1、BRITISH STANDARD BS ISO 18073:2004 BS 6068-2.90:2004 Water quality Determination of tetra- to octa-chlorinated dioxins and furans Method using isotope dilution HRGC/HRMS ICS 13.060.50 BS ISO 18073:2004 This British Standard was published under the authority of the Standards Policy and Strategy Commi
2、ttee on 11 June 2004 BSI 11 June 2004 ISBN 0 580 43868 6 National foreword This British Standard reproduces verbatim ISO 18073:2004 and implements it as the UK national standard. The UK participation in its preparation was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH/3/2,
3、 Physical, chemical and biochemical methods, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this docume
4、nt may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a contract. U
5、sers are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for chan
6、ge, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the ISO title page, pages ii to v, a blank page, pages 1 to 61 and a back cover. The BSI copyr
7、ight date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments Reference number ISO 18073:2004(E)INTERNATIONAL STANDARD ISO 18073 First edition 2004-04-15 Water quality Determination of tetra- to octa-chlorinated dioxins a
8、nd furans Method using isotope dilution HRGC/HRMS Qualit de leau Dosage des dioxines et furanes ttra- octachlors Mthode par dilution disotopes HRGC/SMHR BSISO18073:2004IS:37081 O4002(E) DPlcsid Fremia ihTs PDF file may ctnoian emdebt dedyfepcaes. In ccaocnadrw eith Aebods licensilop gnic,y this file
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11、 the file is suitlbae fosu re yb ISO memdob rebeis. In tlnu ehikletneve y ttah lborp aem leratit gno it is f,dnuo plsaee inform ttneC ehlar Secrteiraat ta the serddaig sleb nevwo. ii BSISO18073:2004ISO 18073:2004(E) iiiContents Page Foreword. v 1 Scope 1 2 Normative references. 1 3 Terms, definition
12、s and abbreviated terms 2 3.1 Terms and definitions. 2 3.2 Abbreviated terms. 3 4 Principle. 4 4.1 Spiking and extraction 4 4.2 Clean-up. 4 4.3 Concentration 4 4.4 Identification 5 4.5 Quantification 6 4.6 Analytical quality. 6 5 Contamination and interferences 6 6 Reagents and standards 8 7 Apparat
13、us and materials 15 7.1 Water sample containers 15 7.2 Equipment for sample preparation . 15 7.3 Extraction apparatus 15 7.4 Filtration apparatus. 15 7.5 Clean-up apparatus. 16 7.6 Concentration apparatus 16 7.7 Other equipment. 17 8 Sample collection, preservation, storage and holding times. 17 9 Q
14、uality assurance/quality control . 18 9.1 General. 18 9.2 Initial precision and recovery (IPR). 20 9.3 Spiking. 20 9.4 Method blanks. 21 9.5 Quality control check sample 21 9.6 Method precision 21 10 Calibration 22 10.1 Operating conditions 22 10.2 Mass spectrometer (MS) resolution 23 10.3 QC limits
15、 and theoretical ion abundance ratios for standards 25 10.4 Retention time. 25 10.5 Isomer specificity 26 10.6 Calibration by isotope dilution 27 10.7 Calibration by internal standard 28 10.8 Combined calibration. 29 11 Sample preparation. 29 11.1 General. 29 11.2 Determination of suspended solids 2
16、9 11.3 Preparation of aqueous samples containing 1 % or less by mass suspended solids 30 12 Extraction and concentration 31 12.1 Extraction of samples with no visible particulates .31 12.2 Soxhlet extraction of filters and/or disks . 31 BSISO18073:2004ISO 18073:2004(E) iv 12.3 Back-extraction with a
17、cid and base 32 12.4 Macro-concentration.33 12.5 Micro-concentration and solvent exchange .34 13 Extract clean-up.35 13.1 General.35 13.2 Gel-permeation chromatography (GPC) .35 13.3 Silica clean-up.36 13.4 Alumina clean-up.37 13.5 Carbon column37 13.6 Florisil clean-up.38 14 HRGC/HRMS analysis.38 1
18、5 System and laboratory performance.38 15.1 General.38 15.2 MS resolution.38 15.3 Calibration verification.39 15.4 GC resolution.39 15.5 Blank.39 16 Qualitative determination.40 17 Quantitative determination.40 17.1 Concentration calculations for isotope dilution 40 17.2 Internal standard recovery a
