EN 15308-2008 7802 Characterization of waste - Determination of selected polychlorinated biphenyls (PCB) in solid waste by using capillary gas chromatography with electron capture .pdf

1、Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIg49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58p

2、olychlorinated biphenyls (PCB) in solid waste by using capillary gas chromatography with electron capture or mass spectrometric detectionICS 13.030.10; 13.030.20; 13.080.10Characterization of waste Determination of selected BRITISH STANDARDBS EN 15308:2008BS EN 15308:2008Licensed Copy: Wang Bin, ISO

3、/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIThis British Standard was published under the authority of the Standards Policy and Strategy Committee BSI 2008ISBN 978 0 580 55630 2on 30 May 2008Amendments/corrigenda issued since publicationDate Commentscontract. Users are res

4、ponsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.National forewordThis British Standard is the UK implementation of EN 15308:2008. The UK participation in its preparation was entrusted by Technical Committee B/508, Waste management

5、, to Subcommittee B/508/3, Characterization of waste.A list of organizations 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 EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15308February 2008IC

6、S 13.030.10; 13.030.20; 13.080.10English VersionCharacterization of waste - Determination of selectedpolychlorinated biphenyls (PCB) in solid waste by using capillarygas chromatography with electron capture or massspectrometric detectionCaractrisation des dchets - Dtermination depolychlorobiphnyles

7、(PCB) slectionns dans les dchetssolides par chromatographie en phase gazeuse capillaireavec dtection par capture dlectrons ou spectromtrie demasseCharakterisierung von Abfllen - Bestimmung ausgewhlterpolychlorierter Biphenyle (PCB) in festem Abfall unterAnwendung der Kapillar-Gaschromatographie mitE

8、lektroneneinfang-Detektion odermassenspektrometrischer DetektionThis European Standard was approved by CEN on 28 December 2007.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 w

9、ithout any alteration. Up-to-date lists and bibliographical references 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 languag

10、e made by translationunder the responsibility of a CEN member into its 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,Fra

11、nce, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NO

12、RMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15308:2008: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308

13、:2008 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Terms and definitions .4 4 Principle5 5 Reagents.5 6 Apparatus .9 7 Safety precautions.10 8 Interferences 10 9 Sample storage 10 10 Pre-treatment11 11 Procedure .11 12 Performance characteristics 19 13 Test report 22 Annex A (i

14、nformative) Examples of GC/MS chromatograms of a calibration standard solution and a contaminated soil sample 23 Annex B (informative) Examples of GC-ECD chromatograms of a calibration standard solution and a cable shredder sample .30 Annex C (informative) Additional validation data 33 C.1 General33

15、 C.2 Type of samples and sample preparation.33 C.3 Homogeneity and stability 34 C.4 Extraction .35 C.5 Clean-up35 C.6 Detection.35 C.7 PCB standard solution 35 Annex D (informative) Summary of general requirements and recommendations 37 Bibliography 38 BS EN 15308:2008Licensed Copy: Wang Bin, ISO/EX

16、CHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 3 Foreword This document (EN 15308:2008) has been prepared by Technical Committee CEN/TC 292 “Characterization of waste”, the secretariat of which is held by NEN. This European Standard shall be given the status of

17、 a national standard, either by publication of an identical text or by endorsement, at the latest by August 2008, and conflicting national standards shall be withdrawn at the latest by August 2008. Attention is drawn to the possibility that some of the elements of this document may be the subject of

18、 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 the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria

19、, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. BS EN 15308:2008Licensed Copy:

20、Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 4 1 Scope This document 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

21、using high-resolution 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 i

22、n this method are dependent on sample intake, the level of interferences as well as instrumental limitations. Under the conditions specified in this standard, minimum concentrations of individual PCB congeners equal or above 0,01 mg/kg dry matter can typically be determined with no interferences pre

23、sent. NOTE 1 For the analysis of PCB in insulating liquids, petroleum products, used oils and aqueous samples is referred to EN 61619, EN 12766-1 and EN ISO 6468, respectively. NOTE 2 The method may be applied to the analysis of other PCB congeners not specified in the scope, but its suitability sho

24、uld be proven by proper in-house validation experiments. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (incl

25、uding any amendments) applies. 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 following terms and definitions apply. 3.1 polychlorinated biphenyl PCB biphenyl substituted by

26、 one to ten chlorine atoms 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 The IUPAC congener numbers are for easy identification; they do not represent the order of chromatographic elution. 3.3 calibration standard solut

27、ion prepared from a secondary standard and/or stock solutions of native polychlorinated biphenyl congeners (PCB) and used to calibrate the response 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 s

28、amples added to the sample before extraction and used for quantification of PCB content BS EN 15308:2008Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 5 3.5 injection standard 13C12-labelled PCB or other PCB that is unlikely to be

29、 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 must be separated to a predefined degree (e. g. R = 0,5) to ensure chro

30、matographic 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: ( )()bjbiRiRjs2wwttR+= (1) where

