Din 38407-42 - 2011

March 2011
DIN 38407-42
D
ICS 13.060.50
German standard methods for the examination of water, waste water

and sludge –
Jointly determinable substances (group F) –
Part 42: Determination of selected polyfluorinated compounds (PFC) in
water – Method using high performance liquid chromatography and
mass spectrometric detection (HPLC/MS-MS) after solid-liquid
extraction (F 42),
English translation of DIN 38407-42:2011-03
Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung –

Gemeinsam erfassbare Stoffgruppen (Gruppe F) –
Teil 42: Bestimmung ausgewählter polyfluorierter Verbindungen (PFC) in Wasser –
Verfahren mittels Hochleistungs-Flüssigkeitschromatographie und
massenspektrometrischer Detektion (HPLC-MS/MS) nach Fest-Flüssig-Extraktion (F 42),
Englische Übersetzung von DIN 38407-42:2011-03
Méthodes normalisées allemandes pour l’analyse des eaux, des eaux résiduaires et des
boues –
Substances déterminables ensemble (groupe F) –
Partie 42: Dosage des composés sélectionnés polyfluorocarbure (PFC) dans l’eaux –
Méthode par chromatographie en phase liquide à haute performance et spectrométrie de
masse (CLHP/MS-MS) après extraction solide-liquide (F 42),
Traduction anglaise de DIN 38407-42:2011-03
Document comprises 43 pages
Translation by DIN-Sprachendienst.
In case of doubt, the German-language original shall be considered authoritative.
© No part of this translation may be reproduced without prior permission of

DIN Deutsches Institut für Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,
has the exclusive right of sale for German Standards (DIN-Normen).
www.din.de !%#`?"
www.beuth.de 07..15 2006128
DIN 38407-42:2011-03
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 ..................................................................................................................................... 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 Sample 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 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 ....................................................................................................................................... 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 Chromatographic conditions for the chromatogram shown in Figure B.1............................... 34
2
DIN 38407-42:2011-03
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
Bibliography .................................................................................................................................................. 43
Figures
Figure B.1 — Chromatographic separation, example 1 .......................................................................... 34
Figure C.1 — Example 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 determination 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 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
Table 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
3
DIN 38407-42:2011-03
Foreword
This document has been prepared by Working Group NA 119-01-03-02-19 AK PFC in Wasser, Klärschlamm
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 held 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 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 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 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 establish appropriate safety and health practices and to ensure
compliance with any national provisions.
4
DIN 38407-42:2011-03
Introduction
Polyfluorinated compounds/chemicals (PFCs) are industrially manufactured, persistent organic compounds,
where some or all hydrogen atoms at the carbon skeleton have 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 contain 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 perfluorooctanoic 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. Animal 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 [1].
5
DIN 38407-42:2011-03
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 µg/l, or
0,025 µg/l for treated waste water.
The applicability 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
Relative
Substance Symbol Formula CAS No.a
molecular mass
Perfluoro-n-butanoic acid PFBA C4HO2F7 214,04 375-22-4
Perfluoro-n-pentanoic acid PFPeA C5HO2F9 264,05 2706-90-3
Perfluoro-n-hexanoic acid PFHxA C6HO2F11 314,05 307-24-4
Perfluoro-n-heptanoic acid PFHpA C7HO2F13 364,06 375-85-9
Perfluoro-n-octanoic acid PFOA C8HO2F15 414,07 335-67-1
Perfluoro-n-nonanoic acid PFNA C9HO2F17 464,08 375-95-1
Perfluoro-n-decanoic acid PFDA C10HO2F19 514,08 335-76-2
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

a CAS No.: Chemical Abstracts Services Registry Number
The 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, particularly 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 convention for quantifying the total content of isomers of the respective
perfluoroalkyl sulfonate or perfluoroalkyl carboxylate.
6
DIN 38407-42:2011-03
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 (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 methods for the examination of water, waste water and sludge —
General information (group A) — Part 11: Sampling of waste water (A 11)
General information (group A) — Part 12: Sampling from barrages and lakes (A 12)
General information (group A) — Part 13: Sampling from aquifers (A 13)
General information (group A) — Part 15: Sampling from running waters (A 15)
General information (group A) — Part 51: Calibration of analytical methods, evaluation of analytical results
and linear calibration functions used to determine the performance characteristics 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 — Specification 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 apply.
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 Germany 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 unfiltrated 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 methods may be applied, provided equivalence with the standardized method has been proved
and documented.
7
DIN 38407-42:2011-03
5 Interferences
5.1 General
Polytetrafluoroethylene-containing materials (PTFE = polytetrafluoroethylene) in contact with the sample are

