SIST EN 17200:2024
(Main)Construction products - Assessment of release of dangerous substances - Analysis of inorganic substances in eluates and digests - Analysis by inductively coupled plasma mass spectrometry (ICP-MS)
Construction products - Assessment of release of dangerous substances - Analysis of inorganic substances in eluates and digests - Analysis by inductively coupled plasma mass spectrometry (ICP-MS)
This document specifies the method for the determination of major, minor and trace elements in eluates and in aqua regia and nitric acid digests of construction products by inductively coupled plasma mass spectrometry (ICP-MS). It refers to the following 67 elements:
aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), boron (B), cadmium (Cd), calcium (Ca), cerium (Ce), caesium (Cs), chromium (Cr), cobalt (Co), copper (Cu), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), gallium (Ga), germanium (Ge), gold (Au), hafnium (Hf), holmium (Ho), indium (In), iridium (Ir), iron (Fe), lanthanum (La), lead (Pb), lithium (Li), lutetium (Lu), magnesium (Mg), manganese (Mn), mercury (Hg), molybdenum (Mo), neodymium (Nd), nickel (Ni), palladium (Pd), phosphorus (P), platinum (Pt), potassium (K), praseodymium (Pr), rubidium (Rb), rhenium (Re), rhodium (Rh), ruthenium (Ru), samarium (Sm), scandium (Sc), selenium (Se), silicon (Si), silver (Ag), sodium (Na), strontium (Sr), sulphur (S), tellurium (Te), terbium (Tb), thallium (Tl), thorium (Th), thulium (Tm), tin (Sn), titanium (Ti), tungsten (W), uranium (U), vanadium (V), ytterbium (Yb), yttrium (Y), zinc (Zn), and zirconium (Zr).
NOTE 1 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.
The working range depends on the matrix and the interferences encountered.
NOTE 2 The limit of detection of most elements will be affected by their natural abundance, ionization behaviour, on abundance of isotope(s) free from isobaric interferences and by contamination (e.g. handling and airborne). Handling contaminations are in many cases more important than airborne ones.
The limit of detection (MDL) will be higher in cases where the determination is likely to be interfered (see Clause 6) or in case of memory effects (see e.g. EN ISO 17294-1).
The method in this document is applicable to construction products and validated for the product types listed in Annex A (informative).
Bauprodukte - Bewertung der Freisetzung von gefährlichen Stoffen - Analyse von anorganischen Stoffen in Aufschlusslösungen und Eluaten - Analyse mit induktiv gekoppeltem Plasma - Massenspektrometrie (ICP-MS)
Dieses Dokument legt Analyseverfahren für die Bestimmung von Haupt-, Neben- und Spurenelementen in Eluaten und in Königswasser- und Salpetersäureaufschlusslösungen von Bauprodukten durch Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) fest. Es bezieht sich auf die folgenden 67 Elemente:
Aluminium (Al), Antimon (Sb), Arsen (As), Barium (Ba), Beryllium (Be), Bismut (Bi), Blei (Pb), Bor (B), Cadmium (Cd), Calcium (Ca), Cäsium (Cs), Cer (Ce), Chrom (Cr), Cobalt (Co), Dysprosium (Dy), Eisen (Fe), Erbium (Er), Europium (Eu), Gadolinium (Gd), Gallium (Ga), Germanium (Ge), Gold (Au), Hafnium (Hf), Holmium (Ho), Indium (In), Iridium (Ir), Kalium (K), Kupfer (Cu), Lanthan (La), Lithium (Li), Lutetium (Lu), Magnesium (Mg), Mangan (Mn), Molybdän (Mo), Natrium (Na), Neodym (Nd), Nickel (Ni), Palladium (Pd), Phosphor (P), Platin (Pt), Praseodym (Pr), Quecksilber (Hg), Rhenium (Re), Rhodium (Rh), Rubidium (Rb), Ruthenium (Ru), Samarium (Sm), Scandium (Sc), Schwefel (S), Selen (Se), Silber (Ag), Silicium (Si), Strontium (Sr), Tellur (Te), Terbium (Tb), Thallium (Tl), Thorium (Th), Thulium (Tm), Titan (Ti), Uran (U), Vanadium (V), Wolfram (W), Ytterbium (Yb), Yttrium (Y), Zink (Zn), Zinn (Sn) und Zirconium (Zr).
