ISO-16000-3-2001.pdf

Reference number ISO 16000-3:2001(E) ©ISO 2001 INTERNATIONAL STANDARD ISO 16000-3 First edition 2001-09-01 Indoor air Part 3: Determination of formaldeyhde and other carbonyl compounds Active sampling method Air intérieur Partie 3: Dosage du formaldéhyde et d'autres composés carbonylés Méthode par échantillonnage actif Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobe's licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which are embedded are licensed to and installed on the computer performing the editing. In downloading this file, parties accept therein the responsibility of not infringing Adobe's licensing policy. The ISO Central Secretariat accepts no liability in this area. Adobe is a trademark of Adobe Systems Incorporated. Details of the software products used to create this PDF file can be found in the General Info relative to the file; the PDF-creation parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below. ©ISO 2001 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing 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 copyrightiso.ch Web www.iso.ch Printed in Switzerland ii© ISO 2001 All rights reserved Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) © ISO 2001 All rights reservediii ContentsPage Foreword.iv Introduction.v 1Scope 1 2Normative references2 3Principle2 4Limitations and interferences.3 4.1General3 4.2Ozone interference 4 5Safety measures 5 6Apparatus.5 7Reagents.7 8Preparation of reagents and cartridges 7 8.1Purification of 2,4-dinitrophenylhydrazine7 8.2Preparation of DNPH-formaldehyde derivative 8 8.3Preparation of DNPH-formaldehyde standards8 8.4Preparation of DNPH-coated silica gel cartridges9 9Procedure.10 9.1Sample collection 10 9.2Process blanks.11 9.3Sample analysis.12 10Calculations19 11Performance criteria and quality assurance.20 11.1General20 11.2Standard Operating Procedures (SOPs) .20 11.3HPLC system performance.21 11.4Sample loss21 12Precision and uncertainty.21 Annex A (informative) Precision and uncertainty22 Annex B (informative) Melting points of DNPH-carbonyl derivatives24 Bibliography25 Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) iv© ISO 2001 All rights reserved 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 3. 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 part of ISO 16000 may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. International Standard ISO 16000-3 was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 6, Indoor air. ISO 16000 consists of the following parts, under the general title Indoor air ?Part 1: General aspects of sampling strategy ?Part 2: Sampling strategy for formaldehyde ?Part 3: Determination of formaldeyhde and other carbonyl compounds Active sampling method ?Part 4: Determination of formaldehyde Diffusive sampling method ?Part 6: Determination of volatile organic compounds in indoor and chamber air by active sampling on TENAX TA sorbent, thermal desorption and gas chromatography using MS/FID ?Part 7: Sampling strategy for determination of airborne asbestos fibre concentrations Annexes A and B of this part of ISO 16000 are for information only. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) © ISO 2001 All rights reservedv Introduction This part of ISO 16000 is intended to be used for characterizing indoor air following the sampling strategy described in ISO 16000-2. It is applicable to formaldehyde and other carbonyl compounds. It has been tested for 14 aldehydes and ketones. Formaldehyde is the simplest carbonyl compound, with one carbon, one oxygen and two hydrogen atoms. In its monomolecular state, it is a colourless, pungent, reactive gas. It has been used in the production of urea-formaldehyde resins, adhesives and insulating foams. Emissions from particle (chip) board and wall insulation are the major sources of formaldehyde in indoor air. Formaldehyde is collected by passing air through a reactive medium that converts the compound to a derivative of lower vapour pressure that is more efficiently retained by the sampler and can be easily analysed. This part of ISO 16000 determines formaldehyde and other carbonyl compounds by reaction with 2,4-dinitrophenylhydrazine coated onto a sorbent to convert them to their corresponding hydrazones, which can be recovered and measured with high sensitivity, precision and accuracy. Other carbonyl compounds that may be emitted into air from solvents, adhesives, cosmetics, and other sources can also be determined using this part of ISO 16000. The sampling procedure is based on U.S. EPA method TO-11 A 1. Formaldehyde and certain other carbonyl compounds have a high toxic potential 2. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- FINAL DRAFT INTERNATIONAL STANDARDISO 16000-3:2001(E) © ISO 2001 All rights reserved1 Indoor air Part 3: Determination of formaldeyhde and other carbonyl compounds Active sampling method 1Scope This part of ISO 16000 describes a procedure for the determination of formaldehyde (HCHO)1?and other carbonyl compounds1)(aldehydes and ketones) in air. The method is specific for formaldehyde but, with modification, at least thirteen other carbonyl compounds can be detected and quantified. It is suitable for determination of formaldehyde and other carbonyl compounds in the concentration range of approximately 1?g/m3to 1 mg/m3. The sampling method gives a time-weighted average (TWA) sample. It can be used for long-term (1 h to 24 h) or short- term (5 min to 60 min) sampling of air for formaldehyde. This part of ISO 16000 describes a sampling and analysis procedure for formaldehyde and other carbonyl compounds that