1、ICS 13.060.50Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung Schlamm und Sedimente(Gruppe S) Teil 23: Bestimmung von 15 polycyclischen aromatischen Kohlenwasserstoffen (PAK) durchHochleistungs-Flssigkeitschromatographie (HPLC) und Fluoreszenzdetektion (S 23)In keeping with
2、current practice in standards published by the International Organization for Standardization(ISO), a comma has been used throughout as the decimal marker.Ref. No. DIN 38414-23 : 2002-02English price group 11 Sales No. 011110.03DEUTSCHE NORM February 200238414-23 No part of this translation may be r
3、eproduced without the 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).Translation by DIN-Sprachendienst.In case of doubt, the German-language original should be consulted as
4、the authoritative text.German standard methods for the examination of water, waste water and sludgeSludge and sediments (group S)Determination of 15 polycyclic aromatic hydrocarbons by high performanceliquid chromatography (HPLC) using fluorescence detection (S 23)Continued on pages 2 to 21.Contents
5、PageForeword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Scope . . . . . . . . . . . . . . . . . . . . . . . .
6、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 Normative references . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 Interfer
7、ence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 Designation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 Apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8、 . . . . . . . . . . . . . . . . . . 57 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 Procedure . . . . . . .
9、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1010 Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1511 Blank tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10、 . . . . . . . . . . . . 1612 Sample analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1613 Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1614 Expression of results . . . . . . . . .
11、 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1615 Test report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1716 Results of interlaboratory testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17Explanator
12、y notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21Page 2DIN 38414-23 : 2002-02ForewordThis standard has been jointly prepared by the Normenausschuss Wasserwesen (Water Practice StandardsCommittee) and Study Group Wasserchemie (Water Chemistry)
13、of the Gesellschaft Deutscher Chemiker (Ger-man Chemists Society) (cf. Explanatory notes).Expert assistance and specialized laboratories will be required to perform the analyses specified in this stan-dard. Existing safety instructions shall be observed.Depending on the objective of the analysis, a
14、check shall be made on a case-by-case basis as to whether andto what extent additional boundary conditions will have to be specified.CAUTION. Users of this standard should be familiar with standard laboratory practice. It is not claimedthat all the safety problems associated with the use of the meth
15、od have been dealt with exhaustivelyhere. It is therefore the responsibility of the user to take appropriate safety precautions and to ensurethat these comply with national regulations.IntroductionPolycyclic aromatic hydrocarbons (PAHs) are by-products of natural and industrial combustion processes
16、andare ubiquitous. Normal surface water sediments may contain up to about 10 mg of the 15 PAHs per kg of drymatter, while the content of sewage sludge of urban origin may be up to about 20 mg per kg of dry matter.Certain PAHs are regarded as, or suspected of being, carcinogenic 1.1 ScopeThe method s
17、pecified in this standard serves to determine selected PAHs (cf. table 1) in sewage sludge andsediments, in concentrations by mass equal to or exceeding 0,05 mg per kg of dry matter.The method may also be extended to cover other PAHs not mentioned here, provided its accuracy is validatedin each case
18、.Table 1: Polycyclic aromatic hydrocarbons to be determined by this methodNo. Chemical nameCAS reg. Empirical Structural Molar mass,no. formula formula in g/mol1 Naphthalene (NA) 91-20-3 C10H8128,182 Acenaphthene (AC) 83-32-9 C12H10154,213 Fluorene (F) 86-73-7 C13H10166,224 Phenanthrene (PH) 85-01-8
19、 C14H10178,245 Anthracene (A) 120-12-7 C14H10178,246 Fluoranthene (FL)1) 206-44-0 C16H10202,267 Pyrene (Py) 129-00-0 C16H10202,26(continued)Page 3DIN 38414-23 : 2002-02Table 1 (concluded)No. Chemical nameCAS Empirical Structural Molar mass,reg. no. formula formula in g/mol8 Benzaanthracene (BaA) 56-
