1、BSI Standards PublicationBS ISO 13914:2013Soil quality Determinationof dioxins and furans anddioxin-like polychlorinatedbiphenyls by gaschromatography with high-resolution mass selectivedetection (GC/HRMS)BS ISO 13914:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementati
2、on of ISO 13914:2013.The UK participation in its preparation was entrusted to TechnicalCommittee EH/4, Soil quality.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract.
3、 Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 72175 5ICS 13.080.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority
4、of theStandards Policy and Strategy Committee on 31 December 2013.Amendments issued since publicationDate Text affectedBS ISO 13914:2013 ISO 2013Soil quality Determination of dioxins and furans and dioxin-like polychlorinated biphenyls by gas chromatography with high-resolution mass selective detect
5、ion (GC/HRMS)Qualit du sol Dtermination des dioxines et furanes comme biphnyls polychlors par chromatographie en phase gazeuse avec spectromtrie de masse haute rsolution (CG/SMHR)INTERNATIONAL STANDARDISO13914First edition2013-12-01Reference numberISO 13914:2013(E)BS ISO 13914:2013ISO 13914:2013(E)i
6、i ISO 2013 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2013All 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 intr
7、anet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished
8、 in SwitzerlandBS ISO 13914:2013ISO 13914:2013(E) ISO 2013 All rights reserved iiiContents PageForeword ivIntroduction v1 Scope . 12 Normative references 23 Abbreviated terms 24 Principle 25 Reagents 35.1 Chemicals . 35.2 Standards . 36 Apparatus and materials 36.1 General . 36.2 Equipment for sampl
9、e preparation . 36.3 Soxhlet extractor . 36.4 Clean-up apparatus . 46.5 Concentration apparatus 46.6 Other equipment . 47 Sample storage and sample pretreatment 57.1 Sample storage 57.2 Sample pretreatment . 58 Extraction and clean-up 58.1 General . 58.2 Extraction 68.3 Clean-up 68.4 Final concentra
10、tion of cleaned sample extract 78.5 Addition of recovery standard . 89 GC/HRMS analysis . 89.1 General . 89.2 Gas chromatographic analysis . 89.3 Mass spectrometric detection 89.4 Minimum requirements for identification of PCDF/PCDD and PCB 109.5 Minimum requirements for quantification of PCDF/PCDD
11、and PCB 109.6 Calibration of the GC/HRMS system 119.7 Quantification of GC/HRMS results 1310 Precision 1511 Test report 15Annex A (informative) Toxic equivalent factors.16Annex B (informative) Repeatability and reproducibility data .18Annex C (informative) Examples of extraction and clean-up methods
12、 21Annex D (informative) Examples of operation of GC/HRMS determination 29Bibliography .33BS ISO 13914:2013ISO 13914:2013(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International
13、 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, a
14、lso 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.
