1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58polychlorinated biphenyls Method using gas chromatography/mass spectrometryICS 13.060.50Water quali
2、ty Determination of dioxin-like BRITISH STANDARDBS ISO 17858:2007BS ISO 17858:2007This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 March 2007 BSI 2007ISBN 978 0 580 50320 7Amendments issued since publicationAmd. No. Date CommentsThis public
3、ation does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations. National forewordThis British Standard was published by BSI. It is the UK implementation o
4、f ISO 17858:2007.The UK participation in its preparation was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on EH/3/2 can be obtained on request to its secretary.Reference numberISO 17858:200
5、7(E)INTERNATIONAL STANDARD ISO17858First edition2007-02-15Water quality Determination of dioxin-like polychlorinated biphenyls Method using gas chromatography/mass spectrometry Qualit de leau Dosage des biphnyls polychlors de type dioxine Mthode par chromatographie en phase gazeuse/spectromtrie de m
6、asse BS ISO 17858:2007ii iiiContents Page Foreword vi Introduction vii 1 Scope . 1 2 Normative references . 1 3 Terms, definitions 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 Iden
7、tification 5 4.5 Quantification 5 4.6 Analytical quality 5 5 Contamination and interferences 5 6 Reagents and standards 6 7 Apparatus and materials 10 7.1 Sampling equipment for discrete sampling. 10 7.2 Equipment for sample preparation . 11 7.3 Extraction apparatus 11 7.4 Filtration apparatus 12 7.
8、5 Clean-up apparatus 12 7.6 Concentration apparatus . 13 7.7 Other equipment . 13 8 Sample collection, preservation, storage and holding times 14 9 Quality assurance (QA)/quality control (QC) . 14 9.1 General. 14 9.2 Initial precision and recovery (IPR). 15 9.3 Spiking . 15 9.4 Recovery of labelled
9、compounds assessment 16 9.5 Method blanks. 16 9.6 QC check sample 16 9.7 Method precision 16 10 Calibration . 17 10.1 Operating conditions 17 10.2 Mass spectrometer (MS) resolution 17 10.3 Ion abundance ratios, minimum levels, signal-to-noise ratios, and absolute retention times. 17 10.4 Retention t
10、ime . 18 10.5 Isomer specificity 18 10.6 Calibration by isotope dilution 18 10.7 Calibration by internal standard 19 10.8 Combined calibration . 19 11 Sample preparation 20 11.1 General. 20 BS ISO 17858:2007iv 11.2 Determination of percent suspended solids 20 11.3 Preparation of aqueous samples cont
11、aining 1 % of suspended solids or less . 21 12 Extraction and concentration 22 12.1 Separatory funnel extraction of filtrates and of aqueous samples that are visibly absent of particles 22 12.2 Solid-phase extraction (SPE) of samples containing less than 1 % suspended solids 22 12.3 Soxhlet extracti
12、on of filters and/or disks . 23 12.4 Back-extraction with acid and base 24 12.5 Macro-concentration. 24 12.6 Micro-concentration and solvent exchange. 26 13 Extract clean-up 26 13.1 General . 26 13.2 Gel permeation chromatography (GPC) . 27 13.3 Silica clean-up . 28 13.4 Alumina clean-up 28 13.5 Car
13、bon column 29 13.6 High performance liquid chromatography (HPLC) 29 13.7 Florisil clean-up. 30 13.8 Silver nitrate/silica column. 31 14 HRGC/HRMS analysis. 31 15 System and laboratory performance 31 15.1 General . 31 15.2 MS resolution. 31 15.3 Calibration verification . 31 15.4 GC resolution. 32 15
14、.5 Blank. 32 16 Qualitative determination. 32 17 Quantitative determination. 32 17.1 Isotope dilution quantification. 32 17.2 Internal standard quantification and labelled-compound recovery. 33 17.3 Concentration in sample 34 17.4 Results and reporting . 35 17.5 Toxic equivalents (TEQ) . 35 18 Analy
15、sis of complex samples 36 18.1 General . 36 18.2 Recovery of labelled compounds 36 19 Pollution prevention . 36 20 Waste management 37 21 Precision 37 Annex A (informative) Example chromatograms 45 Annex B (informative) Use of HRGC/LRMS 47 Annex C (informative) Precision data. 50 Bibliography . 54 T
16、able 1 Dioxin-like PCBs determined by this method . 38 Table 2 Suggested quantification relationships. 39 Table 3 Suggested calibration standard concentrations 40 Table 4 Suggested concentration of dioxin-like PCBs in stock and spiking solutions. 41 Table 5 Typical GC columns and temperature program
