SIST EN ISO 11885:2009
(Main)Water quality - Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (ISO 11885:2007)
Water quality - Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES) (ISO 11885:2007)
ISO 11885:2007 specifies a method for the determination of dissolved elements, elements bound to particles ("particulate") and total content of elements in different types of water (e.g. ground, surface, raw, potable and waste water) for the following elements: aluminium, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, calcium, chromium, cobalt, copper, gallium, indium, iron, lead, lithium, magnesium, manganese, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silver, sodium, strontium, sulfur, tin, titanium, tungsten, vanadium, zinc and zirconium.
Taking into account the specific and additionally occurring interferences, these elements can also be determined in digests of water, sludges and sediments (for example, digests of water as specified in ISO 15587‑1 or ISO 15587‑2). The method is suitable for mass concentrations of particulate matter in waste water below 2 g/l. The scope of this method may be extended to other matrices or to higher amounts of particulate matter if it can be shown that additionally occurring interferences are considered and corrected for carefully. It is up to the user to demonstrate the fitness for purpose.
Wasserbeschaffenheit - Bestimmung von ausgewählten Elementen durch induktiv gekoppelte Plasma-Atom-Emissionsspektrometrie (ICP-OES) (ISO 11885:2007)
Diese Internationale Norm legt ein Verfahren für die Bestimmung von gelösten Elementen, Elementen die an
Partikel gebunden vorliegen („partikulär“) und des Gesamtgehalts an Elementen in verschiedenen Wässern
(z. B. Grund-, Oberflächen-, Roh-, Trink-, und Abwasser) für die folgenden Elemente fest: Aluminium,
Antimon, Arsen, Barium, Beryllium, Bismut, Bor, Cadmium, Calcium, Chrom, Cobalt, Kupfer, Gallium, Indium,
Eisen, Blei, Lithium, Magnesium, Mangan, Molybdän, Nickel, Phosphor, Kalium, Selen, Silicium, Silber,
Natrium, Strontium, Schwefel, Zinn, Titan, Wolfram, Vanadium, Zink und Zirconium.
Unter Berücksichtigung der spezifischen und zusätzlich auftretenden Störungen können diese Elemente auch
in wässrigen Aufschlüssen, mit Aufschlussverfahren für Schlämme und Sedimente (z. B. wässrige Aufschlüsse
nach ISO 15587-1 oder ISO 15587-2) bestimmt werden. Dieses Verfahren ist für Abwässer geeignet,
deren Gehalt an partikulären Stoffen unter 2 g/l liegt. Der Anwendungsbereich des Verfahrens darf auf
andere Matrizes oder höhere Gehalte an partikulären Stoffen ausgedehnt werden, wenn gezeigt werden kann,
dass zusätzlich auftretende Störungen berücksichtigt und entsprechend eliminiert werden. Es ist die Aufgabe
des Anwenders der Norm, die Eignung des Verfahrens für den Zweck zu belegen.
Empfohlene Wellenlängen, Bestimmungsgrenzen und wichtige spektrale Störungen für ausgewählte Elemente
werden in Abschnitt 5 (Tabelle 1) aufgeführt.
Qualité de l'eau - Dosage d'éléments choisis par spectroscopie d'émission optique avec plasma induit par haute fréquence (ICP-OES) (ISO 11885:2007)
L'ISO 11885:2007 prescrit une méthode pour le dosage des éléments dissous, des éléments liés aux particules (particulaires), ainsi que la teneur totale des éléments dans différents types d'eau (par exemple eaux souterraines, de surface, brutes, potables et résiduaires). Cela pour les éléments suivants: aluminium, antimoine, argent, arsenic, baryum, béryllium, bismuth, bore, cadmium, calcium, chrome, cobalt, cuivre, étain, fer, gallium, indium, lithium, magnésium, manganèse, molybdène, nickel, phosphore, plomb, potassium, sélénium, silicium, sodium, strontium, soufre, titane, tungstène, vanadium, zinc et zirconium.
Compte tenu des interférences additionnelles spécifiques observées, ces éléments peuvent également être déterminés dans les minéralisats d'eau, les boues et les sédiments (par exemple minéralisats d'eau comme spécifié dans l'ISO 15587-1 ou l'ISO 15587-2). La méthode est appropriée pour les concentrations en masse des matières en suspension dans les eaux résiduaires inférieures à 2 g/l. Le domaine d'application de cette méthode peut être étendu à d'autres matrices ou à des quantités de matières en suspension plus élevées si les interférences additionnelles qui se produisent sont effectivement prises en considération et corrigées avec attention. La démonstration de l'aptitude à l'emploi de cette méthode incombe à l'utilisateur.
