1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS ISO 28540:2011Water quality Determinationof 16 polycyclic aromatichydrocarbons (PAH) inwater Method using gaschromatography with massspectrometric detection (GC-MS)BS ISO 2854
2、0:2011 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 28540:2011.The UK participation in its preparation was entrusted to TechnicalCommittee EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on this committee can beobtained
3、on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 58732 0ICS 13.060.50Compliance with a British Standard cannot confer immunity fromlegal obligations.This Britis
4、h Standard was published under the authority of theStandards Policy and Strategy Committee on 31 August 2011.Amendments issued since publicationDate Text affectedBS ISO 28540:2011Reference numberISO 28540:2011(E)ISO 2011INTERNATIONAL STANDARD ISO28540First edition2011-08-01Water quality Determinatio
5、n of 16 polycyclic aromatic hydrocarbons (PAH) in water Method using gas chromatography with mass spectrometric detection (GC-MS) Qualit de leau Dtermination de 16 hydrocarbures aromatiques polycycliques (HAP) dans leau Mthode par chromatographie en phase gazeuse avec dtection par spectromtrie de ma
6、sse (CG-SM) BS ISO 28540:2011ISO 28540:2011(E) COPYRIGHT PROTECTED DOCUMENT ISO 2011 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 permiss
7、ion in writing from either ISO at the address below or ISOs 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.org Web www.iso.org Published in Switzerland ii ISO 2011 All rights reserve
8、dBS ISO 28540:2011ISO 28540:2011(E) ISO 2011 All rights reserved iiiContents Page Foreword iv Introduction . v 1 Scope 1 2 Normative references 1 3 Terms and definitions . 1 4 Principle . 2 5 Interferences 4 6 Reagents 4 7 Apparatus . 7 8 Sampling 8 9 Procedure . 8 10 Calibration 11 11 Measurement o
9、f samples 12 12 Identification 12 13 Calculation . 14 14 Expression of results 16 15 Test report 17 Annex A (informative) Examples for GC-MS conditions . 18 Annex B (informative) Precision and accuracy 19 Annex C (informative) Examples of the construction of special apparatus . 22 Annex D (informati
10、ve) Example of chromatograms 24 Annex E (informative) Extraction with extraction disks 26 Bibliography 27 BS ISO 28540:2011ISO 28540:2011(E) iv ISO 2011 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO me
11、mber 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, governme
12、ntal 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 Dire
13、ctives, 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 bod
14、ies 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 28540 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommi
15、ttee SC 2, Physical, chemical and biochemical methods. BS ISO 28540:2011ISO 28540:2011(E) ISO 2011 All rights reserved vIntroduction Polycyclic aromatic hydrocarbons (PAH) occur in nearly all types of water, these substances are adsorbed on solids (sediments, suspended matter) as well as dissolved i
16、n the liquid phase. ISO 179937specifies methods for the determination of 15 PAH by high performance liquid chromatography in drinking water, ground water, and surface water. ISO 7981-13and ISO 7981-24specify methods for the determination of 6 PAH by high performance thin layer chromatography or by h
17、igh performance liquid chromatography in drinking water and ground water. This International Standard describes a method for at least 16 PAH using gas chromatography with mass spectrometric detection (GC-MS) in drinking water, ground water and surface water. Some PAH are known or suspected to cause
18、cancer. Maximum acceptable levels have been set in a number of countries. For instance, the European Council Directive 98/83/EC on the quality of water intended for human consumption (Reference 10) set the maximum acceptable level for benzoapyrene at 0,010 g/l, and for the sum of four specified PAH
19、(benzobfluoranthene, benzokfluoranthene, benzoghiperylene, indeno1,2,3-cdpyrene) at 0,100 g/l. BS ISO 28540:2011BS ISO 28540:2011INTERNATIONAL STANDARD ISO 28540:2011(E) ISO 2011 All rights reserved 1Water quality Determination of 16 polycyclic aromatic hydrocarbons (PAH) in water Method using gas c
