SIST EN 17844:2024
(Main)Construction products - Assessment of release of dangerous substances - Determination of the content of polycyclic aromatic hydrocarbons (PAH) and of benzene, toluene, ethylbenzene and xylenes (BTEX) - Gas chromatographic method with mass spectrometric detection
Construction products - Assessment of release of dangerous substances - Determination of the content of polycyclic aromatic hydrocarbons (PAH) and of benzene, toluene, ethylbenzene and xylenes (BTEX) - Gas chromatographic method with mass spectrometric detection
This document describes two methods for determining the content of polycyclic aromatic hydrocarbons (PAH) and one method for determining the content of benzene, toluene, ethylbenzene and xylenes (BTEX) with gas chromatography with mass spectrometric detection (GC-MS).
See Annex A (normative) for lists of PAH and BTEX that can be determined with this document.
This document is intended to be used for construction products.
In a number of cases additional analysis with high performance liquid chromatography (HPLC) can be necessary to determine a number of compounds. To determine PAH multiple liquid-liquid extraction is used to remove interfering compounds, e.g. maltenes. The tests that led to this document were carried out on different types of roofing material, bitumen and bituminous binders as well as asphalt including one tar containing asphalt (see [Van De Weghe at el., 2018] and [García-Ruiz et al., 2020]).
The detectability limit of the methods for individual compounds in roofing material, asphalt and tar containing asphalt for PAH is 0,5 mg/kg to 1,5 mg/kg and for BTEX 0,1 mg/kg.
Bauprodukte - Bewertung der Freisetzung von gefährlichen Stoffen - Bestimmung des Gehalts an polyzyklischen aromatischen Kohlenwasserstoffen (PAK) und an Benzol, Toluol, Ethylbenzol und Xylol (BTEX) - Gas-chromatographisches Verfahren mit massenspektrometrischer Detektion
Dieses Dokument beschreibt zwei Verfahren zur Bestimmung des Gehalts an polyzyklischen aromatischen Kohlenwasserstoffen (PAK) und ein Verfahren für die Bestimmung des Gehalts an Benzol, Toluol, Ethylbenzol und Xylolen (BTEX) mit Gaschromatographie mit massenspektrometrischer Detektion (GC MS).
Anhang A (normativ) enthält Listen von PAK und BTEX, die mit diesem Dokument bestimmt werden können.
Dieses Dokument ist zur Verwendung für Bauprodukte vorgesehen.
In mehreren Fällen kann eine zusätzliche Analyse mit Hochleistungsflüssigkeitschromatographie erforderlich sein, um eine Reihe von Verbindungen zu bestimmen. Zur Bestimmung von PAK wird eine mehrfache Flüssig-Flüssig-Extraktion verwendet, um störende Verbindungen, wie Maltene, zu entfernen. Die Prüfungen, die zu diesem Dokument geführt haben, wurden an verschiedenen Arten von Dachbahnen, Bitumen und bitumenhaltigen Bindemitteln sowie Asphalt, einschließlich einem teerhaltigen Asphalt, durchgeführt (siehe [Van De Weghe et al., 2018] und [García-Ruiz et al., 2020]).
Die Nachweisgrenze der Verfahren für einzelne Verbindungen in Dachbahnen, Asphalt und teerhaltigem Asphalt liegt für PAK bei 0,5 mg/kg bis 1,5 mg/kg und für BTEX bei 0,1 mg/kg.
Produits de construction - Évaluation de l'émission de substances dangereuses - Détermination de la teneur en hydrocarbures aromatiques polycycliques (HAP) et en benzène, toluène, éthylbenzène et xylènes (BTEX) - Chromatographie en phase gazeuse avec détection par spectrométrie de masse
Le présent document décrit deux méthodes permettant de déterminer la teneur en hydrocarbures aromatiques polycycliques (HAP) et une méthode permettant de déterminer la teneur en benzène, toluène, éthylbenzène et xylènes (BTEX) par chromatographie en phase gazeuse avec détection par spectrométrie de masse (CG-MS).
Voir l'Annexe A (normative) pour une liste des HAP et BTEX pouvant être déterminés à l'aide du présent document.
Le présent document est destiné à être utilisé pour les produits de construction.
Dans certains cas, une analyse supplémentaire par chromatographie liquide à haute performance (HPLC) peut être nécessaire pour déterminer un certain nombre de composés. Pour déterminer les HAP, une extraction liquide-liquide multiple est utilisée afin d'éliminer les interférents, par exemple les maltènes. Les essais conduisant à l'élaboration du présent document ont été réalisés sur différents types de matériaux de couverture, bitumes et liants bitumineux ainsi que d'asphalte, y compris un goudron contenant de l'asphalte (voir [Van De Weghe at el., 2018] et [García-Ruiz et al., 2020]).