Kakovost vode - Določevanje izbranih elementov z optično emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP-OES) (ISO 11885:2007)
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-december-2009
1DGRPHãþD
SIST EN ISO 11885:1998
.DNRYRVWYRGH'RORþHYDQMHL]EUDQLKHOHPHQWRY]RSWLþQRHPLVLMVNR
VSHNWURPHWULMR]LQGXNWLYQRVNORSOMHQRSOD]PR,&32(6,62
Water quality - Determination of selected elements by inductively coupled plasma optical
emission spectrometry (ICP-OES) (ISO 11885:2007)
Wasserbeschaffenheit - Bestimmung von ausgewählten Elementen durch induktiv
gekoppelte Plasma-Atom-Emissionsspektrometrie (ICP-OES) (ISO 11885:2007)
Qualité de l'eau - Dosage d'éléments choisis par spectroscopie d'émission optique avec
plasma induit par haute fréquence (ICP-OES) (ISO 11885:2007)
Ta slovenski standard je istoveten z: EN ISO 11885:2009
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
EUROPEAN STANDARD
EN ISO 11885
NORME EUROPÉENNE
EUROPÄISCHE NORM
May 2009
ICS 13.060.50 Supersedes EN ISO 11885:1997
English Version
Water quality - Determination of selected elements by
inductively coupled plasma optical emission spectrometry (ICP-
OES) (ISO 11885:2007)
Qualité de l'eau - Dosage d'éléments choisis par Wasserbeschaffenheit - Bestimmung von ausgewählten
spectroscopie d'émission optique avec plasma induit par Elementen durch induktiv gekoppelte Plasma-Atom-
haute fréquence (ICP-OES) (ISO 11885:2007) Emissionsspektrometrie (ICP-OES) (ISO 11885:2007)
This European Standard was approved by CEN on 14 May 2009.
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 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 Management Centre has the same status as the
official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2009 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 11885:2009: E
worldwide for CEN national Members.
Contents Page
Foreword .3
Foreword
The text of ISO 11885:2007 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the
International Organization for Standardization (ISO) and has been taken over as EN ISO 11885:2009 by
Technical Committee CEN/TC 230 “Water analysis” the secretariat of which is held by DIN.
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 November 2009, and conflicting national standards shall be withdrawn
at the latest by November 2009.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN ISO 11885:1997.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech
Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.
Endorsement notice
The text of ISO 11885:2007 has been approved by CEN as a EN ISO 11885:2009 without any modification.
INTERNATIONAL ISO
STANDARD 11885
Second edition
2007-08-01
Water quality — Determination of
selected elements by inductively coupled
plasma optical emission spectrometry
(ICP-OES)
Qualité de l'eau — Dosage d'éléments choisis par spectroscopie
d'émission optique avec plasma induit par haute fréquence (ICP-OES)
Reference number
ISO 11885:2007(E)
©
ISO 2007
ISO 11885:2007(E)
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ii © ISO 2007 – All rights reserved
ISO 11885:2007(E)
Contents Page
Foreword. iv
Introduction . v
1 Scope .1
2 Normative references .1
3 Terms and definitions .2
4 Principle.5
5 Recommended wavelengths, limits of quantification and important spectral interferences.5
6 Interferences .9
7 Reagents.11
8 Apparatus .14
9 Sampling and preservation.15
10 Procedure .18
11 Expression of results .20
12 Test report .20
Annex A (informative) Special digestion methods .21
Annex B (informative) Precision data.22
Annex C (informative) Description of the matrices of the samples used for the interlaboratory trial .26
Bibliography .28
ISO 11885:2007(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 11885 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical,
chemical and biochemical methods.
This second edition cancels and replaces the first edition (ISO 11885:1996), which has been technically
revised.
iv © ISO 2007 – All rights reserved
ISO 11885:2007(E)
Introduction
When applying this International Standard, it is necessary in each case, depending on the range to be tested,
to determine if and to what extent additional conditions should be established.
INTERNATIONAL STANDARD ISO 11885:2007(E)
Water quality — Determination of selected elements by
inductively coupled plasma optical emission spectrometry
(ICP-OES)
WARNING — Persons using this International Standard should be familiar with normal laboratory
practice. This International Standard does not purport to address all of the safety problems, if any,
associated with its use. It is the responsibility of the user to establish appropriate safety and health
practices and to ensure compliance with any national regulatory conditions.
IMPORTANT — It is absolutely essential that tests conducted according to this International Standard
be carried out by suitably trained staff.
