SIST-TS CEN/TS 17197:2019+AC:2019

Construction products: Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES)

This Technical Specification specifies the method for the determination of major, minor and trace elements in aqua regia and nitric acid digests and in eluates of construction products by Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES). It refers to the following 44 elements: Aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), boron (B), cadmium (Cd), calcium (Ca), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lanthanum (La), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), mercury (Hg), molybdenum (Mo), neodymium (Nd), nickel (Ni), phosphorus (P), potassium (K), praseodymium (Pr), samarium (Sm), scandium (Sc), selenium (Se), silicon (Si), silver (Ag), sodium (Na), strontium (Sr), sulphur (S), tellurium (Te), thallium (Tl), thorium (Th), tin (Sn), titanium (Ti), tungsten (W), uranium (U), vanadium (V), zinc (Zn), and zirconium (Zr).
For the determination of low levels of As, Se and Sb, hydride generation may be applied. This method is described in Annex D.
NOTE   Construction products include e.g. mineral-based products (S); bituminous products (B); metals (M); wood-based products (W); plastics and rubbers (P); sealants and adhesives (A); paints and coatings (C), see also CEN/TR 16045 [1].
The method in this Technical Specification is applicable to construction products and validated for the product types listed in Annex D.

Bauprodukte - Beurteilung der Freisetzung von gefährlichen Stoffen - Analyse von anorganischen Stoffen in Aufschlusslösungen und Eluaten - Analyse mit induktiv gekoppeltem Plasma - Optische Emissionsspektralanalyse (ICP-OES)

Diese Technische Spezifikation legt die Verfahren zur Bestimmung der Hauptelemente, Nebenelemente und Spurenelemente in Königswasser- und Salpetersäure-Aufschlusslösungen sowie in Eluaten von Bauprodukten mittels optischer Emissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-OES) fest. Sie bezieht sich auf die folgenden 44 Elemente:
Aluminium (Al), Antimon (Sb), Arsen (As), Barium (Ba), Beryllium (Be), Bismut (Bi), Blei (Pb), Bor (B), Cadmium (Cd), Calcium (Ca), Cer (Ce), Chrom (Cr), Eisen (Fe), Kalium (K), Kobalt (Co), Kupfer (Cu), Lanthan (La), Lithium (Li), Magnesium (Mg), Mangan (Mn), Molybdän (Mo), Natrium (Na), Neodym (Nd), Nickel (Ni), Phosphor (P), Praseodym (Pr), Quecksilber (Hg), Samarium (Sm), Scandium (Sc), Schwefel (S), Selen (Se), Silber (Ag), Silicium (Si), Strontium (Sr), Tellur (Te), Thallium (Tl), Thorium (Th), Titan (Ti), Uran (U), Vanadium (V), Wolfram (W), Zink (Zn), Zinn (Sn) und Zirconium (Zr).
Zur Bestimmung geringer Gehalte von As, Se und Sb kann die Hydridbildung verwendet werden. Dieses Verfahren wird in Anhang D beschrieben.
ANMERKUNG Bauprodukte umfassen z. B. mineralische Produkte (S); bituminöse Produkte (B); Metalle (M); Holzprodukte (W); Kunststoff und Gummi (P); Dichtstoffe und Kleber (A); Farben und Beschichtungen (C), siehe auch CEN/TR 16045 [1].
Das Verfahren in dieser Technischen Spezifikation ist für Bauprodukte anwendbar und für die in Anhang D aufgeführten Produkttypen validiert.

Produits de construction - Évaluation des émissions de substances dangereuses - Analyse des substances inorganiques dans les digestats et les éluats - Partie 1: Analyse par plasma inductif couplé – Spectrométrie d'émission optique (ICP‐OES)

Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Analiza anorganskih snovi po razklopu in v izlužkih - Analiza z optično emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP/OES) (vključno s popravkom AC)

