1、ICS 13.060.50Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung; Schlamm und Sedimente(Gruppe S) Teil 24: Bestimmung von polychlorierten Dibenzodioxinen (PCDD) und polychloriertenDibenzofuranen (PCDF) (S 24)In keeping with current practice in standards published by the Interna
2、tional Organization for Standardization(ISO), a comma has been used throughout as the decimal marker.ForewordThis standard has been jointly prepared by the Normenausschuss Wasserwesen (Water Practice StandardsCommittee) and Study Group Wasserchemie (Water Chemistry) of the Gesellschaft Deutscher Che
3、miker(German Chemists Society) (see Explanatory notes).Expert assistance and specialized laboratories will be required to perform the analyses specified in thisstandard. Existing safety instructions shall be observed.Depending on the objective of the analysis, a check shall be made on a case-by-case
4、 basis as to whetherand to what extent additional conditions will have to be specified.Ref. No. DIN 38414-24 : 2000-10English price group 09 Sales No. 010905.02DEUTSCHE NORM October 200038414-24Continued on pages 2 to 15. No part of this translation may be reproduced without the prior permission ofD
5、IN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).German standard methods for the examination of water, waste water and sludgeSludge and sediments (group S)Part 24: Determination of polychlorinat
6、ed dibenzodioxins (PCDDs)and polychlorinated dibenzofurans (PCDFs) (S 24)Translation by DIN-Sprachendienst.In case of doubt, the German-language original should be consulted as the authoritative text.1 ScopeThe method specified in this standard serves to examine sludge and sediments for the presence
7、 of 17 tetra-to octa-substituted PCDDs and PCDFs having chlorine substitution in positions 2, 3, 7 and 8, the methodbeing applicable for minimum concentrations of each component ranging from about 1 ng/kg to 10 ng/kgof dry matter.2 Normative referencesThis standard incorporates, by dated or undated
8、reference, provisions from other publications. Thesenormative references are cited at the appropriate places in the text, and the titles of the publications are listedbelow. For dated references, subsequent amendments to or revisions of any of these publications apply tothis standard only when incor
9、porated in it by amendment or revision. For undated references, the latestedition of the publication referred to applies.DIN 12039 Wide mouth, flat bottom flasks with conical ground glass socket and stopper, forlaboratory useDIN 12252 Conical ground glass stoppers for laboratory useDIN 12449 Extract
10、ion thimbles made of raw paper-making material for laboratory useDIN 12451 Separating funnels with interchangeable stopcocks for laboratory useDIN 12491 Vacuum desiccators for laboratory useDIN 12591 Dimroth condensers with conical ground joint for laboratory useDIN 12680-1 Graduated cylinders for l
11、aboratory useDIN 38414-22 German standard methods for the examination of water, waste water and sludge Sludgeand sediments (group S) Freeze-drying of sludge and determination of freeze-dryingresidue (S 22)DIN EN ISO 1042 Laboratory glassware One-mark volumetric flasks (ISO 1042 : 1998)Klrschlammvero
12、rdnung (German Regulation on the treatment of sewage sludge), as of 15 April 1992, BGBl.(Federal Law Gazette) I, 1992, no. 21, 912934.Gesetz ber Einheiten im Messwesen (German Law on units in metrology), as of 22 February 1985, BGBl. I,1985, No. 11, pp. 409 and 410.Page 2DIN 38414-24 : 2000-103 Prin
13、ciple13C12-labelled PCDD and PCDF standards are added to a freeze-dried sample, which is then extracted withtoluene. After removing interfering impurities from the extract by column chromatography, the PCDDs andPCDFs are separated by capillary gas chromatography and determined by mass spectrometry u
14、sing selectedion monitoring (SIM). Quantification is carried out by calibrating the overall procedure using 13C12-labelledinternal standards.4 InterferenceIn a very few cases, dibenzodioxins and dibenzofurans with mixed halogenation may be superimposed on the13C12-labelled standards. Thus, the PCDF