La limite de détectabilité des méthodes pour les composés individuels de matériaux de couverture, d'asphalte et de goudron contenant de l'asphalte est de 0,5 mg/kg à 1,5 mg/kg pour les HAP et de 0,1 mg/kg pour les BTEX.
Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Določanje policikličnih aromatskih ogljikovodikov (PAH) ter benzena, toluena, etilbenzena in ksilena (BTEX) - Metoda plinske kromatografije z masno spektrometrijo
Ta dokument podaja metodi za določanje vsebnosti policikličnih aromatskih ogljikovodikov (PAH) in metodo za določanje benzena, toluena, etilbenzena in ksilena (BTEX) s plinsko kromatografijo z masno spektrometrično detekcijo (GC-MS).
Glej dodatek A (normativni) za seznam policikličnih aromatskih ogljikovodikov in benzena, toluena, etilbenzena in ksilena, ki jih je mogoče določiti s tem dokumentom.
Ta dokument je namenjen za uporabo za gradbene proizvode.
V številnih primerih bo mogoče treba izvesti dodatno analizo s tekočinsko kromatografijo visoke ločljivost (HPLC)
za določanje števila spojin. Za določanje policikličnih aromatskih ogljikovodikov se uporablja večkratna ekstrakcija tekočina-tekočina
za odstranjevanje motilnih spojin, npr. maltenov. Preskusi, ki so privedli do tega dokumenta, so bili opravljeni na različnih vrstah strešnih materialov, bitumnu in bitumenskih vezivih ter na asfaltu, vključno s katranskim asfaltom (glej [Van De Weghe et al., 2018] in [García-Ruiz et al., 2020]).
Meja zaznavnosti metod za posamezne spojine v strešnem materialu, asfaltu in katranskem
asfaltu za policiklične aromatske ogljikovodike je od 0,5 mg/kg do 1,5 mg/kg, za benzen, toluen, etilbenzen in ksilen pa 0,1 mg/kg.
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
01-april-2024
Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Določanje
policikličnih aromatskih ogljikovodikov (PAH) ter benzena, toluena, etilbenzena in
ksilena (BTEX) - Metoda plinske kromatografije z masno spektrometrijo
Construction products - Assessment of release of dangerous substances - Determination
of the content of polycyclic aromatic hydrocarbons (PAH) and of benzene, toluene,
ethylbenzene and xylenes (BTEX) - Gas chromatographic method with mass
spectrometric detection
Bauprodukte - Bewertung der Freisetzung von gefährlichen Stoffen - Bestimmung des
Gehalts an polyzyklischen aromatischen Kohlenwasserstoffen (PAK) und an Benzol,
Toluol, Ethylbenzol und Xylol (BTEX) - Gas-chromatographisches Verfahren mit
massenspektrometrischer Detektion
Produits de construction - Évaluation de l'émission de substances dangereuses -
Détermination de la teneur en hydrocarbures aromatiques polycycliques (HAP) et en
benzène, toluène, éthylbenzène et xylènes (BTEX) - Chromatographie en phase
gazeuse avec détection par spectrométrie de masse
Ta slovenski standard je istoveten z: EN 17844:2023
ICS:
13.020.99 Drugi standardi v zvezi z Other standards related to
varstvom okolja environmental protection
91.100.01 Gradbeni materiali na Construction materials in
splošno general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
EN 17844
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2023
EUROPÄISCHE NORM
ICS 91.100.01
English Version
Construction products: Assessment of release of
dangerous substances - Determination of the content of
polycyclic aromatic hydrocarbons (PAH) and of benzene,
toluene, ethylbenzene and xylenes (BTEX) - Gas
chromatographic method with mass spectrometric
detection
Produits de construction : Évaluation de l'émission de Bauprodukte: Bewertung der Freisetzung von
substances dangereuses - Détermination de la teneur gefährlichen Stoffen - Bestimmung des Gehalts an
en hydrocarbures aromatiques polycycliques (HAP) et polyzyklischen aromatischen Kohlenwasserstoffen
en benzène, toluène, éthylbenzène et xylènes (BTEX) - (PAK) und an Benzol, Toluol, Ethylbenzol und Xylol
Chromatographie en phase gazeuse avec détection par (BTEX) - Gas-chromatographisches Verfahren mit
spectrométrie de masse massenspektrometrischer Detektion
This European Standard was approved by CEN on 14 August 2023.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2023 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17844:2023 E
worldwide for CEN national Members.
