1、December 2015 English price group 15No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 13.060.50!%Ir*“2387907www.din.d
2、eDIN EN 16691Water 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);English version EN 16691:2015,English translation of DIN EN 16691:201
3、5-12Wasserbeschaffenheit Bestimmung von ausgewhlten polycyclischen aromatischen Kohlenwasserstoffen (PAK) in Gesamtwasserproben Verfahren mittels Festphasenextraktion (SPE) mit SPE-Disks in Verbindung mit Gaschromatographie-Massenspektrometrie (GC-MS);Englische Fassung EN 16691:2015,Englische berset
4、zung von DIN EN 16691:2015-12Qualit de leau Dosage des hydrocarbures aromatiques polycycliques (HAP) selectionns 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);Version anglais
5、e EN 16691:2015,Traduction anglaise de DIN EN 16691:2015-12www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.Document comprises 35 pages 11.152 A comma is used as the decimal marker. National foreword This document (EN 166
6、91:2015) has been prepared by Technical Committee CEN/TC 230 “Water analysis” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was DIN-Normenausschuss Wasserwesen (DIN Standards Committee Water Practice), Working Committee NA 119-01-03-02 UA Organische Verbindunge
7、n of NA 119-01-03 AA Wasseruntersuchung. Designation of the method: 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): Method DIN EN 16691 F 50 Th
8、is standard has been prepared under mandate M/424, which was given to CEN by the European Commission for the development and enhancement of standard methods in support of the Water Framework Directive (WFD) (Directive 2000/60/EC). The method specified in this standard supports the requirements given
9、 in Annex X of the Water Framework Directive (WFD). On the use of dichloromethane as a solvent (see 8.1.2 and 8.1.3): The possibility of dispensing with the use of dichloromethane as a solvent was discussed during the development of this European Standard. However, in developing the method described
10、 here it was shown that using dichloromethane gives the best results, and this solvent was thus used for the international interlaboratory test to validate the method. The German comments to the European draft standard included a warning regarding the adverse effects of dichloromethane on human heal
11、th and the environment. Other solvents that can be used for extraction and for conditioning of the SPE-disks have also been listed (see 5.4). However, Clause 8 on the procedure for conditioning and extraction does not make it sufficiently clear that solvents other than dichloromethane give comparabl
12、e results (e.g. as described by Werres et. al. and Erger et. al., see Bibliography in the National Annex). In principle, alternative extraction methods can be used where the laboratory can demonstrate the suitability of the method used (see Clause 11 for requirements). The possibility of using alter
13、natives is included in 5.4 and Clause 14. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 5725-2 DIN ISO 5725-2 ISO 28540 DIN ISO 28540 DIN EN 16691:2015-12 DIN EN 16691:2015-12 3 Expert assistance and specialized laboratories will be r
14、equired to perform the analyses described in this standard. Existing safety requirements are to be observed. Depending on the objective of the analysis, a check shall be made on a case-by-case basis as to whether and to what extent additional conditions will have to be specified. This standard has b
15、een prepared by the DIN-Normenausschuss Wasserwesen (DIN Standards Committee Water Practice) in collaboration with the Wasserchemische Gesellschaft Fachgruppe in der Gesellschaft Deutscher Chemiker (Water Chemistry Society Division of the German Chemical Society). It is part of the series Deutsche E
16、inheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung (German standard methods for the examination of water, waste water and sludge): Determination of selected polycyclic aromatic hydrocarbons (PAH) in whole water samples Method using solid phase extraction (SPE) with SPE-disks combined wi
17、th gas chromatography mass spectrometry (GC-MS) (F 50). Standard methods published as DIN Standards are obtainable from Beuth Verlag GmbH, either individually or grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche Einheits-verfahren zur Wasser-, Abwasser
18、- und Schlammuntersuchung will continue to be published by Beuth Verlag GmbH and Wiley-VCH Verlag GmbH 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 wat
19、er; 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, ground
20、 water surface water and waste water. DINEN 16691:2015-12EN 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 follow
21、ed 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 t
22、he 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
23、for 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 12
24、0127 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 1933
25、95 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 referen
26、ces 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
27、ISO 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)
28、During the inter-laboratory validation trial the method was tested for all 16 EPA PAH (see Annex B). DIN EN 16691:2015-12 EN 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 w
29、ater sample 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 analyz
30、ed by gas 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 recover
31、y, final 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.
