1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 16167:2012Sludge, treated biowaste and soil Determination of polychlorinated biphenyls (PCB) by gas chromatography with mass selective detection (GC-MS) and gas chromatogra
2、phy with electron-capture detection (GC-ECD)BS EN 16167:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16167:2012. The UK participation in its preparation was entrusted to T e c h n i c a l Committee H/-/4, Environmental testing programmes.A list of organi
3、zations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2012Published by BSI Standards Limited 2012I
4、SBN 978 0 580 56690 5 ICS 13.030.01; 13.080.10 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 September 2012.Amendments issued since publicationDate T e x t
5、a f f e c t e dBS EN 16167:2012EUROPEAN 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 (GC-MS) and gas chro
6、matography 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) Schlamm, behandelter
7、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 bound to comply wit
8、h 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 CEN-CENELEC Manag
9、ement 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 has the same sta
10、tus 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, Luxembourg, Malt
11、a, 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 2012 CEN All rights
12、of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16167:2012: EBS EN 16167:2012EN 16167:2012 (E) 2 Contents Page Foreword 3Introduction .41 Scope 52 Normative references 53 Terms and definitions .64 Principle 65 Interferences 75.1 Interference with
13、 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 procedure
14、s 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 (G
15、C). 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 compa
16、rison results 29Annex B (informative) Examples for retention times of PCBs 31Bibliography . 32BS EN 16167:2012EN 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, biowaste and
17、 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 February 2013
18、. 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 Commiss
19、ion 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 organi
20、c 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 Standard: Aus
21、tria, 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, Swed
22、en, Switzerland, Turkey and the United Kingdom. BS EN 16167:2012EN 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 problems w
23、hen 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 most of the r
24、outine 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 European Stand
25、ard 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 interfering compound
26、s, 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 use of in
27、ternal 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 is applica
28、ble 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 WARNING Per
29、sons 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 to ensure
30、 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. BS EN 16167:2012EN 16167:2012 (E) 5 1 Scope This European Standard specifies a method for quantitative determin
31、ation 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 7012-37-5 PCB5
32、2 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 aCAS-RN Chemi
33、cal 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 of 1 g/kg (exp
34、ressed 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 contains decision t
35、ables 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 edition cited a
36、pplies. 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 and soil Guid
37、ance 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 quality Guide
38、lines 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 function ISO 1851
39、2, Soil quality Guidance on long and short term storage of soil samples BS EN 16167:2012EN 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 chlorine atoms SOURCE:
40、 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: EN 15308:2008, 3.
41、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 procedures for different
42、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 met. Using of spik
43、ing 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 t
44、he methods referred to in 9.2, the test sample is extracted with a suitable solvent. The extract is concentrated by evaporation: If necessary, interfering compounds are removed by a clean-up method suitable for the specific matrix. The eluate is concentrated by evaporation. The extract is analyzed b
45、y gas chromatography. The various compounds are separated using a capillary column with a stationary phase of low polarity. Detection occurs with mass spectrometry (MS) or an electron capture detector (ECD) (see 8.2.1). PCBs are identified and quantified by comparison of relative retention times and
46、 relative peak heights (or peak areas) with respect to internal standards added. The efficiency of the procedure depends on the composition of the matrix that is investigated. BS EN 16167:2012EN 16167:2012 (E) 7 5 Interferences 5.1 Interference with sampling and extraction Use sampling containers of
47、 materials (preferably of steel, aluminium or glass) that do not change the sample during the contact time. Avoid plastics and other organic materials during sampling, sample storage or extraction. Keep the samples from direct sunlight and prolonged exposure to light. During storage of the samples,
48、losses of PCBs may occur due to adsorption on the walls of the containers. The extent of the losses depends on the storage time. 5.2 Interference with GC Substances that co-elute with the target PCB may interfere with the determination. These interferences may lead to incompletely resolved signals a
49、nd may, depending on their magnitude, affect accuracy and precision of the analytical results. Peak overlap does not allow an interpretation of the result. Asymmetric peaks and peaks being broader than the corresponding peaks of the reference substance suggest interferences. Chromatographic separation between the following pairs can be critical. The critical pair PCB28 and PCB31 is used for selection of the capillary column (see 8.2.2). If mo