1 Scope
This International Standard specifies a method for the determination of dissolved elements, elements bound to
particles (“particulate”) and total content of elements in different types of water (e.g. ground, surface, raw,
potable and waste water) for the following elements: aluminium, antimony, arsenic, barium, beryllium,
bismuth, boron, cadmium, calcium, chromium, cobalt, copper, gallium, indium, iron, lead, lithium, magnesium,
manganese, molybdenum, nickel, phosphorus, potassium, selenium, silicon, silver, sodium, strontium, sulfur,
tin, titanium, tungsten, vanadium, zinc and zirconium.
Taking into account the specific and additionally occurring interferences, these elements can also be
determined in digests of water, sludges and sediments (for example, digests of water as specified in
ISO 15587-1 or ISO 15587-2). The method is suitable for mass concentrations of particulate matter in waste
water below 2 g/l. The scope of this method may be extended to other matrices or to higher amounts of
particulate matter if it can be shown that additionally occurring interferences are considered and corrected for
carefully. It is up to the user to demonstrate the fitness for purpose.
Recommended wavelengths, limits of quantification and important spectral interferences for the selected
elements are given in Table 1.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ISO Guide 30, Terms and definitions used in connection with reference materials
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 5667-1, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes and
sampling techniques
ISO 5667-3, Water quality — Sampling — Part 3: Guidance on the preservation and handling of water
samples
ISO 7027, Water quality — Determination of turbidity
ISO 11885:2007(E)
ISO 15587-1, Water quality — Digestion for the determination of selected elements in water — Part 1: Aqua
regia digestion
ISO 15587-2, Water quality — Digestion for the determination of selected elements in water — Part 2: Nitric
acid digestion
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
accuracy
closeness of agreement between test result and the accepted reference value
NOTE The term accuracy, when applied to a set of observed values, describes a combination of random error
components and common systematic error components. Accuracy includes precision and trueness.
3.2
analyte
element(s) to be determined
3.3
background equivalent concentration
BEC
elemental concentration required to produce an analyte signal with the same intensity as a background signal
3.4
calibration blank solution
prepared in the same way as the calibration solution but leaving out the analyte
3.5
calibration solution
solution used to calibrate the instrument, prepared from (a) stock solution(s) or from a certified standard
3.6
calibration check solution
solution of known composition within the range of the calibration solutions, but prepared independently
3.7
determination
entire process from preparing the test sample solution up to and including measurement and calculation of the
final result
3.8
instrument performance check solution
solution used to determine and control the instrument drift for relevant analytes
3.9
linearity
straight line relationship between the (mean) result of measurement (signal) and the quantity (concentration)
of the component to be determined
2 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
3.10
limit of detection
X
LD
smallest amount or concentration of an analyte in the test sample that can be reliably distinguished from zero
NOTE The limit of detection shall be calculated as:
X = 3 s
LD 0
where
X is the limit of detection;
LD
s is the standard deviation of the outlier-free results of at least 3 measurements of a reagent blank solution (3.14)
[ISO 13530]
3.11
limit of quantification
X
LQ
the smallest amount or concentration of an analyte in the test sample which can be determined with a fixed
precision
EXAMPLE Relative standard deviation s = 33,3 %
rel
X==39Xs
LQ LD 0
[ISO 13530]
3.12
mean result
mean value of n results, calculated as intensity (ratio) or as mass concentration (ρ)
NOTE The mass concentration is expressed in units of milligrams per litre, mg/l.
3.13
precision
closeness of agreement between independent test results obtained under prescribed conditions
NOTE Precision depends only on the distribution of random errors and does not relate to true value or the specified
value.
3.14
reagent blank solution
prepared by adding to the solvent the same amounts of reagents as those added to the test sample solution
(same final volume)
3.15
reproducibility
precision under reproducibility conditions
[ISO 3534-2:2006, definition 3.3.10]
3.16
reproducibility conditions
observation conditions where independent test/measurement results are obtained with the same method on
identical test/measurement items in different test or measurement facilities with different operators using
different equipment
[ISO 3534-2:2006, definition 3.3.11]
ISO 11885:2007(E)
3.17
reproducibility standard deviation
standard deviation of test results or measurement results obtained under reproducibility conditions
[ISO 3534-2:2006, definition 3.3.12]
3.18
reproducibility limit
R
reproducibility critical difference for a specified probability of 95 %
[ISO 3534-2:2006, definition 3.3.14]
3.19
repeatability
precision under repeatability conditions
[ISO 3534-2:2006, definition 3.3.5]
3.20
repeatability conditions
observation conditions where independent test/measurement results are obtained with the same method on
identical test/measurement items in the same test or measuring facility by the same operator using the same
equipment within short intervals of time
[ISO 3534-2:2006, definition 3.3.6]
3.21
repeatability standard deviation
standard deviation of test results or measurement results obtained under repeatability conditions
[ISO 3534-2:2006, definition 3.3.7]
3.22
repeatability limit
r
repeatability critical difference for a specified probability of 95 %
[ISO 3534-2:2006, definition 3.3.9]
3.23
stock solution
solution with accurately known analyte concentration(s), prepared from chemicals with an appropriate purity
NOTE Stock solutions are reference materials within the meaning of ISO Guide 30.