15、13C12standards having masses of (M +4)+and (M +6)+occur in thesame retention range as the PCDD masses M+and (M +2)+.5 DesignationDesignation of the method of determining polychlorinated dibenzodioxins (PCDDs) and polychlorinateddibenzofurans (PCDFs) in sludge and sediments by capillary gas chromatog
16、raphy and mass spectrometry (S 24):Method DIN 38414 S 246 ApparatusAny equipment that comes into contact with the sample shall be free of PCDDs and PCDFs within the limits ofdetermination. The glassware used shall be rinsed with an organic solvent (e.g. acetone) prior to analysis.The following equip
17、ment shall be used.6.1 Wide mouth, flat bottom sampling flask, made of brown glass, of nominal capacity 1000 to 5000 ml,fitted with DIN 12252 stopper (e.g. DIN 12039 W 1000 G flat bottom flask).6.2 Vibrating disc mill, mortar or any other suitable grinding equipment.6.3 Oven.6.4 Freezer, capable of
18、maintaining temperatures down to at least 35 C (see DIN 38414-22).6.5 Lyophilizer, capable of maintaining pressures down to 37 Pa (see DIN 38414-22).6.6 Flat bottom dishes, made of aluminium or stainless steel, of diameter 20 cm and rim height about 2,5 cm.6.7 Flat stainless steel test sieves, with
19、a mesh size of about 0,2 mm.6.8 Desiccator (e.g. as in DIN 12491).6.9 Extractor, consisting, for example, of the following components:6.9.1 Round bottom flask, of nominal capacity 500 ml.6.9.2 Soxhlet extractor, of nominal capacity 300 ml.6.9.3 Dimroth condenser (e.g. DIN 12591 D 250-29 condenser).6
20、.9.4 Heater with temperature control device (e.g. flask heater or safety heating jacket).6.9.5 Extraction thimbles (e.g. DIN 12449 extraction thimbles).6.10 Rotary evaporator, with controlled vacuum.6.11 Glass separating column, of internal diameter 20 mm and length about 400 mm, with dispensing ves
21、sel,for preliminary liquid chromatography.6.12 Glass separating column, of internal diameter 10 mm and length about 350 mm, with dispensing vessel,for preliminary liquid chromatography.6.13 Glass separating column, of internal diameter 25 mm and length about 400 mm, with dispensing vessel,for prelim
22、inary liquid chromatography.6.14 Measuring cylinders, of nominal capacities 100 ml and 250 ml (e.g. DIN 12680 ME 100 measuringcylinders).Page 3DIN 38414-24 : 2000-106.15 Separating funnel, of nominal capacity 1000 ml (e.g. DIN 12451 L 1000 separating funnel).6.16 Volumetric flasks, of nominal capaci
23、ties 1 ml, 2 ml, 10 ml and 25 ml (e.g. ISO 1042 A1 C volumetricflasks).6.17 Disposable Pasteur pipettes (e.g. of capacity 2 ml).6.18 Microlitre syringes, of nominal capacities 2 ml, 5 ml, 10 ml and 50 ml and accurate to t 2% (V/V).6.19 Gas chromatograph, fitted with mass spectrometer (GC/MS).6.20 Gl
24、ass or fused silica capillary column, coated with a strongly polar stationary phase and having aninternal diameter of less than 0,5 mm, a length of about 60 m and a film thickness of 0,20 mm to 0,35 mm; thequality of the column shall be checked and 2,3,7,8-tetrachlorodibenzodioxin and 2,3,7,8-tetrac
25、hloro-dibenzofuran shall not be overlapped by other isomers.6.21 Autosampler flasks (e.g. of nominal capacity 100 ml).7 Reagents7.1 GeneralOnly reagents of analytical grade shall be used and the water used shall be distilled water or water of equivalentpurity.All the reagents shall have a purity tha
26、t permits the PCDDs and PCDFs to be determined by mass spectrometrywithin the limits of detection of this method. This shall be checked by blank tests and maintained by additionalclean-up steps, if necessary.The following reagents shall be used.7.2 Basic aluminium oxide, of activity B super I.7.3 Si
27、lica gel 60, of particle size 0,075 mm to 0,2 mm1).7.4 Silver nitrate, AgNO3.7.5 Sulfuric acid, H2SO4, of density 1,84 g/ml.7.6 1moc108/c108 sodium hydroxide solution, NaOH.7.7 Toluene, C7H8, of residue analysis grade.7.8 n-hexane, C6H14, of residue analysis grade.7.9 Dichloromethane, CH2Cl2, of res