20、hromatography with mass spectrometric detection (GC-MS) WARNING Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to
21、 establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions. IMPORTANT It is absolutely essential that tests conducted according to this International Standard be carried out by suitably trained staff. 1 Scope This International Standard specif
22、ies a method for the determination of at least 16 selected PAH (see Table 1) in drinking water and ground water in mass concentrations above 0,005 g/l and in surface water in mass concentrations above 0,01 g/l (for each individual compound). This International Standard can be used for samples contai
23、ning up to 150 mg/l of suspended matter. This method is, with some modification, also suitable for the analysis of waste water. It is possible that this method is applicable to other PAH, provided the method is validated for each case. 2 Normative references The following referenced documents are in
24、dispensable 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 5667-1, Water quality Sampling Part 1: Guidance on the design of sampling programmes a
25、nd sampling techniques ISO 5667-3, Water quality Sampling Part 3: Preservation and handling of water samples ISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration function 3 Te
26、rms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 analyte substance to be determined ISO 15089:20005, 3.2 NOTE Substances determinable by this International Standard are listed in Table 1. BS ISO 28540:2011ISO 28540:2011(E) 2 ISO 2011 All rights re
27、served3.2 calibration solution solution prepared from a secondary standard and/or stock solutions and used to calibrate the response of the instrument with respect to analyte concentration ISO 18073:20048, 3.1.2 3.3 GC-MS determination diagnostic ion selected fragment or molecular ion of the target
28、compound with the highest possible specificity 3.4 injection standard standard mixture added to a sample before injection into the GC-MS apparatus, to monitor variability of instrument response and to calculate internal standard recovery NOTE In this International Standard, the injection standard mi
29、xture contains an isotopically labelled PAH. 3.5 internal standard isotopically labelled PAH or PAH unlikely to be present in the sample, added to samples prior to extraction, against which the concentrations of native substances are calculated 3.6 selected ion monitoring/recording mode SIM/SIR meas
30、uring the intensity of selected diagnostic ions only NOTE Adapted from ISO 22892:20069, 3.8. 4 Principle The PAH (see Table 1) present in the aqueous sample are extracted from the water sample by liquid-liquid extraction with hexane. An internal standard mixture is added to the sample prior to extra
31、ction. The extract is concentrated by evaporation, and the residue taken up in a solvent appropriate for clean-up or GC analysis. NOTE 1 Other volatile solvents can be used as well if it is proven that there is equal or better recovery (recovery mass fraction between 70 % and 110 %). The liquid-liqu
32、id extraction method shall not be used with samples containing more than 150 mg/l of suspended matter. WARNING The use of this International Standard may involve hazardous materials, operations and equipment. This International Standard does not purport to address all the safety problems associated
33、with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. NOTE 2 For samples that contain more than 150 mg/l suspended matter the procedure described in ISO 17858:20
34、076, 4.1, 4.2 and 4.3, can be used. If necessary, extracts of surface water samples can be cleaned by column chromatography prior to analysis. Prior to injection, injection standards are added to each extract, and an aliquot of the extract is injected into the gas chromatograph. PAH are separated on
35、 a suitable fused silica capillary column, coated with a film of cross-linked non-polar polysiloxane or slightly polar modified polysiloxane with an efficient separation. The column shall be suitable for separating benzoapyrene and benzoepyrene. Identification and quantification is performed by mean