likely to interfere with the method. 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 respective 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 vessel 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 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 the elution solution (7.12), e.g. because the solution has expired, can result in
low recoveries.
The volume fraction of methanol in the measurement solution should be chosen to be as high as possible and
shall be at least 40 %. Lower volume fractions of methanol can yield false low results for PFNA, PFDA and
PFOS.
5.3 Interferences encountered during high performance liquid chromatography and mass
spectrometry
PTFE materials which are often used for HPLC equipment may cause blank values, e.g. in the case of PFOA.
Typical contamination sources include vacuum degassers, frits and hoses as well as pump head seals. In the
case of such interferences, degassing of the eluents, for example, can be carried out using helium instead of
vacuum degassers. PTFE frits and hoses shall be replaced by frits and hoses made of special steel or PEEK.
If available, pump head seals made of polyethylene shall be used.
NOTE Blank values yielded by the HPLC equipment can be reduced by means of adsorption columns installed ahead
of the injector. Special adsorption columns are commercially available.
Peak tailing, peak fronting and/or broadened peaks are indicative of interferences in chromatography.
Particles in the measurement solution, e.g. fine fractions of the solid phase material, can block the inlet sieves
or frits, respectively, of the HPLC column and result in interferences due to the increase in pressure; in such
cases the extracts shall be filtered over a syringe filter (8.11) prior to the analysis.
Associated components (matrix) can negatively affect the ionization of the target substances. This may yield
too high/too low quantification results. Such interferences can be detected and corrected by using suitable
internal standards or by spiking the sample with the analytes.
8
DIN 38407-42:2011-03
6 Designation
Designation of the method of determining selected polyfluorinated compounds (PFC) in water using high
performance liquid chromatography and mass spectrometric detection (HPLC/MS-MS) after solid-liquid
extraction (F 42):
Method DIN 38407 — F 42
7 Reagents
7.1 General
As far as available, analytical grade or residue-analytical grade reagents shall be used. The content of
impurities contributing to blank values or causing interfering signals shall be negligible. This shall be checked
in regular intervals (10.6).
Reagents, solvents and water used as eluents shall be suitable for HPLC and mass spectrometry.
7.2 Water, blank value free, e.g. grade 1 water in accordance with DIN ISO 3696.
The quality of the water shall be checked.
7.3 Solid phase material, weak anion exchanger on a polymer base.
7.4 Methanol, CH3OH.
7.5 Acetonitrile, CH3CN.
7.6 Acetic acid, w(CH3COOH) = 100 %.
7.7 Formic acid, w(HCOOH), minimum 98 %.
7.8 Acetone, C3H6O.
7.9 Ammonia solution, w(NH3), minimum 25 %.
7.10 Ammonium acetate, CH3COONH4.
7.11 Wash solution for solid phase extraction, mixture of acetone (7.8), acetonitrile (7.5) and formic acid
(7.7), with a volume ratio of 50:50:1.
7.12 Elution solution for solid phase extraction, mixture of methanol (7.4) and ammonia (7.9), with a
volume ratio (NH3) of 0,1 %.
7.13 Nitrogen for the concentration of extracts, purity of at least 99,99 %.
7.14 Operational gases for the mass spectrometer, in accordance with the specifications of the
instrument manufacturer.
7.15 Reference substances, see Table 1 for substances.
Use only reference substances or solutions having a content of unbranched isomers of at least 95 %.
NOTE Solutions of reference substances are commercially available.
9
DIN 38407-42:2011-03
7.16 Internal standard substances, as in Table C.2, content of at least 95 %.
Make sure that the internal standard substances do not contain detectable concentrations of the substances
to be determined. This shall be checked.
NOTE Solutions are commercially available.
7.17 Preparation of the solutions
Calculate all solutions with regard to the anion content.
Store the solutions at approximately 4 °C, protected against evaporation. These solutions are stable for at
least one year.
7.17.1 Individual solutions of the reference substances
Solutions of the reference substances (7.15) in methanol (7.4), e.g. mass concentration of 50 µg/ml each.
7.17.2 Individual solutions of internal standard substances
Solutions of internal standard substances (7.16) in methanol (7.4), e.g. mass concentration of 50 µg/ml each.
7.17.3 Stock solution (reference substances)
− Prepare a solution of the reference substances with a mass concentration of e.g. 0,5 µg/ml each:
− Fill e.g. 1 ml of each solution of the reference substances (7.17.1) into a 100 ml volumetric flask (8.4) and
make the solution up to the mark with methanol (7.4).
Check the mass concentrations of the substances in the stock solution regularly using a control standard
(7.17.7) (see 11.4).
7.17.4 Stock solution (internal standard substances)
− Prepare a solution of the internal standard substances with a mass concentration of e.g. 1 µg/ml each:
− Fill e.g. 1 ml of each solution of the internal standard substances (7.17.2) into a 50 ml volumetric flask
(8.4) and make the solution up to the mark with methanol (7.4).
7.17.5 Spiking solution (internal standard substances)
− Prepare a solution of the internal standard substances with a mass concentration of e.g. 0,1 µg/ml each:
− Fill e.g. 1 ml of the stock solution (7.17.4) into a 10 ml volumetric flask (8.4) and make the solution up to
the mark with methanol (7.4).
This solution is used for spiking water samples (see 10.2).
7.17.6 Reference solutions
− Prepare the reference solutions by diluting the stock solutions accordingly (7.17.3, 7.17.4). Add the same
amount of internal standards to each reference solution. The mass concentrations of the internal
standards in the reference solutions shall lie in the upper working range.
− Prepare the reference solution, e.g. a solution with a mass concentration of the substances to be
determined and of the internal standard substances of 10 ng/ml each:
10
DIN 38407-42:2011-03
− Fill e.g. 200 µl of stock solution 7.17.3 and 100 µl of stock solution 7.17.4 into a 10 ml volumetric flask
(8.4) and make the solution up to the mark with a mixture of methanol (7.4) and water (7.2) in accordance
with the chromatographic conditions (see 10.4).
In order to avoid interferences, the volume fraction of the organic solvent in the reference solutions shall be at
least 40 % (5.2).
7.17.7 Control standard
Solution of the substances to be determined prepared independently of the stock solution of the reference
substances (7.17.3) and used for testing the calibration in accordance with 11.4, e.g. certified standard
solution from a second source. If available, the control standard should contain the relevant compounds in the
form of a mixture of unbranched and branched isomers.
NOTE Solutions are commercially available.
8 Apparatus
8.1 General
The equipment or any parts of it coming into contact with the water sample or the extract shall be free of
residues which might cause blank values (see Clause 5).
8.2 Sampling vessels, e.g. polypropylene centrifuge tubes, volume 50 ml, graduated and with
polyethylene screw closure. Prior to use, the tubes shall be cleaned with methanol (7.4) and dried.
Using glass bottles with suitable closures is permissible provided it can be ensured that no blank values are
caused.
8.3 Measuring cylinder, nominal volume 50 ml, e.g. graduated measuring cylinder in accordance with
ISO 4788.
8.4 Volumetric flasks, nominal volumes 10 ml, 50 ml and 100 ml, e.g. ISO 1042 — A 50 — C one-mark
volumetric flasks.
8.5 Pipettes, with polypropylene tips.
8.6 Cartridges, made of polypropylene, with polyethylene frits, packed with solid phase material (7.3).
NOTE Ready-to-use cartridges are commercially available.
8.7 Reservoir column, nominal volume 70 ml, with adaptor for cartridges (8.6), made of polypropylene.
8.8 Vacuum or pressure equipment, for carrying out the extraction.
8.9 Sample tubes, made of glass or polypropylene, for collecting and concentrating the eluate, e.g. test
tube, nominal volume 10 ml, with glass stopper NS 14.
8.10 Device for concentrating the extracts, e.g. apparatus for blowing off with nitrogen (7.13).
NOTE The application of rotary evaporators can cause blank values.
8.11 Syringe filter, of low dead volume, e.g. 4 mm in diameter, with membrane made of regenerated
cellulose.
8.12 Sample bottles, suitable for the sample feeding system, e.g. beaded rim bottles, nominal volume 1 ml,
made of polypropylene, with polyethylene snap-on caps (see Clause 5).
11
DIN 38407-42:2011-03
8.13 HPLC column, with pre-column, if appropriate (see Annex B for examples).
8.14 High performance liquid chromatograph, coupled with mass spectrometer, consisting of the following
components:
8.14.1 Degassing equipment, e.g. vacuum degasser.
8.14.2 Analytical pump system, low-pulsation, suitable for binary gradient elution.
8.14.3 Sample feeding system.
8.14.4 Device for the thermostatization of the separating column, e.g. column thermostat.
8.14.5 Mass spectrometric detector (MS), preferably tandem mass spectrometer with electrospray
ionization (ESI).
NOTE For the procedure described in this standard, other MS techniques may be used as well, e.g. time-of-flight mass
spectrometry (TOF-MS), provided the identification of the analytes has been verified and documented for the respective
applications.
9 Sampling
− Take samples as specified in DIN 38402-11, DIN 38402-12, DIN 38402-13, DIN 38402-15 and
DIN ISO 5667-5.
− Use only cleaned vessels (8.2) for sampling and fill them completely with the water sample.
− Store the water sample in a cool place until it is processed, but no longer than 14 days.
10 Procedure
10.1 General
The samples are analysed in the unfiltered state. The pH value of the sample should lie in the range between
pH 6 and pH 8 and shall be adjusted with sodium hydroxide solution or sulfuric acid, if necessary.
10.2 Sample preparation
− Measure the water sample, e.g. 50 ml, add the internal standard substances, and add e.g. 100 µl of the
spiking solution (7.17.5).
− Proceed as described in 10.3.
10.3 Extraction
− Use at least 60 mg of the solid phase material (7.3) for a sample volume of e.g. 50 ml.
− For cleaning and conditioning, successively pour at least 2 ml of the elution solution (7.12), 2 ml of
methanol (7.4) and 2 ml of water (7.2) onto the solid phase material.
Make sure that the solid phase material does not run dry.
NOTE 1 Surface-drying of the solid phase material during conditioning can result in enrichment losses.
12
DIN 38407-42:2011-03
Depending on the solid phase material, the processes of cleaning, conditioning and elution may require the
solvent to act on the solid phase material for some minutes.
− Pour the sample prepared as specified in 10.2 onto the conditioned solid phase material at a flow rate not
exceeding 5 ml/min. Regulate the flow rate by changing the vacuum or the pressure (8.8), respectively.
To collect the sample, a reservoir column (8.7) connected to the cartridge (8.6) via an adaptor can be used.
− Wash the solid phase material successively with water (7.2), wash solution (7.11) and methanol (7.4), e.g.
using 2 ml in each case.
NOTE 2 If necessary, the methanol volume may be up to 5 ml without any analyte losses being caused.
− For the purposes of eluting the adsorbed substances, pour at least 2 ml of the elution solution (7.12) onto
the solid phase material at a flow rate not exceeding 2 ml/min.
− Collect the eluate in a sample tube (8.9).
Completely displace the residual eluent from the cartridge by applying a positive or a negative pressure, and
add it to the eluate.
The solvent and water volumes used for cleaning and conditioning, for washing and for the elution of the
analytes depend on the used mass of the solid phase material (for examples see A.1).
− Concentrate the eluate to dryness, e.g. in a nitrogen stream (7.13, 8.10), at 40 °C.
− Dissolve the residue in e.g. 1 ml using a mixture of solvent and water in accordance with the composition
of the reference solutions (see 7.17.6).
− If necessary, filter the extract through a syringe filter (8.11) and use a partial volume for the analysis.
10.4 High performance liquid chromatography (HPLC)
− Start up the HPLC equipment in accordance with the manufacturer’s instructions.
− For the chromatographic separation, use a suitable HPLC column (8.13) and optimize the separation of
the analytes by means of gradient elution (see Annex B for examples).
− Select the chromatographic conditions such that optimum sensitivity is achieved in the mass
spectrometric detection, where the PFBA retention shall be equal to at least twice the dead volume of the
separating column. The peaks shall be symmetrical and shall not exhibit any interfering broadening of
peaks.
NOTE 1 Usually, optimum conditions for chromatography and detection are achieved with water and methanol in the
presence of ammonium acetate (7.10) and, if appropriate, acetic acid (7.6).
NOTE 2 HPLC columns with RP materials, additionally enabling polar interactions with the analytes to take place, result
in a higher retention time for PFBA and shall be given preference.
Complete separation of the substances does not necessarily have to be achieved, since the mass transfers
sufficiently differ from each other provided it can be ensured that there are no interferences with the
quantitative determination in the case of overlapping peaks.
13
DIN 38407-42:2011-03
Select the injection volume so that no interfering peak broadening occurs.
The standard deviation of the retention times should not exceed 0,05 min in the case of 6 successive runs.
NOTE 3 The maximum volume to be injected depends on the composition of the measurement solutionʼs solvent and on
the internal diameter of the separating column. When using a composition approximately corresponding to the initial
chromatographic conditions, the injection volume of a separating column with an internal diameter of e.g. 2 mm should not
exceed 20 µl.
10.5 Detection
− Start up the mass spectrometer according to the manufacturer’s instructions and select equipment-typical
settings.
− Determine the optimum settings for each substance (Table 1), in the negative mode, to be applied for
ionization under the specified chromatographic conditions, where the ions of the [M-H]- type are formed.
− Choose the substance-specific settings so that two product ions are obtained per substance, if possible.
PFBA yields just one product ion. In the case of PFPeA and PFHxA, the intensity of the second product ion is
usually not sufficient to support positive results (see 13.2).
− Determine and specify the method-specific settings for the source parameters and the MS parameters on
the basis of the less sensitive substances.
− Make sure that branched isomers of the individual analytes are covered. Check the time ranges using a
control standard (7.17.7).
− Choose the mass resolution so that the masses of the ions of co-eluting substances and internal standard
substances are completely separated from each other during spectrometry.
− Each peak should be recorded with at least 12 data points.
NOTE Usually, the measurement signal is smoothed prior to peak integration. Depending on the calculation method,
too few data points can result in an unproportionally high loss of signal intensity. Furthermore, a low number of data points
may negatively affect the reproducibility of the peak integration, particularly in the case of low area or height values,
respectively.
10.6 Blank value measurements
− Check the proper state of the equipment and chemicals by means of regular blank value measurements.
− For carrying out blank value measurement, process and analyse e.g. 50 ml of water (7.2) in the same way
as a sample.
− In the case of blank values exceeding 30 % of the lowest calibrated concentration level, clarify the reason
by systematic examinations and eliminate contamination sources.
− If case blank values derived from the HPLC equipment itself cannot be reduced (see Clause 5), increase
the sample volume accordingly and re-specify the working range.
14
DIN 38407-42:2011-03
11 Calibration
11.1 Principles
The calibration of the method of determination shall be performed under specified chromatographic
conditions. The retention times of the individual analytes and the internal standard substances are required to
be known. When injecting multi-component mixtures, the retention times can be determined on the basis of
the mass of the product ions or by injection of the individual solutions (7.17.1, 7.17.2) under the specified
chromatographic conditions.
− For the calibration, use solutions of unbranched isomers of the analytes (7.15).
− In the case of carboxylic acids, calibrate the respective mass transfer of the highest intensity, in the case
of sulfonic acids, calibrate the mass transfer to the product m/z 80 (see Table C.1).
− Design the total method of determination so that there is a linear dependency of the measurement signal
on the concentration for each substance to be determined.
− Determine, in accordance with DIN 38402-51, the linear working range of the measuring instrument for
each substance to be determined by injecting at least five reference solutions (7.17.6) of different
concentrations.
− Choose a linear calibration range for the method of determination which covers almost the whole range of
the real concentrations, for example a calibration range of 0,01 µg/l to 0,5 µg/l for the examination of
drinking, ground and surface water.
− Re-calibrate the measuring system for each examination series.
− Carry out the calibration with one or several concentration level(s) in the linear working range.
− One-point calibration shall not yield any blank values. The concentration level shall correspond to the
upper application limit of the working range.
− Should it be impossible to neglect the blank values, measure at least one further concentration level near
the lower application limit of the working range and exclude the point of origin from the calculation of the
calibration functions.
− In case of one- and two-point calibrations, make at least three measurements for each concentration
level.
− In case of multi-point calibrations, distribute the concentration levels over the calibration range and
establish the calibration curve in accordance with DIN 38402-51.
− Keep the injection volume constant for both calibration and sample measurement.
The calibration function established for a certain substance is only applicable for the concentration level
covered. Furthermore, it depends on the operational state of the measuring system and needs to be checked
(see 11.4) for each examination using an independent control standard (7.17.7).
Two methods are described for the establishment of the calibration functions:
a) calibration using an external standard (11.2);
b) calibration using an internal standard (11.3).
For the meaning of the indices used in the following text, see Table 2:
15
DIN 38407-42:2011-03
Table 2 — Meaning of the indices
Index Meaning
i Identity of the substance
e Measurand used for calibration
N Concentration level
M Measurement solution
g Mass concentrations found with the recovery
v Mass concentrations given for the recovery
P Sample
I Internal standard
j Serial number in the case of pairs of values
n Number of measurements
11.2 Calibration using an external standard
Carry out this calibration in any case, since it is required for the determination of the recoveries (12.1) when
practising the procedure as well as for optimizing individual working steps of sample processing.
− Inject the reference solutions (7.17.6) to establish the calibration.
− Represent the calibration functions graphically by plotting the measured values yie for each substance i on
the ordinate and the associated mass concentration ρie on the abscissa.
− From the pairs of values yiej and ρiej, determine the calibration curve by linear regression using
Equation (1).
yie = bi ⋅ ρie + ai (1)
where
yie is the measured value (dependent variable) of substance i used in the calibration, depending on ρie,
unit depending on the evaluation method, e.g. area value;
ρie is the mass concentration (independent variable) of substance i in the reference solution, in
nanograms per millilitre, ng/ml;
bi is the slope of the calibration curve of substance i (corresponding to the substance-specific

