1、September 2008DEUTSCHE NORM English price group 16No part of this standard 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 13.030.01; 71.040.50
2、!$R,1“1470914www.din.deDDIN EN 15527Characterization of waste Determination of polycyclic aromatic hydrocarbons (PAH) in wasteusing gas chromatography mass spectrometry (GC/MS)English version of DIN EN 15527:2008-09Charakterisierung von Abfllen Bestimmung von polycyclischen aromatischen Kohlenwasser
3、stoffen (PAK) in Abfall mittelsGaschromatographie-Massenspektrometrie (GC/MS)Englische Fassung DIN EN 15527:2008-09www.beuth.deDocument comprises 39 pagesDIN EN 15527:2008-09 2 National foreword This standard has been prepared by Technical Committee CEN/TC 292 “Characterization of waste” (Secretaria
4、t: NEN, Netherlands). The preliminary work was done by Working Group 5 “Analysis of waste Selected group parameters” of CEN/TC 292. The responsible German body involved in its preparation was the Normenausschuss Wasser-wesen (Water Practice Standards Committee), Technical Committee 119-01-02-02 UA C
5、hemische und physi-kalische Verfahren. The DIN Standards corresponding to the International Standards referred to in the EN are as follows: ISO 14507 DIN ISO 14507 ISO 18287 DIN ISO 18287 ISO 22892 DIN ISO 22892 National Annex NA (informative) Bibliography DIN ISO 14507, Soil quality Pretreatment of
6、 samples for determination of organic contaminants DIN ISO 18287, Soil quality Determination of polycyclic aromatic hydrocarbons (PAH) Gas chromatographic method with mass spectrometric detection (GC-MS) DIN ISO 22892, Soil quality Guidelines for the identification of target compounds by gas chromat
7、ography and mass spectrometry EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15527July 2008ICS 13.030.01; 71.040.50English VersionCharacterization of waste - Determination of polycyclic aromatichydrocarbons (PAH) in waste using gas chromatography massspectrometry (GC/MS)Caractrisation des dchets
8、- Dosage des hydrocarburesaromatiques polycycliques (HAP) dans les dchets parchromatographie en phase gazeuse/spectromtrie demasse (CG/SM)Charakterisierung von Abfllen - Bestimmung vonpolycyclischen aromatischen Kohlenwasserstoffen (PAK) inAbfall mittels Gaschromatographie-Massenspektrometrie(GC/MS)
9、This European Standard was approved by CEN on 29 May 2008.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical reference
10、s concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into it
11、s own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithu
12、ania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN
13、All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15527:2008: EEN 15527:2008 (E) 2 Contents Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Principle6 5 Reagents.6 5.1 General6 5.2 Reagents fo
14、r extraction procedures6 5.3 Reagents for clean-up procedures 6 5.4 Reagents for gas chromatographic analysis7 5.5 Standards .7 6 Apparatus .8 6.1 Extraction and clean-up procedures .8 6.2 Gas chromatograph.9 6.3 Capillary columns9 6.4 Preparation of standard solutions .10 7 Hazards .11 8 Interferen
15、ce 12 8.1 Interference during sampling, storage and extraction 12 8.2 Interference due to co-elution 12 9 Sample conservation.12 10 Pretreatment.12 10.1 General12 10.2 Drying13 10.3 Particle size reduction.13 11 Procedure .13 11.1 Blank .13 11.2 Extraction .13 11.3 Addition of the internal standard
16、solution 14 11.4 Concentration or dilution14 11.5 Clean up of the extract 14 11.6 Addition of the injection standard .15 11.7 Gas chromatographic analysis with mass spectrometric detection15 12 Performance characteristics 19 13 Test report 22 Annex A (informative) Representative chromatograms23 Anne
17、x B (informative) Additional validation data 32 Annex C (informative) Summary of general requirements and recommendations36 Bibliography 37 DIN EN 15527:2008-09 EN 15527:2008 (E) 3 Foreword This document (EN 15527:2008) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”,
18、 the secretariat of which is held by NEN. 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 January 2009, and conflicting national standards shall be withdrawn at the latest by January 2009. Attenti
19、on is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/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 organizations of th
20、e following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovaki
21、a, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DIN EN 15527:2008-09 EN 15527:2008 (E) 4 Introduction Polynuclear aromatic hydrocarbons (PAH) are ubiquitous because of the fact that they are released in appreciable quantities every year into the environment through the combustion of
