1、BRITISH STANDARD BS ISO 11338-2:2003 Stationary source emissions Determination of gas and particle-phase polycyclic aromatic hydrocarbons Part 2: Sample preparation, clean-up and determination ICS 13.040.40 BS ISO 11338-2:2003 This British Standard was published under the authority of the Standards
2、Policy and Strategy Committee on 27 November 2003 BSI 27 November 2003 ISBN 0 580 42984 9 National foreword This British Standard reproduces verbatim ISO 11338-2:2003 and implements it as the UK national standard. The UK participation in its preparation was entrusted by Technical Committee EH/2, Air
3、 quality, to Subcommittee EH/2/1, Stationary source emissions, 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 publications referred to in this
4、document 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 contr
5、act. Users 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 fo
6、r change, 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 23 and a back cover. The BSI
7、 copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments Reference number ISO 11338-2:2003(E)NINRETOITALAN ADNATSDR OSI 183312- tide tsriFino 0-300210-6 Stationary source emissions Determination of gas and pa
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10、omatiques pollcycyiqeuos sus fomre gazeuse et partiuclaire raPti:2 e rPraptanoi sed citnahllsnop ,ruificitano d teretmtanioin BSISO113382:2003IS-83311 O2:(3002E) ii BSISO113382:2003IS-83311 O2:(3002E) iiiContents Page Foreword iv Introduction v 1 Scope 1 2 Normative references. 1 3 Terms and definit
11、ions. 1 4 Principle. 2 4.1 Sampling 2 4.2 Analysis 2 5 Safety measures 2 6 Procedures 2 6.1 HPLC method 2 6.2 GC-MS method 9 7 Limitations and interferences 16 7.1 Limitations. 16 7.2 Interferences 17 Annex A (informative) Maximum UV absorption wavelength and recommended combinations of excitation-e
12、mission wavelengths for HPLC. 18 Annex B (informative) Formulae and physical properties of selected PAH . 19 Annex C (informative) Characteristic ions for GC-MS detection of selected PAH, recovery, and surrogate recovery standards 20 Annex D (informative) Applicability of internal standards for GC-M
13、S detection of selected PAH. 21 Annex E (normative) Summary of performance characteristics of the HPLC method . 22 Bibliography . 23 BSISO113382:2003IS-83311 O2:(3002E) iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO me
14、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
15、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
16、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
17、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 11338-2 was prepared by Technical Committee ISO/TC 146, Air quality, Subcommi
18、ttee SC 1, Stationary source emissions. ISO 11338 consists of the following parts, under the general title Stationary source emissions Determination of gas and particle-phase polycyclic aromatic hydrocarbons: Part 1: Sampling Part 2: Sample preparation, clean-up and determination BSISO113382:2003IS-
19、83311 O2:(3002E) vIntroduction This part of ISO 11338 describes procedures for sample preparation, clean-up and analysis of polycyclic aromatic hydrocarbons (PAHs) (collected from stack and waste gases), based on either high performance liquid chromatography (HPLC) (see Annexes A and E) or gas chrom
20、atography-mass spectrometry (GC-MS) (see Annexes B, C and D). PAHs are emitted to the atmosphere primarily by the combustion of fossil fuels and wood. PAHs are considered to be an important class of environmental carcinogens. The identification and quantification of PAHs emitted from stationary sour
21、ces represent a critical aspect in the assessment of air quality. Stack and waste gases emitted from stationary sources often contain solid particles. Because of the range of their vapour pressures, PAHs are distributed between gas and particle phases. In the atmosphere, PAHs containing four or more
22、 rings tend to adsorb onto particles, while PAHs containing two to four rings tend to be present in gaseous form. However in stack and waste gases, the distribution of PAHs between gas and particle phases depends on the temperature, the mass of emitted particles, particle size, humidity, type and co