ANMERKUNG 1 Bauprodukte umfassen z. B. mineralische Produkte (S), bituminöse Produkte (B), Metalle (M), Holzprodukte (W), Kunststoffe und Gummi (P), Dichtstoffe und Kleber (A), Farben und Beschichtungen (C), siehe auch CEN/TR 16045.
Der Arbeitsbereich hängt von der Matrix und den zu erwartenden Interferenzen ab.
ANMERKUNG 2 Die Nachweisgrenze der meisten Elemente wird durch deren natürliche Häufigkeit, Ionisationsverhalten, Häufigkeit von Isotop(en), die frei von isobaren Interferenzen sind, und durch Kontamination (z. B. durch Handhabung und Luftübertragung) beeinflusst. Handhabungsbedingte Kontaminationen sind in den meisten Fällen von größerer Bedeutung als luftgetragene Kontaminationen.
Die Nachweisgrenze (MDL) wird höher ausfallen, wenn bei der Bestimmung Interferenzen möglich sind (siehe Abschnitt 6) oder Memoryeffekte auftreten (siehe z. B. EN ISO 17294 1).
Die in diesem Dokument beschriebenen Verfahren sind für Bauprodukte geeignet und sind für die in Anhang A (informativ) aufgeführten Produkttypen validiert.
Produits de construction : Évaluation de l'émission de substances dangereuses - Analyse des substances inorganiques dans les digestats et les éluats - Analyse par spectrométrie de masse avec plasma à couplage inductif (ICP-MS)
Le présent document spécifie la méthode de détermination des éléments majeurs, mineurs et des éléments traces dans les éluats et dans les digestats d'eau régale et d'acide nitrique de produits de construction par spectrométrie de masse avec plasma à couplage inductif (ICP-MS). Il fait référence aux 67 éléments suivants :
aluminium (Al), antimoine (Sb), arsenic (As), baryum (Ba), béryllium (Be), bismuth (Bi), bore (B), cadmium (Cd), calcium (Ca), cérium (Ce), césium (Cs), chrome (Cr), cobalt (Co), cuivre (Cu), dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), gallium (Ga), germanium (Ge), or (Au), hafnium (Hf), holmium (Ho), indium (In), iridium (Ir), fer (Fe), lanthane (La), plomb (Pb), lithium (Li), lutécium (Lu), magnésium (Mg), manganèse (Mn), mercure (Hg), molybdène (Mo), néodyme (Nd), nickel (Ni), palladium (Pd), phosphore (P), platine (Pt), potassium (K), praséodyme (Pr), rubidium (Rb), rhénium (Re), rhodium (Rh), ruthénium (Ru), samarium (Sm), scandium (Sc), sélénium (Se), silicium (si), argent (Ag), sodium (Na), strontium (Sr), soufre (S), tellure (Te), terbium (Tb), thallium (Tl), thorium (Th), thulium (Tm), étain (Sn), titane (Ti), tungstène (W), uranium (U), vanadium (V), ytterbium (Yb), yttrium (Y), zinc (Zn) et zirconium (Zr).
NOTE 1 Les produits de construction comprennent par exemple les produits à base de minéraux (S) ; les produits bitumineux (B) ; les métaux (M) ; les produits à base de bois (W) ; les plastiques et les caoutchoucs (P) ; les produits d'étanchéité et les adhésifs (A) ; les peintures et les revêtements (C), voir également le CEN/TR 16045.
L'étendue de mesure dépend de la matrice et des interférences rencontrées.
NOTE 2 La limite de détection de la plupart des éléments sera affectée par leur abondance naturelle, leur comportement d'ionisation, l'abondance du ou des isotopes exempts d'interférences isobariques et par la contamination (par exemple, par manipulation et par voie aérienne). Les contaminations dues à la manipulation sont dans de nombreux cas plus importantes que celles dues à l'air.
La limite de détection (LDM) est plus élevée lorsque la détermination est sujette à des interférences (voir l'Article 6) ou en cas d'effets mémoire (voir par exemple l'EN ISO 17294-1).
La méthode présentée dans le présent document est applicable aux produits de construction et validée pour les types de produits énumérés à l'Annexe A (informative).
Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Analiza anorganskih snovi po razklopu in v izlužkih - Analiza z masno spektrometrijo z induktivno sklopljeno plazmo (ICP-MS)
Ta evropski standard opisuje metodo za določanje glavnih in stranskih elementov ter elementov v sledovih v zlatotopki in izvlečku dušikove kisline ter v izlužkih gradbenih proizvodov z masno spektrometrijo z induktivno sklopljeno plazmo (ICP‐ MS). Sklicuje se na naslednjih 67 elementov:
aluminij (Al), antimon (Sb), arzen (As), barij (Ba), berilij (Be), bizmut (Bi), bor (B), kadmij (Cd), kalcij (Ca), cerij (Ce), cezij (Cs), krom (Cr), kobalt (Co), baker (Cu), disprozij (Dy), erbij (Er), evropij (Eu), gadolinij (Gd), galij (Ga), germanij (Ge), zlato (Au), hafnij (Hf), holmij (Ho), indij (In), iridij (Ir), železo (Fe), lantan (La), svinec (Pb), litij (Li), lutecij (Lu), magnezij (Mg), mangan (Mn), živo srebro (Hg), molibden (Mo), neodim (Nd), nikelj (Ni), paladij (Pd), fosfor (P), platina (Pt), kalij (K), prazeodim (Pr), rubidij (Rb), renij (Re), rodij (Rh), rutenij (Ru), samarij (Sm), skandij (Sc), selen (Se), silicij (Si), srebro (Ag), natrij (Na), stroncij (Sr), žveplo (S), telurij (Te), terbij (Tb), talij (Tl), torij (Th), tulij (Tm), kositer (Sn), titan (Ti), volfram (W), uran (U), vanadij (V), iterbij (Yb), itrij (Y), cink (Zn) in cirkonij (Zr).
OPOMBA 1: 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.
Delovni razpon je odvisen od matrice in motenj, ki se pojavijo.
OPOMBA 2: Na mejo zaznavanja za večino elementov bo vplival njihov delež v naravi, obnašanje ionizacije ali delež izotopov brez izobaričnih interferenc ter onesnaženje (npr. pri ravnanju, v zraku). Onesnaženja pri ravnanju so v veliko primerih pomembnejša od onesnaženja v zraku.
Meja zaznavanja bo višja v primerih, ko obstaja možnost motnje določevanja (glej točko 4) ali v primeru spominskih učinkov (glej npr. EN ISO 17294-1:2006, 8.2).
Ta metoda v tem standardu se uporablja za gradbene proizvode in je potrjena za vrste proizvodov, navedene v dodatku B.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-april-2024
Nadomešča:
SIST-TS CEN/TS 17200:2019+AC:2019
Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Analiza
anorganskih snovi po razklopu in v izlužkih - Analiza z masno spektrometrijo z
induktivno sklopljeno plazmo (ICP-MS)
Construction products - Assessment of release of dangerous substances - Analysis of
inorganic substances in eluates and digests - Analysis by inductively coupled plasma
mass spectrometry (ICP-MS)
Bauprodukte - Bewertung der Freisetzung von gefährlichen Stoffen - Analyse von
anorganischen Stoffen in Aufschlusslösungen und Eluaten - Analyse mit induktiv
gekoppeltem Plasma - Massenspektrometrie (ICP-MS)
Produits de construction : Évaluation de l'émission de substances dangereuses -
Analyse des substances inorganiques dans les digestats et les éluats - Analyse par
spectrométrie de masse avec plasma à couplage inductif (ICP-MS)
Ta slovenski standard je istoveten z: EN 17200:2023
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 17200
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2023
EUROPÄISCHE NORM
ICS 91.100.01 Supersedes CEN/TS 17200:2018+AC:2018
English Version
Construction products: Assessment of release of
dangerous substances - Analysis of inorganic substances in
eluates and digests - Analysis by inductively coupled
plasma mass spectrometry (ICP-MS)
Produits de construction : Évaluation de l'émission de Bauprodukte: Bewertung der Freisetzung von
substances dangereuses - Analyse des substances gefährlichen Stoffen - Analyse von anorganischen
inorganiques dans les digestats et les éluats - Analyse Stoffen in Aufschlusslösungen und Eluaten - Analyse
par spectrométrie de masse avec plasma à couplage mit induktiv gekoppeltem Plasma -
inductif (ICP-MS) Massenspektrometrie (ICP-MS)
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 17200:2023 E
worldwide for CEN national Members.