Contents Page
European foreword . 4
Introduction . 5
1 Scope . 6
2 Normative references . 6
3 Terms and definitions . 6
4 Abbreviations . 9
5 Sample preparation . 10
6 Principle . 10
6.1 Flow chart . 10
6.2 Sample pre-treatment . 10
6.3 Extraction and sample pre-treatment . 10
6.3.1 Determination of PAH . 10
6.3.2 Determination of BTEX . 10
6.4 Gas chromatography determination . 10
6.4.1 Determination of PAH . 10
6.4.2 Determination of BTEX . 11
7 Reagents . 11
8 Equipment and devices . 14
9 Sampling . 15
10 Preservation and pre-treatment of samples . 15
10.1 Sealant and roofing material . 15
10.2 Other construction products . 16
11 Method . 16
11.1 Choice of method . 16
11.2 Method for determining PAH . 16
11.3 Method for determining BTEX . 19
11.4 Calibration . 20
11.5 Identification . 20
11.5.1 Criteria . 20
11.5.2 Gas chromatography criterion . 20
11.5.3 Mass spectrometry criterion . 21
11.6 HPLC analysis . 21
12 Calculation of results . 22
12.1 Calculation of individual PAH contents . 22
12.2 Calculation of PAH contents with correction for recovery . 22
12.3 Calculation of individual BTEX contents. 23
12.4 Rounding . 23
12.5 Calculation of resolution of the different compounds . 23
12.6 Recovery . 24
13 Test performance . 24
14 Test report . 25
Annex A (normative) List of PAH and BTEX . 27
Annex B (informative) Chromatography tube for clean-up of an extract . 28
Annex C (informative) Validation results for content of PAH and BTEX in construction
products . 29
C.1 General . 29
C.2 Precision data for content of PAHs and BTEX in construction products . 29
Annex D (informative) Example settings that can serve as a starting point for the analysis
and detection of PAH and BTEX . 34
D.1 Example settings for the analysis and detection of PAH . 34
D.2 Example settings for the analysis and detection of BTEX . 35
Annex E (informative) Flowchart for determining PAH and BTEX . 37
Bibliography . 39
European foreword
This document (EN 17844:2023) has been prepared by Technical Committee CEN/TC 351 “Construction
products: Assessment of release of dangerous substances”, the secretariat of which is held by NEN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by May 2024, and conflicting national standards shall be
withdrawn at the latest by May 2024.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document has been prepared under a Standardization Request given to CEN by the European
Commission and the European Free Trade Association.
Any feedback and questions on this document should be directed to the users’ national standards body.
A complete listing of these bodies can be found on the CEN website.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and the United
Kingdom.
Introduction
This document deals with the determination of the content of polycyclic aromatic hydrocarbons (PAH)
and of benzene, toluene, ethylbenzene and xylenes (BTEX) with gas chromatography with mass
spectrometric detection (GC-MS). NEN 7331 has been used as basis.
This document is intended to be used for construction products and is suitable for determining:
— the full suite PAH, including the EPA-PAH series ([EPA 8100]);
— six BTEX.
In some cases, additional analysis with high performance liquid chromatography (HPLC) can be
necessary to determine a number of compounds.
The methods described have been subjected to robustness validation [Van De Weghe et al., 2018]. The
detectability limit of the methods for individual compounds in construction products for PAH is
0,5 mg/kg to 1,5 mg/kg and for BTEX 0,1 mg/kg.
This document is part of a modular horizontal approach and belongs to the analytical step. An overview
of all modules which belong to a chain of measurement and the manner how modules are selected is given
in CEN/TR 16220.
In the growing amount of product and sector-oriented test methods it was recognized that many steps in
test procedures are or could be used in test procedures for many products, materials and sectors. It was
supposed that, by careful determination of these steps and selection of specific questions within these
steps, elements of the test procedure could be described in a way that can be used for all materials and
products or for all materials and products with certain specifications.
In this context a horizontal modular approach is adopted in CEN/TC 351. “Horizontal” means that the
methods can be used for a wide range of materials and products with certain properties. “Modular” means
that a test standard developed in this approach concerns a specific step in assessing a property and not
the whole “chain of measurement” (from sampling to analyses). A beneficial feature of this approach is
that “modules” can be replaced by better ones without jeopardizing the standard “chain”.
The use of modular horizontal standards implies the drawing of test schemes as well. Before executing a
test on a certain material or product to determine certain characteristics, it is necessary to draw up a
protocol in which the adequate modules are selected and together form the basis for the entire test
procedure.
1 Scope
This document describes two methods for determining the content of polycyclic aromatic hydrocarbons
(PAH) and one method for determining the content of benzene, toluene, ethylbenzene and xylenes (BTEX)
with gas chromatography with mass spectrometric detection (GC-MS).
See Annex A (normative) for lists of PAH and BTEX that can be determined with this document.
This document is intended to be used for construction products.
In a number of cases additional analysis with high performance liquid chromatography (HPLC) can be
necessary to determine a number of compounds. To determine PAH multiple liquid-liquid extraction is
used to remove interfering compounds, e.g. maltenes. The tests that led to this document were carried
out on different types of roofing material, bitumen and bituminous binders as well as asphalt including
one tar containing asphalt (see [Van De Weghe at el., 2018] and [García-Ruiz et al., 2020]).