19、nd concentration calculations.41 17.3 Concentration in the aqueous sample 42 17.4 Toxicity equivalents (TEQs) .42 18 Analysis of complex samples 44 18.1 General.44 18.2 Recovery of internal standards44 19 Results and reporting.45 Annex A (informative) Application of HRGC/HRMS 46 Annex B (informative
20、) Interlaboratory trial data 51 Annex C (informative) Pollution prevention and waste management .56 Annex D (informative) Additional extraction and clean up techniques.57 Bibliography61 BSISO18073:2004 vForeword ISO (the International Organization for Standardization) is a worldwide federation of na
21、tional 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. Intern
22、ational 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
23、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
24、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 18073 was prepared by Technical Committee ISO/
25、TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. BSISO18073:2004BSISO18073:2004INTENRATIONAL TSANDADR IS:37081 O4002(E)I SO 4002 All irthgs ersedevr 1Water quality Determination of tetra- to octa-chlorinated dioxins and furans Method using isotope dilution HRGC/H
26、RMS 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 establish appropriate safety and health practices a
27、nd to ensure compliance with any national regulatory conditions. Attention is drawn to any relevant national safety regulations. The 2,3,7,8-chloro-substituted PCDDs/PCDFs are among the most toxic of chemicals. All work with PCDDs/PCDFs requires, therefore, the utmost care; the national safety measu
28、res which correspond to those for toxic substances shall be strictly adhered to. 1 Scope This International Standard specifies a method for the determination of tetra- to octa-chlorinated dibenzo-p- dioxins (PCDDs) and dibenzofurans (PCDFs) in waters and waste waters (containing less than 1 % by mas
29、s solids) using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). This International Standard is applicable to the seventeen 2,3,7,8-substituted PCDDs/PCDFs specified in Table 1. The detection limits and quantitation levels in this method are usually dependent on the
30、level of interferences rather than instrumental limitations. The minimum levels (MLs) specified in Table 2 are the levels at which the PCDDs/PCDFs can be determined with no interferences present. The method detection limit (MDL) for 2,3,7,8-TCDD has been determined as 4,4 pg/l based on this method u
31、sing a sample volume of 1 l. Lower detection limits may be achieved by using a larger sample volume. This method is “performance based”. The analyst is permitted to modify the method to overcome interferences or lower the cost of measurements, provided that all performance criteria in this Internati
32、onal Standard are met. The requirements for establishing method equivalency are given in 9.1.2. 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 e
33、dition of the referenced document (including any amendments) applies. ISO 3696:1987, Water for analytical laboratory use Specification and test methods ISO 5667-1, Water quality Sampling Part 1: Guidance on the design of sampling programmes ISO 5667-2, Water quality Sampling Part 2: Guidance on samp
34、ling techniques ISO 6879:1995, Air Quality Performance characteristics and related concepts for air quality measuring methods. BSISO18073:20041IS:37081 O4002(E) 2 I SO 4002 All irthgs ersedevr3 Terms, definitions and abbreviated terms 3.1 Terms and definitions For the purposes of this document, the
35、terms and definitions given in ISO 6879:1995 and the following apply. 3.1.1 analyte PCDD or PCDF tested for by this method Note See Table 1 for a list of compounds. 3.1.2 calibration standard solution prepared from a secondary standard and/or stock solutions and used to calibrate the response of the
36、 instrument with respect to analyte concentration 3.1.3 calibration verification standard midpoint calibration standard that is used to verify calibration 3.1.4 congener any one of the 210 individual PCDDs/ PCDFs 3.1.5 internal standard 13 C 12 -labelled 2,3,7,8-PCDD/PCDF analogue added to samples p