3.24
test sample
prepared from the laboratory sample (for example by grinding, homogenizing)
3.25
test sample solution
solution prepared with the fraction (test portion) of the test sample according to the appropriate specifications,
such that it can be used for the envisaged measurement
4 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
3.26
total element concentration
concentration of elements determined on an unfiltered sample following digestion or the sum of concentrations
of elements as determined in the dissolved state (9.5.1) and bound in the particulate fraction (9.5.2) of a
sample
3.27
trueness
bias
closeness of agreement between the average value obtained from a large series of test results and an
accepted reference value
NOTE The measure of trueness is usually expressed in terms of bias (bias = sum of systematic error components).
4 Principle
The basis of the method is the measurement of emission of light by an optical spectroscopic technique.
Samples are nebulized and the aerosol that is produced is transported to the plasma torch where excitation
occurs. Characteristic emission spectra are produced by a radio-frequency inductively coupled plasma (ICP).
The spectra are dispersed by a grating spectrometer and the intensities of the lines are monitored by a
detector. The signals from the detector(s) are processed and controlled by a computer system. A suitable
background correction technique is used to compensate for variable background contributions to the
determination of trace elements.
5 Recommended wavelengths, limits of quantification and important spectral
interferences
Elements for which this International Standard applies along with the recommended wavelengths and typical
estimated limits of quantification (LOQ) are listed in Table 1 as far as data are available from the
interlaboratory trial (see Annex B). Actual working detection limits are dependent on the type of
instrumentation, detection device and sample introduction system used and on the sample matrix. Therefore,
these concentrations can vary between different instruments.
Additionally, Table 1 lists the most important spectral interferences at the recommended wavelengths for
analysis.
ISO 11885:2007(E)
a b
Table 1 — Recommended wavelengths , achievable limits of quantification (X )
LQ
for different types of instruments and important spectral Interferences
Element Wavelength Approx. X Interfering elements
LQ
Radial viewing Axial viewing
nm µg/l µg/l
Ag 328,068 (20) (4) Fe, Mn, Zr
338,289 (20) (10) Cr, Fe, Zr, Mn
Al 167,079 1 2 Fe, Pb
308,215 100 17 Fe, Mn, OH, V
396,152 10 6 Cu, Fe, Mo, Zr
As 188,979 18 14 Al, Cr, Fe, Ti
193,696 5 14 Al, Co, Fe, W, V
197,197 (100) 31 Al, Co, Fe, Pb, Ti
B
182,528 (6) — S
208,957 (5) (7) Al, Mo
249,677 10 5 Co, Cr, Fe
249,772 4 24 Co, Fe
Ba 230,425 — 3 —
233,527 2 0,5 Fe, V
455,403 6 0,7 Zr
493,408 (3) 0,4 -
Be 313,042 (2) (0,1) Fe
313,107 — (0,3) V
234,861 (5) (0,1) —
Bi 223,060 (40) (17) Co, Cu, Ti, V
306,770 (80) (165) Fe, Mo, V
Ca 315,887 100 13 Co, Mo
317,933 26 4 Fe, V
393,366 0,4 25 V, Zr
422,673 — — V, Mo, Zr
Cd 214,441 1 0,9 As, Cr, Fe, Sc, Sb
226,502 4 0,2 As, Co, Fe, Ni
228,802 2 0,5 As, Co, Sc
Co 228,616 6 1 Ti
238,892 10 3 Fe
6 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
Table 1 (continued)
Element Wavelength Approx. X Interfering elements
LQ
Radial viewing Axial viewing
nm µg/l µg/l
Cr 205,559 1 5 Be, Fe, Mo, Ni, Ti
267,719 4 2 Mn, P, V
283,563 (10) (2) Fe, Mo, V, W
284,324 (10) — Fe
Cu
324,754 9 2 Cr, Fe, Mo, Ti
327,396 4 3 Co, Ti
Fe 238,204 14 (3) Co
259,940 6 2 Co
271,441 — — —
Ga
287,424 — — Cr
294,364 — — Fe, Ti
417,204 — — Fe, V
In 230,605 — — Fe
325,609 — — Mn
410,175 — — Ce
K 766,490 66 20 Ar, Ba, Mg
769,896 — (230) Ba
Li 460,290 900 (700) Ar, Fe
670,778 6 10 Ar
Mg 279,078 33 19 Fe
279,553 1 7 Fe
285,213 4 14 Cr
Mn 257,610 1 0,4 Cr, Fe, Mo, W
293,305 (20) (8) Al, Cr, Fe, Ti
Mo 202,031 (30) (2) Al, Fe, Ni