Ta tehnična specifikacija opisuje metodo za določanje glavnih in stranskih elementov ter elementov v sledovih v zlatotopki in izvlečku dušikove kisline ter v izlužkih gradbenih proizvodov z optično emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP/OES). Sklicuje se na naslednjih 44 elementov: aluminij (Al), antimon (Sb), arzen(As), barij (Ba), berilij(Be), bizmut (Bi), bor (B), kadmij (Cd), kalcij (Ca), cerij (Ce), krom (Cr), kobalt (Co), baker (Cu), železo (Fe), lantan (La), svinec (Pb), litij (Li), magnezij (Mg), mangan (Mn), živo srebro (Hg), molibden (Mo), neodim (Nd), nikelj (Ni), fosfor (P), kalij (K), prazeodim (Pr), samarij (Sm), skandij (Sc), selen (Se), silicij (Si), srebro (Ag), natrij (Na), stroncij (Sr), žveplo (S), telurij (Te), talij (Tl), torij (Th), kositer (Sn), titan (Ti), volfram (W), uran (U), vanadij (V), cink (Zn) in cirkonij (Zr).
Za določanje nizke ravni As, Se in Sb se lahko uporabi hidridna metoda. Ta metoda je opisana v dodatku D.
OPOMBA:   Gradbeni proizvodi vključujejo npr. mineralne proizvode (S); bitumenske proizvode (B); kovine (M); lesne proizvode (W); plastične mase in gume (P); tesnila in lepila (A); barve in premaze (C), glej tudi CEN/TR 16045 [1].
Metoda v tej tehnični specifikaciji se uporablja pri gradbenih proizvodih in je potrjena za vrste proizvodov, navedene v dodatku D.

General Information

• Status: Withdrawn
• Publication Date: 08-Jan-2019
• Withdrawal Date: 10-Mar-2024
• ICS: 13.020.99 - Other standards related to environmental protection
• ICS: 91.100.01 - Construction materials in general
• Technical Committee: NES - Dangerous substances
• Current Stage: 9900 - Withdrawal (Adopted Project)
• Start Date: 11-Mar-2024
• Due Date: 03-Apr-2024
• Completion Date: 11-Mar-2024
• Directive: 305/2011 - Regulation (eu) No 305/2011 of the European Parliament and of the Council of 9 march 2011 laying down harmonised conditions for the marketing of construction products and repealing council directive 89/106/eec
• Mandate: M/366 - Concerning the execution of standardisation work for the development of horizontal standardised assessment methods for harmonized approcaches relating to dangerous substances under the construction products directive (CPD)
• Ref Project: CEN/TS 17197:2018+AC:2018 - Construction products: Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES)

Relations

• Replaces: SIST-TS CEN/TS 17197:2019 - Construction products - Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES)
• Effective Date: 01-Feb-2019
• Replaced By: SIST EN 17197:2024 - Construction products - Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by inductively coupled plasma optical emission spectrometry (ICP-OES)
• Effective Date: 01-Apr-2024

Standards Content (Sample)

SLOVENSKI STANDARD
01-februar-2019
1DGRPHãþD
SIST-TS CEN/TS 17197:2019
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Construction products: Assessment of release of dangerous substances - Analysis of
inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma -
Optical Emission Spectrometry (ICP-OES)
Bauprodukte - Beurteilung der Freisetzung von gefährlichen Stoffen - Analyse von
anorganischen Stoffen in Aufschlusslösungen und Eluaten - Analyse mit induktiv
gekoppeltem Plasma - Optische Emissionsspektralanalyse (ICP-OES)
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SDUSODVPDLQGXFWLIFRXSOp±6SHFWURPpWULHG
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Ta slovenski standard je istoveten z: CEN/TS 17197:2018+AC:2018
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.

CEN/TS 17197:2018+AC
TECHNICAL SPECIFICATION
SPÉCIFICATION TECHNIQUE
December 2018
TECHNISCHE SPEZIFIKATION
ICS 91.100.01 Supersedes CEN/TS 17197:2018
English Version
Construction products: Assessment of release of
dangerous substances - Analysis of inorganic substances in
digests and eluates - Analysis by Inductively Coupled
Plasma - Optical Emission Spectrometry (ICP-OES)
Produits de construction: Évaluation des émissions de Bauprodukte - Beurteilung der Freisetzung von
substances dangereuses - Analyse des substances gefährlichen Stoffen - Analyse von anorganischen
inorganiques dans les digestats et les éluats - Partie 1: Stoffen in Aufschlusslösungen und Eluaten - Analyse
Analyse par plasma inductif couplé - Spectrométrie mit induktiv gekoppeltem Plasma - Optische
d'émission optique (ICP-OES) Emissionsspektralanalyse (ICP-OES)
This Technical Specification (CEN/TS) was approved by CEN on 2 April 2018 for provisional application and includes
Corrigendum issued by CEN on 19 December 2018.