37、rior to extraction against which the concentrations of native PCDDs and PCDFs are calculated 3.1.6 keeper high boiling-point solvent added to the sampling standard solution 3.1.7 method blank aliquot of reagent water that is treated exactly as a sample through the complete analytical procedure inclu
38、ding extraction, clean-up, identification and quantification including all the relevant reagents and materials 3.1.8 operational performance characteristics influence of the physical and chemical environment and maintenance problems, for example; mains voltage, temperature, supply of certain substan
39、ces, set-up time, period of unattended operation See ISO 6879:1995 3.1.9 pattern chromatographic print of any series of PCDD/PCDF isomers 3.1.10 PCDD/PCDF isomers PCDDs or PCDFs with identical chemical compositions but different structures 3.1.11 profile graphic representation of the sums of the iso
40、mer concentrations of the PCDDs and the PCDFs BSISO18073:20042IS:37081 O4002(E) I SO 4002 All irthgs ersedevr 33.1.12 recovery standard 13 C 12 -labelled 2,3,7,8-chloro-substituted PCDD/PCDF, added before injection into the GC 3.1.13 spiking addition of 13 C 12 -labelled PCDD/PCDF standards 3.1.14 s
41、tatistical performance characteristics quantification, for measured values, of the possible deviations resulting from the random part of the measuring process, e.g. repeatability or instability See ISO 6879:1995 3.2 Abbreviated terms DCDPE decachlorodiphenyl ether GC/MS gas chromatography/mass spect
42、rometry GPC gel-permeation chromatography HpCDD heptachlorodibenzo-p-dioxin HpCDF heptachlorodibenzofuran HpCDPE heptachlorodiphenyl ether HPLC high-performance liquid chromatography HRGC high-resolution gas chromatography HRMS high-resolution mass spectrometry HxCDD hexachlorodibenzo-p-dioxin HxCDF
43、 hexachlorodibenzofuran HxCDPE hexachlorodiphenyl ether MDL method detection limit ML minimum level (see Table 2) NCDPE nonachlorodiphenyl ether OCDD octachlorodibenzo-p-dioxin OCDF octachlorodibenzofuran OCDPE octachlorodiphenyl ether PCDD/PCDF polychlorinated dibenzo-p-dioxin/dibenzofuran PeCDD pe
44、ntachlorodibenzo-p-dioxin PeCDF pentachlorodibenzofuran BSISO18073:20043IS:37081 O4002(E) 4 I SO 4002 All irthgs ersedevrPTFE polytetrafluoroethylene SIM selected ion monitoring TCDD tetrachlorodibenzo-p-dioxin TCDF tetrachlorodibenzofuran TEF toxic equivalent factor TEQ toxic equivalent 4 Principle
45、 4.1 Spiking and extraction Internal standards, analogues of the 2,3,7,8-substituted PCDDs/PCDFs labelled with a stable isotope (see Table 1) in a suitable solvent such as acetone, are spiked into a 1 l aqueous sample containing less than 1 % by mass solids. A minimum of one labelled standard per ho
46、mologue group is used and the sample is extracted by one of two procedures as specified in 4.1 a) or 4.1 b). a) Samples containing no visible particles are extracted with dichloromethane in a separatory funnel or by solid-phase extraction. The extract is concentrated for clean-up. b) Samples contain
47、ing visible particles are vacuum filtered through a glass-fibre filter. The filter is extracted in a Soxhlet extractor using toluene and the filtrate is extracted with dichloromethane in a separatory funnel. The dichloromethane extract is concentrated and combined with the Soxhlet extract prior to c
48、lean-up. Other solvents and extraction techniques may be substituted, provided that all the performance criteria can be met. 4.2 Clean-up After extraction, sample extracts are cleaned up to remove interfering components. Sample clean-ups may include back-extraction with acid and/or base, and gel-per
49、meation, alumina, silica, Florisil 1)or activated- carbon chromatography. 4.3 Concentration After clean-up, the extract is concentrated to near dryness. Prior to injection, recovery standards are added to each extract, and an aliquot of the extract is injected into the gas chromatograph. The analytes are separated by the GC and detected by a high-resolution mass spectrometer. Two exact masses are monitored for each analyte. Resolution equal to