204,597 (50) (6) Co, Cr
Na
330,237 (20) 300 Zn
588,995 20 200 Ar, V
589,592 93 20 Ba
Ni 221,648 10 2 Si
231,604 15 2 Co, Sb
P
177,434 500 (16) Cu
178,221 25 13 Fe, I
213,618 500 50 Co, Cu, Fe, Mo, Zn
214,915 330 9 Al, Co, Cu, Mg
ISO 11885:2007(E)
Table 1 (continued)
Element Wavelength Approx. X Interfering elements
LQ
Radial viewing Axial viewing
nm µg/l µg/l
Pb 220,353 14 5 Al, Co, Fe, Ti
283,305 (70) (20) Cr, Fe
S
180,669 13 33 As, Ca
181,975 39 17 Cr, Mo
Sb 206,834 (100) (4) Co, Cr, Fe, Mg, Mn
217,582 (100) (18) Pb, Fe
Se 196,089 (100) (7) —
203,984 (100) (7) Cr, Sb
Si 212,412 3 (13) Mo
251,611 20 10 —
288,158 (30) 24 Cr
Sn 189,988 (100) (60) Cr, Ti
235,485 (100) (200) Cd, Mo
283,998 — (120)
Sr 407,771 2,6 0,6 Cr
421,552 0,1 0,1 —
460,733 (10) (3) —
Ti
334,941 (5) (2) Cr
336,123 (10) (1) —
337,280 (10) — —
368,521 (10) — Co, Cr
V 290,881 (10) — Fe, Mo
292,402 (10) (3) Cr, Fe, Mo, V
310,229 (10) (0,7) Cr, Mg
311,071 (10) (1) Cr, Fe, Mn, Ti
W 202,998 (60) — Ni, Zn
207,912 (30) (10) Ni, Mo, V
209,860 (60) (20) —
222,589 (60) (30) Cr, Cu, Ni
239,711 (60) — —
Zn 202,548 — (3) Cr, Cu, Co, Ni
206,200 13 5 Cr
213,857 3,3 1 Cu, Fe, Ni
8 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
Table 1 (continued)
Element Wavelength Approx. X Interfering elements
LQ
Radial viewing Axial viewing
nm µg/l µg/l
Zr 339,197 — (2) Mo
343,823 (10) (0,3) —
354,262 (50) (1) —
NOTE 1 X : Definition of the limit of quantification (X ) according to definition 3.11.
LQ LQ
NOTE 2 Most X data derive from the Interlaboratory trial (see Annex B). Participants were asked to report their
LQ
X calculated according to definition 3.11. In Table 1, the median of the reported data for the matrix drinking water is
LQ
given. Data reported in brackets derive from other sources.
a
Wavelength in Table 1 according to NIST tables for basic atomic spectroscopic data
(http://physics.nist.gov/PhysRefData/Handbook/)
b
As some wavelengths are only recommended for vacuum instruments and not recommended for purged
instruments, the choice of wavelengths for a specific instrument should be carried out with respect to the
manufacturer’s recommendation.
Because of the differences between various models of satisfactory instruments, no detailed instrumental
operating instructions can be provided. Instead, the analyst will need to refer to the instructions provided by
the manufacturer of the particular instrument.
6 Interferences
6.1 General
Several types of interference effects can contribute to inaccuracies in the determination of elements. They are
also termed matrix effects.
In order to avoid interferences, whenever a new or unusual sample matrix is encountered, the method in use
should be carefully reviewed if it is suitable for this type of sample or a new method should be developed. In
order to validate the method, measurements of suitable reference materials are to be carried out. Additionally,
comparison tests may be performed with other analytical techniques such as atomic absorption spectrometry
or ICP-MS.
Interferences can be classified as follows.
6.2 Spectral interferences
6.2.1 General
These types of interferences are caused by light of other elements present in the matrix. The error is additive.
Typically, they cause an erroneously high reading. In the case of background influences, low readings can
also occur. The most important spectral interferences are listed in Table 1.
6.2.2 Spectral overlap
6.2.2.1 Overlap of a spectral line from another element
During method development, the goal is to avoid line overlap by the choice of an alternate, undisturbed line. If
this is not possible, these effects can be compensated by utilizing computer correction of the raw data.
ISO 11885:2007(E)
6.2.2.2 Unresolved overlap of molecular band spectra
If possible, an undisturbed line should be chosen. If this is not possible, these effects can be compensated by
utilizing computer correction of the raw data.