15、 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 eleme
16、nts 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
17、 (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 ISOs adheren
18、ce to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe committee responsible for this document is ISO/TC 190, Soil quality, Subcommittee SC 3, Chemical methods and soil characteristics.iv ISO 2013 All rights reservedBS ISO 139
19、14:2013ISO 13914:2013(E)IntroductionTwo groups of related chlorinated aromatic ethers are known as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). They consist of a total of 210 individual substances (congeners): 75 PCDDs and 135 PCDFs.A group of chlorinated arom
20、atic compounds similar to polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) is known as polychlorinated biphenyls (PCBs) which consist of 209 individual substances.PCDDs and PCDFs can form in the combustion of organic materials. They also occur as undesirable by-pro
21、ducts in the manufacture or further processing of chlorinated organic chemicals. PCDDs/PCDFs enter the environment via these emission paths and through the use of contaminated materials. In fact, they are universally present at very small concentrations. The 2,3,7,8-substituted congeners are toxicol
22、ogically significant. Toxicologically much less significant than the tetrachlorinated to octachlorinated dibenzo-p-dioxins/dibenzofurans are the 74 monochlorinated to trichlorinated dibenzo-p-dioxins/dibenzofurans.PCBs have been produced over a period of approximately 50 y until the end of the 1990s
23、 for the purpose of different uses in open and closed systems, e.g. as electrical insulators or dielectric fluids in capacitors and transformers, as specialized hydraulic fluids, or as a plasticizer in sealing material. Worldwide, more than 1 million tons of PCBs were produced.PCDD/Fs as well as PCB
24、s are emitted during thermal processes such as waste incineration. In 1997, a group of experts of the World Health Organization (WHO) fixed toxicity equivalent factors (TEF) for PCDDs and 12 PCBs, known as dioxin-like PCBs (see Annex A). These 12 dioxin-like PCBs consist of four non-ortho PCBs and e
25、ight mono-ortho PCBs (no or only one chlorine atoms in 2-, 2-, 6- and 6-position), having a planar or mostly planar structure. Dioxin-like PCBs can contribute considerably to the total WHO-TEQ.Only skilled operators who are trained in handling highly toxic compounds should apply the method described
26、 in this International Standard.This International Standard is applicable for several types of matrices and validated for municipal sludge (see Annex B for the results of the validation). ISO 2013 All rights reserved vBS ISO 13914:2013BS ISO 13914:2013Soil quality Determination of dioxins and furans
27、 and dioxin-like polychlorinated biphenyls by gas chromatography with high-resolution mass selective detection (GC/HRMS)WARNING Persons using this International Standard should be familiar with usual laboratory practice. This International Standard does not purport to address all of the safety probl
28、ems, if any, associated with its use. It is the responsibility of the user to 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 carri
29、ed out by suitably trained staff.1 ScopeThis International Standard specifies a method for quantitative determination of 17 2,3,7,8-chlorine substituted dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls in sludge, treated biowaste, and soil using liquid column chromatogra
30、phic clean-up methods and GC/HRMS.The analytes to be determined with this International Standard are listed in Table 1.Table 1 Analytes and their abbreviationsSubstance AbbreviationTetrachlorodibenzo-p-dioxin TCDDPentachlorodibenzo-p-dioxin PeCDDHexachlorodibenzo-p-dioxin HxCDDHeptachlorodibenzo-p-d
31、ioxin HpCDDOctachlorodibenzo-p-dioxin OCDDTetrachlorodibenzofuran TCDFPentachlorodibenzofuran PeCDFHexachlorodibenzofuran HxCDFHeptachlorodibenzofuran HpCDFOctachlorodibenzofuran OCDFPolychlorinated biphenyl PCBTrichlorobiphenyl TCBTetrachlorobiphenyl TeCBPentachlorobiphenyl PeCBHexachlorobiphenyl H
32、xCBHeptachlorobiphenyl HpCBDecachlorobiphenyl DecaCBThe limit of detection depends on the kind of sample, the congener, the equipment used, and the quality of chemicals used for extraction and clean-up. Under the conditions specified in this International Standard, limits of detection better than 1
33、ng/kg (expressed as dry matter) can be achieved.INTERNATIONAL STANDARD ISO 13914:2013(E) ISO 2013 All rights reserved 1BS ISO 13914:2013ISO 13914:2013(E)This method is “performance based”. It is permitted to modify the method if all performance criteria given in this method are met.NOTE In principle
