CEN/TS 17200:2018+AC:2018

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

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 - 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), cesium (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 [1].
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 will be higher in cases where the determination is likely to be interfered (see Clause 4) or in case of memory effects (see e.g. EN ISO 17294-1:2006, 8.2).
The method in this Technical Specification is applicable to construction products and validated for the product types listed in Annex B.

Bauprodukte - Bewertung der Freisetzung von gefährlichen Stoffen - Analyse von anorganischen Stoffen in Aufschlusslösungen und Eluaten - Analyse mit Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS)

Diese Technische Spezifikation legt die Analysenverfahren für die Bestimmung von Haupt-, Neben- und Spurenelementen in Königswasser- und Salpetersäureaufschlusslösungen sowie Eluaten von Bauprodukten durch Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) fest. Sie 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), Cer (Ce), Caesium (Cs), 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 [1].
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 wird höher ausfallen, wenn bei der Bestimmung Interferenzen möglich sind (siehe Abschnitt 4) oder Memoryeffekte auftreten (siehe z. B. EN ISO 17294-1:2006, 8.2).
Die in dieser Technischen Spezifikation beschriebenen Verfahren sind für Bauprodukte geeignet und sind für die in Anhang B aufgeführten Produkttypen validiert.

Produits de construction: Évaluation des émissions de substances dangereuses - Analyse des substances inorganiques dans les digestats et les éluats - Analyse par spectrométrie de masse avec plasma à couplage inductif

Gradbeni proizvodi - Ocenjevanje sproščanja nevarnih snovi - Analiza anorganskih snovi po razklopu in v izlužkih - Analiza z masno spektrometrijo z induktivno sklopljeno plazmo (ICP/MS) (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 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 [1].
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).
Metoda v tej tehnični specifikaciji se uporablja pri gradbenih proizvodih in je potrjena za vrste proizvodov, navedene v dodatku B.

General Information

• Status: Withdrawn
• Publication Date: 18-Dec-2018
• Withdrawal Date: 13-Apr-2025
• ICS: 91.100.01 - Construction materials in general
• Technical Committee: CEN/TC 351 - Construction Products - Assessment of release of dangerous substances
• Drafting Committee: CEN/TC 351/WG 5 - Content and eluate analysis in construction products
• Current Stage: 9960 - Withdrawal effective - Withdrawal
• Start Date: 22-Nov-2023
• Completion Date: 14-Apr-2025
• 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: SIST-TS CEN/TS 17200:2019+AC:2019 - Construction products: Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)

Relations

• Merged From: CEN/TS 17200:2018 - Construction products: Assessment of release of dangerous substances - Analysis of inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS)
• Effective Date: 31-Oct-2018
• Replaced By: EN 17200:2023 - 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)
• Effective Date: 19-Jan-2023

Standards Content (Sample)

SLOVENSKI STANDARD
01-februar-2019
1DGRPHãþD
SIST-TS CEN/TS 17200:2019
*UDGEHQLSURL]YRGL2FHQMHYDQMHVSURãþDQMDQHYDUQLKVQRYL$QDOL]DDQRUJDQVNLK
VQRYLSRUD]NORSXLQYL]OXåNLK$QDOL]D]PDVQRVSHNWURPHWULMR]LQGXNWLYQR
VNORSOMHQRSOD]PR,&306YNOMXþQRVSRSUDYNRP$&
Construction products: Assessment of release of dangerous substances - Analysis of
inorganic substances in digests and eluates - Analysis by Inductively Coupled Plasma -
Mass Spectrometry (ICP-MS)
Bauprodukte - Beurteilung 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 des émissions de substances dangereuses -
Analyse des substances inorganiques dans les digestats et les éluats - Analyse par
spectrométrie de masse avec plasma à couplage inductif
Ta slovenski standard je istoveten z: CEN/TS 17200:2018+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 17200:2018+AC
TECHNICAL SPECIFICATION
SPÉCIFICATION TECHNIQUE
December 2018
TECHNISCHE SPEZIFIKATION
ICS 91.100.01 Supersedes CEN/TS 17200:2018
English Version
Construction products: Assessment of release of
dangerous substances - Analysis of inorganic substances in
digests and eluates - Analysis by Inductively Coupled
Plasma - Mass Spectrometry (ICP-MS)
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 - Analyse Stoffen in Aufschlusslösungen und Eluaten - Analyse
par spectrométrie de masse avec plasma à couplage mit induktiv gekoppeltem Plasma -
inductif Massenspektrometrie (ICP-MS)
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 17200:2018+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 . 7
4 Symbols and abbreviations . 9
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 . 10
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 . 16
9.4.4 Variable isotope ratio . 16
9.5 Sample measurement . 16
10 Calculation . 16
10.1 Calculation for digests of construction products . 16
10.2 Calculation for eluates of construction products . 17
11 Expression of results . 17
12 Performance characteristics . 17
12.1 General . 17
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 Precision . 17
13 Test report . 18
Annex A (informative) Method detection limit (MDL) and precision data for soil, sludge
and biowaste . 20
Annex B (informative) Validation results for construction products . 28
B.1 Introduction. 28
B.2 Performance data . 28
Bibliography . 29