The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to
submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard.

CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS
available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in
parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATIO N

EUROPÄISCHES KOMITEE FÜR NORMUN G

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2018 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 17197:2018+AC:2018 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 Symbols and abbreviations . 8
5 Principle . 8
6 Interferences . 9
7 Reagents . 10
8 Apparatus . 12
9 Procedure. 12
9.1 Test sample . 12
9.2 Test portion . 13
9.3 Instrument set up . 13
9.3.1 General requirements . 13
9.3.2 Inter-element correction . 13
9.3.3 Internal standard . 13
9.3.4 Instrument performance check . 13
9.4 Calibration . 14
9.4.1 Linear calibration function . 14
9.4.2 Non-linear calibration function . 14
9.4.3 Standard addition calibration . 14
9.5 Sample measurement . 14
10 Calculation . 15
10.1 Calculation for digests of construction products . 15
10.2 Calculation for eluates of construction products . 15
11 Expression of results . 15
12 Performers characteristics . 16
12.1 General . 16
12.2 Blank . 16
12.3 Calibration check . 16
12.4 Interference . 16
12.5 Recovery . 16
12.6 Precision . 16
13 Test report . 17
Annex A (informative) Wavelengths, spectral interferences and estimated method
detection limits . 19
Annex B (informative) Method detection limit (MDL) and precision data for soil, sludge
and biowaste . 23
Annex C (informative) Inter element correction (IEC) . 27
Annex D (normative) Determination of arsenic, antimony and selenium using hydride-
generation ICP-OES . 29
D.1 Scope . 29
D.2 Principle . 29
D.3 Apparatus . 29
D.4 Reagents and solutions . 30
D.5 Procedure . 31
Bibliography . 33

European foreword
This document (CEN/TS 17197:2018+AC:2018) 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.
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 supersedes CEN/TS 17197:2018.
This document includes the corrigendum 1 which corrects two values in D.4.8 and D.4.9.
The start and finish of text introduced or altered by corrigendum is indicated in the text by tags ˜™
This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association.
Two similar documents have been developed for drinking water, surface water and waste water and
different types of waste respectively, see Annex B.
According to the CEN/CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Introduction
Following an extended evaluation of available methods for content and eluate analysis in construction
products (CEN/TR 16045 [1]) it was concluded that multi element analysis methods have preference
over methods developed for single elements or small groups of elements. This implies that for inorganic
substances ICP methods are preferred for the analysis of extracts obtained from digestion or eluates
obtained from leaching.
This document has been adopted from the work carried out in the context of CEN/TC 400
(project HORIZONTAL) and is very similar to EN 16170:2016, Sludge, treated biowaste and soil -
Determination of elements using inductively coupled plasma optical emission spectrometry (ICP-OES) [2].
This Technical Specification is part of a modular horizontal approach which was 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). Beneficial features of this approach are that modules can be replaced
by better ones without jeopardizing the standard chain and duplication of work of in different
Technical Committees for Products can be avoided as far as possible.
The modules that relate to the standards developed in CEN/TC 351 are specified
in CEN/TR 16220:2011, Construction products: Assessment of release of dangerous substances –
Complement to sampling [3] which distinguishes between the modules. This Technical Specification
belongs to the analytical step.
The use of modular horizontal standards implies the drawing of test schemes as well. Before executing
a test on a certain construction 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 Technical Specification specifies the method for the determination of major, minor and trace
elements in aqua regia and nitric acid digests and in eluates of construction products by Inductively
Coupled Plasma – Optical Emission Spectrometry (ICP-OES). It refers to the following 44 elements:
Aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), boron (B),
cadmium (Cd), calcium (Ca), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe),
lanthanum (La), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), mercury (Hg),
molybdenum (Mo), neodymium (Nd), nickel (Ni), phosphorus (P), potassium (K), praseodymium (Pr),
samarium (Sm), scandium (Sc), selenium (Se), silicon (Si), silver (Ag), sodium (Na), strontium (Sr),
sulphur (S), tellurium (Te), thallium (Tl), thorium (Th), tin (Sn), titanium (Ti), tungsten (W),
uranium (U), vanadium (V), zinc (Zn), and zirconium (Zr).
For the determination of low levels of As, Se and Sb, hydride generation may be applied. This method
is described in Annex D.
NOTE Construction products include e.g. mineral-based products (S); bituminous products (B); metals (M);
wood-based products (W); plastics and rubbers (P); sealants and adhesives (A); paints and coatings (C),
see also CEN/TR 16045 [1].
The method in this Technical Specification is applicable to construction products and validated for the
product types listed in Annex D.
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.
CEN/TS 16637-2, Construction products — Assessment of release of dangerous substances — Part 2:
Horizontal dynamic surface leaching test
CEN/TS 16637-3, Construction products — Assessment of release of dangerous substances — Part 3:
Horizontal up-flow percolation test
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
CEN/TS 17196, Construction products — Assessment of release of dangerous substances — Digestion by
aqua regia for subsequent analysis of the major, minor and trace elements
EN ISO 3696:1995, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987)
EN ISO/IEC 17025, General requirements for the competence of testing and calibration laboratories
(ISO/IEC 17025)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:

Under preparation. Stage at the time of publication: prEN 17087:2017.
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.1
digest
solution resulting from acid digestion of a sample
[SOURCE: EN 16687:2015, 3.2.8]
3.2
eluate
solution obtained from a leaching test
[SOURCE: EN 16687:2015, 4.2.7]
3.3
analyte
determinand
element, ion or substance to be determined by an analytical method
[SOURCE: EN 16687:2015, 4.1.11]
3.4
sample
portion of material selected from a larger quantity of material
Note 1 to entry: The manner of selection of the sample should be prescribed in a sampling plan.
Note 2 to entry: The term “sample” is often accompanied by a prefix (e.g. laboratory sample, test sample)
specifying the type of sample and/or the specific step in the sampling process to which the obtained material
relates.
[SOURCE: EN 16687:2015, 3.1.5]
3.5
test sample
analytical sample
sample, prepared from the laboratory sample, from which test portions are removed for testing or for
analysis
[SOURCE: EN 16687:2015, 3.2.2]
3.6
test portion
analytical portion
amount of the test sample taken for testing/ analysis, usually of known weight or volume
EXAMPLE 1 A bag of aggregates is delivered to the laboratory (the laboratory sample). For test purposes a
certain amount of the aggregate is dried, the result is the test sample. Afterwards the column for a percolation test
is filled with a test portion of dried aggregate.
EXAMPLE 2 A piece of flooring is delivered to the laboratory (the laboratory sample). For the purpose of
digestion a certain amount is size reduced, the result is the test sample. From the size-reduced test sample a test
portion is taken to execute the digestion. If the digest is to be analysed afterwards e.g. by ICP-MS, the whole
amount of the digest is the laboratory sample again (and without any further treatment also the test sample), the
amount taken for the analytical procedure the test portion.
[SOURCE: EN 16687:2015, 3.2.3]
3.7
instrument detection limit
IDL
smallest analyte concentration that can be detected with a defined statistical probability using a
contaminant free instrument and a blank calibration solution
Note 1 to entry: Usually determined by three times the repeatability standard deviation (3 × Sr) calculated from
multiple measurements (n > 8) of a solution within a single run
[SOURCE: EN 16687:2015, 4.1.13]
3.8
method detection limit
MDL
smallest analyte concentration that can be detected with a specified analytical method including sample
preparation with a defined statistical probability
Note 1 to entry: Usually determined by three times the repeatability standard deviation (3 × Sr) calculated from
multiple measurements (n > 8) on different days and in different matrix solutions which contain a low analyte
concentration.
[SOURCE: EN 16687:2015, 4.1.12]
4 Symbols and abbreviations
ICP Inductively coupled plasma
ICS Interference check solution
IDL Instrumental detection limit
IEC Inter-element correction
MDL Method detection limit (limit of detection)
MS Mass spectrometry
OES Optical emission spectrometry
5 Principle
This method describes multi-elemental determinations by ICP-OES using sequential or simultaneous
optical systems and axial or radial viewing of the plasma. The instrument measures characteristic
emission spectra by optical spectrometry. Samples are nebulized and the resulting aerosol is
transported to the plasma torch. Element-specific emission spectra are produced by a radio-frequency
inductively coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of
the emission lines are monitored by photosensitive devices. Background correction is required for trace
element determination. Background correction is not required in cases of line broadening where a
background correction measurement would actually degrade the analytical result. Additional
interferences and matrix effects shall be recognized and appropriate corrections made; tests for their
presence are described.
Alternatively, users may choose multivariate calibration methods (e.g. Multicomponent Spectral
Fitting). In this case, point selections for background correction are superfluous since whole spectral
regions are processed.
For the determination of low levels of As, Se and Sb, hydride generation may be applied. This method is
described in Annex D.
6 Interferences
Spectral interferences are caused by background emission from continuous or recombination
phenomena, stray light from the line emission of high concentration elements, overlap of a spectral line
from another element, or unresolved overlap of molecular band spectra.
Background emission and stray light can usually be compensated for by subtracting the background
emission determined by measurements adjacent to the analyte wavelength peak. Spectral scans of
samples or single element solutions in the analyte regions may indicate when alternate wavelengths are