17、s . 42 BS ISO 17858:2007vTable 6 Examples of toxic equivalent factors 43 Table 7 Congener function groups and ions 44 Table B.1 TetraCBs . 49 Table B.2 PentaCBs 49 Table B.3 HexaCBs 49 Table B.4 HeptaCBs 49 Table C.1 Spiking amounts transferred to sample bottles . 50 Table C.2 Samples 1 and 2 (forti
18、fied industrial effluent) Statistical summary. 51 Table C.3 Sample 3 (unfortified industrial effluent) Statistical summary. 52 Table C.4 Sample 4 (HPLC water) Statistical summary 53 BS ISO 17858:2007vi Foreword ISO (the International Organization for Standardization) is a worldwide federation of nat
19、ional 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. Interna
20、tional 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 r
21、ules 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 a
22、t 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 17858 was prepared by Technical Committee ISO/T
23、C 147, Water quality, Subcommittee SC 2, Physical, chemical and biochemical methods. BS ISO 17858:2007viiIntroduction When using this International Standard, it may be necessary in some cases to determine whether and to what extent particular problems will require the specification of minor addition
24、al conditions. BS ISO 17858:2007blank1Water quality Determination of dioxin-like polychlorinated biphenyls Method using gas chromatography/mass spectrometry WARNING Persons using this International Standard should be familiar with normal laboratory practice. This International Standard does not purp
25、ort 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 and to ensure compliance with any national regulatory conditions. Attention is drawn to any relevant national safety regulations. The
26、non-ortho and mono-ortho PCBs are co-planar and are among the most toxic of chemicals. All work with dioxin-like PCBs requires therefore the utmost care; the national safety measures which correspond to those for toxic substances shall be strictly adhered to. IMPORTANT It is absolutely essential tha
27、t tests conducted according to this International Standard be carried out by suitably trained staff. 1 Scope This International Standard specifies a method for the determination of dioxin-like tetra- to hepta-chlorinated biphenyls (PCBs) in waters and wastewaters (containing less than 1 % suspended
28、solids) using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The method is optimized for dioxin-like PCBs, but can include other co-planar compounds such as polychlorinated dioxins and furans (PCDDs/PCDFs) and polychlorinated naphthalenes (PCNs). This method can be
29、 used to determine dioxin-like PCBs in other matrices (e.g. biota, sediments, air); however, additional clean-up steps and techniques can be required for samples with high organic loadings. This method is applicable to the twelve non- and mono-ortho PCBs designated by the World Health Organization,
30、as well as to other PCBs and co-planar compounds. The detection limits and quantification levels in this method are dependent on the level of interferences as well as instrumental limitations. The minimum levels (ML) in Table 2 are the levels at which the dioxin-like PCBs can typically be determined
31、 with no interferences present. 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 method are met. The requirements for establishing method equivalency are given
32、 in 9.2. 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 edition of the referenced document (including any amendments) applies. ISO 3696, Water f
33、or analytical laboratory use Specification and test methods ISO 5667-1, Water quality Sampling Part 1: Guidance on the design of sampling programmes and sampling techniques ISO 5667-2, Water quality Sampling Part 2: Guidance on sampling techniques BS ISO 17858:20072 3 Terms, definitions and abbrevia
34、ted terms 3.1 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1.1 analyte dioxin-like polychlorinated biphenyl tested for by this method See Table 1. 3.1.2 calibration standard solution prepared from a secondary standard and/or stock solutions an
35、d used to calibrate the response of the instrument with respect to analyte concentration 3.1.3 calibration verification standard VER midpoint calibration standard that is used to verify calibration 3.1.4 certified reference material CRM quality control sample used to determine accuracy and precision
