1、March 2011 English price group 17No part of this translation may be reproduced without 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).ICS 13.060.50!%#?“2006128www.din.deDDI
2、N 38407-42German standard methods for the examination of water, waste waterand sludge Jointly determinable substances (group F) Part 42: Determination of selected polyfluorinated compounds (PFC) inwater Method using high performance liquid chromatography andmass spectrometric detection (HPLC/MS-MS)
3、after solid-liquidextraction (F 42),English translation of DIN 38407-42:2011-03Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung Gemeinsam erfassbare Stoffgruppen (Gruppe F) Teil 42: Bestimmung ausgewhlter polyfluorierter Verbindungen (PFC) in Wasser Verfahren mittels Hochlei
4、stungs-Flssigkeitschromatographie undmassenspektrometrischer Detektion (HPLC-MS/MS) nach Fest-Flssig-Extraktion (F 42),Englische bersetzung von DIN 38407-42:2011-03Mthodes normalises allemandes pour lanalyse des eaux, des eaux rsiduaires et desboues Substances dterminables ensemble (groupe F) Partie
5、 42: Dosage des composs slectionns polyfluorocarbure (PFC) dans leaux Mthode par chromatographie en phase liquide haute performance et spectromtrie demasse (CLHP/MS-MS) aprs extraction solide-liquide (F 42),Traduction anglaise de DIN 38407-42:2011-03www.beuth.deDocument comprises 43 pagesTranslation
6、 by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.071155 DIN 38407-42:2011-03 2 A comma is used as the decimal marker. Contents Page Introduction 5 1 Scope . 6 2 Normative references . 7 3 Terms and definitions 7 4 Principle . 7 5 Interferences .
7、 8 5.1 General . 8 5.2 Interferences encountered during extraction and processing of extracts . 8 5.3 Interferences encountered during high performance liquid chromatography and mass spectrometry . 8 6 Designation . 9 7 Reagents 9 8 Apparatus 11 9 Sampling 12 10 Procedure 12 10.1 General . 12 10.2 S
8、ample preparation 12 10.3 Extraction 12 10.4 High performance liquid chromatography (HPLC) 13 10.5 Detection 14 10.6 Blank value measurements . 14 11 Calibration . 15 11.1 Principles . 15 11.2 Calibration using an external standard 16 11.3 Calibration using an internal standard . 17 11.4 Calibration
9、 check 18 12 Determination of recoveries 19 12.1 Recoveries of the method 19 12.2 Recovery rates of internal standards . 20 13 Evaluation 21 13.1 General . 21 13.2 Verification of individual substances . 21 13.3 Calculation of the individual result . 22 14 Expression of results . 23 15 Test report .
10、 23 16 Performance data 23 Annex A (informative) Examples of sorbents, working conditions and recovery rates . 27 A.1 Examples of sorbents and working conditions suitable for solid-phase extraction . 27 Annex B (informative) Examples of suitable HPLC columns and chromatograms . 34 B.1 Chromatographi
11、c conditions for the chromatogram shown in Figure B.1. 34 B.2 Chromatographic conditions for the chromatogram shown in Figure B.2. 35 B.3 Chromatographic conditions for the chromatogram shown in Figure B.3. 36 B.4 Chromatographic conditions for the chromatogram shown in Figure B.4. 37 DIN 38407-42:2
12、011-03 3 B.5 Chromatographic conditions for the chromatogram shown in Figure B.5 . 38 Annex C (informative) Examples of selected diagnostic ions for identification and quantification . 39 Annex D (informative) Examples for the expansion of the method . 41 Annex E (informative) Explanatory notes . 42
13、 Bibliography 43 Figures Figure B.1 Chromatographic separation, example 1 34 Figure B.2 Chromatographic separation, example 2 35 Figure B.3 Chromatographic separation, example 3 36 Figure B.4 Chromatographic separation, example 4 37 Figure B.5 Chromatographic separation, example 5 38 Figure C.1 Exam
14、ple of a MS chromatogram of a surface water sample (extract shows branched and unbranched perfluorinated carboxylic acids) 40 Figure C.2 Example of a MS chromatogram of a surface water sample (extract shows branched and unbranched perfluorinated sulfonic acids) 40 Tables Table 1 Substances whose det
15、ermination has been tested using this method. 6 Table 2 Meaning of the indices 16 Table 3 Example of the assignment of internal standard substances to the analytes 17 Table 4 Performance data for HPLC/MS-MS measurement 24 Table 5 Performance data for drinking water . 25 Table 6 Performance data for
16、ground water 25 Table 7 Performance data for surface water 26 Table 8 Performance data for treated waste water 26 Table A.1 Examples of recovery rates Ultra pure water (as in 7.2) . 30 Table A.2 Examples of recovery rates Drinking water . 31 Table A.3 Examples of recovery rates Surface water 32 Tabl