desirable because of severe spectral interference. These scans will also show whether the most
appropriate estimate of the background emission is provided by an interpolation from measurements
on both sides of the wavelength peak or by measured emission on only one side. The locations selected
for the measurement of background intensity will be determined by the complexity of the spectrum
adjacent to the wavelength peak. The locations used for routine measurement shall be free of off-line
spectral interference (inter-element or molecular) or adequately corrected to reflect the same change in
background intensity as occurs at the wavelength peak.
Spectral overlaps may be avoided by using an alternate wavelength or can be compensated by equations
that correct for inter-element contributions. Instruments that use equations for inter-element
correction require the interfering elements be analysed at the same time as the element of interest.
When operative and uncorrected, interferences will produce false positive determinations and be
reported as analyte concentrations. The interferences are listed in Table A.1.
Physical interferences are effects associated with the sample nebulization and transport processes.
Changes in viscosity and surface tension can cause significant inaccuracies, especially in samples
containing high dissolved solids or high acid concentrations. If physical interferences are present, they
shall be reduced by diluting the sample, by using an internal standard or a high solids nebulizer. They
can also be minimized by matrix matching particularly by matching the acid concentration.
Chemical interferences include molecular compound formation, ionization effects, and solute
vaporization effects. Normally, these effects are not significant with the ICP technique, but if observed,
can be minimized by careful selection of operating conditions (radio-frequency power, observation
position, gas flow rate and so forth), by buffering of the sample, by matrix matching, and by standard
addition procedures. Chemical interferences are highly dependent on matrix type and the specific
analyte element.
Memory interferences result when analytes in a previous sample contribute to the signals measured in a
new sample. Memory effects can result from sample deposition in the uptake tubing or to the nebulizer
and from the build up of sample material in the plasma torch and spray chamber. The occurrence
memory effects depend on the element and can be minimized by flushing the system with a rinse blank
between samples. The possibility of memory interferences should be recognized within an analytical
run and suitable rinse times should be used to reduce them. The rinse times necessary for a particular
element shall be estimated prior to analysis during method development.
7 Reagents
7.1 General
For the determination of elements at trace and ultra trace level, the reagents shall be of adequate purity.
The concentration of the analyte or interfering substances in the reagents and the water should be
negligible compared to the lowest concentration to be determined.
7.2 Water, complying with grade 1 as defined in EN ISO 3696:1995 for all sample preparations and
dilutions.
7.3 Nitric acid, c(HNO ) = 16 mol/l, ρ ~ 1,4 kg/l.
NOTE Nitric acid is available both as ρ(HNO3) = 1,40 kg/l (w(HNO3) = 650 g/kg) and ρ(HNO3) = 1,42 kg/l
(w(HNO3) = 690 g/kg). Both are suitable for use in this method provided they have a minimal content of the
analytes of interest.
7.4 Hydrochloric acid, c(HCl) = 12 mol/l, ρ ~ 1,18 kg/l.
7.5 Single-element standard stock solutions
Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Fe, Hg, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Pr, (total) S, Si,
Sb, Sc, Se, Sm, Sn, Sr, Te ,Ti, Th, Tl, U, V, W, Zn, Zr, c = 1 000 mg/l each.
Both single-element stock solutions and multi-element stock solutions with adequate specification
stating the acid used and the preparation technique are commercially available. Single element
solutions can be made from high purity metals.
These solutions are considered to be stable for more than one year, but in reference to guaranteed
stability, the recommendations of the manufacturer should be considered.
7.6 Multi-element standard stock solutions
7.6.1 General
Depending on the scope, different multi-element calibration solutions may be necessary. In general,
when combining multi-element calibration solutions, their chemical compatibility and the possible
hydrolysis of the components shall be regarded. Care shall be taken to prevent chemical reactions (e.g.
precipitation).
NOTE In multi element standards precipitation of Ag, Ba or Pb can occur; Ag is only stable in high
hydrochloric acid concentrations or nitric acid.
The multi-element calibration solutions are considered to be stable for several months, if stored in the
dark. This does not apply to multi-element calibration solutions that are prone to hydrolysis, in