Contents Page
European foreword . 4
Introduction . 5
1 Scope . 6
2 Normative references . 6
3 Terms and definitions . 7
4 Abbreviations . 8
5 Principle . 9
6 Interferences . 9
6.1 General . 9
6.2 Spectral interferences . 9
6.2.1 Isobaric elemental interferences . 9
6.2.2 Isobaric molecular and doubly charged ion interferences . 9
6.3 Non-spectral interferences .10
7 Reagents .10
8 Apparatus .13
9 Procedure.14
9.1 Test sample .14
9.2 Test portion .14
9.3 Instrument set up .14
9.4 Calibration .15
9.4.1 Calibration function .15
9.4.2 Standard addition calibration .15
9.4.3 Determination of correction factors .15
9.4.4 Variable isotope ratio .15
9.5 Sample measurement .15
10 Calculation .16
10.1 Calculation for digests of construction products .16
10.2 Calculation for eluates of construction products .16
11 Expression of results .16
12 Performance characteristics .16
12.1 General .16
12.2 Blank .17
12.3 Calibration check .17
12.4 Internal standard response .17
12.5 Interference .17
12.6 Recovery .17
12.7 Indicative values for MDL .17
13 Test performance .17
14 Test report .18
Annex A (informative) Validation results for analysis of inorganic substances in eluates
and digests from construction products . 20
A.1 General . 20
A.2 Precision data for analysis of eluates from construction products . 20
A.3 Precision data for analysis of aqua regia digests from construction products . 27
Annex B (informative) Indicative values for MDL . 34
Bibliography . 35
European foreword
This document (EN 17200:2023) 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 supersedes CEN/TS 17200:2018+AC:2018.
In comparison with the previous edition, the following technical modifications have been made:
— the addition of performance data and data from intercomparison validation;
— alignment of terms and definitions within the working groups of CEN/TC 351, i.e. through the revised
version of EN 16687.
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
Following an extended evaluation of available methods for content and eluate analysis in construction
products (CEN/TR 16045) 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 standard has been adopted from the work carried out in the context of CEN/TC 400 (project
HORIZONTAL) and is very similar to EN 16171.
The outcome of the analysis of materials that due to considerations of reuse/recycling could fall under
an evaluation as construction products would be considered to fall within the uncertainties as specified
by the respective methods and as such would not require an additional analysis, thus avoiding double
testing.
NOTE 1 A similar method has been validated for the determination of elements in aqua regia digests
(EN ISO 54321) for the following matrices: municipal sludge, industrial sludge, sludge from electronic industry, ink
waste sludge, sewage sludge, biowaste, compost, composted sludge, agricultural soil, sludge amended soil, waste,
city waste incineration fly ash (“oxidised” matrix), city waste incineration bottom ash (“silicate” matrix), ink waste
sludge (organic matrix), electronic industry sludge (“metallic” matrix), sewage sludge (BCR 146R), city waste
incineration ash (BCR 176).
NOTE 2 A similar method has been validated for the determination of elements in hydrochloric (HCl), nitric
(HNO ) and tetrafluoroboric (HBF ) or hydrofluoric (HF) acid mixture digests (EN 13656) for the following
3 4
matrices: city waste incineration ash (BCR176/BCR176R), ink waste sludge (organic matrix), electronic industry
sludge (“metallic” matrix), sediment, coal fly ash, steel slag, copper slag, city waste incineration fly ash (“oxidised”
matrix), city waste incineration bottom ash (“silicate” matrix), sewage sludge (BCR 146R).
This document 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, which
distinguishes between the modules. This document 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 document specifies the method for the determination of major, minor and trace elements in eluates
and in aqua regia and nitric acid digests of construction products by inductively coupled plasma mass
spectrometry (ICP-MS). It refers to the following 67 elements:
aluminium (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), boron (B),
cadmium (Cd), calcium (Ca), cerium (Ce), caesium (Cs), chromium (Cr), cobalt (Co), copper (Cu),
dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), gallium (Ga), germanium (Ge), gold (Au),
hafnium (Hf), holmium (Ho), indium (In), iridium (Ir), iron (Fe), lanthanum (La), lead (Pb), lithium (Li),
lutetium (Lu), magnesium (Mg), manganese (Mn), mercury (Hg), molybdenum (Mo), neodymium (Nd),
nickel (Ni), palladium (Pd), phosphorus (P), platinum (Pt), potassium (K), praseodymium (Pr), rubidium
(Rb), rhenium (Re), rhodium (Rh), ruthenium (Ru), samarium (Sm), scandium (Sc), selenium (Se), silicon
(Si), silver (Ag), sodium (Na), strontium (Sr), sulphur (S), tellurium (Te), terbium (Tb), thallium (Tl),
thorium (Th), thulium (Tm), tin (Sn), titanium (Ti), tungsten (W), uranium (U), vanadium (V), ytterbium
(Yb), yttrium (Y), zinc (Zn), and zirconium (Zr).