response factor), unit depending on the evaluation method, e.g. area value × millilitres per
nanogram, ml/ng;
ai is the intercept of the calibration curve of substance i on the ordinate, unit depending on the
evaluation method, e.g. area value; the intercept is omitted in the case of one-point calibration.
16
DIN 38407-42:2011-03
11.3 Calibration using an internal standard
The use of internal standards for the quantitative analysis minimizes errors which might occur during sample
preparation and mass spectrometric measurement (see Clause 5). Furthermore, recovery rates are included
in the calculation and matrix-related changes of the recoveries corrected where applicable.
− For the calibration, use 13C labelled compounds of at least PFBA, PFHxA, PFOA and PFOS as internal
standards (Table C.2).
− If no internal standards of the same structure are used for the substances, give reference to other internal
standards. During sample preparation, chromatography and mass spectrometric measurement, the
internal standard should act like the substance to be determined (for an example, see Table 3).
− If necessary and available, use further isotopic labelled compounds as internal standards (see Table C.2).
Table 3 — Example of the assignment of internal standard substances to the analytes
Internal standard substance Assigned analytes

13C
4-PFBA PFBA
13C
2-PFHxA PFPeA, PFHxA, PFBS, PFHxS
13C
4-PFOA PFHpA, PFOA, PFNA, PFDA
13C
4-PFOS PFOS
− Prior to the extraction, add the internal standards of known mass to the measured water sample; add
spiking solution (7.17.5), e.g. 100 µl.
− Choose the amount of the internal standards so that in the case of complete recovery, their mass
concentrations in the measurement solution are equal to those in the reference solutions.
− Determine the mass of the internal standards using Equation (2).
mIiP = ρIie ⋅ VM (2)
where
mIiP is the mass of the internal standard I of substance i to be added to the water sample, in
nanograms, ng;
ρIie is the chosen mass concentration of the internal standard I of substance i in the reference solution,
in nanograms per millilitre, ng/ml;
VM is the volume of the measurement solution used for injection, in millilitres, ml.
− For establishing the calibration, inject reference solutions containing all substances to be determined and
the internal standards (7.17.6).
− For a graphical representation of the calibration functions, plot for each substance i the measured value
ratios yie/yIie on the ordinate and the associated mass concentration ratios ρie/ρIie on the abscissa.
17
DIN 38407-42:2011-03
− From the pairs of values yiej/yIiej and ρiej/ρIiej, determine the calibration curve by linear regression using
Equation (3).
y ie ρ
= bi ⋅ ie + ai (3)
y Iie ρIie
where
yie is the measured value (dependent variable) of substance i used in the calibration, depending on
ρie, unit depending on the evaluation method, e.g. area value;
yIie is the measured value of the internal standard I of substance i used in the calibration, unit
depending on the evaluation method, e.g. area value;
ρie is the mass concentration (independent variable) of substance i in the reference solution, in
ρIie is the mass concentration of the internal standard I of substance i in the reference solution, in
bi is the slope of the calibration curve yie/yIie, depending on the ratio ρie/ρIie, dimensionless;
ai is the intercept of the calibration curve on the ordinate; the intercept is omitted in the case of one-
point calibration, dimensionless.
11.4 Calibration check
Check the validity of the calibration functions for each examination series as specified in 11.3, using an
independent control standard (7.17.7).
The control standard shall contain all substances to be determined and the internal standard substances. The
mass concentrations of the internal standards in the control standard shall be equal to those in the reference
solutions.
− Inject the control standard (7.17.7) at least twice and determine the mass concentrations using
Equation (3).
− Calculate the relative accuracy of the calibration using Equation (4).
100
∑ (ρi − ρR )2
i =1
vρ = ⋅ (4)
ρR n −1
where
vρ is the relative accuracy of the calibration, in percent, %;
ρi is the determined mass concentration of substance i, in nanograms per millilitre, ng/ml, or