The detectability limit of the methods for individual compounds in roofing material, asphalt and tar
containing asphalt for PAH is 0,5 mg/kg to 1,5 mg/kg and for BTEX 0,1 mg/kg.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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.
EN 58, Bitumen and bituminous binders — Sampling bituminous binders
EN 12594, Bitumen and bituminous binders — Preparation of test samples
EN 16687:2023, Construction products: Assessment of release of dangerous substances — Terminology
EN 17087, Construction products: Assessment of release of dangerous substances — Preparation of test
portions from the laboratory sample for testing of release and analysis of content
EN ISO 15009, Soil quality — Gas chromatographic determination of the content of volatile aromatic
hydrocarbons, naphthalene and volatile halogenated hydrocarbons — Purge-and-trap method with
thermal desorption (ISO 15009)
ISO 20595, Water quality — Determination of selected highly volatile organic compounds in water —
Method using gas chromatography and mass spectrometry by static headspace technique (HS-GC-MS)
3 Terms and definitions
For the purposes of this document, the terms and definitions given in EN 16687:2023 and the following
apply.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at https://www.electropedia.org/
3.1
asphalt
homogenous mixture typically of coarse and fine aggregates, filler aggregate and bituminous binder
which is used in the construction of a pavement
Note 1 to entry: Asphalt can include one or more additives to enhance the laying characteristics, performance or
appearance of the mixture.
[SOURCE: EN 13108-1:2016, 3.1.8]
3.2
bitumen
virtually not volatile, adhesive and waterproofing material derived from crude petroleum, or present in
natural asphalt, which is completely or nearly completely soluble in toluene, and very viscous or nearly
solid at ambient temperatures
Note 1 to entry: Some grades of bitumen are used in both paving and industrial applications, e.g. certain
penetration-graded bitumens are used for industrial purposes such as in the manufacture of roofing felts and other
waterproofing membranes.
[SOURCE: EN 12597:2014, 2.2]
3.3
blank value
test result obtained by carrying out the test procedure in the absence of a test portion
[SOURCE: EN 16687:2023, 3.3.1.10; modified – Note 1 to entry removed]
3.4
clean-up
purification of a crude extract to remove interfering compounds
[SOURCE: EN 16687:2023, 3.2.2.27; modified – Note 1 to entry removed]
3.5
external standard
known quantity of the target analytes that is measured in the same series as the solution to be measured
and is used for identification and quantification
[SOURCE: EN 16687:2023, 3.2.2.20]
3.6
extract
solution resulting from extraction of a sample with a solvent
[SOURCE: EN 16687:2023, 3.2.2.13]
3.7
extraction
dissolution of substances in a solvent for subsequent chemical analysis
[SOURCE: EN 16687:2023, 3.2.2.14; modified – Note 1 to entry removed ]
3.8
final extract
solution that is obtained after clean-up of the Soxhlet extract through a purification stage
[SOURCE: EN 16687:2023, 3.2.2.18]
3.9
injection standard
known quantity of a substance (where applicable deuterated) not present in the sample, that after the
clean-up step is added to the analytical portion
[SOURCE: EN 16687:2023, 3.2.2.19]
3.10
laboratory sample
sample or subsample(s) sent to or received by the laboratory
[SOURCE: EN 16687:2023, 3.2.2.1; modified – Notes to entry removed]
3.11
method detection limit
MDL
lowest analyte concentration that can be detected with a specified analytical method including sample
preparation with a defined statistical probability
[SOURCE: EN 16687:2023, 3.3.1.12; modified – Note 1 to entry removed]
3.12
product matrix
main composition of the product dictating the manner of sample preparation and the type of digestion or
extraction for later chemical analysis
[SOURCE: EN 16687:2023, 3.1.1.2; modified – Note 1 to entry removed]
3.13
sample
portion of material selected from a larger quantity of material
[SOURCE: EN 16687:2023, 3.2.1.5; modified – Notes to entry removed]
3.14
Soxhlet extract
solution that is obtained after extraction of a solid subsample by the Soxhlet technique for determining
organic compounds
[SOURCE: EN 16687:2023, 3.2.2.17]
3.15
Soxhlet extraction
chemical pre-treatment of a solid subsample, where the organic compounds to be determined are
dissolved by the Soxhlet technique
[SOURCE: EN 16687:2023, 3.2.2.16]
3.16
surrogate standard
known quantity of a substance (where applicable isotope labelled) not present in the sample, which is
added to the Soxhlet extract in order to determine the recovery
[SOURCE: EN 16687:2023, 3.2.2.26]
3.17
test portion
analytical portion
amount of the test sample taken for testing/analysis purposes, usually of known dimension, mass or
volume
[SOURCE: EN 16687:2023, 3.2.2.3; modified – Examples removed]
3.18
test sample
analytical sample
sample, prepared from the laboratory sample, from which test portions are removed for testing or for
analysis
[SOURCE: EN 16687:2023, 3.2.2.2]
4 Abbreviations
For the purposes of this document, the following abbreviations apply.