NOTE 1 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.
The working range depends on the matrix and the interferences encountered.
NOTE 2 The limit of detection of most elements will be affected by their natural abundance, ionization behaviour,
on abundance of isotope(s) free from isobaric interferences and by contamination (e.g. handling and airborne).
Handling contaminations are in many cases more important than airborne ones.
The limit of detection (MDL) will be higher in cases where the determination is likely to be interfered
(see Clause 6) or in case of memory effects (see e.g. EN ISO 17294-1).
The method in this document is applicable to construction products and validated for the product types
listed in Annex A (informative).
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 16637-2, Construction products: Assessment of release of dangerous substances — Part 2: Horizontal
dynamic surface leaching test
EN 16637-3, Construction products: Assessment of release of dangerous substances — Part 3: Horizontal
up-flow percolation
EN 16687:2023, Construction products: Assessment of release of dangerous substances — Terminology
EN 17196, Construction products: Assessment of release of dangerous substances — Digestion by aqua regia
for subsequent analysis of inorganic substances
EN ISO 17294-1:2006, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-
MS) — Part 1: General guidelines (ISO 17294-1:2004)
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
analyte
determinant
element, ion or substance to be determined by an analytical method
[SOURCE: EN 16687:2023, 3.3.1.11]
3.2
aqua regia
solution obtained by mixing one volume of nitric acid and three volumes of hydrochloric acid
[SOURCE: EN 16687:2023, 3.2.2.10]
3.3
digest
solution resulting from acid digestion of a sample
[SOURCE: EN 16687:2023, 3.2.2.8]
3.4
eluate
solution obtained from a leaching test
[SOURCE: EN 16687:2023, 3.3.2.8]
3.5
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
[SOURCE: EN 16687:2023, 3.3.1.13 – modified, Note 1 to entry removed]
3.6
laboratory sample
sample or sub-sample(s) sent to or received by the laboratory
[SOURCE: EN 16687:2023, 3.2.2.1 – modified, Notes to entry removed]
3.7
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]
3.8
sample
portion of material selected from a larger quantity of material
[SOURCE: EN 16687:2023, 3.2.1.5 – modified, Notes to entry removed]
3.9
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]
3.10
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.
FEP Hexafluoroethene propene
HDPE High-density polyethylene
ICP Inductively coupled plasma
ICS Interference check solution
IDL Instrumental detection limit
IEC Inter-element correction
LOD Limit of detection
MS Mass spectrometry
OES Optical emission spectrometry
PFA Perfluoroalkoxy alkane
PTFE Polytetrafluoroethylene
PVC Polyvinylchloride
QC Quality control
5 Principle
This method describes the multi-elemental determination of analytes by ICP-MS in (diluted) nitric acid
or aqua regia digests. The method measures ions produced by a radio-frequency inductively coupled
plasma. Analyte species originating in a liquid are nebulised and the resulting aerosol is transported by
argon gas into the plasma. The ions produced by high temperatures of the plasma are entrained in the
plasma gas and introduced, by means of an interface, into a mass spectrometer, sorted according to their
mass-to-charge ratios and quantified with a detector (e.g. channel electron multiplier). Interferences
shall be assessed and valid corrections applied. Interference correction shall include compensation for
background ions contributed by the plasma gas, reagents, and constituents of the sample matrix.
6 Interferences
6.1 General
Non-spectral interferences shall be in accordance with 6.1 of EN ISO 17294-1:2006.
6.2 Spectral interferences
6.2.1 Isobaric elemental interferences
Isobaric elemental interferences are caused by isotopes of different elements of closely matched nominal
mass-to-charge ratio and which cannot be separated due to an insufficient resolution of the mass
114 114
spectrometer in use (e.g. Cd and Sn).
Element interferences from isobars may be corrected for taking into account the influence from the
interfering element. The isotopes used for correction shall be free of interference if possible. Correction
options are often included in the instrument software.