micrograms per litre, µg/l;
ρR is the mass concentration of substance i in the control standard (reference value), in nanograms
per millilitre, ng/ml, or micrograms per litre, µg/l;
n is the number of measurements.
The value of the relative accuracy should be lower than 15 %.
18
DIN 38407-42:2011-03
12 Determination of recoveries
12.1 Recoveries of the method
For practising and optimizing the extraction, determine recovery for each substance i for different
concentration levels. Determine also the recoveries of the internal standards (examples in Table A.1).
− Spike e.g. 50 ml of water (7.2) with a reference solution (7.17.6), process and analyse it in the same way
as a real water sample.
− Determine the mass concentrations of the analytes and of the internal standard substances by external
calibration (11.2) using Equations (5) and (6). Determine the recoveries using Equation (7).
( y i − ai ) ρ iM
ρ iNg = = (5)
bi ⋅ F F
with
V
F= P (6)
VM
ρ iNg
AiN = ⋅f (7)
ρ iNv
where
ρiNg is the mass concentration of substance i found for concentration level N, in micrograms per litre,
µg/l;
yi is the measured value of substance i in the measurement solution, unit depending on the
evaluation method, e.g. area value;
ai, bi see Equation (1);
ρiM is the mass concentration of substance i in the measurement solution, in nanograms per millilitre,
ng/ml;
F is the enrichment factor, dimensionless;
VP is the volume of the extracted water sample, in millilitres, ml;
VM see Equation (2);
AiN is the recovery rate of substance i for concentration level N, in percent, %;
ρiNv is the given mass concentration of substance i for concentration level N, in micrograms per litre,
µg/l;
f is the conversion factor, here: f = 100.
19
DIN 38407-42:2011-03
The values are recovery rates for the whole analytical process, which are usually expected to lie in the range
between 70 % and 110 % (see Table A.1) when using water according to 7.2. If these values are not obtained,
interferences are present. Such interferences can have been caused by the extraction, the processing of the
eluates and/or the mass spectrometric measurement. They shall be detected by the systematic examination of
individual working steps, and shall be eliminated.
When analysing the samples, the recovery rate Ai obtained by extraction, and particularly by mass
spectrometric detection, can be influenced by matrix (see 5.2, 5.3). Those influences can be detected and
corrected by using internal standards. The recovery rates of the internal standards, AIi, are a measure of the
analyte recovery over the whole analytical process, for each individual sample. They shall be determined in
accordance with 12.2 and shall lie in a range between 50 % and 150 %.
NOTE Usually recovery rates between 70 % and 110 % are obtained (see Tables A.2 and A.3) in the examination of
drinking, ground and surface water. A low recovery rate results in a higher limit of determination.
12.2 Recovery rates of internal standards
− Calculate the recovery rates of internal standards using Equation (8):
ρ IiM
AIi = . f (8)
ρ Iie
with
mIiP
ρ Iie = (9)
VM
where
AIi is the recovery rate of the internal standard I of substance i, in percent, %;
ρIiM is the mass concentration of the internal standard I of substance i in the measurement solution, in
ρIie see Equation (2);
mIiP see Equation (2);
f is the conversion factor, here: f = 100.
NOTE The recovery rates of the internal standards can be stated in the test report, provided a value of 1 is assumed
for the mass concentration of the internal standard ρIie in the reference solution.
20
DIN 38407-42:2011-03
13 Evaluation
13.1 General
In addition to the unbranched isomers, samples often contain branched compounds of the PFCs to be
determined. Under the usual chromatographic conditions, the branched isomers of a substance are to a large
extent separated from the unbranched compound and, in most cases, detected immediately prior to it (for an
example, see Figures C.1 and C.2).
When quantifying individual PFCs, this standard does not differentiate between unbranched and branched
isomers. For the evaluation, the whole peak area of the detected isomers of a substance is determined and
evaluated by calibrating the respective unbranched compound.
NOTE 1 When quantifying the isomers, the respective response of the unbranched compound obtained in the calibration
is taken as a basis. This is based on the assumption that the response values of the branched isomers are similar to the
response value of the unbranched compound. The error resulting from the deviation of the response values is estimated to
be lower than the non-inclusion of the branched PFCs.
NOTE 2 In the case of PFOS, the peak area of the branched isomers can be of the same order of magnitude, and partly
even higher, than that of the unbranched compound. For the other PFCs, the proportion of the branched isomers is usually
below 20 %, relative to the peak area of the respective unbranched compound.
13.2 Verification of individual substances
A calibrated substance (unbranched) is assumed to be detected in a sample if a signal is recorded in the

MS-MS chromatogram of the mass trace of a product ion of this substance, its retention time being equal to
that of the corresponding reference substance determined under standard conditions, with a tolerance of
± 0,15 min.
− In order to verify a positive result, use a second product ion, if available, which needs to be detected at
the same retention time. The ratio of the product ionsʼ intensities should correspond to the ratio of those
ions determined for the reference substance under standard conditions, with a tolerance of ± 30 %. The
tolerance may amount to up to 50 % at the lower application limit, and particularly at the detection limit of
the analytical procedure.
− In cases of doubt, for substances where no second product ion is formed (PFBA) or the intensity of the
second product ion is too low for the purposes of verification (PFPeA, PFHxA), verify the identity on the
basis of the retention at a stationary phase of another selectivity (for examples, see Annex B).
− In the case of a positive result for a calibrated substance (unbranched), further signals occurring in the
MS-MS chromatogram of the mass trace of a product ion of this analyte are regarded as branched
isomers of the analyte. The position of the branched compounds in the chromatogram can be verified, as
far as possible, by measuring the control standard (7.17.7).
NOTE 1 Under the usual chromatographic conditions, several signals of branched isomers can occur with PFOS, while
with the other PFCs, in most cases just one additional signal is recorded (see Figures C.1 and C.2).
− If a second product ion is available for the analytes, this mass transfer shall also be indicated with the
branched isomers at the same retention time.
In the case of branched isomers, the intensity ratios cannot be used for verifying positive results, since they
cannot completely be separated from each other under the usual chromatographic conditions, and their
response values differ from each other.
NOTE 2 Another possibility to verify positive results is to determine the accurate mass, e.g. by time-of-flight mass
spectrometry (TOF-MS).
21
DIN 38407-42:2011-03
13.3 Calculation of the individual result
− Calculate the mass concentration ρiP of substance i in the water sample using Equation (10) or (12):
y iM
− ai
y IiM ρ m
ρ iP = ⋅ ρ IiP = iM ⋅ IiP (10)
bi ρ IiM VP
with
mIiP = ρ Iie ⋅ VM (11)
ρ Iie VM
ρiP = ρiM ⋅ (12)
ρ IiM VP
where
ρiP is the mass concentration of substance i in the water sample, in micrograms per litre, µg/l;
yiM is the measured value of substance i in the measurement solution, unit depending on the
evaluation method, e.g. area value;
yIiM is the measured value of the internal standard I of substance i in the measurement solution, unit
depending on the evaluation method, e.g. area value;
ρIiP is the given mass concentration of the internal standard I of substance i in the water sample, in
micrograms per litre, µg/l;
ρiM is the mass concentration of substance i in the measurement solution, in nanograms per millilitre,
ng/ml;
ρIiM is the mass concentration of the internal standard I of substance i in the measurement solution, in
mIiP is the mass of the internal standard I of substance i added to the sample volume, in micrograms,
µg, see Equation (2);
ρIie see Equation (2);
VP is the sample volume, in litres, l;
ai, bi see Equation (3).
If the working range calibrated in accordance with Clause 11 is exceeded by individual analytes when
measuring the water samples, the measurement solution shall be diluted in order to adapt the mass
concentrations of the analytes to fit the calibrated working range.
− Ensure that the recovery rate of the internal standard (12.2) in the diluted measurement solution is at least
20 %.
− If higher dilutions are required, dilute the sample accordingly with water (7.2), reprocess and analyse
again in accordance with Clause 10; take the dilution factor into account when calculating the individual
result.
22
DIN 38407-42:2011-03
14 Expression of results
The analytical results obtained using this standard are subject to a measurement uncertainty which needs to
be taken into account when interpreting the results. The Leitfaden zur Abschätzung der Messunsicherheit aus
Validierungsdaten (DEV A0-4) describes methods for estimating measurement uncertainty. The uncertainty of
measurement is to be preferably indicated as the expanded measurement uncertainty. To this end, the
combined standard uncertainty determined – expressed as the standard deviation or coefficient of variation –
is multiplied by a coverage factor of 2, for a confidence level of approximately 95 %.
If a laboratory does not have suitable validation data, the expanded measurement uncertainty can also be
estimated by multiplying the coefficient of variation of reproducibility, CVR, obtained in the interlaboratory trial
(see Tables 4 to 8) by the factor 2. However, the expanded measurement uncertainty estimated in this
manner can only be used as a guide, and cannot take the place of estimating uncertainty on the basis of the
laboratory’s own internal data.
NOTE The measurement uncertainty depends on the concentration and the matrix and is greatest in the lower working
range.
The analytical result for a substance shall be reported as the sum of all isomers (branched and unbranched).
Report the mass concentrations of the substances listed in Table 1 in micrograms per litre, rounded to two
significant figures.
EXAMPLES PFOA: 0,092 µg/l

0,15 µg/l
1,5 µg/l
15 Test report
The test report shall contain at least the following information:
a) a reference to this standard (DIN 38407-42);
b) the identity of the water sample;
c) sampling, sample transport and sample preparation;
d) sample processing;
e) expression of result in accordance with Clause 14;
f) any deviation from this method and report of circumstances that may have affected the result.
16 Performance data
The performance data given in Tables 4 to 8 were determined in an interlaboratory trial carried out in January
2010. Further details on the interlaboratory trial are included in the validation document.
In accordance with the requirements of this standard, only those data sets were included in the evaluation of
the interlaboratory trial, that yielded recoveries of the internal standards in the range of 50 % to 150 %
(see 12.1).
27 single values (PFBA, PFDA and PFOS) out of 900 single values did not meet these requirements.
23
DIN 38407-42:2011-03
Table 4 — Performance data for HPLC/MS-MS measurement
Compound l n nAP x xsoll η sR CVR sr CVr
% µg/l µg/l % µg/l % µg/l %
PFBA 18 54 0,0 0,103 0 0,100 0 103,1 0,010 99 10,7 0,003 88 3,8