28、idue analysis grade.7.10 Benzene, C6H6, of residue analysis grade.7.11 17 13C12-labelled PCDD and PCDF standards having chlorine substitution in positions 2, 3, 7 and 8:13C12-2,3,7,8-tetrachlorodibenzodioxin (tetra-CIDD);13C12-1,2,3,7,8-pentachlorodibenzodioxin (penta-CIDD);13C12-1,2,3,6,7,8-hexachl
29、orodibenzodioxin (hexa-CIDD);13C12-1,2,3,4,7,8-hexachlorodibenzodioxin (hexa-CIDD);13C12-1,2,3,7,8,9-hexachlorodibenzodioxin (hexa-CIDD);13C12-1,2,3,4,6,7,8-heptachlorodibenzodioxin (hepta-CIDD);13C12-octachlorodibenzodioxin (octa-CIDD)and1) The particle size is denoted commercially by 70 mesh to 23
30、0 mesh. (Use of the unit mesh is prohibited inGermany for official and commercial purposes by the Gesetz ber Einheiten im Messwesen.)Page 4DIN 38414-24 : 2000-1013C12-2,3,7,8-tetrachlorodibenzofuran (tetra-CIDF);13C12-1,2,3,7,8-pentachlorodibenzofuran (penta-CIDF);13C12-2,3,4,7,8-pentachlorodibenzof
31、uran (penta-CIDF);13C12-1,2,3,4,7,8-hexachlorodibenzofuran (hexa-CIDF);13C12-1,2,3,6,7,8-hexachlorodibenzofuran (hexa-CIDF);13C12-2,3,4,6,7,8-hexachlorodibenzofuran (hexa-CIDF);13C12-1,2,3,7,8,9-hexachlorodibenzofuran (hexa-CIDF);13C12-1,2,3,4,6,7,8-heptachlorodibenzofuran (hepta-CIDF);13C12-1,2,3,4
32、,7,8,9-heptachlorodibenzofuran (hepta-CIDF);13C12-octachlorodibenzofuran (octa-CIDF).7.1213C12-labelled 1,2,3,4-tetrachlorodibenzodioxinThe actual concentration of commercially available 13C12-labelled standard solutions shall be checked (e.g. bycomparison with certified standard solutions) and corr
33、ected if the concentration differs by more than 10 %.7.13 Standard solution, consisting of all the PCDD and PCDF standards (not 13C12-labelled) having chlorinesubstitution in positions 2, 3, 7 and 8 (see table 1).7.14 Silver nitrate/silica gel adsorbent, to be prepared by dissolving 10 g of AgNO3in
34、40 ml of water in a100 ml conical flask, adding the solution in portions to 90 g of silica gel 60, shaking the mixture until it ishomogeneous and allowing it to stand for 30 minutes.Place the mixture in an oven heated to 70 C, allow the temperature to rise to 125 C in the course of five hoursand act
35、ivate the mixture at 125 C for 15 hours. Store the mixture in a brown bottle.7.15 Sulfuric acid/silica gel adsorbent, to be prepared by adding 44 g of sulfuric acid in portions to 56 g ofactivated silica gel 60 and shaking until the mixture is homogeneous. Store the mixture in a desiccator in a seal
36、edglass bottle.7.16 Sodium hydroxide solution/silica gel adsorbent, to be prepared by adding 33 g of sodium hydroxidesolution in portions to 67 g of silica gel 60, shaking until the material is homogenous and pourable. Store themixture in a sealed glass bottle.7.17 Internal standard solution, prepar
37、ed in toluene in a 10 ml volumetric flask and having concentrationsof 5 pg/ml for tetra-CIDD and tetra-CIDF, 10 pg/ml for penta-, hexa- and hepta-CIDD and penta-, hexa- andhepta-CIDF, and 20 pg/ml for octa-CIDD and octa-CIDF.7.18 Standard solution for checking the accuracy of recovery, consisting of
38、 a solution of 13C12-labelled1,2,3,4-tetrachlorodibenzodioxin prepared in toluene in a 10 ml volumetric flask and having a concentration of50 pg/ml. The concentrations of internal standard and accuracy of recovery standard in the test solution shallbe in the same order of magnitude.7.19 Standard sol
39、ution for determining retention times, consisting of a solution of the PCDDs and PCDFs(as in subclause 7.13), prepared in toluene in a 10 ml volumetric flask and having concentrations of 5 pg/ml fortetra-CIDD and tetra-CIDF, 10 pg/ml for penta-, hexa- and hepta-CIDD and penta-, hexa- and hepta-CIDF
40、and20 pg/ml for octa-CIDD and octa-CIDF.The internal standard solution and the solution for checking the accuracy of recovery shall be kept in glassvessels having ground glass stoppers and cooled to at least 18 C. They shall be allowed to come to ambienttemperature and become homogenized before use.
