1、BSI Standards PublicationBS EN 16691:2015Water quality Determinationof selected polycyclic aromatichydrocarbons (PAH) in wholewater samples Methodusing solid phase extraction(SPE) with SPE-disks combinedwith gas chromatography massspectrometry (GC-MS)BS EN 16691:2015 BRITISH STANDARDNational forewor
2、dThis British Standard is the UK implementation of EN 16691:2015.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 on request to its secretary.This publica
3、tion does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2015. Published by BSI Standards Limited 2015ISBN 978 0 580 84469 0ICS 13.060.50Compliance with a British Standard cannot confer immunity fr
4、omlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 30 September 2015.Amendments/corrigenda issued since publicationDate Text affectedBS EN 16691:2015EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16691 September 2015 ICS
5、 13.060.50 English Version Water quality - Determination of selected polycyclic aromatic hydrocarbons (PAH) in whole water samples - Method using solid phase extraction (SPE) with SPE-disks combined with gas chromatography mass spectrometry (GC-MS) Qualit de leau - Dosage des hydrocarbures aromatiqu
6、es polycycliques (HAP) slectionns dans des chantillons deau totale - Mthode par extraction en phase solide (SPE) avec disques SPE, avec couplage chromatographie en phase gazeuse-spectromtrie de masse (CG-SM) Wasserbeschaffenheit - Bestimmung von ausgewhlten polycyclischen aromatischen Kohlenwasserst
7、offen (PAK) in Gesamtwasserproben - Verfahren mittels Festphasenextraktion (SPE) mit SPE-Disks in Verbindung mit Gaschromatographie Massenspektrometrie (GC-MS) This European Standard was approved by CEN on 27 June 2015. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which
8、stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This Europ
9、ean Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are
10、 the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Rom
11、ania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by
12、 any means reserved worldwide for CEN national Members. Ref. No. EN 16691:2015 EBS EN 16691:2015EN 16691:2015 (E) 2 Contents Page European foreword . 3 1 Scope 5 2 Normative references 5 3 Principle . 6 4 Interferences 6 4.1 Interferences with sampling, extraction and concentration . 6 4.2 Interfere
13、nces with GC 6 5 Reagents . 7 6 Apparatus . 9 7 Sampling 10 8 Procedure 11 8.1 Sample preparation and extraction 11 8.1.1 Sample preparation . 11 8.1.2 Conditioning of SPE-disk . 11 8.1.3 Extraction and elution 11 8.1.4 Solvent concentrating . 12 8.1.5 Solvent change. 12 8.2 Gas chromatographic cond
14、itions 12 8.3 Blank measurement 12 9 Calibration 12 9.1 General . 12 9.2 Calibration by internal standard 13 10 Measurement of samples . 14 10.1 Mass spectrometric (MS) conditions . 14 10.2 Sample measurement . 14 11 Identification of individual compounds by means of GC-MS (SIM) 14 12 Calculation 16
15、 12.1 Recovery of internal standards . 16 12.2 Concentration in the sample 17 13 Expression of results . 17 14 Test report 18 Annex A (informative) Suitable gas chromatographic conditions and example chromatograms GC-conditions 19 Annex B (informative) Repeatability and reproducibility data . 22 Ann
16、ex C (informative) Dilution Schedules for standards . 26 Annex D (informative) Silica clean-up . 28 Annex E (informative) Examples of suitable solid-phase extraction disks (SPE-disks) 29 Bibliography . 30 BS EN 16691:2015EN 16691:2015 (E) 3 European foreword This document (EN 16691:2015) has been pr
17、epared by Technical Committee CEN/TC 230 “Water analysis”, the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by March 2016, and conflicting national standards s
18、hall be withdrawn at the latest by March 2016. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN an
19、d/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Cze
20、ch Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdo
21、m. BS EN 16691:2015EN 16691:2015 (E) 4 Introduction WARNING Persons using this European Standard should be familiar with usual laboratory practice. This European 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
22、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 European Standard be carried out by suitably trained staff. Polycyclic aromatic hydrocarbons (PAH) are prior
23、ity substances listed in Annex X of the EU Water Framework Directive (WFD, Directive 2000/60/EC) for which environmental quality standards (EQS) have been set at EU level for inland as well as other surface waters to protect the aquatic environment against chemical pollution (Directive 2008/105/EC).