6.2.3 Background influences
Background influences include
1) background contribution from continuous or recombination phenomena, and
2) background contribution from stray light generated from the line emission of high concentration
elements.
The effect of background interferences can usually be compensated by background correction adjacent to the
analyte line.
6.2.4 Detecting spectral interferences
If the peak shape changes in comparison to the peak shape generated by a single element solution, line
overlap can be suspected. Background changes are best identified by overlaying spectra of blank, standards
and samples. Also, the comparison of results for a given element measured at different lines will indicate
spectral interferences.
6.3 Non-spectral interferences
6.3.1 Physical interferences
These are generally considered to be effects associated with the sample nebulization and other transport
processes of the sample from the sample container to the plasma.
They are caused by the change in viscosity, density and/or surface tension. They may result in significant
errors especially in samples containing high dissolved solids and/or acid concentrations. These types of
interferences can be reduced by matrix-matching (if the concentrations of the analytes are high enough,
dilution of the sample may be the preferred way), the use of an internal standard (provided no excitation
interferences are encountered) and/or utilization of the method of standard addition.
6.3.2 Excitation interferences
Depending on the relation of the room (operating) temperature to the plasma temperature, the change of the
plasma temperature due to the introduction of sample may cause an increase or decrease of the signal. In
addition, elements which readily release electrons may change the electron density in the plasma, which may
influence the distribution between atomic and ionic transitions. Alkaline metals (Li, K, Na) are highly
susceptible to excitation interferences, particularly on axial viewing.
6.3.3 Chemical interferences
They are characterized by molecular compound formation, variation of oxidation state and solute vaporization
effects. These interferences are very rare. However, when encountered, they may cause serious errors.
EXAMPLE Release of hydrogen sulfide gas rather than sulfate, iodine vapours rather than iodide or iodate.
Care shall be taken to ensure the same chemical state, if these effects are observed.
10 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
6.3.4 Detecting non-spectral interferences
In order to detect the non-spectral interferences, recovery experiments should be performed.
a) Dilution
If the analyte concentration is sufficiently high (at least a factor of 10 above the instrumental detection
limit after dilution), the results of the analysis of a dilution needs to agree within ± 10 % of those obtained
on the undiluted sample (or within some acceptable control limit that has been established for that
matrix).
b) Standards additions (spike recovery)
The recovery of a spike addition added at a minimum level of 10× the instrumental detection limit
(maximum 100×) to the original determination needs to be recovered to within 80 % to 120 % or within the
established control limit for that matrix. If not, suspect a matrix effect.
The use of a standard addition analysis procedure can usually compensate for non-spectral interferences.
6.4 Compensation of non-spectral interferences by the use of internal standards
The use of internal standards is in some cases a suitable method to correct for interferences. The approach
involves the addition of a known amount of a substance or material to the sample. The sample is then
analysed and the responses for the determinand and the added (internal) standard are measured. The
observation for the internal standard is then used to relate the determinand signal to the determinand
concentration. The effect on analytical error and the type of likely error will vary according to the exact
approach adopted.
Usually, there is an initial, conventional calibration relating the responses for all elements to their
concentrations. Consequently, each subsequent analysis depends on the internal standard as a means of
adjusting for changes in instrumental sensitivity, possibly caused by changes in sample uptake or by drift in
detector response. Here, care needs to be taken to eliminate factors (such as the efficiency of excitation)
which affect the standard and one or more of the determinands to different extents since these will lead to
systematic error. Unless the size of response for the internal standard is the same as that for all elements of
interest (which is most unlikely), nonlinearity of response can also lead to error. This may well go undetected,
since it is rare to make a range of internal standard additions.
As a consequence, this calibration approach will increase the random error by the random variation
associated with the internal standardization. However, overall precision may still be better than otherwise,
since the consequent control over drift, etc., may improve the observed total standard deviation.
7 Reagents
7.1 General requirements
For the determination of elements at trace and ultra-trace level, use reagents 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.
Unless otherwise specified, dry all salts for 1 h at 105 °C.
Standard stock solutions may be purchased or prepared from high purity grade chemicals or metals.
Traceable standard solutions are to be preferred.
ISO 11885:2007(E)
7.2 Water, complying with grade 1 as defined in ISO 3696 for all sample preparation and dilutions.
7.3 Nitric acid, ρ (HNO ) = 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(HNO ) = 690 g/kg]. Both are suitable for use in this method provided there is negligible content of the analytes of
interest.
7.4 Hydrogen peroxide, w(H O ) = 30 %.
2 2
On the determination of phosphorus, attention should be paid to a possible stabilization of hydrogen peroxide
with phosphoric acid as this will affect the determination of phosphorus.