PFPeA 17 51 5,6 0,057 7 0,060 0 96,2 0,005 73 9,9 0,003 18 5,5
PFHxA 16 48 11,1 0,020 2 0,020 0 100,8 0,001 30 6,4 0,000 76 3,8
PFHpA 18 54 0,0 0,050 2 0,050 0 100,4 0,006 61 13,2 0,002 65 5,3
PFOA 18 54 0,0 0,032 0 0,030 0 106,7 0,003 69 11,5 0,0010 5 3,3
PFNA 16 48 11,1 0,078 8 0,080 0 98,5 0,004 94 6,3 0,001 97 2,5
PFDA 15 45 16,7 0,086 2 0,090 0 95,8 0,006 83 7,9 0,002 51 2,9
PFBS 17 51 5,6 0,063 3 0,061 8 102,4 0,005 49 8,7 0,001 79 2,8
PFHxS 14 42 17,6 0,019 5 0,019 0 102,6 0,001 45 7,4 0,000 41 2,1
PFOS 17 51 5,6 0,039 5 0,038 2 103,4 0,004 71 11,9 0,001 13 2,9
l number of laboratories after outlier rejection
n number of test results after outlier rejection
nAP percentage of outliers
x overall mean of results (without outliers), in micrograms per litre, µg/l
xsoll conventional true value of the analytical sample, in micrograms per litre, µg/l
η recovery rate, in percent, %

sR reproducibility standard deviation, in micrograms per litre, µg/l
CVR coefficient of variation of reproducibility, %
sr repeatability standard deviation, in micrograms per litre, µg/l
CVr coefficient of variation of repeatability, %
24
DIN 38407-42:2011-03
Table 5 — Performance data for drinking water
PFBA 15 45 11,8 0,088 6 0,085 8 103,3 0,009 56 10,8 0,004 38 4,9

PFPeA 17 51 5,6 0,016 9 0,018 0 94,2 0,002 90 17,1 0,001 14 6,7
PFHxA 18 54 0,0 0,015 7 0,014 3 110,0 0,002 21 14,1 0,000 81 5,1
PFHpA 16 48 11,1 0,027 5 0,028 6 96,0 0,003 85 14,0 0,002 17 7,9
PFOA 17 51 5,6 0,014 5 0,014 3 101,6 0,002 39 16,5 0,001 04 7,1
PFNA 16 48 11,1 0,041 9 0,042 9 97,6 0,003 95 9,4 0,001 94 4,6
PFDA 17 51 0,0 0,026 4 0,028 6 92,3 0,007 31 27,7 0,003 44 13,0
PFBS 16 48 11,1 0,054 9 0,046 2 118,8 0,014 98 27,3 0,002 35 4,3
PFHxS 16 48 11,1 0,014 2 0,013 4 106,0 0,002 24 15,7 0,000 86 6,0
PFOS 17 51 5,6 0,029 3 0,030 4 96,2 0,006 75 23,1 0,004 11 14,0
See Table 4 for key to symbols.
Table 6 — Performance data for ground water
PFBA 18 54 0,0 0,115 2 0,114 3 100,8 0,011 22 9,7 0,005 13 4,5

PFPeA 15 45 16,7 0,064 6 0,066 7 96,8 0,009 31 14,4 0,002 12 3,3
PFHxA 16 48 11,1 0,022 1 0,022 2 99,6 0,002 83 12,8 0,000 88 4,0
PFHpA 15 45 16,7 0,052 4 0,055 6 94,2 0,007 64 14,6 0,002 39 4,6
PFOA 17 51 5,6 0,035 2 0,033 3 105,8 0,005 92 16,8 0,001 43 4,1
PFNA 17 51 5,6 0,082 4 0,088 9 92,7 0,008 30 10,1 0,003 98 4,8
PFDA 17 51 0,0 0,085 7 0,100 0 85,7 0,021 96 25,6 0,007 36 8,6
PFBS 17 51 5,6 0,075 7 0,068 7 110,2 0,012 50 16,5 0,005 99 7,9
PFHxS 17 51 5,6 0,021 7 0,021 1 103,0 0,003 19 14,7 0,001 57 7,2
PFOS 17 51 5,6 0,042 8 0,045 5 94,1 0,007 20 16,8 0,002 62 6,1
25
DIN 38407-42:2011-03
Table 7 — Performance data for surface water
PFBA 13 39 23,5 0,128 4 0,131 7 97,5 0,012 96 10,1 0,002 62 2,0

PFPeA 18 54 0,0 0,072 9 0,075 0 97,2 0,012 97 17,8 0,003 97 5,4
PFHxA 18 54 0,0 0,026 6 0,025 0 106,3 0,003 05 11,5 0,001 14 4,3
PFHpA 16 48 11,1 0,060 4 0,062 5 96,7 0,008 16 13,5 0,001 78 3,0
PFOA 15 45 16,7 0,040 7 0,041 5 98,1 0,005 67 13,9 0,001 01 2,5
PFNA 16 48 11,1 0,092 9 0,100 0 92,9 0,010 20 11,0 0,003 36 3,6
PFDA 15 45 16,7 0,092 1 0,112 5 81,9 0,018 73 20,3 0,004 36 4,7
PFBS 15 45 16,7 0,106 3 0,104 5 101,7 0,018 37 17,3 0,003 83 3,6
PFHxS 18 54 0,0 0,027 7 0,023 8 116,4 0,005 36 19,3 0,002 53 9,1
PFOS 18 54 0,0 0,052 9 0,056 8 93,2 0,009 93 18,8 0,003 48 6,6
Table 8 — Performance data for treated waste water
PFBA 15 45 0,0 0,327 9 0,331 2 99,0 0,035 43 10,8 0,021 18 6,5

PFPeA 16 48 11,1 0,169 6 0,179 6 94,4 0,048 20 28,4 0,005 82 3,4
PFHxA 15 45 16,7 0,065 7 0,067 7 97,1 0,005 79 8,8 0,001 47 2,2
PFHpA 15 45 16,7 0,141 0 0,148 8 94,7 0,026 76 19,0 0,005 79 4,1
PFOA 16 48 11,1 0,098 8 0,106 3 92,9 0,012 29 12,4 0,003 28 3,3
PFNA 17 51 5,6 0,206 6 0,231 7 89,2 0,028 65 13,9 0,009 65 4,7
PFDA 15 45 11,8 0,215 3 0,260 9 82,5 0,051 85 24,1 0,011 76 5,5
PFBS 17 51 5,6 0,212 5 0,192 8 110,2 0,067 47 31,7 0,009 41 4,4
PFHxS 17 51 5,6 0,059 2 0,054 3 108,9 0,011 13 18,8 0,003 24 5,5
PFOS 15 45 11,8 0,117 2 0,130 0 90,2 0,016 60 14,2 0,005 20 4,4
26
DIN 38407-42:2011-03
Annex A
(informative)
Examples of sorbents, working conditions and recovery rates
A.1 Examples of sorbents and working conditions suitable for solid-phase extraction
A.1.1 Sorbent: Strata-X-AW 1), 200 mg, 6 ml cartridge
Conditioning: 8 ml of 0,1 % ammonia in methanol, 4 ml of methanol, 4 ml of water

Sample: pH 7 to 8, addition of 2 ml of methanol, flow rate approximately 2,5 ml/min
Washing 1: 4 ml of water
Washing 2: 4 ml of 1 % formic acid in acetone-acetonitrile 1:1
Washing 3: 4 ml of methanol
Drying: No drying
Elution: 8 ml of 0,1 % ammonia in methanol
Processing: Evaporate the eluate to dryness under a stream of nitrogen at 40 °C,
dissolve the residue in 500 µl of methanol-water 1:1
A.1.2 Sorbent: Strata-X-AW1), 60 mg, 3 ml cartridge

Sample: pH 7 to 8
Drying: No drying
Elution: 2 ml of 0,1 % ammonia in methanol, application time 5 min
dissolve the residue by adding 1 ml of methanol-water 4:6

Sample: pH 7 to 8
Drying: No drying
Elution: 3 × 800 µl of 0,1 % ammonia in methanol, application time 5 min each
Processing: Evaporate the eluate to dryness under a stream of nitrogen,
dissolve the residue in 1 ml of methanol-water 1:1
1) Strata-X-AW is an example of a suitable product available commercially. This information is given for the convenience
of users of this document and does not constitute an endorsement by DIN of this product.
27
DIN 38407-42:2011-03
A.1.4 Sorbent: CHROMABOND HR-XAW 2), 60 mg, 3 ml cartridge

Sample: pH 7 to 8
Drying: No drying
Elution: 3 × 0,8 ml of 0,1 % ammonia in methanol
dissolve the residue in 500 µl of methanol-water 6:4
Conditioning: 2 × 2 ml of 0,1 % ammonia in methanol, 2 ml of methanol, 2 × 2 ml of water