32、 PAH are 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 qua
33、ntification 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 s
34、tainless 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 c
35、ontact 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 component
36、s may occur 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 batc
37、h, thus 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 m
38、easurement 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 incom
39、pletely 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 reac
40、hed, a suitable capillary column shall be chosen, capable to meet the required resolution. DIN EN 16691:2015-12 EN 16691:2015 (E) 7 A chromatographic resolution of R 0,8 is required for benzobfluoranthene, benzokfluoranthene and benzojfluoranthene (m/z 252). If the criterion cannot be reached for be
41、nzojfluoranthene, the sum of the co-eluting PAH shall be given in the test report. Co-eluting mass fragments of dibenzoa,hanthracene und dibenzoa,canthracene (m/z 276) may lead to interferences with indeno1,2,3-cdpyrene. The resolution shall be assessed if adjustments in the chromatographic system h
42、ave been made which may affect the resolution, e. g. shortening of the separation column, installation of a new column. The chromatographic resolution is calculated according to Figure 1 and Formula (1). Key: X time Y intensity tR1, tR2 retention time of eluting substances 1 and 2 in seconds (s) wb1
43、, wb2 peak width at the base of each peak in seconds (s) Figure 1 Resolution of chromatographic peaks =+R2 R1b1 b2()2ttRww(1) where R is the resolution; tR1, tR2 Retention time of eluting substances 1 and 2 in seconds (s); wb1, wb2 peak width at the base of each peak in seconds (s). 5 Reagents The r
44、eagents shall be free from impurities possibly interfering with the GC-MS analysis. Use solvents and reagents of sufficient purity, i.e. with negligibly low impurities compared with the concentration of analytes to be determined. As reagents use, as far as available, “residual grade”, “picograde” or
45、 better in order to obtain clean blanks. Check blanks regularly and establish proper charge control. If necessary, apply additional cleaning steps. DIN EN 16691:2015-12 EN 16691:2015(E)8 5.1 Water, complying to grade 1 according to EN ISO 3696, or equivalent. 5.2 Operating gases for the gas chromato
46、graphy mass spectrometry, of high purity and according to the manufacturers specifications. 5.3 Nitrogen of high purity, i.e. minimum 99,996 % by volume, for concentration by evaporation. 5.4 Solvents for extraction, chromatography and preparation of reference solutions. A variety of solvents may be
47、 used depending on the procedural step and the availability of commercial stock solutions, e. g. - acetone, C3H6O, (boiling point: 56 C); - dichloromethane, CH2Cl2, (boiling point: 39,7 C); - toluene, C7H8, (boiling point: 111 C); - iso-hexane, C6H14, (boiling point: 60 C). 5.5 Sodium sulfate, Na2SO
48、4, anhydrous, pre-cleaned by heating to 500 C for 4 h or free of interfering compounds. Store the dried sodium sulfate in an Erlenmeyer with a glass stopper (6.12) in the desiccator (6.11). The shelf life is 6 months. 5.6 Silica, average particle size approximately 40 m, heated at 450 C for 3 h and
49、stored in a desiccator to ensure maximum activity. 5.7 Stock solutions: For the shelf life of the stock solutions see analysis certificate of the stock solution. 5.7.1 Stock solution of internal standards (deuterated PAH standards), see Table 22). 13C-isotopically labelled PAH standards may also be used as internal standards. 5.7.2 Stock solution of the 7 target substances (native reference PAH standards), see Table 2. 5.7.3 Stock solution injection standard 1,2,3,4-Tetrachloron