31、tRjand tRiare the retention times of the two peaks i and j (sec), and wbiand wbjare the peak widths of i and j (sec) at base 4 Principle A proper test portion is extracted with a mixture of organic solvents by an appropriate extraction technique (e. g. shaking, soxhlet, sonication), partitioned agai

32、nst water and the organic layer separated. The obtained extracts are concentrated and, if appropriate, cleaned-up. Sample cleanup procedures may include sulphuric acid treatment, Dimethylsulfoxide/n-Hexan partitioning, column chromatography on alumina and silica. Tetrabutylammonium sulfite (TBA) or

33、copper may be used to remove sulfur if required. The extract is analyzed 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-ECD, extracts are analy

34、zed using two columns of different polarity. Quantification is conducted by the internal standard method. NOTE 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. 5 Reagents 5.1 General All reagents shall

35、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. 5.2.2 Hexane like solvents with a boiling range of 36 C to 98 C, e. g. petroleum ether, n-hexane, n-heptane. BS EN

36、15308:2008Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 6 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 magn

37、esium perchlorate or another suitable drying reagent. The anhydrous 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, can be used in the clean-up of sample extracts: acidic alumina,

38、 activate by heating to 130 C for a minimum of 12 h; 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 d

39、isappeared. Allow the aluminium oxide to condition before use for some 16 h, sealed from the air. NOTE 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 te

40、trabutylammonium hydrogen sulfate in a mixture of equal volumina of water and 2-propanol, c(C4H9)4NHSO4) = 0,1 mol/l, with sodium sulfite. NOTE 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 infl

41、ammable. Suitable precautions should be taken. 5.3.3.1 Copper-(II)sulfate pentahydrate, Cu5SO4 5 H2O. 5.3.3.2 Hydrochloric acid, HCl, c = 2 mol/l. 5.3.3.3 Zinc granules, particle size 0,3 mm to 1,4 mm. 5.3.3.4 Anionic detergent aqueous solution (e. g. 35 % m/V n-dodecane-1-sulfonic acid sodium salt

42、(CH3(CH2)11SO3Na). 5.3.3.5 Deoxygenated water. 5.3.4 Silica silver nitrate clean up 5.3.4.1 Silica gel (60 m to 200 m). 5.3.4.2 Silver nitrate, AgNO3.5.3.4.3 Preparation of silica gel impregnated with silver nitrate. Dissolve 10 g of AgNO3in 40 ml of water and give this mixture in portions to 90 g s

43、ilica. Shake the mixture until it is homogenous and leave standing it for 30 min. Put the mixture into a drying oven at 70 C. Within 5 h increase the temperature from 70 C up to 120 C. Activate the mixture for 15 h at 125 C. Store the mixture in brown glass bottles. BS EN 15308:2008Licensed Copy: Wa

44、ng Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 7 5.3.5 Commercially available benzenesulfonic acid/silica gel cartridges, 3 ml 5.3.6 Dimethylsulfoxide/n-hexane partitioning 5.3.6.1 Dimethylsulfoxide (DMSO). 5.3.6.2 n-hexane. 5.3.7 Sulphuric acid c

45、lean-up 5.3.7.1 Sulphuric acid, 95 % to 97 %. 5.3.8 Silica gel/sulphuric acid clean-up 5.3.8.1 Silica/H2SO444 %: Pour 28 g of activated silica and 22 g of sulfuric acid in a flask, stopper air tight and shake thoroughly until disappearance of all agglomerates. 5.3.8.2 Silica/NaOH 33% 1N: pour 33,5 g

46、 of activated silica and 16,5 g 1N NaOH in a flask, stopper air tight and shake thoroughly until disappearance of all agglomerates. 5.3.9 Commercially available silica cartridges, 3 ml or 6 ml 5.3.10 Florisil clean up 5.3.10.1 Florisil1)100 mesh to 200 mesh, activated by heating to 600 C for a minim

47、um of 2 h. 5.3.10.2 Iso-octane. 5.3.10.3 Iso-octane/Toluene 95/5. 5.4 Reagents for gas chromatographic analysis 5.4.1 Operating gases for gas chromatography, of high purity and in accordance with manufacturers specifications. 5.5 Standard compounds 5.5.1 Calibration standards Use the following PCB f

48、or the calibration: PCB-28: 2,4,4-trichlorobiphenyl (CAS number: 7012-37-5); PCB-52: 2,2,5,5-tetrachlorobiphenyl (CAS number: 35693-99-3); PCB-101: 2,2,4,5,5-pentachlorobiphenyl (CAS number: 37680-37-2); PCB-118: 2,3,4,4,5-pentachlorobiphenyl (CAS number: 31508-00-6); PCB-138: 2,2,3,4,4,5-hexachloro

49、biphenyl (CAS number: 35056-28-2); 1) Florisil is a trade name for a prepared diatomaceous substance, mainly consisting of anhydrous magnesium silicate. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of this product . Equivalent products may be used if it can be shown to lead to comparable results. BS EN 15308:2008Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 07/08/2008 03:31, Uncontrolled Copy, (c) BSIEN 15308:2008 (E) 8 P