17、e A.4 Examples of recovery rates Treated waste water (effluents) . 33 Table C.1 Selected diagnostic ions (target compounds) 39 Table C.2 Selected diagnostic ions (internal standards) 39 DIN 38407-42:2011-03 4 Foreword This document has been prepared by Working Group NA 119-01-03-02-19 AK PFC in Wass
18、er, Klrschlamm und Boden of the Working Committee NA-119-01-03 AA Wasseruntersuchung of the Normenausschuss Wasserwesen (NAW) (Water Practice Standards Committee). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. DIN shall not be h
19、eld responsible for identifying any or all such patent rights. This standard has been prepared jointly with the Wasserchemische Gesellschaft (German Water Chemistry Society), a division of the Gesellschaft Deutscher Chemiker (German Chemistry Society) (see Annex E). Expert assistance and specialized
20、 laboratories will be required to perform the analyses described in this standard. Existing safety regulations are to be observed. Depending on the objective of the analysis, a check shall be made on a case-by-case basis as to whether and to what extent additional boundary conditions will have to be
21、 specified. This standard is part of the series Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung Gemeinsam erfassbare Stoffgruppen (Gruppe F) (German standard methods for the examination of water, waste water and sludge Jointly determinable substances (group F). An overview
22、of the groups A to T of the German Standard Methods is given in Annex E. WARNING Users of this standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety aspects, if any, associated with its use. It is the responsibility of the user to es
23、tablish appropriate safety and health practices and to ensure compliance with any national provisions. DIN 38407-42:2011-03 5 Introduction Polyfluorinated compounds/chemicals (PFCs) are industrially manufactured, persistent organic compounds, where some or all hydrogen atoms at the carbon skeleton h
24、ave been replaced by fluorine atoms. Because of their special properties and stability, some of these compounds are used as surfactants in fire extinguishing foams, galvanic baths and the photochemical industry. A great variety of chemical products used for impregnating paper, textiles and leather c
25、ontain these compounds in the form of components of active ingredients or of production-related contaminations or degradation products thereof. PFCs may enter the water cycle as a result of manufacture, application and disposal. The compounds which have been examined most often, so far, are perfluor
26、ooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Therefore, these substances are used as indicator substances for the presence of PFCs. Longer-chain compounds such as PFOS and PFOA accumulate in the blood and the liver, and their half-lives in the human body amount to several years. A
27、nimal testing has revealed a number of toxic effects caused by these compounds, particularly with regard to tumour growth and reproductive toxicity. Therefore, apart from a few exceptions, PFOS and any compounds derived from these are no longer permitted to be used or marketed in the European Union
28、1. DIN 38407-42:2011-03 6 1 Scope This standard specifies a method for the determination of selected perfluoroalkylated substances in drinking, ground and surface water as well as treated waste water. The lower limit of application is 0,01 g/l, or 0,025 g/l for treated waste water. The applicability
29、 of the method to further substances, not listed in Table 1, or to further types of water is not excluded, but needs to be checked on a case-by-case basis. Table 1 Substances whose determination has been tested using this method Substance Symbol Formula Relative molecular mass CAS No.aPerfluoro-n-bu
30、tanoic acid PFBA C4HO2F7214,04 375-22-4 Perfluoro-n-pentanoic acid PFPeA C5HO2F9264,05 2706-90-3 Perfluoro-n-hexanoic acid PFHxA C6HO2F11314,05 307-24-4 Perfluoro-n-heptanoic acid PFHpA C7HO2F13364,06 375-85-9 Perfluoro-n-octanoic acid PFOA C8HO2F15414,07 335-67-1 Perfluoro-n-nonanoic acid PFNA C9HO
31、2F17464,08 375-95-1 Perfluoro-n-decanoic acid PFDA C10HO2F19514,08 335-76-2 Perfluoro-n-butanesulfonic acid PFBS C4HO3F9S 300,10 375-73-5 Perfluoro-n-hexanesulfonic acid PFHxS C6HO3F13S 400,11 355-46-4 Perfluoro-n-octanesulfonic acid PFOS C8HO3F17S 500,13 1763-23-1 aCAS No.: Chemical Abstracts Servi
32、ces Registry NumberThe technical manufacture of perfluoroalkyl compounds by means of electrolytic fluorination of hydrocarbon starting materials results in isomeric mixtures. Therefore, in addition to unbranched isomers, the samples to be examined may also often comprise branched isomers, particular
