis of amines, aminoisocyanates, and
isocyanates. Only amines and aminoisocyanates ar
...