20、55-3 C18H12228,309 Chrysene (CH) 218-01-9 C18H12228,3010 Benzobfluoranthene (BbFL)1) 205-99-2 C20H12252,3211 Benzokfluoranthene (BkFL)1) 207-08-9 C20H12252,3212 Benzoapyrene (BaPy)1) 50-32-8 C20H12252,3213 Dibenzahanthracene (DahA) 53-70-3 C22H14278,3514 Benzoghiperylene (BghiPE)1) 191-24-2 C22H1227
21、6,3415 Indeno1,2,3-cdpyrene (IN)1) 193-39-5 C22H12276,34NOTE: The PAHs listed are the so-called US EPA priority pollutants, with the exception of acenaphthene,which cannot be determined by this method since it is non-fluorescent.1) Classified as PAHs in the Trinkwasserverordnung2 Normative reference
22、sThis standard incorporates, by dated or undated reference, provisions from other publications. These norma-tive references are cited at the appropriate places in the text, and the titles of the publications are listed below.For dated references, subsequent amendments to or revisions of any of these
23、 publications apply to thisstandard only when incorporated in it by amendment or revision. For undated references, the latest edition ofthe publication referred to applies.DIN 12216 Laboratory glass tube ends with knuckle threadDIN 12242-1 Conical ground joints on laboratory glassware Dimensions and
24、 tolerancesDIN 12252 Conical ground glass stoppers for laboratory useDIN 12680-2 Graduated cylinders with ring marks for laboratory useDIN 12691 Class AS fast-delivery one-mark bulb pipettes, with a waiting time of 15 seconds, for laboratoryusePage 4DIN 38414-23 : 2002-02DIN 38402-51 German standard
25、 methods for the examination of water, waste water and sludge General information (group A) Calibration of analytical methods, evaluation of analyti-cal results and linear calibration functions used to determine the performance charac-teristics of analytical methods (A 51)DIN 38407-18 German standar
26、d methods for the examination of water, waste water and sludge Substance group analysis (group F) Determination of 15 polycyclic aromatic hydrocar-bons by high performance liquid chromatography (HPLC) using fluorescence detection(F 18)DIN 38414-11 German standard methods for the examination of water
27、, waste water and sludge Sludge and sediments (group S) Sampling of sediments (S 11)DIN 38414-21 German standard methods for the examination of water, waste water and sludge Sludge and sediments (group S) Determination of six selected polycyclic aromatichydrocarbons by high performance liquid chroma
28、tography (HPLC) using fluorescencedetection (S 21)DIN 38414-22 German standard methods for the examination of water, waste water and sludge Sludge and sediments (group S) Freeze-drying of sludge and determination of freeze-drying residue (S 22)DIN EN 12880 Characterization of sludges Determination o
29、f dry residue and water contentDIN EN ISO 1042 Laboratory glassware One-mark volumetric flasks (ISO 1042 : 1998)DIN EN ISO 4796-2 Laboratory glassware Bottles Part 2: Conical neck bottles (ISO 4796-2 : 2000)DIN EN ISO 5667-13 Water quality Sampling Part 13: Guidance on sampling of sludges from sewag
30、e andwater treatment works (ISO 5667-13 : 1997)DIN EN ISO 5667-15 Water quality Sampling Part 15: Guidance on preservation and handling of sludgesand sediment samples (ISO 5667-15 : 1999)1 IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans; Polynuclear AromaticCompound
31、s Part 1: Chemicals, Environmental and Experimental Data: International Agency for Researchon Cancer, 1983: 32.2 Verordnung zur Novellierung der Trinkwasserverordnung (German Regulation amending the German Drink-ing Water Regulation), as of 21 May 2001, BGBl. (German Federal Law Gazette) I, No. 24,
32、p. 959980.3 VDLUFA. Die Untersuchung von Bden (The examination of soil). VDLUFA method manual, Vol. VII,Darmstadt: VDLUFA-Verlag, 1995.4 Merkblatt No. 1. Bestimmung von polyzyklischen aromatischen Kohlenwasserstoffen (PAK) in Bodenproben(Determination of polycyclic aromatic hydrocarbons (PAHs) in so
33、il samples), Essen: LandesumweltamtNRW, 1994.5 Klrschlammverordnung (German Regulation on the treatment of sewage sludge), BGBl I, No. 21, 1992,pp. 912934.6 Biostoffverordnung (German Regulation on the handling of biological substances), BGBl I, 1999, No. 4,pp. 5060.7 Engelhardt, H., Hochdruck-Flssi
34、gkeitschromatographie (High-pressure liquid chromatography), 2nded.,Berlin, Heidelberg, New York: Springer-Verlag, 1977.8 Meyer, V., Praxis der Hochleistungs-Flssigkeitschromatographie (High performance liquid chromatogra-phy practice), 7thed., Frankfurt am Main: Otto Salle Verlag, Verlag Sauerlnder