7.5 Sulfuric acid, ρ (H SO ) = 1,84 g/ml.
2 4
7.6 Hydrochloric acid, ρ (HCl) = 1,16 g/ml.
7.7 Hydrochloric acid, c(HCl) = 0,2 mol/l.
7.8 Ammonium sulfate, (NH ) SO .
4 2 4
7.9 Element stock solutions, of
Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, In, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn,
Sr, Ti, V, W, Zn, Zr,
ρ = 1 000 mg/l each.
Stock solutions are reference materials as defined in ISO Guide 30. Both single-element stock solutions and
multi-element stock solutions with adequate specification stating the acid used and the preparation technique
are commercially available. Element stock solutions with different concentrations of the analytes (for example
100 mg/l) are also allowed.
These solutions are considered to be stable for more than one year, but in reference to guaranteed stability,
the recommendations of the manufacturer should be considered.
7.10 Intermediate mixed standard solutions
7.10.1 General
Depending on the scope, different multi-element standard solutions may be necessary. In general, when
preparing multi-element standard solutions, chemical compatibility and the possible hydrolysis of their
components shall be regarded. Take care to prevent chemical reactions (for example, precipitation).
The examples given below also consider the different sensitivities of various spectrometers.
The multi-element standard solutions are considered to be stable for several months, if stored in the dark.
In reference to guaranteed stability of all standard solutions, see the manufacturer's recommendations.
Depending on the complexity of the sample matrix, it may be necessary to use matrix matched standards.
This should be checked carefully.
On composing multi-element standard solutions, take into account the chemical compatibility and the possible
hydrolysis of the initial compounds, as well as spectral interferences. In order to avoid interferences, add the
digestion reagents (e.g. nitric acid, sulfuric acid, aqua regia) to the standard solutions.
12 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
7.10.2 Multi-element standard solution A
ρ (Al, Cd, Co, Cr, Cu, Ga, Fe, In, Pb, Li, Mn, Mo, Ni, V, Zn, Bi, Si, W, Zr) = 1 mg/l.
Pour in about 250 ml of water (7.2) to a 1 000 ml volumetric flask.
Add 5 ml of nitric acid (7.3).
Pipette (1 ± 0,01) ml of each element stock solution (Al, Cd, Co, Cr, Cu, Fe, Pb, Li, Mn, Mo, Ni, V, Zn, Bi, Si, W,
Zr) (7.9) to the 1 000 ml volumetric flask.
Make up to volume with water (7.2) and transfer to a suitable storage bottle.
7.10.3 Multi-element standard solution B
ρ (Sn, Ti, As, Se, Sb) = 10 mg/l.
Pour in about 250 ml of water (7.2) to a 1 000 ml volumetric flask.
Add 5 ml of hydrochloric acid (7.6).
Pipette (10 ± 0,1) ml of each element stock solution (Sn, Ti, As, Se, Sb) (7.9) to the 1 000 ml volumetric flask.
Make up to volume with water (7.2) and transfer to a suitable storage bottle.
7.10.4 Multi-element standard solution C
ρ (Ba, Be, Sr) = 0,1 mg/l.
Pour in about 250 ml of water (7.2) to a 1 000 ml volumetric flask.
Add 5 ml of nitric acid (7.3).
Pipette (0,1 ± 0,002) ml of each element stock solution (Ba, Be, Sr) (7.9) to the 1 000 ml volumetric flask.
Make up to volume with water (7.2) and transfer to a suitable storage bottle.
7.10.5 Element standard solution D
ρ (Ag) = 1 mg/l.
Pour in about 250 ml of water (7.2) to a 1 000 ml volumetric flask.
Add 5 ml of nitric acid (7.3). Add 10 ml of hydrochloric acid (7.6) to stabilize silver as AgCl .
Pipette (1,0 ± 0,01) ml of silver stock solution (7.9) to the 1 000 ml volumetric flask.
Make up to volume with water (7.2) and transfer to a suitable storage bottle.
7.10.6 Element standard solution E
ρ (B) = 10 mg/l.
Pour in about 250 ml of water (7.2) to a 1 000 ml volumetric flask.
Add 5 ml of nitric acid (7.3).
Pipette (10 ± 0,1) ml of boron stock solution (7.9) to the 1 000 ml volumetric flask.
ISO 11885:2007(E)
Make up to volume with water (7.2).
Prepare this standard in polymethylpentene (PMP) or other flasks made of suitable plastics materials. Element
standard solutions C, D and E, i.e. Ba, Ag and B, are known to cause problems by precipitation under certain
circumstances; it is recommended that separate standard solutions are prepared.
Boron will result in an extended wash-out from the sample introduction system, which consequently may result
in erroneously high results. Therefore, the B concentrations should be set as low as possible in order to avoid
carry-over.