Sample: pH 7 to 8, addition of 2 ml of methanol, flow rate 2,5 ml/min
Drying: No drying
Elution: 2 × 2 ml of 0,1 % ammonia in methanol, application time 5 min
dissolve the residue in 1 ml of methanol-water-ammonia 50:50:0,02
A.1.6 Sorbent: Oasis WAX2), 60 mg, 3 ml cartridge

Sample: Addition of 2 ml of methanol
Drying: No drying
Elution: 2 × 4 ml of 0,1 % ammonia in methanol
dissolve the residue in 500 µl of methanol, add 500 µl of water
2) CHROMABOND HR-XAW, Strata-X-AW and Oasis WAX are examples of suitable products available commercially.
This information is given for the convenience of users of this document and does not constitute an endorsement by
DIN of these products.
28
DIN 38407-42:2011-03
A.1.7 Sorbent: Strata-X-AW 3), 60 mg, 3 ml cartridge

Sample: pH 7 to 8
Drying: No drying
Elution: 3 ml of 0,1 % ammonia in methanol, application time 4 min
dissolve the residue in 0,5 ml of methanol-water 1:1

Sample: pH 7 to 8
Drying: No drying
Elution: 2 × 3 ml of 0,1 % ammonia in methanol
dissolve the residue in 0,5 ml of methanol-water 7:3
3) Strata-X-AW is an example of a suitable product available commercially. This information is given for the convenience
of users of this document and does not constitute an endorsement by DIN of this product.
29
DIN 38407-42:2011-03
NOTE Recovery rates given in Tables A.1 and A.2 were determined in different laboratories. Required sample volumes
vary depending on the sensitivity of the respective mass spectrometer.
Table A.1 — Examples of recovery rates – Ultra pure water (as in 7.2)
Laboratory 1 2 3 3 3 4
Working A1.1 A1.2 A1.3 A1.3 A1.4 A1.3
conditions
VP (ml) 50 10 20 20 10 20
N (µg/l) 0,1 0,1 0,01 0,1 0,1 0,1

n 4 4 4 4 4 10
Compound Ai s Ai s Ai s Ai s Ai s Ai s
PFBA 97,6 2,5 98,1 1,8 109 8,3 104 6,4 99,8 4,0 91 8,1
PFPeA 94,1 2,7 94,8 1,6 96,0 10,9 105 4,6 104 2,2 116 6,6
PFHxA 92,1 4,1 96,5 1,7 94,2 3,7 101 7,5 101 2,2 114 5,1
PFHpA 90,8 5,2 97,3 2,2 112 8,0 108 6,9 105 1,9 90 9,8
PFOA 90,7 3,0 99,7 5,7 102 8,1 109 2,7 105 2,8 83 6,6
PFNA 92,9 3,3 104 9,9 95,9 7,8 105 8,2 105 2,6 104 3,5
PFDA 85,3 4,9 96,3 11,2 77,0 9,0 78,6 1,5 91,8 2,2 77 7,7
PFBS 101 2,5 97,6 1,7 102 11,8 103 3,3 102,8 3,0 78 6,3
PFHxS 103 3,2 97,2 1,4 95,4 9,3 102 5,5 101 0,6 87 4,1
PFOS 97,0 4,0 94,9 3,7 92,1 2,0 104 10,3 97,5 3,1 83 3,9
PFUnAa — — — — — — — — — — 93 7,4
PFDoAa — — — — — — — — — — 58 4,7
PFDSa — — — — — — — — — — 70 8,2
13C
4-PFBA
88,7 3,7 97,7 1,5 74,9 5,9 86,0 3,6 99,8 4,1 84 6,0
13C
2-PFHxA
86,6 3,7 95,1 1,1 95,0 5,4 88,9 10,6 107 1,5 89 6,6
13C
4-PFOA
91,3 2,2 97,0 5,1 95,6 9,7 87,1 5,4 103 2,6 88 5,6
13C
4-PFOS
81,7 2,4 90,6 6,5 86,6 4,3 93,6 4,0 92,7 2,7 88 3,2
Key:
VP volume of water sample, in millilitres, ml
N concentration level, spiking concentration in micrograms per litre, µg/l

n number of measurements at concentration level N over the total procedure
Ai mean recovery rate of substance i at concentration level N, in percent, %
s standard deviation of recovery rate, in percent, %

NOTE Evaluation with external standard without consideration of recovery rates.
a Additional analytes: PFUnA (Perfluoro-n-undecanoic acid), PFDoA (Perfluoro-n-dodecanoic acid), PFDS (Perfluoro-n-
decanesulfonic acid).
30
DIN 38407-42:2011-03
Table A.2 — Examples of recovery rates – Drinking water
Working
A1.1 A1.1 A1.5 A1.2 A1.3 A1.3
conditions
Analytical values pH 8,3 pH 7,6 pH 7,3 pH 8,3
Sample TOC 0,8 mg/l TOC 0,3 mg/l TOC 1,3 mg/l TOC 0,9 mg/l
γ 28 mS/m γ 44 mS/m γ 67 mS/m γ 19 mS/m
GH(°dH) = 5,5 GH(°dH) = 14,9 GH(°dH) = 12 GH(°dH) = 3,8
VP (ml) 50 50 50 10 20 20
N (µg/l) 0,01 0,1 0,1 0,1 0,01 0,1

n 4 4 4 4 4 4
PFBA 119 0,4 97,7 4,1 98,1 1,4 96,1 3,3 93,2 2,2 112 2,2
PFPeA 91,5 0,2 98,7 2,5 94,1 2,5 92,7 0,6 82,4 8,0 107 2,7
PFHxA 109 0,2 98,3 3,4 91,5 4,5 92,4 1,3 83,4 3,4 101 5,2
PFHpA 94,9 0,3 101 3,5 95,0 1,5 93,5 3,1 97,4 11,6 110 3,1
PFOA 120 0,6 105 3,5 95,0 2,9 97,3 6,2 96,6 7,2 109 1,5
PFNA 99,7 0,5 95,0 4,1 93,6 6,7 94,8 5,2 90,8 4,6 93,9 4,7
PFDA 81,8 0,2 82,6 7,0 85,3 6,8 77,0 4,4 57,6 9,5 68,1 3,2
PFBS 123 0,5 98,5 3,4 100 1,5 94,8 2,4 87,5 11,5 102 1,3
PFHxS 131 0,6 100 3,8 103 2,7 93,2 1,4 84,4 2,6 103 2,4
PFOS 98,7 0,2 86,9 6,4 82,9 2,8 77,5 3,3 83,1 7,6 96,8 2,8
13C
4-PFBA
95,8 4,5 93,4 5,8 109 1,7 97,3 1,8 78,8 13,1 99,7 7,3
13C
2-PFHxA
95,6 4,1 93,3 2,2 106 3,3 94,4 1,3 88,2 12,5 101 5,0
13C
4-PFOA
97,2 5,9 95,1 4,7 105 4,2 98,2 3,9 88,1 7,4 93,3 4,2
13C
4-PFOS
77,5 4,5 76,1 6,0 85,9 3,8 77,1 5,3 86,6 7,5 88,2 7,4
See Table A.1 for key to symbols.

NOTE Evaluation with external standard without consideration of recovery rates. Results in the original sample have
been taken into account.
31
DIN 38407-42:2011-03
Table A.3 — Examples of recovery rates – Surface water
Working
A1.1 A1.2 A1.2 A1.6 A1.6 A1.1
conditions
River Swist Rhein Lippe Ruhr Stever Wupper
Meckenheim Düsseldorf Wesel Witten Haltern Opladen
Analytical values pH 8,5 pH 8,0 pH 8,0 pH 7,7 pH 7,8 pH 7,9
Sample TOC 3,1 mg/l TOC 8,6 mg/l TOC 3,2 mg/l TOC 3,1 mg/l
γ 69 mS/m γ 63 mS/m γ 165 mS/m γ 41 mS/m γ 66,7 mS/m γ 49 mS/m
GH(°dH) = 13 GH(°dH) = 21 GH(°dH) = 7,3
VP (ml) 50 10 10 50 50 50
N (µg/l) 0,1 0,1 0,1 0,1 0,1 0,1

n 4 3 4 3 3 2
PFBA 99,2 1,4 102 6,9 111 2,8 78,7 3,5 78,7 0,6 92,1 0,0
PFPeA 94,3 2,1 93,9 3,7 101 2,2 87,7 4,2 93,0 1,0 96,6 0,0
PFHxA 98,0 1,1 91,3 2,8 103 1,7 92,0 4,4 94,0 1,0 99,1 0,5
PFHpA 96,3 2,5 91,1 2,4 100 0,9 87,0 3,5 87,0 1,0 102 0,3
PFOA 97,9 2,1 96,1 2,9 102 1,2 85,3 3,0 76,7 1,9 103 0,2
PFNA 93,2 3,9 80,6 3,9 83,9 4,4 80,3 3,1 60,3 2,5 95,0 0,5
PFDA 81,9 5,8 57,2 4,6 52,9 8,4 65,0 6,2 39,3 3,5 88,0 0,0
PFBS 103 1,4 93,3 4,0 87,5 1,4 95,0 2,6 98,0 1,7 99,1 0,0
PFHxS 99,2 1,9 92,4 2,2 94,3 1,4 90,0 3,6 90,0 3,5 98,4 0,7
PFOS 82,2 4,6 81,1 6,4 59,3 6,0 64,2 3,6 41,7 2,3 91,2 1,8
13C
4-PFBA
99,8 6,4 99,2 3,6 106,8 2,4 74,7 4,2 73,7 1,5 97,5 0,2
13C
2-PFHxA
94,7 6,6 90,8 2,3 102,2 1,7 87,7 4,2 88,7 1,5 98,8 1,5
13C
4-PFOA
97,1 5,2 96,0 3,2 100,7 1,2 85,3 3,0 76,0 1,6 100 1,3
13C
4-PFOS
77,4 5,0 71,0 6,0 63,3 6,5 65,2 4.2 40,0 2,6 89,9 1,8
13C
5-PFNA
a — — — — 89,3 2,9 — — — — 94,0 5,0
13C
2-PFDA
a — — — — 57,1 8,2 63,3 5,9 36,0 4,0 89,1 0,8
18O
2-PFHxS
a — — — — — — 88,0 2,6 86,7 1,5 100 1,5