BTEX Alkylated benzenes: sum of benzene, toluene, ethylbenzene and xylenes
NOTE 1 A list of BTEX is in Table A.2.
DTL Detection limit
GC Gas chromatography
HPLC High performance liquid chromatography
NOTE 2 High pressure liquid chromatography is an (outdated) synonym.
HRGC High-resolution gas chromatography
LLE Liquid-liquid extraction, also known as solvent extraction and partitioning
LOD Limit of detection
MQL Method quantification limit
MS Mass spectrometry;
Mass selective detection
PAH Polycyclic aromatic hydrocarbon(s)
NOTE 3 A list of PAHs is in Table A.1.
PLE Pressurized liquid extraction
SIM Single ion monitoring
SLE Solid-liquid extraction
5 Sample preparation
To obtain test samples for extraction (and analysis) guidance on sample preparation as specified in
EN 17087 shall be applied. The sample shall be analysed for the total content of substances of interest.
Precautions shall be taken before and during transport of the laboratory sample as well as during the
time in which the samples are preserved in the laboratory before being analysed, to avoid alteration of
the sample (see CEN/TR 16220).
Extracts are susceptible to change due to physical or chemical reactions which can take place between
the time of extraction and the analysis.
It is therefore essential to take the necessary precautions to minimize these reactions and in the case of
many parameters to analyse the extract with a minimum of delay. The maximum delay is given in the
respective analytical standards.
6 Principle
6.1 Flow chart
The method for determination of PAH and BTEX is summarized schematically in Annex E (informative).
6.2 Sample pre-treatment
The quantity of construction product that is processed is reduced prior to grinding by quartering
according to EN 17087. This procedure is repeated until a suitable quantity of subsample is obtained. The
construction product is reduced cryogenically prior to analysis according to EN 17087. For some samples
such as for very open asphalt concrete, cryogenic pre-reduction with a jaw crusher may be performed.
If bitumen, bituminous products or bitumen containing materials are tested according to this document,
a representative subsample shall be taken as described in EN 58 and EN 12594. Pre-treatment may be
chosen here according to the methods described above, e.g. for bitumen and bituminous binders, but for
some materials direct sampling is also permitted.
6.3 Extraction and sample pre-treatment
6.3.1 Determination of PAH
A known quantity of the homogenized sample is extracted with petroleum ether (7.14) for about 16 h
with a Soxhlet extraction set-up. Part of the extract is purified according to one of the two methods
described and the final extract is then analysed for PAH with GC-MS.
6.3.2 Determination of BTEX
A known quantity of the homogenized sample is extracted with methanol (7.1) for about 24 h. The final
extract is analysed after dilution with water with the purge-and-trap method and GC-MS or headspace-
GC-MS.
6.4 Gas chromatography determination
6.4.1 Determination of PAH
For the separation a column with a slightly polar stationary phase is used.
NOTE Examples are also given in 11.2.8 and in Annex D (informative).
Injection takes place via a non-discriminating technique, such as on-column injection or splitless
injection. Detection takes place using mass spectrometry. Calibration and quantification take place by
measurement of an external standard.
The hexane extract of clean-up method PAH 1 (7.19), that is reprocessed for the gas chromatographic
determination with mass selective detection, may, after additional clean-up with aluminium oxide and
conversion to acetonitrile, further be tested with HPLC for the determination of the chrysene content.
6.4.2 Determination of BTEX
A known quantity of the final extract is placed in the purge vessel after dilution with water. In the case of
online systems, the sample is transferred into a suitable sample bottle and injected by the equipment into
the purge vessel. A known quantity of the injection standard is then placed in the purge vessel. After
injection via an injection technique such as purge-and-trap, the compounds to be measured are separated
on a slightly polar or medium polar column and detected with mass spectrometry. Calibration and
quantification take place by measurement of an external standard.
NOTE The method described here is fully in accordance with EN ISO 15009.
7 Reagents
Use only reagents of at least analytical grade. These substances shall be free of interfering compounds.
Check this beforehand by carrying out a blank determination (see 11.2.2 and 11.3.2).
WARNING —The use of this document may involve hazardous materials, operations and equipment. It is
the responsibility of the user of this document to establish appropriate measures to ensure the safety and
health of personnel prior to application of the document and to fulfil statutory and regulatory
requirements for this purpose.
7.1 Methanol [CAS 67-56-1].
7.2 Hexane [CAS 110-54-3].
7.3 Surrogate standard.
Preferably choose compounds, of which the undeuterated form is similar to a target analyte in the sample.
The following may be used:
— anthracene-d [CAS 1719-06-8] for determining PAH;
— chrysene-d [CAS 1719-03-5] for determining PAH;
— naphthalene-d [CAS 1146-65-2] for determining PAH;
— ethylbenzene-d [CAS 25837-05-2] for determining BTEX.
