EN 15308-2016 en Characterization of waste - Determination of selected polychlorinated biphenyls (PCB) in solid waste by gas chromatography with electron capture or mass spectromet.pdf

1、BS EN 15308:2016Characterization of waste Determination of selectedpolychlorinated biphenyls(PCB) in solid waste by gaschromatography with electroncapture or mass spectrometricdetectionBSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 15308:2016 BRITISH STANDARDN

2、ational forewordThis British Standard is the UK implementation of EN 15308:2016. Itsupersedes BS EN 15308:2008 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee EH/4, Soil quality.A list of organizations represented on this committee can beobtained on req

3、uest to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016. Published by BSI Standards Limited 2016ISBN 978 0 580 95591 4ICS 13.030.10; 13.030.20; 13.080.10Comp

4、liance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 October 2016.Amendments/Corrigenda issued since publicationDate Text affectedBS EN 15308:2016EUROPEAN STANDARD NORME

5、 EUROPENNE EUROPISCHE NORM EN 15308 October 2016 ICS 13.030.10; 13.030.20; 13.080.10 Supersedes EN 15308:2008English Version Characterization of waste - Determination of selected polychlorinated biphenyls (PCB) in solid waste by gas chromatography with electron capture or mass spectrometric detectio

6、n Caractrisation des dchets - Dtermination de polychlorobiphnyles (PCB) slectionns dans les dchets solides par chromatographie en phase gazeuse avec dtection par capture dlectrons ou spectromtrie de masse Charakterisierung von Abfllen - Bestimmung ausgewhlter polychlorierter Biphenyle (PCB) in feste

7、m Abfall unter Anwendung der Kapillar-Gaschromatographie mit Elektroneneinfang-Detektion oder massenspektrometrischer Detektion This European Standard was approved by CEN on 21 September 2016. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions fo

8、r 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 European Standard exists in thre

9、e 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 the national standards bod

10、ies 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, Romania, Slovakia, Slovenia, S

11、pain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldw

12、ide for CEN national Members. Ref. No. EN 15308:2016 EBS EN 15308:2016EN 15308:2016 (E) 2 Contents PageEuropean foreword . 4 Introduction 5 1 Scope 6 2 Normative references 6 3 Terms and definitions . 6 4 Principle . 7 5 Reagents . 8 5.1 General 8 5.2 Reagents for extraction and drying 8 5.3 Reagent

13、s for clean-up procedures 8 5.4 Reagents for gas chromatographic analysis . 10 5.5 Standard compounds 10 5.5.1 Calibration standards . 10 5.5.2 Internal and injection standards 10 6 Apparatus 11 6.1 Extraction and clean-up procedures . 11 6.1.1 General . 11 6.1.2 Extraction procedures 11 6.1.3 Clean

14、-up procedures . 12 6.2 Gas chromatograph . 12 6.3 Capillary columns 12 7 Safety precautions . 12 8 Interferences . 13 9 Sample storage 13 10 Pretreatment . 13 10.1 General . 13 10.2 Drying . 13 10.3 Particle size reduction 13 11 Procedure 14 11.1 Blank . 14 11.2 Extraction 14 11.2.1 Extraction by s

15、haking or sonification . 14 11.2.2 Soxhlet extraction 14 11.3 Clean-up . 15 11.3.1 General . 15 11.3.2 Aluminium oxide clean-up 15 11.3.3 Silica cartridge clean-up 15 11.3.4 Silica H2SO4clean-up . 1511.3.5 Florisilclean-up 15 11.3.6 TBA clean-up 16 11.3.7 Pyrogenic copper clean-up . 16 BS EN 15308:2

16、016EN 15308:2016 (E) 3 11.3.8 AgNO3/silica clean-up . 16 11.3.9 DMSO/n-hexane partitioning clean-up . 17 11.3.10 Benzenesulfonic acid/silica cartridge clean-up 17 11.4 Gas chromatographic analysis . 17 11.4.1 General . 17 11.4.2 Optimizing the gas chromatograph 17 11.4.3 Detectors 17 11.4.4 Check on