particular solutions of Bi, Mo, Sn, Sb, Te, W, Hf and Zr.
7.6.2 Multi-element standard stock solution A at the mg/l level may contain the following
elements:
Ag, Al, As, B, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, La, Li, Mn, Ni, Pb, Rb, Sr, Th, Tl, U, V, Se, Zn.
Use nitric acid for stabilization of standard solution A.
7.6.3 Multi-element standard stock solution B at the mg/l level may contain the following
elements:
Mo, Sb, Sn, W, Zr
Use hydrochloric acid (7.4) for stabilisation of multi-element standard stock solution B. Other elements
of interest may be added to the standard stock solution, provided that the resulting multi-element
solution is stable.
7.6.4 Multi-element standard stock solution C at the mg/l level may contain the following
elements:
Ca, Mg, Na, K, P, S.
Use nitric acid (7.3) for stabilisation of multi-element standard stock solution C.
7.7 Multi-element calibration solutions
Prepare in one or more steps calibration solutions at the highest concentration of interest. If more
concentration levels are needed, prepare those similarly in an equidistant concentration range.
Add acids (7.3 and/or 7.4) to match the acid concentration of samples closely.
If traceability of the values is not established check the validity by comparison with a (traceable)
independent standard.
Check the stability of the calibration solutions.
7.8 Internal standard solution
The use of an internal standard can be a suitable method to correct for non spectral interferences.
The approach involves the addition of a known amount of a substance to the sample and calibration
solutions. The ratio of responses of the analyte and the internal standard are measured in the sample
and calibration solution. The observation for the internal standard is used to relate the analyte signal
to the analyte concentration.
The choice of elements for an internal standard solution depends on the analytical problem.
The solution of this/these internal standard(s) should cover the mass range of interest.
The concentrations of the selected elements (used as internal standard) should be negligibly low
in the digests of samples. The elements Sc, Y, In and Rh have been found suitable for this purpose.
Generally, a suitable concentration of the internal standard in samples and calibration solutions
is 1 mg/l to 10 mg/l.
7.9 Calibration blank
Prepare the calibration blank by acidifying water (7.2) to the same concentrations of the acids found
in the calibration solutions, digests and eluates.
7.10 Method blank
The method blank shall contain all of the reagents in the same volumes as used in the processing of the
samples. The method blank shall be carried through the complete procedure and contain the same acid
concentration in the final solution as the sample solution used for analysis.
7.11 Calibration check solution
Prepare the calibration check solution, purchased from a different supplier, by acidifying water (7.2)
to the same concentration of the acids used in the calibration solutions, using the same standards
used for calibration at an upper concentration level.
7.12 Interference check solution (ICS)
If interference cannot be excluded (see Table A.1) prepare the interference check solution to contain
known concentrations of interfering elements that will provide an adequate test of the correction
factors. The choice of the concentration and interfering element are matrix dependent.
Avoid two or more interferents for an analyte in the same interference check solution. Spike the sample
with the analytes of interest, particularly those with known interferences at 0,5 to 1 mg/l. In the
absence of measurable analyte, overcorrection could go undetected because a negative value could be
reported as zero. If the particular instrument will display overcorrection as a negative number,
this spiking procedure will not be necessary.
8 Apparatus
8.1 Inductively coupled argon plasma emission spectrometer
— Computer-controlled emission spectrometer with background correction;
— Radio-frequency generator;
— Optional mass flow controller for argon nebulizer gas supply;
— Optional peristaltic pump;
— Optional auto sampler;
— Argon gas supply - high purity (e.g. ≥ 99,95 %).
NOTE The ICP-OES instruments come in different varieties i.e. axial or radial viewing or a combination of
both. Axial viewing gives more signal intensity due to the increased observation path length of the normal
analytical zone of the plasma. This will in most cases lead to a higher signal but an increase of interference relative
to radial viewing is commonly observed for many elements. Most instruments however have special adaptations
to overcome the excessive interference by radiation from the bullet zone and molecular region of the plasma.
Especially for low UV (e.g. Pb, Zn, As, Cd, P, Se and S) the Signal to Background Ratio’s are more or less the same