7.4 Injection standard.
Choose compounds for the injection standard that are physically and chemically similar to the
compounds to be analysed, but not present in the sample. The following may be used:
[CAS 17777-56-9] for determining PAH;
— triphenylene-d12
— trifluorotoluene [CAS 98-08-8] for determining BTEX;
— 6-methylchrysene [CAS 1705-85-7] for determining chrysene with HPLC.
6-methylchrysene is used specifically for any HPLC analysis following the GC-MS analysis (11.6).
7.5 Stock solution for PAH determination.
Prepare, where applicable starting from a commercial standard solution, a stock solution with a content
of 200 mg/l of each separate compound (Table A.1) in hexane (7.2).
This solution has a shelf life of at least two years, provided it is stored in the dark and at ≤ −20 °C.
NOTE Due to the hazards associated with working in particular with PAH in solid form, it is not recommended
to make up standard solutions oneself. Ampoules containing PAH mixtures are commercially available.
7.6 Stock solution for BTEX determination.
Prepare, where applicable starting from a commercial standard solution, a stock solution with a content
of 5 mg/l of each individual compound (Table A.2) in methanol (7.1).
This solution has a shelf life of at least six months, provided it is stored in the dark and at ≤ −20 °C.
7.7 Surrogate standard solution for PAH determination.
Dissolve 10 mg of naphthalene-d8 (7.3), 10 mg of anthracene-d10 (7.3), 10 mg of chrysene-d12 (7.3) and
10 mg of 6-methylchrysene (7.4) in 100 ml of hexane (7.2). The content of each separate PAH is 100 mg/l.
The surrogate standard solution has a shelf life of at least six months, provided it is stored in a cool (≤4 °C)
and dark place.
7.8 Surrogate standard solution for BTEX determination.
Dissolve 50 mg ethylbenzene-d (7.3) in 100 ml methanol (7.1). Pipette 5 ml of this solution into a 50 ml
measuring flask and dilute with methanol to 50 ml. The content of ethylbenzene-d is 50 mg/l.
The surrogate standard solution has a shelf life of at least three months, provided it is stored in a cool
(≤4 °C) and dark place.
7.9 Injection standard solution for PAH determination.
Dissolve 10 mg of triphenylene-d (7.4) in 100 ml of hexane (7.2). The content of triphenylene-d is then
12 12
100 mg/l. This solution has a shelf life of at least two months, provided it is stored in a dark and cool place
(≤4 °C).
7.10 Injection standard solution for BTEX determination.
Dissolve 25 mg of trifluorotoluene (7.4) in 100 ml of methanol (7.1). Pipette 100 μl into a 100 ml
measuring flask and dilute with methanol to 100 ml.
This solution has a shelf life of at least six months, provided it is stored in the dark and at ≤ −20 °C.
Repeat the dilution step with 10 ml of the above solution and dilute with methanol to 100 ml. The content
of trifluorotoluene is then 25 μg/l.
7.11 Toluene [CAS 108-88-3].
7.12 Water, with a specific conductivity not higher than 0,2 mS/m at 25 °C.
7.13 Acetone (C H O) [CAS 67-64-1].
3 6
7.14 Petroleum ether (PE), with a boiling point between 40 °C and 60 °C [CAS 8032-32-4].
7.15 Dimethyl sulfoxide ((CH ) SO; DMSO) [CAS 67-68-5].
3 2
Dimethyl sulfoxide can contain interfering naphthalene and pyrene. Before using a new batch of dimethyl
sulfoxide determine whether the naphthalene content and the pyrene content are less than 75 μg/l. For
determination of the pyrene content, follow a blank determination according to 11.2.5.
7.16 Sodium chloride solution, mass concentration ρ(NaCl) = 40 g/l.
7.17 Sodium sulphate (Na SO ), anhydrous [CAS 7757-82-6].
2 4
7.18 Acetonitrile (ACN) [CAS 75-05-8].
7.19 External standard solution for PAH determination according to method 1.
Starting from the stock, injection standard and surrogate standard solution, prepare an external standard
solution in hexane (7.2). Pipette 100 μl of the stock solution for PAH (7.5) into a 100 ml measuring flask
that is half full of hexane. Add to this 500 μl of surrogate standard solution for PAH determination (7.7)
and 1 ml injection standard solution (7.9) and dilute with hexane to 100 ml. The content of the separate
PAH is then 0,2 mg/l, the content of each surrogate standard 0,5 mg/l and the content of injection
standard 1 mg/l.
This solution has a shelf life of at least three months, provided it is stored in a dark and cool place (≤4 °C).