17、 method performance . 18 11.4.5 GC-MS determination 19 11.4.6 GC-ECD determination 21 12 Calculation 22 13 Test report 22 Annex A (informative) Performance characteristics 23 A.1 General . 23 A.2 Type of samples and sample preparation . 23 A.3 Homogeneity and stability 24 A.4 Extraction 25 A.5 Clean

18、-up . 25 A.6 Detection 25 A.7 PCB standard solution 25 Annex B (informative) Examples of GC-MS chromatograms of a calibration standard solution and a contaminated soil sample 29 Annex C (informative) Examples of GC-ECD chromatograms of a calibration standard solution and a cable shredder sample 36 A

19、nnex D (normative) Calculation method for the estimation of total PCB content . 39 Annex E (informative) Summary of general requirements and recommendations 48 Bibliography . 49 BS EN 15308:2016EN 15308:2016 (E) 4 European foreword This document (EN 15308:2016) has been prepared by Technical Committ

20、ee CEN/TC 444 “Test methods for the characterization of solid matrices”, 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 April 2017, and conflicting nation

21、al standards shall be withdrawn at the latest by April 2017. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 15308:2008.

22、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, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Ger

23、many, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 15308:2016EN 15308:2016 (E) 5 Introduction Polychlorinated biphenyls (PCB) have b

24、een widely used as additives in industrial applications where chemical stability has been required. This stability on the other hand creates environmental problems when PCBs are eventually released into the environment. Since some of these PCB compounds are highly toxic, their presence in the enviro

25、nment (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 routine laboratories following the preceding steps for sampling, pretreatment, extraction, clean-up by measurement of specific PCB by me

26、ans of gas chromatography in combination with mass spectrometric detection (GC-MS) or gas chromatography with electron capture detector (GC-ECD). Taking into account the different matrices and possible interfering compounds, this European Standard does not contain one single possible way of working.

27、 Several choices are possible, in particular relating to clean-up. Detection with both Mass Spectrometry and Electron Capture is possible. Two different extraction procedures and nine clean-up procedures are described. The use of internal and injection standards is described in order to have an inte

28、rnal check on choice of the extraction and clean-up procedure. This European Standard has been validated on seven solid waste which are typically contaminated with PCB (building debris, cable shredder, contaminated soil, electronic waste, sealant waste, shredder light fraction and waste wood). Valid

29、ation data are given in Annex A (informative). BS EN 15308:2016EN 15308:2016 (E) 6 1 Scope This European Standard specifies a method for quantitative determination of seven polychlorinated biphenyl congeners (PCB-28, PCB-52, PCB-101, PCB-118, PCB-138, PCB-153 and PCB-180) in solid waste using high-r

30、esolution gas chromatography with electron capture or mass spectrometric detection. The basic content of this standard is identical to that of the Horizontal PCB-standard and is therefore also applicable to soil, sludge and treated bio-waste. The detection and the quantification limits in this metho

31、d are dependent on sample intake, the level of interferences as well as instrumental limitations. Under the conditions specified in this standard, minimum amounts of individual PCB congeners equal or above 0,01 mg/kg dry matter can typically be determined with no interferences present. NOTE For the

32、analysis of PCB in insulating liquids, petroleum products, used oils and aqueous samples is referred to EN 61619, EN 127661 and EN ISO 6468 respectively. The method may be applied to the analysis of other PCB congeners not specified in the scope, but its suitability should be proven by proper in-hou

33、se validation experiments. 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 applies. For undated references, the latest edition of the referenced do

34、cument (including any amendments) applies. EN 12766-1, Petroleum products and used oils - Determination of PCBs and related products - Part 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using an electron capture detector (ECD) EN 12766-2, Petroleum products and

35、 used oils - Determination of PCBs and related products - Part 2: Calculation of polychlorinated biphenyl (PCB) content EN 14346, Characterization of waste - Calculation of dry matter by determination of dry residue or water content 3 Terms and definitions For the purposes of this document, the foll

36、owing terms and definitions apply. 3.1 polychlorinated biphenyl PCB biphenyl substituted by one to ten chlorine atoms 3.2 congener member of the same kind, class or group of chemicals Note 1 to entry: Any one of the two hundred and nine individual PCB. Note 2 to entry: The IUPAC congener numbers are