23、ncentration of PAH. During sampling, sample storage and preparation of the sample, losses of PAH can occur and prevent quantitative analysis. These losses can be the result of the volatility of two- and three-ring PAHs, the physical- chemical instability of PAHs in the presence of light, O 3 , NO x
24、, SO 2 , HCl and certain heavy metals. BSISO113382:2003blank 3002:283311OSISBINTENRATIONAL TSANDADR IS-83311 O2:(3002E)1Stationary source emissions Determination of gas and particle-phase polycyclic aromatic hydrocarbons Part 2: Sample preparation, clean-up and determination 1 Scope This part of ISO
25、 11338 specifies procedures for sample preparation, clean-up and analysis for the determination of gas and particle-phase polycyclic aromatic hydrocarbons (PAH) in stack and waste gases. The analytical methods are capable of detecting sub-microgram concentrations of PAH per cubic metre of sample, de
26、pending on the type of PAH and the flue gas volume sampled. The methods described in this part of ISO 11338 are based on either high performance liquid chromatography (HPLC) or gas chromatography-mass spectrometry (GC-MS). NOTE ISO 11338-1 describes three methods and specifies minimum requirements f
27、or the sampling of PAH in stack and waste gases. 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 an
28、y amendments) applies. ISO 4225:1994, Air quality General aspects Vocabulary 3 Terms and definitions For the purposes of this document, the terms and definitions given in ISO 4225 and the following apply. 3.1 polycyclic aromatic hydrocarbon PAH compound that contains two or more fused aromatic rings
29、 made up of carbon and hydrogen atoms 3.2 stationary source emission gas emitted by a stationary plant or process and transported to a chimney for dispersion into the atmosphere 3.3 accelerated solvent extractor ASE equipment that accelerates the traditional extraction process by using solvent at el
30、evated temperatures NOTE Pressure is applied to the sample extraction cell to maintain the heated solvent in a liquid state during the extraction. BSISO113382:2003IS-83311 O2:(3002E) 2 4 Principle 4.1 Sampling A representative sample is collected from the gas passing through a duct under isokinetic
31、conditions with the use of a suitable sampling device. The particulate phase is collected on a suitable filter and the gas phase is trapped by condensation onto an adsorbent e.g. styrene-divinylbenzene polymer resin (XAD-2), polyurethane foam or other adsorbent of comparable efficiency. 4.2 Analysis
32、 After sampling, the sample is removed from the sampling equipment. The parts of the sampling equipment which have been in contact with the sample are washed with solvent. The washings are then combined with the filter(s) and adsorbent and then extracted with a suitable organic solvent, with the use
33、 of a Soxhlet extractor or other validated method, e.g. accelerated solvent extractor (ASE). The extract is concentrated by means of a rotary evaporator, followed by further concentration under nitrogen if necessary. Sample clean-up may be necessary before quantification. An aliquot of the concentra
34、ted sample is analysed either by reversed phase high performance liquid chromatography (HPLC) or by gas chromatography-mass-spectrometry (GC-MS). The concentration of each PAH is calculated from the mass of PAH (particle- and gas-phase) determined during analysis and the volume of flue gas sampled c
35、orrected to appropriate reference conditions. 5 Safety measures All PAH should be treated as potential carcinogens. The user should be familiar with the chemical and physical properties of PAH. Measures shall be taken to prevent PAH in solid form, extract or solution coming into contact with the bod
36、y. PAH can co-distil with the solvent and may cling to the outside of glassware with ground glass stoppers. Owing in particular to the risks associated with working with PAH in solid form, self-preparation of standard solutions is ill-advised. The use of commercially available standard solutions 1)m