35、, 1994.9 Unger, K. K. Handbuch der HPLC Teil 1: Leitfaden fr Anfnger und Praktiker (HPLC Handbook Part 1:Manual for beginners and practitioners), 2nded., Darmstadt: GIT Verlag, 1995.3 PrincipleTwo methods are described for preparing sewage sludge and sediment samples.In method A, the PAHs are extrac
36、ted from the homogenized original sample in the presence of water and sodiumchloride with a mixture of acetone and petroleum benzine 3. An aliquot of the organic phase is then evaporateddown in the presence of dimethylformamide and the extract is adjusted with solvent to a specified volume forHPLC.I
37、n method B, the homogenized sample is freeze dried or dried in air and the PAHs are extracted from the drysample with tetrahydrofuran at 40 C in an ultrasonic bath 4. An aliquot of the extract is diluted with methanoland analysed.The PAHs are separated by gradient elution HPLC for identification and
38、 quantification by fluorescence detec-tion.NOTE: No extract purification method is suggested in this standard since the standard silica gel or modifiedsilica gel methods are virtually incapable of removing minor constituents and generally result in PAH losses.Page 5DIN 38414-23 : 2002-024 Interferen
39、ce4.1 Sampling and sample preparationDue attention shall be paid to the requirements set out in DIN 38414-11 and DIN EN ISO 5667-13. The equip-ment and containers used for sampling, transportation, storage and preparation shall be made of materials thatdo not alter the PAH content of the sample mate
40、rial during the time it is in contact with them. The use of plasticmaterials for sampling shall be avoided since adsorption of PAHs on the walls may result in losses.Losses of more readily volatile PAHs (naphthalene, acenaphthene and fluorene) may occur on drying if samplesare prepared by method B (
41、cf. clause 9). The peroxide content of the unstabilized tetrahydrofuran used forextraction in this method (cf. subclauses 7.3 and 9.4.2) shall be regularly checked since high concentrationsby mass of peroxides result in the loss of some PAHs through oxidation.4.2 HPLCSubstances that exhibit or suppr
42、ess fluorescence and have chromatographic properties similar to those of thePAHs to be determined may interfere with the analysis and, depending on their concentration, may affect theaccuracy of the result. Depending on the selectivity of the phase system, interference may occur, particularlywhen de
43、termining naphthalene, acenaphthene, fluorene and dibenzahanthracene, and will be due to thepresence of minor constituents and, for example, alkylated PAHs. Asymmetrical peaks and peaks that arebroader than those of the reference substances are indicative of peak superimpositions. The identity of pe
44、akscan be checked by recording excitation spectra and, where appropriate, emission spectra (cf. subclause 9.5.3).In the chromatograms, the PAHs are in some cases not completely isolated from the minor constituents andthe correctness of the peak integration in every chromatogram shall be checked. If
45、isolation of the PAHs isincomplete, peak height is to be preferred to peak area for quantitative evaluation.Perylene is often superimposed on benzobfluoranthene if the standard phase systems are used, but with anappropriate choice of wavelength combination, the influence of the superimposition on th
46、e quantitative resultfor the latter is negligible (cf. table 2).Residues of solvents such as petroleum benzine or acetone in the test solution will affect the reproducibility ofthe retention times and result in an additional peak broadening in the case of bi- and tri-cyclic compounds.Since their eff
47、ect is a function of the concentration of solvents and the nature of the phase system, they shallbe removed completely during the treatment of the extracts from the test solution (cf. subclause 9.3.2).5 DesignationDesignation of the method of determining 15 polycyclic aromatic hydrocarbons (PAHs) by
48、 high performanceliquid chromatography (HPLC) using fluorescence detection (S 23):Method DIN 38414 S 236 Apparatus6.1 GeneralThe glassware used shall be free of PAHs. This can usually be ensured by treating it with water containing asurfactant and then rinsing it with acetone.The following equipment
49、 shall be used.6.2 Wide mouth, flat bottom flask, made of brown glass, of nominal capacity 1 000 ml, fitted with B 60/46stopper as in DIN 12252 (e.g. ISO 4796-2 1000 WJ laboratory flask).NOTE: Alternatively, 1 000 ml wide neck brown glass flasks with a screw cap and an aluminium-lined polytheneseal may be used for sampling.6.3 Measuring cylinders, of nominal capacities 10 ml, 50 ml and 1 000 ml (e.g. DIN 12680 MH 10 measur-ing cylinders).NOTE: Glass and/or polytetrafluoroethylene