36、s of mass spectrometry using electron impact ionization (EI). BS ISO 28540:2011ISO 28540:2011(E) ISO 2011 All rights reserved 3Table 1 Polycyclic aromatic hydrocarbons determinable by this International Standard Name Structure Name Structure Chemical formula Chemical formula Molar mass Molar mass %
37、carbon % carbon CAS number CAS number Naphthalene Fluorene C10H8 13H10128,17 g/mol 166,22 g/mol 93,75 % C 93,59 % C 91-20-3 86-73-7Acenaphthylene Acenaphthene C12H8C12H10152,20 g/mol 154,21 g/mol 94,6 % C 93,05 % C 208-96-8 83-32-9Anthracene Phenanthrene C14H10 14H10178,23 g/mol 178,23 g/mol 94,05 %
38、 C 94,05 % C 120-12-7 85-01-8Pyrene Fluoranthene C16H10C16H10202,26 g/mol 202,26 g/mol 95,0 % C 95,0 % C 129-00-0 206-44-0Chrysene Benzoaanthracene C18H12 18H12228,29 g/mol 228,29 g/mol 94,45 % C 94,45 % C 218-01-9 56-55-3BenzokfluorantheneaBenzobfluorantheneaC20H12C20H12252,32 g/mol 252,32 g/mol 95
39、,2 % C 95,2 % C 207-08-9 205-99-2Indeno1,2,3-cdpyreneaBenzoapyreneaC22H12 20H12276,34 g/mol 252,32 g/mol 95,6 % C 95,2 % C 193-39-5 50-32-8BenzoghiperyleneaDibenzoa,hanthraceneaC22H12C22H14276,34 g/mol 278,35 g/mol 95,6 % C 94,7 % C 191-24-2 53-70-3aCompound specified by Council Directive 98/93/EC (
40、Reference 10). BS ISO 28540:2011ISO 28540:2011(E) 4 ISO 2011 All rights reserved5 Interferences 5.1 Interferences with sampling, extraction, and concentration Use sampling containers of materials that do not affect the analyte content during the contact time (preferably of stainless steel or glass).
41、 Avoid plastics and other organic materials during sampling, sample storage or extraction. Care should be taken when using surfactants for cleaning sample containers, because they may lead to the formation of emulsions during liquid-liquid extraction. If automatic samplers are used, avoid the use of
42、 silicone or rubber material for the tubes. If these materials are present, ensure that the contact time is minimized. Rinse the sampling line with the water to be sampled before taking the test sample. Use ISO 5667-1 and ISO 5667-3 for guidance. Keep the test samples away from direct sunlight and p
43、rolonged exposure to light. Store the samples in amber containers. Clear glass bottles are suitable as well, but then the samples shall be kept in a dark place. During storage of the test samples, losses of PAH may occur due to adsorption on to the walls of the containers. The extent of the losses m
44、ay depend on the storage time. 5.2 Interferences with GC-MS Substances that co-elute with the target PAH may interfere with the determination. These interferences may lead to incompletely resolved signals and may, depending on their magnitude, affect accuracy and precision of the analytical results.
45、 Non-symmetrical peaks and peaks broader than the corresponding peaks of the reference substance suggest interferences. Chromatographic separation between dibenzoa,hanthracene and indeno1,2,3-cdpyrene is most critical. Due to their molecular mass differences, quantification can be made by mass selec
46、tive detection. When incomplete resolution is encountered, peak integration shall be checked and, when necessary, the baseline corrected. Sufficient resolution (e.g. not less than R = 0,8) between the peaks of benzobfluoranthene and benzokfluoranthene as well as of benzoapyrene and benzoepyrene is t
47、o be set as quality criterion for the capillary column. Benzojfluoranthene cannot be separated from benzokfluoranthene and benzobfluoranthene. It is possible that triphenylene is not completely separated from benzoaanthracene and chrysene. If this is the case, state this fact in the test report. NOT
48、E Benzojfluoranthene, benzoepyrene, and triphenylene are not part of the 16 target analytes. 6 Reagents WARNING The use of this International Standard may involve hazardous materials, operations and equipment. This International Standard does not purport to address all the safety problems associated
49、 with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. During the analysis, unless otherwise stated, use only reagents of recognized analytical grade, “for residue analysis” or “for GC analysis”, where appropriate, and distilled or demineralized water or water of equivalent purity. Otherwise, pay
