DIN EN 16167-2012 Sludge treated biowaste and soil - Determination of polychlorinated biphenyls (PCB) by gas chromatography with mass selective detection (GC-MS) and gas chromatogr.pdf

1、November 2012 Translation by DIN-Sprachendienst.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).I

2、CS 13.080.10; 13.030.01!$B+“1923108www.din.deDDIN EN 16167Sludge, treated biowaste and soil Determination of polychlorinated biphenyls (PCB) by gaschromatography with mass selective detection (GC-MS) and gaschromatography with electron-capture detection (GC-ECD);English version EN 16167:2012,English

3、 translation of DIN EN 16167:2012-11Schlamm, behandelter Bioabfall und Boden Bestimmung von polychlorierten Biphenylen (PCB) mittels Gaschromatographie mitmassenspektrometrischer Detektion (GC-MS) und Gaschromatographie mitElektroneneinfangdetektion (GC-ECD);Englische Fassung EN 16167:2012,Englische

4、 bersetzung von DIN EN 16167:2012-11Boues, bio-dchets traits et sols Dtermination des biphnyles polychlors (PCB) par chromatographie en phasegazeuse-spectromtrie de masse (CG-SM) et chromatographie en phase gazeuse avecdtection par capture dlectrons (CG-DCE);Version anglaise EN 16167:2012,Traduction

5、 anglaise de DIN EN 16167:2012-11www.beuth.deDocument comprises 36 pagesIn case of doubt, the German-language original shall be considered authoritative.10.12 DIN EN 16167:2012-11 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC

6、 400 “Project Committee Horizontal standards in the fields of sludge, biowaste and soil” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the Normenausschuss Wasserwesen (WaterPractice Standards Committee), Working Committee NA 119-01-02 Abfall- und Bodenunter

7、suchungNA119-01-02-02 AA Chemische und physikalische Verfahren. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 5725-2 DIN ISO 5725-2 ISO 8466-1 DIN 38402-51 ISO 18512 DIN ISO 18512 ,DIN EN 16167:2012-11 3 National Annex NA (informative

8、) Bibliography DIN 38402-51, German standard methods for the examination of water, waste water and sludge General information (group A) Calibration of analytical methods, evaluation of analytical results and linear calibration functions used to determine the performance characteristics of analytical

9、 methods (A 51) DIN ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method DIN ISO 18512, Soil quality Guidance on long and short term storage of soil samples DI

10、N EN 16167:2012-11 4 This page is intentionally blank EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16167 August 2012 ICS 13.030.01; 13.080.10 English Version Sludge, treated biowaste and soil Determination of polychlorinated biphenyls (PCB) by gas chromatography with mass selective detection

11、 (GC-MS) and gas chromatography with electron-capture detection (GC-ECD) Boues, bio-dchets traits et sols Dtermination des biphnyles polychlors (PCB) par chromatographie en phase gazeuse-spectromtrie de masse (CG-SM) et chromatographie en phase gazeuse avec dtection par capture dlectrons (CG-DCE) Sc

12、hlamm, behandelter Bioabfall und Boden Bestimmung von polychlorierten Biphenylen (PCB) mittels Gaschromatographie mit massenspektrometrischer Detektion (GC-MS) und Gaschromatographie mit Elektroneneinfangdetektion (GC-ECD) This European Standard was approved by CEN on 24 May 2012. CEN members are bo

13、und to comply with the CEN/CENELEC Internal Regulations which 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

14、CEN-CENELEC 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 translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre

15、 has the same status as the official versions. CEN members are 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,

16、 Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 201

17、2 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16167:2012: E EN 16167:2012 (E) 2 Contents Page Foreword 3Introduction .41 Scope 52 Normative references 53 Terms and definitions .64 Principle 65 Interferences 75.1 Interference wi

18、th sampling and extraction .75.2 Interference with GC 76 Safety remarks .77 Reagents .87.1 General 87.2 Reagents for extraction .87.3 Reagents for clean-up .87.4 Gas chromatographic analysis . 117.5 Standards 117.6 Preparation of standard solutions 138 Apparatus 138.1 Extraction and clean-up procedu

19、res 138.2 Gas chromatograph 149 Sample storage and preservation . 159.1 Sample storage . 159.2 Sample pretreatment 1510 Procedure 1510.1 Blank test . 1510.2 Extraction 1510.3 Concentration 1710.4 Clean-up of the extract . 1810.5 Addition of the injection standard 2110.6 Gas chromatographic analysis

20、(GC). 2110.7 Mass spectrometry (MS) 2210.8 Electron capture detection (ECD) . 2611 Performance characteristics . 2812 Precision 2813 Test report . 28Annex A (informative) Repeatability and reproducibility data . 29A.1 Materials used in the interlaboratory comparison study . 29A.2 Interlaboratory com

21、parison results 29Annex B (informative) Examples for retention times of PCBs 31Bibliography . 32DIN EN 16167:2012-11EN 16167:2012 (E) 3 Foreword This document (EN 16167:2012) has been prepared by Technical Committee CEN/TC 400 “Project Committee - Horizontal standards in the fields of sludge, biowas

22、te and soil”, 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 February 2013, and conflicting national standards shall be withdrawn at the latest by Februar

23、y 2013. Attention 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. This document has been prepared under a mandate given to CEN by the European C

24、ommission and the European Free Trade Association. The preparation of this document by CEN is based on a mandate by the European Commission (Mandate M/330), which assigned the development of standards on sampling and analytical methods for hygienic and biological parameters as well as inorganic and