24、 With the exception of metals, the EQSs are expressed as total concentrations in the whole water sample. Furthermore, analytical methods used in WFD monitoring need to meet certain requirements as regards the minimum limit of quantification and the maximum tolerable measurement uncertainty (Directiv
25、e 2009/90/EC). So far, there is no standardized method available for the determination of PAH in whole water samples fulfilling those requirements. Hence, the European Commission mandated CEN to develop or improve standards in support of the implementation of the monitoring requirements of WFD. Dire
26、ctive 2008/105/EC has been amended by Directive 2013/39/EU, however, this standard has been developed for the analysis of PAH as listed in Annex A of Directive 2008/105/EC. Organic compounds as specified in the WFD occur in nearly all types of water. These substances are adsorbed on solids (sediment
27、s, suspended matter) as well as dissolved in the liquid phase. A large group of these compounds are polycyclic aromatic hydrocarbons (PAH). There are further standards for the analytical determination of PAH in water and waste water: EN ISO 17993 describes a method for the determination of 15 PAH by
28、 high performance liquid chromatography/UV detection in drinking water, ground water and surface water; ISO 7981-1 and ISO 7981-2 describe methods for the determination of 6 PAH by high performance thin layer chromatography or by high performance liquid chromatography in drinking water and ground wa
29、ter; ISO 28540 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; ISO/TS 28581 describes a method for the determination of polycyclic hydrocarbons and pesticide residues in drinking water, groun
30、d water surface water and waste water. BS EN 16691:2015EN 16691:2015 (E) 5 1 Scope This European Standard specifies a method for the determination of 7 polycyclic aromatic hydrocarbons (PAH) in whole water samples listed in Table 1. The method uses solid-phase disk extraction with SPE-disks followed
31、 by gas chromatography-mass spectrometry (GC-MS). It is applicable to the analysis of PAHs in surface water containing suspended particulate matter (SPM) up to 500 mg/l (whole water samples), drinking water and groundwater. The lower and upper limit of the working range depends on the matrix, on the
32、 specific compound to be analyzed and on the sensitivity of the mass spectrometric detection unit. The limit of quantification (LOQ) determined in the validation is given in Table 1. The upper limit of the working range is approximately 2 000 ng/l. This method is, with some modifications suitable fo
33、r the analysis of waste water. This method is applicable to other PAH1), provided the method is validated for each PAH. Table 1 Polycyclic aromatic hydrocarbons (PAH) determined by this method Substance Molecular formula Molar mass EC numberaCAS-RNbLOQcg/mol ng/l anthracene C14H10178,23 2043711 1201
34、27 0,24 fluoranthene C16H10202,26 2059124 206440 2,1 benzobfluoranthene C20H12252,32 2059119 205992 0,56 benzokfluoranthene C20H12252,32 2059166 207089 0,44 benzoapyrene C20H12252,32 2000285 50328 0,33 benzoghiperylene C22H12276,34 2058838 191242 0,44 indeno1,2,3-cdpyrene C22H12276,34 2058932 193395
35、 0,42 aEC Number: European inventory of existing commercial substances (EINECS) or European list of notified chemical substances (ELINCS). bCAS-RN: Chemical Abstracts Service Registry Number. cFor the determination of the LOQ the procedure given in NEN 7777+C1:2012 12 was used. 2 Normative reference
36、s The 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 undated references, the latest edition of the referenced document (including any amendments) applies. EN IS
37、O 1042, Laboratory glassware - One-mark volumetric flasks (ISO 1042) EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696) EN ISO 5667-1, Water quality - Sampling - Part 1: Guidance on the design of sampling programmes and sampling techniques (ISO 5667-1) 1) Du
38、ring the inter-laboratory validation trial the method was tested for all 16 EPA PAH (see Annex B). BS EN 16691:2015EN 16691:2015 (E) 6 EN ISO 5667-3, Water quality - Sampling - Part 3: Preservation and handling of water samples (ISO 5667-3) 3 Principle PAH (see Table 1) present in the whole water sa
39、mple are extracted by liquid-solid extraction using an adsorption disk. An internal standard mixture is added to the sample prior to extraction. The extract is concentrated by evaporation, and the residue is dissolved in a solvent appropriate for clean-up or GC-analysis. The extract is analyzed by g
40、as chromatography separation with a low resolution mass spectrometry detection using electron impact (EI) ionization mode (6.4). The concentration of the component is calculated using calibration lines (see Clause 9) and internal standards added before extraction with a correction for recovery, fina
41、l volume and detector response. If necessary, extracts (of surface water samples) can be cleaned by column chromatography prior to analysis. (see Annex D). Prior to injection, an injection standard is added to each extract, and an aliquot of the extract is injected into the gas chromatograph. PAH ar
42、e separated on a suitable fused silica capillary column (6.5) with an efficient separation e. g. coated with a film of cross-linked non-polar polysiloxane or slightly polar modified polysiloxane. The column shall be suitable for separating benzoapyrene and benzoepyrene. Identification and quantifica
43、tion is performed by means of mass spectrometry using electron impact ionization (EI) (6.4). 4 Interferences 4.1 Interferences with sampling, extraction and concentration Use sampling containers of materials (6.1) that do not affect the analyte content during the contact time, preferably of stainles
44、s steel or glass. Avoid plastics and organic materials other than polytetrafluoroethene (PTFE) during sampling, sample storage at (3 2)C or extraction. If automatic samplers are used, avoid the use of silicone or rubber material for the tubes. If these materials are present, ensure that the contact
45、time is minimized. Rinse the sampling line with the water to be sampled before taking the test sample. EN ISO 5667-1 and EN ISO 5667-3 provide guidance. Storage temperature is at (3 2)C. For sampling and sample preservation see Clause 7. During storage of the test samples, losses of components may o
46、ccur due to adsorption on the walls of the containers. The extent of the losses may depend on the storage time. Commercially available solid-phase extraction disks (SPE-disks) differ frequently in quality. Variations in the selectivity of the materials also frequently occur from batch to batch, thus
47、 possibly causing significant deviations in extraction yield. This does not basically impair their suitability, apart from a resulting higher detection limit for individual substances. To ensure that the measuring results show high trueness and precision, use materials of one batch for both measurem
48、ent and calibration. Avoid major fluctuations in the extraction times and elution procedures within one sample sequence when analysing the samples. 4.2 Interferences with GC Substances with similar retention times and masses as the target PAH may lead to interferences and overlapping or incompletely
49、 resolved peaks in the chromatogram. Depending on their intensity those co-eluents can affect the trueness of the analysis. A chromatographic resolution of R 0,8 is required for anthracene and phenanthrene (m/z 178) and benzoapyrene and benzoepyrene (m/z 252) . If the criterion cannot be reached, a suitable capillary column shall be chosen, capable to meet the required resolution. BS EN 16691:2015EN 16691:2015 (E) 7 A chromatographic resolution of R 0,8 is required for benzobfluoranthene, benzok