a Additional internal standards: 13C 13C 13C -PFDA
5-PFNA (Perfluoro-n-nonanoic acid, labelled), 2 (Perfluoro-n-
decanoic acid, 13C labelled), 18O2-PFHxS (Perfluoro-n-hexanesulfonic acid, 18O labelled).
32
DIN 38407-42:2011-03
Table A.4 — Examples of recovery rates – Treated waste water (effluents)
Working
A1.1 A1.2 A1.3 A1.2 A1.7
conditions
Analytical values pH 7,7 pH 8,1 pH 7,3 pH 7,5 not reported not reported
Sample TOC 6,8 mg/l TOC 147 mg/l TOC 14,2 mg/l TOC 8,4 mg/l
γ 99,6 mS/m γ 233 mS/m γ 71 mS/m γ 51 mS/m
GH(°dH) = 23 GH(°dH) = 0,5
VP (ml) 50 10 20 45 50 50
N (µg/l) 0,10 0,10 0,10 0,20 0,15 0,10

n 5 3 3 4 5 4
PFBA 97,1 3,3 96 7,0 91,7 3,5 83 5,9 99,8 1,9 88 1

PFPeA 93,3 2,7 89 5,7 91,6 0,8 101 5,4 104 1,4 84 4
PFHxA 90,8 1,9 100 6,8 90,6 1,9 105 2,4 95,8 1,1 98 2
PFHpA 95,0 2,7 105 5,7 96,3 0,6 103 6,6 106 3,3 102 3
PFOA 98,8 3,4 107 5,0 97,3 1,4 99 5,8 102,5 1,7 100 6
PFNA 88,0 4,1 102 1,5 97,7 2,1 100 6,6 99,2 2,9 107 4
PFDA 78,2 7,3 92 2,3 95,6 2,3 84 5,3 98,1 1,0 102 3
PFBS 103 2,3 99 1,9 87,8 2,4 86 3,5 109 2,3 84 4
PFHxS 100 1,7 85 4,7 94,3 1,2 92 6,8 103 4,4 81 3
PFOS 75,9 7,4 67 2,5 93,6 3,1 74 6,9 105 1,9 103 10
13C 99,7 — 101 4,5 86,9 1,8 78 6,8 101 4,9 87 2
4--PFBA
13C
2-PFHxA
101 — 104 5,4 88,4 0,5 89 3,6 98,4 1,4 96 2
13C
4-PFOA
97,2 — 105 3,7 91,7 1,8 95 4,8 94,7 1,3 77 5
13C
4-PFOS
74,3 — 63 3,5 92,4 2,2 71 3,4 98,2 3,8 125 11
13C
5-PFNA
a — — 106 3,2 — — 84 3,4 96,5 2,5 127 18
13C
2-PFDA
a — — 86 0,9 — — 90 6,4 98,1 1,0 116 5
18O
2-PFHxS
a — — — — — — 91 6,9 — — 86 5

a Additional internal standards: 13C 13C 13C -PFDA
5-PFNA (Perfluoro-n-nonanoic acid, labelled), 2 (Perfluoro-n-
decanoic acid, 13C labelled), 18O -PFHxS (Perfluoro-n-hexanesulfonic acid, 18O labelled).
2
33
DIN 38407-42:2011-03
Annex B
(informative)
Examples of suitable HPLC columns and chromatograms
B.1 Chromatographic conditions for the chromatogram shown in Figure B.1

HPLC column: ZORBAX Eclipse XDB-C18 4) 3,5 µm, 100 mm × 2 mm,
pre-column Synergi Fusion-RP4), 4 µm, 4 mm × 2 mm
Injection volume: 20 µl PFC standard solution, ρi = 1 ng/ml
Mobile phase: A: 5 mmol/l ammonium acetate in water
B: 0,05 % acetic acid in methanol
Linear gradient program (B %): 35 % at 0 min, increase to 95 % at 20 min
Flow rate: 0,25 ml/min
Column temperature: 40 °C
Pressure: 115 bar (starting conditions)
Key
X Time, min 5 PFHpA A 13C
4 PFBA
Y Signal intensity 6 PFHxS B 13C
2 PFHxA
1 PFBA 7 PFOA C 13C
4 PFOA
2 PFPeA 8 PFNA D 13C
4 PFOS
3 PFBS 9 PFOS
4 PFHxA 10 PFDA
Additional analytes: 11 PFUnA 12 PFDoA
Figure B.1 — Chromatographic separation, example 1
4) ZORBAX Eclipse XDB-C18 and Synergi Fusion-RP are examples of suitable products available commercially. This
information is given for the convenience of users of this document and does not constitute an endorsement by DIN of
these products.
34
DIN 38407-42:2011-03

HPLC column: NUCLEODUR C18Pyramid 5) 3 µm, 125 mm × 2 mm,
pre-column Synergi Max-RP5), 4 µm, 4 mm × 2 mm
Mobile phase: A: 10 mmol/l ammonium acetate in water-methanol 75:25
B: 10 mmol/l ammonium acetate in acetonitrile-methanol 75:25
Linear gradient program (B %): 0 % at 0 min, increase to 30 % at 5 min,
30 % at 5 min, increase to 55 % at 8 min,
55 % at 8 min, increase to 80 % at 19 min
Key
See key in Figure B.1 for peak number.
Additional analytes:
11 PFUnA
12 PFDoA
13 PFHpS (Perfluoro-n-heptanesulfonic acid)
14 PFDS (Perfluoro-n-decanesulfonic acid)
5) NUCLEODUR C18 Pyramid and Synergi Max-RP are examples of suitable products available commercially. This
information is given for the convenience of users of this document and does not constitute an endorsement by DIN of
these products.
35
DIN 38407-42:2011-03

HPLC column: Synergi Fusion-RP 6) 4 µm, 100 mm × 2 mm,
Mobile phase: A: 2 mmol/l ammonium acetate, 0,1 % acetic acid in methanol,
B: 2 mmol/l ammonium acetate, 0,1 % acetic acid in water-methanol 90:10
Gradient program (A %): 25 % at 0 min, keep at the level until 4 min,
70 % at 20 min, decrease to 30 % at 20,5 min
and keep at the level until 25 min
Key
Additional internal standards:
E 13C5 PFNA
F 13C
2 PFDA
6) Synergi Fusion-RP is an example of a suitable product available commercially. This information is given for the
convenience of users of this document and does not constitute an endorsement by DIN of this product.
36
DIN 38407-42:2011-03

HPLC column: Synergi Fusion-RP 7) 2,5 µm, 100 mm × 2 mm,
Injection volumn: 20 µl PFC standard solution, ρi = 1 ng/ml
B: 0,05 % acetic acid in methanol
Linear gradient program (B %): 35 % at 0 min, increase to 95 % at 20 min
Key
7) Synergi Fusion-RP is an example of a suitable product available commercially. This information is given for the
convenience of users of this document and does not constitute an endorsement by DIN of this product.
37
DIN 38407-42:2011-03

HPLC column: AQUITY UPLC-BEH-Shield RP18 8) 1,7 µm,
100 mm × 2,1 mm
B: 2 mmol/l ammonium acetate in methanol
Linear gradient program (B %): 30 % at 0 min, keep at the level until 0,5 min,
30 % at 0,5 min, increase to 90 % at 5 min
Key
Additional internal standards:
F 13C2 PFDA
G 18O
2 PFHxS
8) AQUITY UPLC-BEH-Shield RP18 is an example of a suitable product available commercially. This information is
given for the convenience of users of this document and does not constitute an endorsement by DIN of this product.
38
DIN 38407-42:2011-03
Annex C
(informative)
Examples of selected diagnostic ions for identification and quantification
Table C.1 — Selected diagnostic ions (target compounds)
Compound ESI mode Quantification Identification

Precursor ion 1st product ion 2nd product ion
(Qualifier)
m/za m/z m/z
PFBA neg 213 169 —