36、 of method 3.1.5 congener member of the same kind, class or group EXAMPLE Any one of the 209 individual PCBs. 3.1.6 critical pair pair of isomers that must be separated to a predefined degree (e.g. 25 % valley) to ensure chromatographic separation meets minimum quality criteria 3.1.7 dioxin-like iso
37、mer PCB with identical chemical composition but different structure 3.1.8 homologue group complete group of isomers EXAMPLE Tetrachlorobiphenyls. 3.1.9 isotope dilution method using labelled (usually 13C12) internal standards to correct for losses during sample preparation and analysis 3.1.10 keeper
38、 solvent high boiling point solvent added to the sampling standard solution BS ISO 17858:200733.1.11 method blank aliquot of reagent water that is treated exactly as a sample through the complete analytical procedure including extraction, clean-up, identification and quantification including all the
39、 relevant reagents and materials 3.1.12 operational performance characteristics influence of the physical and chemical environment and maintenance problems, for example, mains voltage, temperature, supply of certain substances, set-up time, period of unattended operation 3.1.13 pattern chromatograph
40、ic fingerprint of any series of PCB isomers 3.1.14 profile graphic representation of the sums of the isomer concentrations of the PCBs 3.1.15 spiking addition of 13C12-labelled PCB standards of which the recovery is calculated and used to correct values of native analytes of interest 3.1.16 statisti
41、cal performance characteristics quantification, for measured values, of the possible deviations resulting from the random part of the measuring process, e.g. repeatability or instability 3.1.17 toxic equivalent factor TEF relative toxicity to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) 3.1.18 toxic e
42、quivalent quantity TEQ sum of toxic equivalents of each individual congener 3.2 Abbreviated terms CRM certified reference material GC/MS gas chromatography/mass spectrometry GPC gel permeation chromatography HPLC high-performance liquid chromatography HRGC high-resolution gas chromatography HRMS hig
43、h-resolution mass spectrometry IPR initial precision and recovery LRMS low-resolution mass spectrometry MDL method detection limit ML minimum level (see Table 2) PAR precision and recovery PCB polychlorinated biphenyl BS ISO 17858:20074 PCDD/PCDF polychlorinated dibenzo-p-dioxin/dibenzofuran PCN pol
44、ychlorinated naphthalene PFK perfluorokerosene SIM selected ion monitoring SPE solid-phase extraction TEF toxic equivalent factor TEQ toxic equivalent quantity VER calibration verification standard 4 Principle 4.1 Spiking and extraction Stable isotopically labelled analogues of dioxin-like PCBs (dil
45、uted in a suitable solvent such as acetone) are spiked into a 1 litre aqueous sample (a sample containing less than 1 % suspended solids). A minimum of one labelled standard per homologue group is used and the sample is extracted by one of three procedures noted in 4.1 a), 4.1 b) and 4.1 c). If the
46、sample contains more than 1 % solid material, the solid portion can be analysed directly after filtration or drying and the aqueous portion can be discarded. a) Samples containing no visible particles are extracted with dichloromethane 6.4 f) in a separatory funnel or by solid-phase extraction. The
47、extract is concentrated for clean-up. b) Samples containing 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 6.4 f) in a separatory funnel. The dichloromethane extract i
48、s concentrated and combined with the Soxhlet extract prior to clean-up. c) The sample is vacuum filtered through a glass-fibre filter on top of a solid-phase extraction (SPE) disk. The filter and disk are eluted with suitable solvent mixtures or extracted in a Soxhlet or pressure filtration extracto
49、r, and the extract is concentrated for clean-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 to remove interfering components. Sample clean-up procedures can include washes with acid and/or base, gel permeation, alumina, silica, Florisil1)and activated carbon chromatography. High-performance liquid chromatography (HPLC) can be used for further isolati