25、organic determinants, aiming to make these standards applicable to sludge, treated biowaste and soil as far as this is technically feasible. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standar

26、d: 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, Romania, Slovakia, Slovenia, Spain

27、, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 16167:2012-11EN 16167:2012 (E) 4 Introduction Polychlorinated biphenyls (PCB) have been widely used as additives in industrial applications where chemical stability has been required. This stability on the other hand creates environmental

28、problems when PCBs are eventually released into the environment. Since some of these PCB compounds are highly toxic, their presence in the environment (air, water, soil, sediment and waste) is regularly monitored and controlled. At present determination of PCB is carried out in these matrices in mos

29、t of the routine laboratories following the preceding steps for sampling, pretreatment, extraction, clean-up by measurement of specific PCB by means of gas chromatography in combination with mass spectrometric detection (GC-MS) or gas chromatography with electron capture detector (GC-ECD). This Euro

30、pean Standard was developed in the European project HORIZONTAL. It is the result of a desk study “3-12 PCB” and aims at evaluation of the latest developments in assessing PCBs in sludge, soil, treated biowaste and neighbouring fields. Taken into account the different matrices and possible interferin

31、g compounds, this European Standard does not contain one single possible way of working. Several choices are possible, in particular relating to clean-up. Detection with both MS-detection and ECD-detection is possible. Two different extraction procedures are described and 11 clean-up procedures. The

32、 use of internal and injection standards is described in order to have an internal check on choice of the extraction and clean-up procedure. The method is as far as possible in agreement with the method described for PAHs (see CEN/TS 16181). It has been tested for ruggedness. This European Standard

33、is applicable and validated for several types of matrices as indicated in Table 1 (see also Annex A for the results of the validation). Table 1 Matrices for which this European Standard is applicable and validated Matrix Materials used for validation Sludge Municipal sewage sludge Biowaste Compost W

34、ARNING 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 establish appropriate safety and health practices and

35、 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. DIN EN 16167:2012-11EN 16167:2012 (E) 5 1 Scope This European Standard specifies a method for quantit

36、ative determination of seven selected polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB118, PCB138, PCB153 and PCB180) in sludge, treated biowaste and soil using GC-MS and GC-ECD (see Table 2). Table 2 Target analytes of this European Standard Target analyte CAS-RNa PCB28 2,4,4-trichlorobiphenyl

37、7012-37-5 PCB52 2,2,5,5-tetrachlorobiphenyl 35693-99-3 PCB101 2,2,4,5,5-pentachlorobiphenyl 37680-37-2 PCB118 2,3,4,4,5-pentachlorobiphenyl 31508-00-6 PCB138 2,2,3,4,4,5-hexachlorobiphenyl 35056-28-2 PCB153 2,2,4,4,5,5-hexachlorobiphenyl 35065-27-1 PCB180 2,2,3,4,4,5,5-heptachlorobiphenyl 35065-29-3

38、 aCAS-RN Chemical Abstracts Service Registry Number. The limit of detection depends on the determinants, the equipment used, the quality of chemicals used for the extraction of the sample and the clean-up of the extract. Under the conditions specified in this European Standard, limit of application

39、of 1 g/kg (expressed as dry matter) can be achieved. Sludge and treated biowaste may differ in properties and also in the expected contamination levels of PCBs and presence of interfering substances. These differences make it impossible to describe one general procedure. This European Standard conta

40、ins decision tables based on the properties of the sample and the extraction and clean-up procedure to be used. 2 Normative references 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 e

41、dition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 15934, Sludge, treated biowaste, soil and waste Calculation of dry matter fraction after determination of dry residue or water content EN 16179, Sludge, treated biowaste

42、 and soil Guidance for sample pretreatment EN ISO 5667-15, Water quality Sampling Part 15: Guidance on the preservation and handling of sludge and sediment samples (ISO 5667-15) EN ISO 16720, Soil quality Pretreatment of samples by freeze-drying for subsequent analysis (ISO 16720) EN ISO 22892, Soil

43、 quality Guidelines for the identification of target compounds by gas chromatography and mass spectrometry (ISO 22892) ISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration fun

44、ction ISO 18512, Soil quality Guidance on long and short term storage of soil samples DIN EN 16167:2012-11EN 16167:2012 (E) 6 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 polychlorinated biphenyl PCB biphenyl substituted by one to ten chlo

45、rine atoms SOURCE: EN 15308:2008, 3.1 3.2 congener member of the same kind, class or group of chemicals, e.g. anyone of the two hundred and nine individual PCB Note 1 to entry: The IUPAC congener numbers are for easy identification; they do not represent the order of chromatographic elution. SOURCE:

46、 EN 15308:2008, 3.2 3.3 critical pair pair of congeners that will be separated to a predefined degree (e.g. R = 0,5) to ensure chromatographic separation meets minimum quality criteria SOURCE: EN 15308:2008, 3.6 4 Principle Due to the horizontal character of this European Standard, different procedu

47、res for different steps (modules) are allowed. Which modules should be used depends on the sample. A recommendation is given in this European Standard. Performance criteria are described and it is the responsibility of the laboratories applying this European Standard to show that these criteria are

48、met. Using of spiking standards (internal standards) allows an overall check on the efficiency of a specific combination of modules for a specific sample. But it does not necessarily give the information upon the extensive extraction efficiency of the native PCB bonded to the matrix. After pretreatment according to the methods referred to in 9.2, the test sample is extracted with a suitable