for both types. Several instruments are equipped with dual view by using additional mirrors. This allows
the choice by the operator to select the most suitable option but can give limitations use due to the lower light
intensity and because of different torch design (longer neck), lead to faster blockage and decreased long term
stability. For environmental samples axial viewing can be advantageous.
8.2 Volumetric flasks
Volumetric flasks shall be of suitable precision and accuracy.
8.3 Volumetric pipets
Volumetric pipets shall be of suitable precision and accuracy.
NOTE It is advised to avoid dispensing of a volume of less than 50 µl by means of a pipet.
9 Procedure
9.1 Test sample
The test sample is a particle free digest obtained by CEN/TS 17196 or an eluate obtained by CEN/TS
16637-2 or CEN/TS 16637-3.
9.2 Test portion
The test portion may be directly obtained from the digest or may be diluted from the test sample to
accommodate the measurement range or to dilute the matrix. The acidity of the test portion shall match
the acidity of calibration solutions.
Ensure that all elements are present in a non-volatile form. Volatile species shall be converted to
non-volatile ones, e.g. sulphide oxidation by hydrogen peroxide.
9.3 Instrument set up
9.3.1 General requirements
Adjust the instrumental parameters of the ICP-OES system in accordance with the manufacturer’s
manual. Develop a method (set of instrument parameters) depending on the type of samples
and matrices to be measured.
Define the wavelengths of the analytes of interest and the need for corresponding corrections according
to Table A.1. Alternatively, apply multivariate calibration procedures.
Define the rinsing times depending on the length of the flow path; the time for rinsing the sample
introduction system between the subsequent samples shall be long enough to rinse all the analytes
of interest from the system.
NOTE 1 A guideline for method development and instrument set up is given in Van der Wiel [4].
NOTE 2 ICP-OES has excellent multi-element capability. Nevertheless it does not mean that all elements can be
analysed during one measurement run. The sensitivity of determination depends on numerous parameters
(nebulizer flow, radio-frequency power, viewing height etc.). The optimal instrument settings cannot be reached
for all elements at once.
9.3.2 Inter-element correction
Investigate whether the interfering elements in Table A.1 may results in measured values higher than
three times the IDL or 0,5 times the lowest concentration to be reported. If so, correct for interference.
See Annex C for determining the IEC factors.
9.3.3 Internal standard
If the types of samples to be measured strongly vary, matrix matching may not be possible. Investigate
the application of an internal standard to reduce the effect of the mismatch on analyte sensitivity. The
internal standard method can be applied independently from the calibration procedure.
If the internal standard procedure insufficiently reduces matrix effects, apply standard addition
calibration (9.4.3).
The use of an internal standard is recommended. Add the internal standard solution (7.8) to all
solutions to be measured. On-line dilution and mixing of the sample flow with internal standard
solution by means of the peristaltic pump of the nebulizer is common practice. In such case the
calibration solutions are diluted the same way as the sample solutions.
The mass concentration of the reference-elements shall be the same in all solutions. Divide the response
of the analyte by the response of the internal standard in the calibration solution(s) and use this ratio in
the calibration function.
9.3.4 Instrument performance check
About 30 min prior to measurement, adjust the instrument to working condition.
Before each series of measurement check the sensitivity and the stability of the system and minimize
interference e.g. by using the interference check solution (7.12).
Check the resolution and the mass calibration as often as required by the manufacturer.
Check the wavelength calibration as often as required by the manufacturer.
9.4 Calibration
9.4.1 Linear calibration function
If more than two concentration levels, including zero, are used apply weighted linear regression to
obtain the linear calibration function.
NOTE 1 ICP-OES provides a large measurement range. The dispersion of blank measurements is usually much
smaller than the dispersion at full scale. Ordinary linear regression assumes that the dispersion is constant over
the entire range. As a consequence a much higher percentage of the calculated intercepts is out of the range
expected from the spread of blanks: a non-zero blank value is calculated that is actually not there. Weighted linear
regression forces the line through points of low dispersion, resulting in the expected intercept dispersion.
Unfortunately, many data systems cannot handle weighted regression. An alternative, but less efficient, approach