7.20 External standard solution for PAH determination according to method 2.
Starting from the stock, injection standard and surrogate standard solution, prepare an external standard
solution in toluene (7.11). Pipette 100 μl of the stock solution for PAH (7.5) into a 100 ml measuring flask
that is half full of toluene. Add to this 500 μl surrogate standard solution for PAH determination (7.7) and
1 ml injection standard solution (7.9) and dilute with toluene to 100 ml. The content of the separate PAH
is then 0,2 mg/l, the content of each surrogate standard 0,5 mg/l and the content of injection standard
1 mg/l.
This solution has a shelf life of at least three months, provided it is stored in a dark and cool place (≤4 °C).
7.21 External standard solution for BTEX determination.
Pipette 2 ml of the stock solution BTEX (7.6) into a 100 ml measuring flask that is half full of methanol
(7.1). Add to this 200 μl surrogate standard solution for BTEX determination (7.8) and dilute with
methanol to 100 ml. The content of the separate BTEX and surrogate standard is 100 μg/l.
This solution has a shelf life of at least two months, provided it is stored in a dark and cool place (≤4 °C).
7.22 Deactivated aluminium oxide.
Dry aluminium oxide W200 basic or neutral of Brockmann activity class Super I for 16 h at 150 °C. Leave
to cool in a desiccator and add 11 g of water (7.13) per 89 g aluminium oxide. Shake until all the lumps
have disappeared and leave the material to condition for at least 16 h in an airtight sealed vessel.
Aluminium oxide W200 with a Brockman activity of Super I is a commercially available product. This information
is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of
the product named. Equivalent products may be used if they can be shown to lead to the same results.
8 Equipment and devices
8.1 Normal laboratory equipment and devices.
Check the equipment and devices listed below before use for proper operation and the absence of
interfering elements that can affect the result of the test.
Clean the glassware to be used according to the normal procedure, followed by rinsing with acetone
(7.13) and petroleum ether (7.14).
8.2 Shaker, capable of producing shaking movements in a horizontal direction with a frequency of
−1 −1
50 min to 300 min .
8.3 Gas chromatograph, fitted with a non-discriminating injection system (for example on-column
injection) with a mass spectrometric detector and a capillary column with a slightly polar stationary
phase, (for example a CP-SIL 8 ; length: 30 m, internal diameter: 0,32 mm, film thickness: 0,5 μm, or
a column with comparable properties). For BTEX determination the GC-MS system is equipped with
a purge-and-trap or headspace module.
NOTE 1 During the validation process research has shown that the ion trap detection (ITD) technique is
unsuitable for measurements on extracts that come from bituminous materials. The Quadrupole technique is
however suitable.
NOTE 2 Take into account that the precolumn in case of on-column injection might need replacement after five
to ten samples. The separation in particular of benzo[b]fluoranthene and benzo[k]fluoranthene in the external
standard solution can be used as an indication of whether replacement of the precolumn is necessary.
NOTE 3 It has been found that a column with a thicker stationary phase gives better separation and requires less
maintenance.
NOTE 4 During the validation it was found that the use of a programmed temperature vaporizing (PTV) injector
leads to a lower load on the analysis system.
8.4 Extractor.
Soxhlet 100 ml extraction set-up with suitable condenser, a 250 ml round bottomed flask, a 250 ml
evaporation bowl and a heating jacket or water bath, suitable for heating the round bottomed flask
evenly.
8.5 Extraction thimbles, to fit within the extractor (8.4).
NOTE The usual size of cellulose thimbles is 33 mm × 118 mm, with a thickness of 1,5 mm.
8.6 Quartz wool, washed with petroleum ether (7.15).
WARNING — Working with quartz wool can cause health hazards due to the occurrence of fine quartz
particles. Fine quartz particles are mainly taken up by inhalation. Fine quartz particles are harmful for
the lung (e.g. silicosis). In addition, fine quartz particles are harmful for the eyes after direct contact (see
[GESTIS, 2022]). Hazard from fine quartz particles shall be prevented by safety measures according to
statutory national and European provisions for this purpose.
8.7 Separating funnels, 250 ml and 1 000 ml.
CP SIL 8 is a commercially available product. This information is given for the convenience of users of this
European Standard and does not constitute an endorsement by CEN of the product named. Equivalent products
may be used if they can be shown to lead to the same results.
8.8 Rotating film evaporator, connected to a water jet or vacuum pump and fitted with a water bath
that can be heated to 80 °C.
8.9 Calibrated pointed glass tubes, 20 ml.
8.10 40 °C water bath or heating block.
8.11 Glass chromatography tube, see Figure B.1 in Annex B (informative).
8.12 High performance liquid chromatograph.
NOTE An excitation wavelength of 268 nm can be used and an emission wavelength of 383 nm. These
wavelengths give a good sensitivity for determining the chrysene concentration in the extract.
9 Sampling
Sampling is not part of the method specified in this document. Guidance on sampling of construction
products with regard to the assessment of dangerous substances is given in CEN/TR 16220 and in
EN 17087.
NOTE For roofing material it is often necessary to take a full cross-section of a sheet since the material is
inhomogeneous. For a drilling core in a monolithic product, such as asphalt, one can base this on a whole drilling
core or part of it.