7.10.7 Multi-element standard solution F
ρ (Ca, Mg, Na, K, S, P) = 100 mg/l.
Pipette (100 ± 0,1) ml of each element stock solution (Ca, Mg, Na, K, S, P) (7.9) in a 1 000 ml volumetric flask.
Add 5 ml of nitric acid (7.3).
Make up to volume with water (7.2) and transfer to a suitable storage bottle.
7.11 Reagent blank solution
Place 50 ml of nitric acid (7.3) and 1 000 ml of water (7.2) into an HDPE or PP container. For ultra-trace
analysis, polytetrafluorethylene (PTFE) containers should be used. Prior to analysis, make sure that the acid
matrix and concentration of the reagent blank solution is the same as in the standard and sample solutions.
8 Apparatus
8.1 General requirements
The stability of samples, measuring and calibration solutions depends to a high degree on the container
material. Check the material according to the specific purpose. For the determination of elements in a very low
concentration range, glass or polyvinyl chloride (PVC) should not be used. Instead, it is recommended to use
perfluoroalkoxy (PFA), hexafluoroethene propene (FEP) or quartz containers, cleaned with hot, concentrated
nitric acid in a closed system. For the determination of elements in a higher concentration range, high density
polyethene (HDPE) or polytetrafluoroethene (PTFE) containers are also acceptable for sample collection.
Immediately before use, wash all labware thoroughly with diluted nitric acid [for example, w(HNO ) = 10 %],
and rinse several times with water (7.2).
The use of piston pipettes is allowed. It enables the preparation of lower volumes of calibration solutions. The
application of dilutors is also allowed. Test each batch of pipette tips and disposable plastics vessels for
impurities.
NOTE Operating conditions: Because of the differences between various makes and models of satisfactory
instruments, no detailed operating instructions can be provided.
8.2 Radiofrequency generator.
8.3 Mass-flow controller.
A mass-flow controller on the nebulizer gas supply is recommended.
NOTE The plasma is very sensitive to variations in the gas flow rate of the nebulizer gas.
14 © ISO 2007 – All rights reserved
ISO 11885:2007(E)
8.4 Nebulizer, with variable speed peristaltic pump.
Common nebulizers are the concentric nebulizer (for example, Meinhard), the cross-flow nebulizer, the
V-groove nebulizer and a cyclonic chamber with or without baffles. Other types of nebulizers may also be
used if it can be shown that they are fit for purpose.
8.5 Ultrasonic nebulizer.
If very low concentration ranges are to be achieved, ultrasonic nebulizers are recommended. In this special
type of nebulizer the sample solution is pumped through a tube that ends near the transducer plate that
vibrates at an ultrasonic frequency. The amount of aerosol produced (the efficiency) is typically 10 % to 20 %
of the quantity of the pumped solution. As this is very high, the aerosol needs to be dried (desolvated) before
being introduced into the plasma, which otherwise extinguishes. The aerosol is transported to the plasma by
the nebulizer gas.
Disadvantages of the ultrasonic nebulizer include its greater susceptibility to matrix effects, diminished
tolerance to high dissolved solid contents (approximately > 0,5 % m/v) and a longer rinsing time.
Vapour generation apparatuses for hydride or cold vapour can also be used for sample introduction.
8.6 Inductively coupled plasma optical emission spectrometer.
Computer-controlled optical emission spectrometer with background correction.
8.7 Argon gas supply.
Argon gas with a sufficient purity grade, for instance > 99,95 %.
8.8 General labware.
A range of volumetric flasks, Erlenmeyer flasks and pipettes.
8.9 Storage bottles, for the stock, standard, calibration and sample solutions.
For the determination of elements in a normal concentration range, high density polyethene (HDPE) or
polytetrafluoroethene (PTFE) bottles are sufficient for the storage of samples. For the determination of
elements in an ultra-trace level, bottles made from perfluoroalkoxy (PFA) or hexafluoroethene propene (FEP)
should be preferred. Check the suitability of the chosen containers.
8.10 Acid dispensers, variable volume.
8.11 Filtration equipment.
Membrane filtration equipment and membrane filters of a medium pore size 0,45 µm reserved for trace
element determination.
Glass or PTFE filtering apparatus are recommended to avoid possible contamination or adsorption with metal
elements. Test each batch of membrane filters for impurities.
9 Sampling and preservation
9.1 General requirement
Carry out the sampling as specified in ISO 5667-1 and ISO 5667-3.
The mass concentrations of the elements may change rather rapidly after sampling due to adsorption or
desorption effects. This is of special importance, for example in the case of As, Ag, B, Bi, Sb, Se, Sn, Ti, W
ISO 11885:2007(E)
and Zr. The choice of the container
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