involves collection from air onto cartridges coated with 2,4-dinitrophenylhydrazine (DNPH) and subsequent analysis by high performance liquid chromatography (HPLC) with detection by ultraviolet absorption 1, 3. The procedures described are written specifically for the sampling and analysis of formaldehyde in air using an adsorbent cartridge and HPLC. The method also permits the determination of other aldehydes and ketones collected from air. This part of ISO 16000 is applicable to the following carbonyl compounds: Formaldehyde Benzaldehyde 2,5-Dimethylbenzaldehyde Isovaleraldehyde o-Tolualdehyde Acetaldehyde Butyraldehyde Propionaldehyde p-Tolualdehyde Acetone Valeraldehyde Crotonaldehyde Hexanal m-Tolualdehyde 1? Instead of the nomenclature according to IUPAC regulations, the more common names are used in this International Standard: formaldehyde: methanal acetaldehyde: ethanal acetone: 2-propanone butyraldehyde: butanal crotonaldehyde: 2-butenal isovaleraldehyde: 3-methylbutanal propionaldehyde: propanal m-tolualdehyde: 3-methylbenzaldehyde o-tolualdehyde: 2-methylbenzaldehyde p-tolualdehyde: 4-methylbenzaldehyde valeraldehyde: pentanal Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) 2© ISO 2001 All rights reserved 2Normative references The following normative documents contain provisions which, through reference in this text, constitute provisions of this part of ISO 16000. For dated references, subsequent amendments to, or revisions of, any of these publications do not apply. However, parties to agreements based on this part of ISO 16000 are encouraged to investigate the possibility of applying the most recent editions of the normative documents indicated below. For undated references, the latest edition of the normative document referred to applies. Members of ISO and IEC maintain registers of currently valid International Standards. ISO 9000-1:1994; Quality management and quality assurance standards Part 1: Guidelines for selection and use. ISO 9000-2:1997; Quality management and quality assurance standards Part 2: Generic guidelines for the application of ISO 9001, ISO 9002 and ISO 9003. ISO 16000-1, Indoor air Part 1: General aspects of sampling strategy. ISO 16000-2, Indoor air Part 2: Sampling strategy for formaldehyde. ISO 16000-4, Indoor air Part 4: Determination of formaldehyde Diffusive sampling method. ISO 17025:1999; General requirements for the competence of testing and calibration laboratories. EN 45001:1989; General criteria for the operation of testing laboratories. 3Principle ThispartofISO 16000involvesdrawingairthroughacartridgecontainingsilicagelcoatedwith 2,4-dinitrophenylhydrazine (DNPH) reagent. The principle of the method is based on the specific reaction of carbonyl group with DNPH in the presence of an acid to form stable derivatives according to the reaction shown in Figure 1. The DNPH derivatives are analysed for the parent aldehydes and ketones utilizing high performance liquid chromatography (HPLC) with UV detection or diode array detection. The detection has been extended to other carbonyl compounds that can be determined as outlined in 9.3.5. This part of ISO 16000 instructs the user on how to prepare sampling cartridges from commercially available chromatographic grade silica gel cartridges by the application of acidified DNPH to each cartridge. Alternatively, pre-coated DNPH silica gel cartridges are available and are recommended since they are generally more uniform in manufacture and possess lower blank levels. However, if commercial cartridges are used they shall be demonstrated to meet the performance criteria of this part of ISO 16000. Another advantage of commercial cartridges is that they are available with larger particle-size silica gel that results in a lower pressure-drop across the cartridge. These low pressure-drop cartridges may be more suitable for sampling air using battery-powered personal sampling pumps. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/12/2007 21:20:11 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 16000-3:2001(E) © ISO 2001 All rights reserved3 Key Ralkyl or aromatic groups for ketones, or H for aldehydes R?alkyl or aromatic groups, for ketones Figure 1 Reaction of carbonyl compounds 4Limitations and interferences 4.1General The sampling flowrate, as described in this part of ISO 16000, has been validated for sampling rates up to 1,5 l/min. This flowrate limitation is principally due to the high pressure drop (?8 kPa at 1,0 l/min) across the user- prepared silica gel cartridges, which have particle sizes of 55?m to 105?m. These cartridges are not generally compatible with battery-powered pumps used in personal sampling equipment (e.g. those used by industrial hygienists). The solid-sorbent sampling procedure is specific for sampling and analysis of formaldehyde. Interferences in this method are caused by certain isomeric aldehydes or ketones that may be unresolved by the HPLC system when analysing for other aldehydes and ketones. Organic compounds that have the same retention times and significant absorbance at 360 nm as the DNPH derivative of formaldehyde will interfere. Such interferences can often be overcome by altering the separation conditions (for example, using alternative HPLC columns or mobile phase compositions). Formaldehyde contamination of the DNPH reagent is a frequently encountered problem. The DNPH shall be purified by multiple recrystallizations in UV-grade acetonitrile. Recrystallization is accomplished, at 40 ?C to 60 ?C, by slow evaporation of the solvent to maximize crystal size. Impurity levels of carbonyl compounds in the DNPH