37、inimizes the risk of exposure. All glassware containing PAH solutions shall therefore be handled with solvent-resistant gloves. Any contamination can be revealed in ultraviolet light by fluorescence. PAH are most dangerous in solid form, becoming electrostatically charged. Therefore PAH should be we
38、ighed in a glove box. Unused samples and contaminated equipment, glassware and clothing shall be disposed of properly, taking into account the relevant regulations. 6 Procedures 6.1 HPLC method 6.1.1 General This subclause describes the preparation, sample clean-up and analytical method for determin
39、ing the concentration of polycyclic aromatic hydrocarbons (PAH) in stack and waste gases using high pressure liquid chromatography (HPLC). 1) Standard Reference Material (SRM) 1647: Priority Pollutant Polynuclear Aromatic Hydrocarbons, a certified solution of 16 PAH in acetonitrile. This solution is
40、 an example of a suitable product available commercially from The National Institute of Standards and Technology (NIST), US Department of Commerce, Gaithersburg, MD, USA. This information is given for the convenience of users of this part of ISO 11338 and does not constitute an endorsement by ISO of
41、 this product. BSISO113382:2003IS-83311 O2:(3002E) 36.1.2 Reagents and materials 6.1.2.1 Acetonitrile, HPLC grade. 6.1.2.2 n-Hexane, HPLC grade. 6.1.2.3 Methanol, HPLC grade. 6.1.2.4 Pentane, HPLC grade. 6.1.2.5 Diethyl ether, reagent grade, preserved with 2 % ethanol, HPLC grade. 6.1.2.6 Silica gel
42、, high purity grade, type 60, 70 mesh to 23 mesh. 6.1.2.7 Sodium sulfate, anhydrous, reagent grade, dried by heating at 300 C for at least 4 h. 6.1.2.8 Recovery standards for HPLC: 2-methylchrysene or 6-methylchrysene, purity at least 98 %. 6.1.2.9 Compressed gases: high purity helium for degassing
43、the mobile phase and high purity nitrogen for sample concentration. 6.1.2.10 Aluminium foil. 6.1.2.11 Glass wool. 6.1.3 Apparatus 6.1.3.1 Soxhlet extractor, capacity 100 ml to 200 ml, and appropriate condenser. 6.1.3.2 Glass-fibre filter, precleaned by heating for 3 h at 200 C or to an acceptable bl
44、ank level. 6.1.3.3 Round-bottom flasks, capacity 100 ml and either 250 ml or 500 ml depending on the capacity of the Soxhlet extractor. 6.1.3.4 Rotary evaporator system, capable of producing a maximum vacuum of 0,1 MPa (1,0 bar), and with a water bath that can be heated to 50 C. 6.1.3.5 Kuderna Dani
45、sh concentrators, capacity 500 ml, including 10 ml graduated concentrator tubes with ground-glass stoppers, and a 3-ball macro-Snyder column. 6.1.3.6 Nitrogen evaporative concentrator: nitrogen blow-down apparatus with flowrate control and temperature-controlled water bath, evaporator tubes of volum
46、e 1 ml to 10 ml. 6.1.3.7 Separation funnels, of capacity 100 ml and 250 ml. 6.1.3.8 Glass chromatography column. 6.1.3.9 Conical tubes, of 10 ml capacity. 6.1.3.10 Extraction thimbles, pre-extracted with methanol. 6.1.3.11 Laboratory refrigerator, capable of cooling to less than 4 C or freezer, capa
47、ble of cooling to less than 15 C. 6.1.3.12 Bumping granules, solvent extract. 6.1.3.13 Oven, capable of maintaining 500 C. BSISO113382:2003IS-83311 O2:(3002E) 4 6.1.3.14 High Performance Liquid Chromatography (HPLC) system, consisting of constant-flow pumps adjusted with gradient controller, an inje
48、ctor capable of injecting sample volumes up to 20 l, a means of controlling the column temperature within the range 29 C to 40 C 1 C, a fluorescence detector with programmable excitation and emission wavelengths and a UV detector adjusted to a wavelength of 229 nm, and accessories including column s
49、upplies, recorders and gases. 6.1.3.15 HPLC separation column, of glass or stainless steel 20 mm to 250 mm long and 3 mm to 4,6 mm internal diameter (ID), based on silica, derivatized with C18 alkyl chains, of particle size 3 m to 5 m. 6.1.3.16 HPLC guard column, stainless steel column for use in reversed phase chromatography (10 mm long by 2 mm ID, screen mesh 1 m, frit 0,5 m) or other suitable columns. Guard columns should al