6.2.2 Isobaric molecular and doubly charged ion interferences
Isobaric molecular and doubly-charged ion interferences in ICP-MS are caused by ions consisting of more
40 35 + 40 35 + 75
than one atom or charge, respectively. Examples include Ar Cl and Ca Cl ion on the As signal and
98 16 + 114 +
Mo O ions on the Cd signal. Natural isotope abundances are available from the literature. However,
the most precise coefficients for an instrument will be determined from the ratio of the net isotope signals
observed for a standard solution.
The accuracy of these types of equations is based upon the constancy of the observed isotopic ratios for
the interfering species. Corrections that presume a constant fraction of a molecular ion relative to the
“parent” ion have not been found to be reliable, e.g. oxide levels can vary with operating conditions. If a
correction for an oxide ion is based upon the ratio of parent-to-oxide ion intensities, the correction shall
be adjusted for the degree of oxide formation by the use of an appropriate oxide internal standard
previously demonstrated to form a similar level of oxide as the interferent.
Other possibilities to correct for isobaric and doubly charged ion interferences are the use of an
instrument with collision/reaction cell technology or high resolution ICP-MS.
The response of the analyte of interest shall be corrected for the contribution of isobaric molecular and
doubly charged interferences if their impact can be higher than three times the IDL or higher than half
the lowest concentration to be reported.
6.3 Non-spectral interferences
Physical interferences are associated with the sample nebulisation and transport processes as well as
with ion-transmission efficiencies. Nebulisation and transport processes can be affected if a matrix
component causes a change in surface tension or viscosity. Changes in matrix composition can cause
significant signal suppression or enhancement. Dissolved solids can deposit on the nebuliser tip of a
pneumatic nebuliser and on the cones.
It is recommended to keep the level of total dissolved solids below 0,2 % (2,000 g/l) to minimize
deposition of solids in the sample introduction system of the plasma torch. An internal standard can be
used to correct for physical interferences if it is carefully matched to the analyte so that the two elements
are similarly affected by matrix changes. Other possibilities to minimize non-spectral interferences are
matrix matching, particularly matching of the acid concentration, and standard addition.
When intolerable physical interferences are present in a sample, a significant suppression of the internal
standard signals (to less than 30 % of the signals in the calibration solution) will be observed. Dilution of
the sample (e.g. fivefold) will usually eliminate the problem.
7 Reagents
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 shall be
negligible compared to the lowest concentration to be determined.
7.1 Water, with a specific conductivity not higher than 0,2 mS/m at 25 °C.
7.2 Nitric acid, molar concentration c(HNO ) = 16 mol/l, mass concentration ρ ~ 1,4 g/ml.
NOTE Nitric acid is available both as ρ(HNO ) = 1,40 g/ml (w(HNO ) = 650 g/kg) and ρ(HNO ) = 1,42 g/ml
3 3 3
(w(HNO3) = 690 g/kg). Both are suitable for use in this method provided they have a minimal content of the analytes
of interest.
7.3 Hydrochloric acid, c(HCl) = 12 mol/l, ρ ~ 1,18 g/ml.
7.4 Single element standard stock solutions.
Ag, Al, As, Au, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, In, Ir, K, La, Li, Lu,
Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, (total) S, Sb, Sc, Se, Si, Sm, Sn, Sr, Tb, Te, Th, Ti, Tl,
Tm, U, V, W, Y, Yb, Zn, Zr, c = 10 mg/l - 10 000 mg/l each.
Preferably, nitric acid preservation shall be applied in order to minimize interferences by polyatomic
species. Bi, Hg, Hf, Mo, Sn, Sb, Te, W and Zr might need hydrochloric acid for preservation and digestion.
These solutions are considered to be stable for more than one year, but in reference to guaranteed
stability, the recommendations of the manufacturer shall be considered.
Commercially available multi-element stock solution may be used for the same purpose.
7.5 Multi-element standard stock solutions.
7.5.1 General
Depending on the scope, different multi-element calibration solutions can 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 1 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.
Mercury standard solutions can be stabilized by adding 1 ppm Au in nitric acid or by adding hydrochloric
acid (up to 0,6 %).
NOTE 2 When Au is used as modifier the instrument is not suitable for accurate Au determination.
Multi-element standard solutions with more elements are allowed, provided that these solutions are
stable.