European foreword
This document (CEN/TS 17200:2018+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 17200:2018.
This document includes the corrigendum 1 which corrects a value in 6.3.
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.
A similar document has been developed for drinking water, surface water and waste water and
different types of waste respectively, see Annex A.
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 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, Sludge, treated biowaste and soil - Determination of
elements using inductively coupled plasma mass spectrometry (ICP-MS) [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,
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 - 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), cesium (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 [1].
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 will be higher in cases where the determination is likely to be interfered (see
Clause 4) or in case of memory effects (see e.g. EN ISO 17294-1:2006, 8.2).
The method in this Technical Specification is applicable to construction products and validated for the
product types listed in Annex B.
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
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)
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 following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• 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
laboratory sample
sample or subsample(s) sent to or received by the laboratory
Note 1 to entry: When the laboratory sample is further prepared by subdividing, cutting, sawing, coring, mixing,
drying, grinding, and curing or by combinations of these operations, the result is the test sample. When no
preparation of the laboratory sample is required, the laboratory sample is the test sample. A test portion is
removed from the test sample for the performance of the test/analysis or for the preparation of a test specimen.
Note 2 to entry: The laboratory sample is the final sample from the point of view of sample collection but it is
the initial sample from the point of view of the laboratory.
[SOURCE: EN 16687:2015, 3.2.1]
3.6
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]
3.7
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]
3.8
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]
3.9
limit of quantification
LOQ
lowest value of an analyte (determinant) that can be determined with an acceptable level of accuracy
and precision, generally determined as three times the limit of detection of the method
[SOURCE: EN 16687:2015, 4.1.14]
3.10
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
FEP Hexafluoroethene propene
HDPE High-density polyethylene
ICP Inductively coupled plasma
ICS Interference check solution
IDL Instrumental detection limit
IEC Inter-element correction
LOQ Limit of quantification
MDL Method detection limit (limit of detection)
MS Mass spectrometry
OES Optical emission spectrometry
PFA Perfluoroalkoxy alkane
PTFE Polytetrafluorethylene
PVC Polyvinylchloride
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 nebulized 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
Detailed information on spectral and non-spectral interferences is given in EN ISO 17294-1:2006, 6.1.
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
114 114
mass 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
40 35 + 40 35 +
more than one atom or charge, respectively. Examples include Ar Cl and Ca Cl ion on the
75 98 16 + 114 +
As signal and 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 instrumental detection
limit or higher than half the lowest concentration to be reported.
6.3 Non spectral interferences
Physical interferences are associated with the sample nebulization and transport processes as well as
with ion-transmission efficiencies. Nebulization 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 nebulizer tip of a
pneumatic nebulizer 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
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(HNO3) = 16 mol/l, ρ ~ 1,4 kg/l.
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(HNO ) = 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, 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 should be applied in order to minimize interferences by polyatoms.
Bi, Hg, Hf, Mo, Sn, Sb, Te, W and Zr may 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 should be considered.
Commercially available multi-element stock solution can be used for the same purpose.
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 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.
7.6.2 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.
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 diluted 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 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 – 100 000 counts/s). The use of a collision/reaction cell
may require higher concentrations.
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 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 should 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 should allow count rates of more than
10 counts per second.
7.12 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-
c(Ca) = 2 500 mg/l; c(Cl ) = 2 000 mg/l; c(PO ) = 500 mg/l and c(SO ) = 500 mg/l
4 4
and for digests also
c(Ca) = 1 000 mg/l; c(Fe) = 500 mg/l; c(Na) = 500 mg/l and c(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 should 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 should be washed thoroughly with diluted nitric acid (e.g. w(HNO ) = 10 %), and then
rinsed several times with water (7.2).
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
A mass spectrometer with inductively coupled plasma (ICP) suitable for multi-element and isotope
analysis is required. The spectrometer should 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
r r
mass of an atom 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 nebulizer 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) may
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 nebulizer flow adjustment but makes an internal standard
obligatory.
8.4 Nebulizer with variable speed peristaltic pump
The speed of the pump shall not be to 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 %
Reaction gas: He, H high purity (i.e. > 99,99 %)
8.6 Glassware
— Volumetric flasks;
— Erlenmeyer flasks;
— 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 may be sufficient for the storage of samples.
9 Procedure
9.1 Test sample
The test sample is a particle free digest obtained by CEN/TS 17196 or an elutate obtained by CEN/TS
16637-2 and 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. sulfide 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 set up 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 (7.8) to the
interference check solution (7.12), to all multi-element calibration solutions (7.7), to the blank
calibration solutions (7.9), and to all measuring solutions. On-line 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 (7.11).
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
(nebulizer 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
s
(V ) to two separate but equal portions of the sample solution (or its dilution). Minimise dilution or
b
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.
9.4.3 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 (7.12) 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 (7.11).
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