PFPeA neg 263 219 119
PFHxA neg 313 269 119
PFHpA neg 363 319 169
PFOA neg 413 369 169
PFNA neg 463 419 219
PFDA neg 513 469 219
PFBS neg 299 80 99
PFHxS neg 399 80 99
PFOS neg 499 80 99
a mass to charge ratio
Table C.2 — Selected diagnostic ions (internal standards)
Compound Relative molecular mass ESI mode Precursor ion Product ions
m/z m/z
13C
4-PFBA 218,01 neg 217 172
13C
2-PFHxA 316,04 neg 315 270/119
18O
2-PFHxS 404,09 neg 403 103
13C
4-PFOA 418,04 neg 417 372/169
13C
4-PFOS 504,10 neg 503 80/99
13C
5-PFNA 469,04 neg 468 423/223/219
13C
2-PFDA 516,07 neg 515 470/220/219
Optimized m/z values may deviate from values given in Tables C.1 and C.2, and shall therefore preferably be
determined under chromatographic conditions.
39
DIN 38407-42:2011-03
Key
+ Branched isomers
I Unbranched isomers
See Figure B.2 for chromatographic conditions.
Figure C.1 — Example of a MS chromatogram of a surface water sample (extract shows branched and
unbranched perfluorinated carboxylic acids)
Key
+ Branched isomers
I Unbranched isomers
See Figure B.2 for chromatographic conditions.
Figure C.2 — Example of a MS chromatogram of a surface water sample (extract shows branched and
unbranched perfluorinated sulfonic acids)
40
DIN 38407-42:2011-03
Annex D
(informative)
Examples for the expansion of the method
The expansion of the method is not covered by this document and shall, therefore, be checked on a
case-by-case basis.
In combination with solid phase extraction, it is in principle possible to expand the method by substances
exhibiting one acid functional group in the molecule, e.g. by the substances perfluoroundecanoic acid,
perfluorododecanoic acid, perfluoroheptane sulfonic acid, perfluorodecane sulfonic acid, perfluorododecane
sulfonic acid and 1H,1H,2H,2H-perfluorooctane sulfonic acid.
Telomeric alcohols, on the other hand, cannot be covered, since they are not enriched under the prescribed
conditions of solid phase extraction. These limitations do not apply in the case of a determination without
enrichment.
41
DIN 38407-42:2011-03
Annex E
(informative)
Explanatory notes
This standard has been prepared by Normenausschuss Wasserwesen (Water Practice Standards Committee)
in collaboration with the Wasserchemische Gesellschaft (German Water Chemistry Society), a division of the
Gesellschaft Deutscher Chemiker (German Chemistry Society). It is part of the series Deutsche
Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung (German standard methods for the
examination of water, waste water and sludge):
“Determination of selected polyfluorinated compounds (PFC) in water - Method using high performance liquid
chromatography and mass spectrometric detection (HPLC/MS-MS) after solid-liquid extraction (F 42)”.
Standard methods published as DIN Standards are obtainable from Beuth Verlag GmbH, either individually or
grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche
Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung will continue to be published by Wiley-
VCH Verlag GmbH & Co. KgaA and Beuth Verlag GmbH.
All standard methods relevant to the Abwasserverordnung (Waste Water Regulation – AbwV 9)) – included in
the Regulation § 57, paragraph 1, No. 1 of the Gesetz zur Ordnung des Wasserhaushalts (German Water
Management Act – together with the Abwasserverordnung and the Gesetz zur Ordnung des Wasserhaushalts
and other valid administrative regulations on waste water have been published as a loose-leaf collection
Analysenverfahren in der Abwasserverordnung – Rechtsvorschriften und Normen, with Supplement 1 (DIN
Standards), Supplement 2 (DIN EN and DIN EN ISO Standards) and Supplement 3 (DIN, DIN EN and DIN EN
ISO Standards).
Standards or draft standards bearing the group title “German standard methods for the examination of water,
waste water and sludge” are classified under the following categories (main titles):
General information (group A) (DIN 38402)
Sensory analysis (group B) (DIN 38403)
Physical and physicochemical parameters (group C) (DIN 38404)
Anions (group D) (DIN 38405)
Cations (group E) (DIN 38406)
Jointly determinable substances (group F) (DIN 38407)
Gaseous constituents (group G) (DIN 38408)
Parameters characterizing effects and substances (group H) (DIN 38409)
Microbiological methods (group K) (DIN 38411)
Test methods using water organisms (group L) (DIN 38412)
Biological-ecological methods of analysis (group M) (DIN 38410)
Individual constituents (group P) (DIN 38413)
Sludge and sediments (group S) (DIN 38414)
Bio-assays with microorganisms (group T) (DIN 38415)
In addition to the methods described in the DIN 38402 to DIN 38415 series of standards, there are a number
of European Standards available, which also form part of the collection of German standard methods.
Information on Parts of these series of standards that have already been published can be obtained from the
offices of the Normenausschuss Wasserwesen, telephone + 49 (30) 2601-2448, or from Beuth Verlag GmbH,
Am DIN-Platz, Burggrafenstr. 6, 10787 Berlin, Germany.
9) Registered in the DITR database of DIN Software GmbH, obtainable from: Beuth Verlag GmbH, 10772 Berlin.
42
DIN 38407-42:2011-03
Bibliography
ISO/TS 13530, Water quality — Guidance on analytical quality control for chemical and physicochemical
water analysis
[1] Directive 2006/122/EC of the European Parliament and of the Council of 12 December 2006 amending
for the 30th time Council Directive 76/769/EEC on the approximation of the laws, regulations and
administrative provisions of the Member States relating to restrictions on the marketing and use of
certain dangerous substances and preparations (perfluorooctane sulfonates)
[2] DEV A0-4, Leitfaden zur Abschätzung der Messunsicherheit aus Validierungsdaten — Verfahren
A0-4 10) (Guide for the assessment of measurement uncertainty from validation data — Method A0-4)
10) Obtainable from: Beuth Verlag GmbH, 10772 Berlin or Wiley-VCH Verlag GmbH & Co. KGaA, Boschstraße 12,
69469 Weinheim.
43

Din 38407-42 - 2011

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Din 38407-42 - 2011

Uploaded by

Copyright:

Available Formats

March 2011

German standard methods for the examination of water, waste water

Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung –

Document comprises 43 pages

© No part of this translation may be reproduced without prior permission of

A comma is used as the decimal marker.

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 — Example of a MS chromatogram of a surface water sample (extract shows

Figure C.2 — Example of a MS chromatogram of a surface water sample (extract shows

Table 2 — Meaning of the indices .............................................................................................................. 16

Table 4 — Performance data for HPLC/MS-MS measurement ................................................................ 24

Table 5 — Performance data for drinking water....................................................................................... 25

Table 6 — Performance data for ground water ........................................................................................ 25

Table 7 — Performance data for surface water ........................................................................................ 26

Table 8 — Performance data for treated waste water .............................................................................. 26

Table A.2 — Examples of recovery rates – Drinking water ..................................................................... 31

Table A.3 — Examples of recovery rates – Surface water ...................................................................... 32

Table C.1 — Selected diagnostic ions (target compounds).................................................................... 39

Table C.2 — Selected diagnostic ions (internal standards) .................................................................... 39

Perfluoro-n-pentanoic acid PFPeA C5HO2F9 264,05 2706-90-3

Perfluoro-n-hexanoic acid PFHxA C6HO2F11 314,05 307-24-4

Perfluoro-n-heptanoic acid PFHpA C7HO2F13 364,06 375-85-9

Perfluoro-n-octanoic acid PFOA C8HO2F15 414,07 335-67-1

Perfluoro-n-nonanoic acid PFNA C9HO2F17 464,08 375-95-1

Perfluoro-n-decanoic acid PFDA C10HO2F19 514,08 335-76-2

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

The technical manufacture of perfluoroalkyl compounds by means of electrolytic fluorination of hydrocarbon

3 Terms and definitions

Polytetrafluoroethylene-containing materials (PTFE = polytetrafluoroethylene) in contact with the sample are

5.2 Interferences encountered during extraction and processing of extracts

Method DIN 38407 — F 42

The quality of the water shall be checked.

7.3 Solid phase material, weak anion exchanger on a polymer base.

7.4 Methanol, CH3OH.

7.5 Acetonitrile, CH3CN.

7.6 Acetic acid, w(CH3COOH) = 100 %.

7.7 Formic acid, w(HCOOH), minimum 98 %.

7.8 Acetone, C3H6O.

7.9 Ammonia solution, w(NH3), minimum 25 %.

7.10 Ammonium acetate, CH3COONH4.

7.13 Nitrogen for the concentration of extracts, purity of at least 99,99 %.

7.15 Reference substances, see Table 1 for substances.

NOTE Solutions of reference substances are commercially available.

7.16 Internal standard substances, as in Table C.2, content of at least 95 %.

NOTE Solutions are commercially available.

7.17 Preparation of the solutions

Calculate all solutions with regard to the anion content.

7.17.1 Individual solutions of the reference substances

7.17.2 Individual solutions of internal standard substances

7.17.3 Stock solution (reference substances)

7.17.4 Stock solution (internal standard substances)

7.17.5 Spiking solution (internal standard substances)

This solution is used for spiking water samples (see 10.2).

7.17.6 Reference solutions

7.17.7 Control standard

NOTE Solutions are commercially available.

8.5 Pipettes, with polypropylene tips.