22、organic materials such as coal, fuel oils, petrol, wood, refuse and plant materials. Since some of these PAH compounds are carcinogenic or mutagenic, their presence in the environment (air, water, soil, sediment and waste) are regularly monitored and controlled. At present, the determination of PAH
23、is carried out in these matrices in most of the routine laboratories following the preceding steps for sampling, pre-treatment, extraction, clean-up by measurement of specific PAH by means of gas chromatography in combination with mass spectrometric detection(GC-MS) or by HPLC in combination with UV
24、-DAD- or Fluorescence-detection (HPLC-UV-DAD/FLD). However, the different matrices covered in this standard may contain a lot of contaminants. For this reason, the GC-MS method seems to be most appropriate for waste analysis. DIN EN 15527:2008-09 EN 15527:2008 (E) 5 1 Scope This European Standard sp
25、ecifies the quantitative determination of 16 polynuclear aromatic hydrocarbons (PAH) according to the priority list of the Environmental Protection Agency (EPA, 1982). This European Standard is applicable for wastes such as contaminated soil, sludge and rubble, bitumen or waste containing bitumen. T
26、his European Standard describes a gas chromatographic method with mass spectrometric detection (GC-MS). Under the conditions specified in this document, a typical lower limit of application of 0,1 mg/kg for each individual PAH can be achieved. NOTE 1 This method may be applied to the analysis of oth
27、er PAH compounds not specified in the scope provided its applicability has been proven by proper in-house validation experiments. NOTE 2 For some materials, e. g. bitumen, the lower limit of application of 0,1 mg/kg cannot be achieved due to interferences. NOTE 3 Under certain circumstances the meth
28、od may be applicable to PAH concentrations lower than 0,1 mg/kg but it is in the responsibility of the laboratory to provide proper validation data for such low concentrations. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated
29、 references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 14346, Characterization of waste Calculation of dry matter by determination of dry residue or water content EN 15002, Characterization of waste Pr
30、eparation of test portions from the laboratory sample ISO 14507, Soil quality Pretreatment of samples for determination of organic contaminants 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 analyte selected polynuclear aromatic hydrocarbons
31、 (PAH) with 2 to 6 condensed aromatic rings (see Table 1) 3.2 calibration standard solution of PAH prepared from a secondary standard and/or stock solutions of native PAH and deuterated PAH used to calibrate the response of the instrument 3.3 extraction standard deuterated PAH or native (unlabeled)
32、PAH of medium volatility that are unlikely to be present in waste added to the sample before extraction and used for control of the extraction efficiency DIN EN 15527:2008-09 EN 15527:2008 (E) 6 3.4 internal standard deuterated PAH added to the sample after extraction and used for quantification of
33、the concentrations of PAH in the sample 3.5 injection standard deuterated or native PAH that are unlikely to be present in waste samples added to the sample extract before injection into the GC, to monitor variability of instrument response and the recovery of the internal/extraction standards 4 Pri
34、nciple The PAH are extracted from the sample by use of acetone and a hexane-like solvent. If appropriate, the obtained extract is purified by adsorption column chromatography. The extract is analysed by gas chromatography with mass spectrometric detection (GC-MS) using capillary columns of low polar
35、ity. Concentrations of PAH are quantified using an internal-standard-method. 5 Reagents 5.1 General All reagents shall be of recognised analytical grade. The suitability of the reagents shall be checked by running a blank determination as described in 11.1. 5.2 Reagents for extraction procedures 5.2
36、.1 Reagents for extraction by shaking/sonication 5.2.1.1 Acetone. 5.2.1.2 Petroleum ether (Boiling range 40 C to 60 C) or n-hexane or iso-hexane or cyclohexane (hexane-like solvents with a boiling range between 30 C and 68 C are allowed). 5.2.1.3 Sodium chloride, anhydrous. 5.2.1.4 Distilled water o
37、r water of equivalent quality. 5.2.1.5 Anhydrous sodium sulphate, heated for at least 6 h to 550 C 20 C, cooled to about 200 C in the furnace and then to ambient temperature in a desiccator containing magnesium perchlorate or a suitable alternative. The anhydrous sodium sulphate shall be kept carefu
38、lly sealed. Commercial available anhydrous sodium sulphate is also applicable. 5.2.2 Reagents for Soxhlet extraction 1:1 (v/v) mixtures of acetone/petroleum ether (boiling range 40 C to 60 C) or acetone/ n-hexane or acetone/iso-hexane or acetone/cyclohexane. 5.3 Reagents for clean-up procedures 5.3.