10 Preservation and pre-treatment of samples
10.1 Sealant and roofing material
Store the samples according to EN 17087.
Reduce the quantity of sealant or roofing material being processed prior to grinding by quartering
according to EN 17087. To do this, divide the material into quarters with a sharp knife. Choose opposite
quarters for further treatment.
Repeat this procedure a few times until a suitable quantity of subsample is obtained. Add the subsample
thus obtained and reduce the material further with a knife into pieces of approximately 1 cm .
Cryogenically grind part of this – after treatment with liquid nitrogen – and store this analysis sample in
a cool (≤4 °C) and dark place until the analysis.
NOTE 1 The purpose of sampling is to obtain a representative subsample. This is why it is necessary for most
roofing materials to process the full width of a sheet since roofing materials are not always homogenous. This is for
example due to the presence of an adhesive edge.
NOTE 2 For the cryogenic grinding of roofing materials good experience has been gained with an IKA M20 mill
fitted with a stainless steel star-shaped cutter.
The ground sample in some cases consists of two different materials:
— A fibrous material that for example could come from the inlaid materials (polyester and glass fibre)
which are used as reinforcement in sealant or roofing material, and
— A fine grained material that consists mainly of bitumen.
If the whole reduced sample is not processed, a representative analysis sample of this subsample shall be
taken.
10.2 Other construction products
Cryogenically reduce construction products according to EN 17087.
In the case of some samples such as samples of very open asphalt concrete, cryogenic pre-reduction with
a jaw crusher can be necessary. To do this, cool the material with liquid nitrogen and then reduce it with
a jaw crusher to a particle size of D < 4 mm. If possible cryogenically reduce the material further with a
rotary knife mill or disintegrator to a particle size D < 1 mm. Store the material after this in a cool (≤4 °C)
and dark place.
NOTE Not all types of asphalt can be reduced further with a rotary knife mill; some sorts can adhere together.
Process drilling cores complete or per layer required, depending on the client’s requirements. Divide the
cores or layers into pieces of approximately 4 cm to 6 cm by sawing or with a hammer and chisel.
Cryogenically cool the material and grind with a jaw crusher to a particle size D < 4 mm. If possible
cryogenically reduce the material further with a rotary knife mill or disintegrator to a particle size of
D < 1 mm. Store the material after this in a cool (≤4 °C) and dark place.
If pure bitumen is to be tested, pre-reduction is not necessary. In that case, take a representative
subsample. This may for example be done by cooling the material in liquid nitrogen and then crushing it,
for example with a hammer and chisel.
11 Method
11.1 Choice of method
For determination of PAH, proceed according to 11.2.
For determination of BTEX, proceed according to 11.3.
11.2 Method for determining PAH
11.2.1 Choice of method
For the blank determination proceed further according to 11.2.2.
For the determination of the recovery and for the determination of PAH in a sample proceed according
to 11.2.3.
11.2.2 Blank determination
For each measurement series carry out a blank determination (without a sample). Use an extraction
thimble (8.5) for this and proceed further according to 11.2.5.
When taking a new batch of dimethyl sulphoxide (7.15) into use for clean-up method PAH 1 (11.2.5), first
carry out a blank clean-up, because it has been found that naphthalene and pyrene can be present in
dimethyl sulphoxide. The naphthalene content and pyrene content of the dimethyl sulphoxide in the
blank shall be less than 75 μg/l.
11.2.3 Determination of the recovery and determination of PAH content in a sample
Weigh around 10 g (m) subsample of the sealant or roofing material to the nearest 1 mg in an extraction
thimble (8.5) or weigh around 20 g (m) subsample of construction product to the nearest 1 mg in an
extraction thimble. Seal the thimble with quartz wool (8.6). Proceed further according to 11.2.4.
NOTE Since the bitumen content of sealant and roofing material is (50 % to 60 %) higher than that of asphalt
(5 % to 12 %), a smaller quantity of sealant and roofing material is weighed.
11.2.4 Extraction
Extract for at least 16 h in the extractor (8.4) with 200 ml (V ) petroleum ether (7.14) until the
condensate is colourless. Transfer the condensate into a 200 ml measuring flask. Then rinse the round
bottomed flask twice with 5 ml petroleum ether and add this to the condensate in the measuring flask.
Dilute to 200 ml with petroleum ether.
For the clean-up method PAH 1 proceed further according to 11.2.5.
For the clean-up method PAH 2 proceed further according to 11.2.7.
11.2.5 Clean-up method PAH 1
11.2.5.1 Transfer of extract
Place 40 ml hexane (7.2) in a 1 000 ml separating funnel (8.7). Add to this 2 ml (V ) of the extract (11.2.4)
and 200 ml dimethyl sulphoxide (7.15).
For the determination of recovery proceed according to 11.2.5.2.
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