34、, this method can also be applied for sediments, mineral wastes, and for vegetation. It is the responsibility of the user of this International Standard to validate the application for these matrices. For measurement in complex matrices like fly ashes adsorbed on vegetation, it can be necessary to f
35、urther improve the clean-up. This can also apply to sediments and mineral wastes.2 Normative referencesThe 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 undate
36、d references, the latest edition of the referenced document (including any amendments) applies.ISO 14507, Soil quality Pretreatment of samples for determination of organic contaminants3 Abbreviated termsPCB polychlorinated biphenylsPCDD/PCDF or PCDD/F polychlorinated dibenzo-p-dioxins/dibenzofuransI
37、-TEF NATO/CCMS international toxic equivalent factor, proposed by NATO-CCMS in 1988 (for a detailed description, see Annex A)I-TEQ international toxic equivalent, obtained by multiplying the mass determined with the corresponding I-TEF including PCDDs and PCDFs (for a detailed description, see Annex
38、 A). Should only be used for comparison with older dataWHO-TEF toxic equivalent factor, proposed by WHO in 2005 (for detailed description, see Annex A)WHO-TEQ toxic equivalent, obtained by multiplying the mass determined with the corresponding WHO-TEF including PCDD, PCDF, and PCB (for detailed desc
39、ription, see Annex A). WHO-TEQPCB, WHO-TEQPCDD/Fshould be used to distinguish different compound classes4 PrincipleThis International Standard is based on the use of gas chromatography/mass spectrometry combined with the isotope dilution technique to enable the separation, detection, and quantificat
40、ion of PCDD/PCDF and dioxin-like PCB in sludge, biowaste, and soil. For the isotope dilution method, 17 labelled PCDD/F and 12 labelled PCB internal standards are used. The extracts for the GC-MS measurements contain one or two recovery standards. The gas chromatographic parameters offer information
41、 which enables the identification of congeners (position of chlorine substitutes) whereas the mass spectrometric parameters enable the differentiation between isomers with different numbers of chlorine substitutes and between dibenzo-p-dioxins, furans, and PCBs.13C12-labelled PCDD/F and PCB congener
42、s are added to the sample prior to extraction and GC/HRMS measurement. Losses during extraction and clean-up are detected and compensated by using these added congeners as internal standards for quantification together with recovery standards which are added just before the GC/HRMS analysis. For the
43、 determination of these substances, it is necessary to separate PCBs from PCDDs/PCDFs and vice versa.The main purpose of the clean-up procedure of the raw sample extract is the removal of sample matrix components, which can overload the separation method, disturb the quantification, or otherwise 2 I
44、SO 2013 All rights reservedBS ISO 13914:2013ISO 13914:2013(E)severely impact the performance of the identification and quantification method and the separation of PCDD/F from dioxin-like PCB. Furthermore, the enrichment of the analytes in the final sample extract is achieved. Extraction procedures a
45、re usually based on Soxhlet or equivalent extraction methods of dried, preferably freeze-dried, samples. Sample clean-up is usually carried out by multi-column liquid chromatographic techniques using different adsorbents. The determination of PCDD/Fs and PCBs is based on quantification by the isotop
46、e dilution technique using GC/HRMS.5 Reagents5.1 ChemicalsSolvents used for extraction and clean-up shall be of pesticide grade or equivalent quality and checked for blanks. Adsorbents like aluminium oxide, silica gel, diatomaceous earth, and others used for clean-up shall be of analytical grade qua
47、lity or better and pre-cleaned and activated if necessary.NOTE See Annex C for a specific list of solvents and chemicals.5.2 Standards 13C12-spiking solution for PCDD/F (internal standard); 13C12-spiking solution for PCB (internal standard); calibration solutions PCDD/F; calibration solutions PCB; r
48、ecovery standard PCDD/F; recovery standard PCB.NOTE See Annex C for examples of concentration of the standard solutions.6 Apparatus and materials6.1 GeneralThe apparatus and materials listed below are meant as minimum requirements for “conventional” sample treatment with Soxhlet extraction and colum
49、n chromatographic clean-up. Additional apparatus and materials may be necessary due to different methods of sample extraction and clean-up methods.6.2 Equipment for sample preparation6.2.1 Laboratory fume hood, of sufficient size to contain the sample preparation equipment listed below.6.2.2 Desiccator.6.2.3 Balances, consisting of an analytical type capable of weighing 0,1 mg and a top-loading type capable of weighing 10 mg.6.3 Soxhlet extractor6.3.1 Soxhlet, 50 mm internal diameter, 150 ml or 250 ml capacity with 500 ml round botto