39、1 Clean-up A Aluminium oxide 5.3.1.1 Aluminium oxide basic or neutral, specific surface 200 m2/g, activity Super I. DIN EN 15527:2008-09 EN 15527:2008 (E) 7 5.3.1.2 Preparation of deactivated aluminium oxide. Add 10 g of water to 90 g of aluminium oxide (5.3.1.1). Shake until all lumps have disappea
40、red. Allow the aluminium oxide to equilibrate before use for some 16 h, sealed from air. Use it for a maximum of 2 weeks. 5.3.2 Clean up B- Silica gel 60 5.3.2.1 Silica gel 60, particle size 63 m to 200 m. 5.3.2.2 Preparation of silica gel 60 with a water content of 10 % (w/w). Silica gel 60, heated
41、 for at least 3 h at 450 C, cooled down and stored in a desiccator containing magnesium perchlorate or another suitable drying agent. Before use, heat it once again at least for 5 h at 130 C in a drying oven. Then allow to cool in a desiccator to ambient temperature. Transfer the silica gel to a fla
42、sk and add 10 % water (w/w). Shake for 5 min intensively by hand until all lumps have disappeared and then for 2 h in a shaking machine. Store the deactivated silica gel sealed from air and use it for maximum of one week. 5.4 Reagents for gas chromatographic analysis Carrier gas for gas chromatograp
43、hy, e. g. helium of suitable purity. 5.5 Standards 5.5.1 Calibration standards, extraction standards and internal standards Choose internal/extraction standard substances whose physical and chemical properties (such as extraction behaviour, retention time) are similar to those of the compounds to be
44、 analysed. Deuterated PAH should be used as internal standards for the GC-MS method for evaluation of results. Verify the stability of the internal/extraction standards regularly. Table 1 contains native and a minimum number of deuterated PAH to be used for calibration of specific analytes. The use
45、of isotope dilution (each native PAH is quantified with respect to his labelled analogue) is recommended. NOTE Certified solutions of PAH and single solid PAH substances with certified purity are commercially available. DIN EN 15527:2008-09 EN 15527:2008 (E) 8 Table 1 Native PAH and deuterated PAH P
46、AH reference substances for calibration Internal/extraction standard substances: (deuterated PAH) Naphthalene (CAS No. 91-20-3) Naphthalene- D8Acenaphthene (CAS No.83-32-9) Acenaphthene-D10Acenaphthylene (CAS No.208-96-8) Fluorene (CAS No.86-73-7) Anthracene (CAS No.120-12-7) Phenanthrene (CAS No. 8
47、5-01-8) Phenanthrene-D10 (extraction standard) Fluoranthene (CAS No.206-44-0) Pyrene (CAS No.129-00-0) Benzo(a)anthracene (CAS No.56-55-3) Benzo(a)anthracene-D12Chrysene (CAS.No.218-01-9) Benzo(b)fluoranthene (CAS No. 205-99-2) Benzo(k)fluoranthene (CAS No.207-08-9) Benzo(a)pyrene (CAS No.50-32-8) B
48、enzo(a)pyrene-D12Indeno(1,2,3-cd)pyrene (CAS No.193-39-5) Dibenzo(ah)anthracene (CAS No.53-70-3) Benzo(ghi)perylene (CAS No.191-24-2) Perylene-D125.5.2 Injection standards A deuterated PAH is added to the final extract before GC-MS injection to check the recovery of the deuterated internal/extractio
49、n standards. Suitable injection standards are 1-methylnaphthalene-D10, benzo(e)pyrene-D10and triphenylene-D12. 6 Apparatus 6.1 Extraction and clean-up procedures Customary laboratory glassware. All glassware and material that comes into contact with the sample or extract shall be free of PAH and any interfering compounds. 6.1.1 Extraction procedures 6.1.1.1 Glass sample bottles of appropriate size with glass stopper or screw top and polytetrafluorethene seal (PTFE). DIN EN 15527:2008-09 EN 15527:2008 (E) 9 6.1.1.2 Shakin