7.5.2 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 (7.2) for stabilization of standard solution A.
7.5.3 Multi-element standard stock solution B at the mg/l level may contain the following elements:
Mo, Sb, Sn, W, Zr.
Use hydrochloric acid (7.3) for stabilization 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.
7.5.4 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 (7.2) for stabilization of multi-element standard stock solution C.
7.6 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.
Add acids (7.2 and/or 7.3) 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 diluted calibration solutions.
7.7 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) shall cover the mass range of interest. The concentrations of the
selected elements (used as internal standard) shall be negligibly low in the digests of samples. The
elements In, Lu, Re, Ge and Rh have been found suitable for this purpose.
Generally, a suitable concentration of the internal standard in samples and calibration solutions is 10 μg/l
to 50 μg/l (or optimized to ± 50 000 counts/s – 100 000 counts/s). The use of a collision/reaction cell
might require higher concentrations.
7.8 Calibration blank.
Prepare the calibration blank by acidifying water (7.1) to the same concentrations of the acids found in
the calibration solutions, eluates and digests.
7.9 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.
7.10 Optimization solution.
The optimization solution serves for mass calibration and for optimization of the instrumental settings,
e.g. adjustment of maximal sensitivity with respect to minimal oxide formation rate and minimal
formation of doubly charged ions. It shall contain elements covering the total mass range, as well as
elements prone to a high oxide formation rate or to the formation of doubly charged ions. The
composition of the optimization solution depends on the elements of interest, instrument and
manufactures recommendations. An optimization solution containing e.g. Mg, Cu, Rh, In, Ba, La, Ce, U and
Pb is suitable. Li, Be and Bi are less suitable because they tend to cause memory effects at higher
concentrations.
The mass concentrations of the elements used for optimization shall allow count rates of more than
10 counts per second.
7.11 Interference check solution
The interference check solutions are used to determine the corresponding factors for the correction
equations. High demands are made concerning the purity of the basic reagents due to the high mass
concentrations.
Interference check solutions shall contain all the interferences of practical relevance at a concentration
level at the same range as expected in the samples (see also 12.5). Leaving out an interfering element is
permitted if it can be demonstrated that its impact is negligible and lasting. In unusual situations, other
interfering elements shall also be investigated for relevance.
EXAMPLE An example of the composition of an interference check solution is:
- 3- 2-
ρ(Ca) = 2 500 mg/l; ρ(Cl ) = 2 000 mg/l; ρ(PO ) = 500 mg/l and ρ (SO ) = 500 mg/l
4 4
and for digests also:
ρ(Ca) = 1 000 mg/l; ρ(Fe) = 500 mg/l; ρ(Na) = 500 mg/l and ρ(Al) = 500 mg/l.
8 Apparatus
8.1 General requirements
The stability of samples, measuring, and calibration solutions depends to a high degree on the container
material. The material shall be checked according to the specific purpose. For the determination of
elements in a very low concentration range (sub ppb), glass or PVC shall not be used. Instead, it is
recommended to use PFA, FEP or quartz containers, cleaned with diluted, high quality nitric acid or hot,
concentrated nitric acid in a closed system. For the determination of elements in a higher concentration
range, HDPE or PTFE containers are also allowed for the collection of samples. Immediately before use,
all glassware shall be washed thoroughly with diluted nitric acid (e.g. w(HNO ) = 10 %), and then rinsed
several times with water (7.1).
The limit of detection of most elements will be affected by blank contamination and this will depend
predominantly on the laboratory air-handling facilities available.
The use of piston pipettes is permitted and also enables the preparation of smaller volumes of calibration
solutions. The application of dilutors is also allowed. Every charge of pipette tips and single-use plastics
vessels shall be tested for impurities.
For more detailed information on the instrumentation see EN ISO 17294-1:2006, Clause 5.
8.2 Mass spectrometer, with inductively coupled plasma (ICP) suitable for multi-element and isotope
analysis. The spectrometer shall be capable of scanning a mass range from 5 m/z (AMU) to 240 m/z
(AMU) with a resolution of at least 1 m /z peak width at 5 % of peak height (m = relative mass of an atom
r r
species; z = charge number). The instrument may be fitted with a conventional or extended dynamic
range detection system.