37、 for easy identification; they do not represent the order of chromatographic elution. BS EN 15308:2016EN 15308:2016 (E) 7 3.3 calibration standard solution prepared from a secondary standard and/or stock solutions of native polychlorinated biphenyl congeners (PCB) and used to calibrate the response

38、of the instrument with respect to analyte concentration 3.4 internal standard 13C12-labelled PCB or other PCB that are unlikely to be present in waste samples added to the sample before extraction and used for quantification of PCB content 3.5 injection standard 13C12-labelled PCB or other PCB that

39、is unlikely to be present in waste samples added to the sample extract before injection into the gas chromatograph, to monitor variability of instrument response and the recovery of the internal standards 3.6 critical pair pair of congeners that needs to be separated to a predefined degree (e. g. R

40、= 0,5) to ensure chromatographic separation meets minimum quality criteria 3.7 resolution Rsdifference in retention times between the maxima of the two peaks i and j, which constitute the critical pair, divided by the arithmetic mean of the peak widths of i and j at base, calculated as: ( )( )=+Rj R

41、isbi bj2 ttRww(1) where tRjand tRiare the retention times of the two peaks i and j (sec), andwbiand wbjare the peak widths of i and j (sec) at base4 Principle A proper test portion is extracted with a mixture of organic solvents by an appropriate extraction technique (e.g. shaking, soxhlet, sonicati

42、on), partitioned against water and the organic layer separated. The obtained extracts are concentrated and, if appropriate, cleaned-up. Sample clean-up procedures may include sulphuric acid treatment, Dimethylsulfoxide/n-Hexan partitioning, column chromatography on alumina and silica. Tetrabutylammo

43、nium sulfite (TBA) or copper may be used to remove sulfur if required. The extract is analysed by gas chromatography with either mass spectrometric (GC-MS) or electron capture detection (GC-ECD). In case of GC-MS analysis quantification is performed by the isotope dilution technique. In case of GC-E

44、CD, extracts are analysed using two columns of different polarity. Quantification is conducted by the internal standard method. In case of plastic shredder a pure non-polar solvent should be used for extraction to prevent dissolving of the polymer matrix as far as possible. BS EN 15308:2016EN 15308:

45、2016 (E) 8 5 Reagents 5.1 General All reagents shall be of recognized analytical grade. Running a blank determination as described in 11.1 shall check the purity of the reagents used. 5.2 Reagents for extraction and drying 5.2.1 Acetone (2-propanone), (CH3)2CO. 5.2.2 Hexane like solvents with a boil

46、ing range of 36 C to 98 C, e.g. petroleum ether, n-hexane, n-heptane. 5.2.3 Anhydrous sodium sulfate, 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 another suitable drying reagent. The a

47、nhydrous sodium sulfate shall be kept carefully sealed. 5.3 Reagents for clean-up procedures 5.3.1 Aluminium oxide clean-up: 5.3.1.1 One of two types of alumina, acidic or basic, which can be used in the clean-up of sample extracts: acidic alumina, activate by heating to 130 C for a minimum of 12 h;

48、 basic alumina, activate by heating to 600 C for a minimum of 24 h. Preparation of deactivated aluminium oxide, the aluminium oxide is deactivated with 10 % water. To 90 g of aluminium oxide (5.3.1.1) add 10 g of water. Shake until all lumps have disappeared. Allow the aluminium oxide to condition b

49、efore use for some 16 h, sealed from the air. ICN Alumina Super I or an equivalent may be used without activation. 5.3.2 TBA sulfite reagent for sulfur removal: 5.3.2.1 Tetrabutylammonium reagent (TBA sulfite reagent): saturate a solution of tetrabutylammonium hydrogen sulfate in a mixture of equal volumina of water and 2-propanol, c(C4H9)4NHSO4) = 0,1 mol/l, with sodium sulfite. 25 g of sodium sulfite should be sufficient for 100 ml of solution. 5.3.3 Pyrogenic copper for sulfur removal: WARNING Pyrogenic copper is spontaneously inflammable. Suitabl