is ordinary linear regression where the line is forced through the blank value or through zero. The most
inexpensive way however is a (single or multiple) two point calibration. If calibration lines are linear, as they are
usually in ICP-OES, this procedure is valid and efficient.
If weighted linear regression is not possible apply linear regression forced through the blank value or
through zero. In the latter case check regularly by running a blank sample whether the assumption on
the absence of a blank value is justified.
NOTE 2 Weighted linear regression is not suitable for lower element concentrations.
A two point calibration is allowed if the calibration function is linear, which usually is the case. Check
regularly with a calibration solution of known dilution whether the assumption on linearity is justified.
Instead of one measurement per level more measurements can be performed to reduce the uncertainty
of the calibration line.
9.4.2 Non-linear calibration function
Alkali and alkaline earth metals may have non-linear response curves due to ionization and self-
absorption effects.
Calculate the calibration function from weighted polynomial regression (second degree).
If this option is not possible use polynomial regression under the condition that the function is forced
through the blank or through zero. In the latter case check regularly whether the assumption on the
absence of a blank value is justified.
9.4.3 Standard addition calibration
Add a known amount of standard solution (Vs) of the analyte and an equal amount of blank solution (Vb)
to two separate but equal portions of the sample solution (or its dilution). Minimise dilution or correct
for spike dilution. The added amount of standard solution should be between 0,4 and 2 times the
expected sample mass concentration. Measure both solutions as a sample solution. Determine the
‘measured spike concentration' as the difference in mass concentration between the two spiked sample
portions. Use the ratio ‘true spike concentration’ versus ‘measured spike concentration’ as a correction
factor for the initially measured concentration of the sample portion.
9.5 Sample measurement
Run one or more calibration solutions and a calibration blank.
Run the interference check solution(s) to establish interference correction or to check presence of
interference.
Every 25 samples or less and at the beginning and end, run a calibration blank and a calibration check
solution of an independent source (7.11).
Every (e.g.) 50 samples and at the end of a run, analyse an interference check solution (ICS) (7.12).
Run all samples including one or more method blanks.
Run at least one post digestion spiked sample from the series to check recovery.
NOTE 1 If standard addition calibration is applied to all samples it is advised to leave out recovery check.
Whenever a new or unusual sample matrix is encountered check:
— matrix effects by running the spike sample;
— matrix effects by running a fivefold diluted sample;
— inter-element interference analysing a different wavelength.
NOTE 2 It is essential that the analyte concentrations after dilution be at least higher than twice the lowest
concentration to be reported.
10 Calculation
10.1 Calculation for digests of construction products
Calculate the element concentration in the digested construction product:
c−c ××f 100
( )
10 a
(1)
w=
m×dw
where
c is the concentration of the element in the test sample [μg/l];
c is the concentration of the element in the blank [μg/l];
f is the dilution factor of the test portion;
a
w is the mass fraction of the element in the solid sample [μg/g] or [mg/kg];
m is the mass of the digested sample [g];
dw is the dry weight of the sample [%].
10.2 Calculation for eluates of construction products
For eluates the calculations are described in the respective CEN/TS 16637-2 and CEN/TS 16637-3.
11 Expression of results
State as many significant digits as are acceptable according to the precision of the measuring values, but
not more than three significant digits.
12 Performers characteristics
12.1 General
The performance of this analytical method in terms of repeatability and reproducibility needs to be
verified in connection with the validation of digestion methods for construction products using aqua
regia. The digest is used as validation sample in this case .
12.2 Blank
The result of the calibration blank check shall be less than 3 times the IDL or 0,5 times the lowest
concentration to be reported.
12.3 Calibration check
The result of the calibration check solution shall not deviate more than 10 % from the previous
measurement or be within 10 % of the theoretical concentration. Recalibrate the instrument in case of
exceeding this limit.
12.4 Interference
The magnitude of uncorrected background and spectral interference shall not be higher
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