8.3 Mass-flow controller.
A mass-flow controller on the nebuliser gas supply is strongly recommended. Mass-flow controllers for
the plasma gas and the auxiliary gas are preferred. A cooled spray chamber (cold water or Peltier) can be
of benefit in reducing some types of interferences (e.g. from polyatomic oxide species).
NOTE The plasma is very sensitive to variations in the gas flow rate. For older instruments a flow restrictor in
combination with elevated pressure can be used for nebuliser flow adjustment but makes an internal standard
obligatory.
8.4 Nebuliser with variable speed peristaltic pump.
The speed of the pump shall not be too low and the number of rolls as high as possible to provide a stable
signal.
8.5 Gas supply, Argon gas with high purity grade, i.e. > 99,99 % and reaction gas: He, H high purity
(i.e. > 99,99 %).
8.6 Glassware, e.g. volumetric flasks, Erlenmeyer flasks and pipettes.
8.7 Storage bottles for the stock, standard, calibration and sample solutions, preferably made
from PFA or FEP.
For the determination of elements in a higher concentration range (>sub ppb) glass, HDPE or PTFE
bottles can be sufficient for the storage of samples.
9 Procedure
9.1 Test sample
The test sample shall be a particle free digest obtained by EN 17196 or an eluate obtained by EN 16637-2
or EN 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
Adjust the instrumental parameters of the ICP-MS system in accordance with the manufacturer’s manual.
A guideline for method and instrument setup is given in EN ISO 17294-1.
Define the isotopes and the need for corresponding corrections. See EN ISO 17294-1:2006, 6.3.2, for
a method to determine these factors. Alternatively, apply multivariate calibration procedures.
Define the rinsing times depending on the length of the flow path; in the case of wide working range of
analyte mass concentrations in the measuring solutions, allow longer rinsing periods.
The use of an internal standard is recommended. Add the internal standard solution (7.7) to the
interference check solution (7.11), to all multi-element calibration solutions (7.6), to the blank calibration
solutions (7.8), and to all measuring solutions. Online dilution and mixing of the sample flow with internal
standard solution by means of the peristaltic pump of the nebuliser is commonly used. 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. A mass concentration
of 10 µg/l to 50 µg/l (or optimized to ± 50 000 counts/s – 100 000 counts/s) is often suitable.
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 optimization solution (7.10).
Check the resolution and the mass calibration as often as required by the manufacturer.
NOTE ICP-MS 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
(nebuliser flow, radio-frequency power, lens voltage, lens voltage mode, etc.). The optimal instrument settings
cannot be reached for all elements at once.
9.4 Calibration
9.4.1 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-MS provides a wide 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-MS, 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 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 Standard addition calibration
Add a known amount of standard solution (V ) of the analyte and an equal amount of blank solution (V )
s b
to two separate but equal portions of the sample solution (or its dilution). Minimize dilution or correct
for spike dilution. The added amount of standard solution shall 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.
9.4.3 Determination of correction factors
The need for the use of correction factors is determined during method development. In order to evaluate
and to update the correction factors, measure the interference check solutions (7.11) at regular intervals
within a measuring cycle.
9.4.4 Variable isotope ratio
Take into account the possible discrepancies in the isotope composition between the calibration
solutions and the measuring solutions (e.g. relevant for Li, Pb).
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 (7.10).
Every 50 samples or less and at the end of a run, analyse an interference check solution (ICS) (7.11).
Run all samples including one or more method blanks.
Run at least one post digestion spiked sample from the series to check recovery.
NOTE If standard addition calibration is applied to all samples it is advised to leave out recovery check.
Some elements (for example Ag, B, Be, Hg, Li, Th) are rinsed very slowly from the sample inlet system.
Check whether a high sample count rate has an effect on the next measurement result.
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 isotope.
10 Calculation
10.1 Calculation for digests of construction products
Calculate the mass fraction of the element in the digested construction product according to Formula (1).
ρ −ρ ××f 100
( )
10 a
w= (1)
m× dw
where
w is the mass fraction of the element in the solid sample, in μg/g or mg/kg;
ρ is the concentration of the element in the test sample, in μg/l;
ρ is the concentration of the element in the blank, in μg/l;
f is the dilution factor of the test portion;
a
m is the mass of the digested sample, in g;
dw is the dry weight of the sample, in g.
10.2 Calculation for eluates of construction products
For eluates the calculations are described in the respective EN 16637-2 and EN 16637-3.
11 Expression of results
Sta
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.
Loading comments...