33、ly in the case of the compounds PFOA, PFHxS and PFOS. As far as PFOS is concerned, significant amounts of branched isomers may be present in environmental samples. Since branched isomers can only partly be separated by means of chromatography, the method described in this standard specifies a conven
34、tion for quantifying the total content of isomers of the respective perfluoroalkyl sulfonate or perfluoroalkyl carboxylate. DIN 38407-42:2011-03 7 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition
35、cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. DIN 32645, Chemical analysis Decision limit, detection limit and determination limit under repeatability conditions Terms, methods, evaluation DIN 38402-11, German standard method
36、s for the examination of water, waste water and sludge General information (group A) Part 11: Sampling of waste water (A 11) DIN 38402-12, German standard methods for the examination of water, waste water and sludge General information (group A) Part 12: Sampling from barrages and lakes (A 12) DIN 3
37、840-13, German standard methods for the examination of water, waste water and sludge General information (group A) Part 13: Sampling from aquifers (A 13) DIN 38402-15, German standard methods for the examination of water, waste water and sludge General information (group A) Part 15: Sampling from ru
38、nning waters (A 15) DIN 38402-51, German standard methods for the examination of water, waste water and sludge General information (group A) Part 51: Calibration of analytical methods, evaluation of analytical results and linear calibration functions used to determine the performance characteristics
39、 of analytical methods (A 51) DIN EN ISO 1042, Laboratory glassware One-mark volumetric flasks DIN EN ISO 4788, Laboratory glassware Graduated measuring cylinders DIN EN ISO 4796-2, Laboratory glassware Bottles Part 2: Conical neck bottles DIN ISO 3696, Water for analytical laboratory use Specificat
40、ion and test methods DIN ISO 5667-5, Water quality Sampling Part 5: Guidance on sampling of drinking water from treatment works and piped distribution systems 3 Terms and definitions For the purposes of this document, the terms and definitions given in DIN 32645 and DIN 38402-51 and the following ap
41、ply. 3.1 poly- and perfluorinated compounds PFC commonly used international abbreviation for organic compounds with a multiple fluorinated alkyl chain; the term is also used in the broader sense for perfluorinated compounds NOTE The abbreviation PFT (German: perfluorierte Tenside) is only used in Ge
42、rmany and not internationally. This is a collective term covering synthetically manufactured persistent organic chemicals not occurring in nature which have special surface-active properties and a fully fluorinated (perfluorinated) alkyl chain. 4 Principle The substances are enriched from the unfilt
43、rated water sample by solid phase extraction at a weak anion exchanger, and eluted with ammoniacal methanol. Identification and quantitative determination are performed by means of high performance liquid chromatography coupled with mass spectrometric detection (HPLC/MS-MS). NOTE Enrichment-free met
44、hods may be applied, provided equivalence with the standardized method has been proved and documented. DIN 38407-42:2011-03 8 5 Interferences 5.1 General Polytetrafluoroethylene-containing materials (PTFE = polytetrafluoroethylene) in contact with the sample are likely to interfere with the method.
45、In order to avoid blank values, apparatus made of materials such as glass, steel, PEEK (polyether ether ketone), polypropylene or polyethylene shall preferably be used for sampling, extraction and analysis. NOTE 1 Ultrapure PTFE materials are largely free of the substances to be determined. The resp
46、ective hose materials are commercially available. In the case of the substances PFNA, PFDA and PFOS, losses may result from adsorption to the vessel wall. These losses depend on the nature of the sample and, for PFOS, amount to less than 10 % in most cases. NOTE 2 Losses due to sorption to the vesse
47、l wall can be reduced by mixing the sample in the sampling vessel with methanol (volume fraction of 5 %) and shaking it several times prior to processing it. When evaluating the results, the dilution factor (f = 1,05) shall be taken into consideration. 5.2 Interferences encountered during extraction
48、 and processing of extracts Commercially available solid phase materials often vary in nature. Contamination can negatively affect ionization and interfere with the quantitative determination. Quality and selectivity can vary from batch to batch. Recovery of individual compounds can vary depending on the concentration and nature of the sample. Therefore, regular determination of the recoveries is required (12.1). A too low ammonia content in t