41、 The contents of the vessels shall be checked to determinewhether solvent has evaporated and a correction made if necessary.As an alternative, the internal standard solutions may be divided into portions in sample bottles and the contentsof one or more standard bottles (depending on the expected con
42、centration) added for each analysis.7.20 99,999 % (m/m) nitrogen, N2.7.21 Styrene/divinylbenzene copolymer, of particle size 0,036 to 0,071 mm2), with 3 % crosslinking.7.22 Cyclohexane, C6H12, of residue analysis grade.7.23 Ethyl acetate, C4H8O2, of residue analysis grade.2) Designated commercially
43、as 200 mesh to 400 mesh. Cf. footnote 1.Page 5DIN 38414-24 : 2000-107.24 Quartz wool, roasted, for example, for 30 minutes at 1100 C.7.25 99,999 % (m/m) helium, He.7.26 Anhydrous sodium sulfate, Na2SO4, roasted at 550 C.7.27 Acetone, C3H6O, of residue analysis grade.8 SamplingClean the wide mouth, f
44、lat bottom flasks (do not use plastic flasks) and rinse them with acetone before use. Afterthe acetone has evaporated, invert the flasks and bake them for at least one hour at 150 C. Pour the samplematerial into the cleaned flask and, if it is not possible to analyse it immediately, store it at 4 C
45、in the dark untilit is processed.9 Procedure9.1 Sample preparation9.1.1 DryingTreat the sample as described in DIN 38414-22, i.e. deep-freeze the homogenized sample at a temperature ofat least 35 C and then lyophilize it to constant mass. Reduce the dry sample in size using grinding equipment.9.1.2
46、ExtractionAdd, for example, 50 ml of internal standard to a known mass (e.g. 50 g) of the sample pretreated as in subclause9.1.1 and extract it with about 450 ml of toluene in a Soxhlet extractor for a time that is sufficient for about200 extraction cycles.9.1.3 Purification of extract9.1.3.1 Extrac
47、tion with sulfuric acidIf the sample is not heavily polluted, the procedure described in this subclause need generally not be carried outand the extract can immediately be concentrated to 10 ml.Carefully shake the toluene extract with 300 ml of sulfuric acid in a separating funnel, avoiding heating.
48、 Afterthe phases have separated, extract the organic phase with about 500 ml of water and filter through sodiumsulfate. Rinse the sodium sulfate with about 50 ml of toluene and concentrate the extract to about 10 ml.9.1.3.2 Treatment using a column packed with sulfuric acid/sodium hydroxideStarting
49、from the bottom, pack the column with a 10 mm layer of sodium sulfate, add 3 g of silica gel, 5 g ofsodium hydroxide/silica gel, 3 g of silica gel, and 15 g of sulfuric acid/silica gel.After prewashing the packed column with 100 ml of n-hexane, apply the extract concentrated to 10 ml (seesubclause 9.1.3.1), rinse four times with 5 ml of n-hexane each time and elute with 200 ml of n-hexane.Concentrate the eluate to about 3 ml.9.1.3.3 Treatment using a column packed with aluminium oxideThe aluminium oxide shall have the highest possible activity, with
