SIST-TS CEN/TS 16319:2012
(Main)Fertilizers - Determination of trace elements - Determination of cadmium, chromium, lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution
Fertilizers - Determination of trace elements - Determination of cadmium, chromium, lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution
This document specifies a method for the determination of the content of cadmium, chromium, nickel and lead in fertilizers with inductively coupled plasma atomic emission spectrometry (ICP-AES) after extraction with aqua regia. Limits of quantification are dependant on the sample matrix as well as on the instrument, but can roughly be expected to be 0,3 mg/kg for Cd and 1 mg/kg for Cr, Ni and Pb.
Düngemittel und Calcium-/Magnesium-Bodenverbesserungsmittel - Bestimmung von Elementspuren - Bestimmung von Cadmium, Chrom, Blei und Nickel mit Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach Königswasseraufschluss
Diese Technische Spezifikation legt ein Verfahren zur Bestimmung des Gehalts an Cadmium, Chrom, Nickel und Blei in Düngemitteln mit Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach Königswasseraufschluss fest. Die Bestimmungsgrenzen sind sowohl von der Probenmatrix als auch vom eingesetzten Gerät abhängig, werden jedoch etwa bei 0,3 mg/kg für Cd und 1 mg/kg für Cr, Ni und Pb erwartet.
Engrais - Dosage des éléments traces - Détermination du cadmium, chromium, plomb et nickel par spectrométrie d'émission atomique avec plasma induit par haute fréquence (ICP-AES) après digestion à l'eau régale
La présente spécification technique spécifie une méthode permettant de déterminer la teneur en cadmium,
chrome, nickel et plomb dans les engrais par spectrométrie d’émission atomique avec plasma à couplage
inductif (ICP-AES) après extraction à l’eau régale. Les limites de quantification dépendent de la matrice de
l’échantillon ainsi que de l’instrument, mais peuvent être attendues de l’ordre de 0,3 mg/kg pour Cd et 1 mg/kg
pour Cr, Ni et Pb.
Gnojila - Določevanje elementov v sledovih - Določevanje kadmija, kroma, svinca in niklja z atomsko emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP/AES) po raztapljanju v zlatotopki
Ta dokument določa metodo za določevanje vsebnosti kadmija, kroma, niklja in svinca v gnojilih z atomsko emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP-AES) po ekstrakciji z zlatotopko. Meje kvantifikacije so odvisne od matrice vzorca in instrumenta, vendar za Cd običajno znašajo približno 0,3 mg/kg, za Cr, Ni in Pb pa 1 mg/kg.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST-TS CEN/TS 16319:2012
01-junij-2012
*QRMLOD'RORþHYDQMHHOHPHQWRYYVOHGRYLK'RORþHYDQMHNDGPLMDNURPDVYLQFD
LQQLNOMD]DWRPVNRHPLVLMVNRVSHNWURPHWULMR]LQGXNWLYQRVNORSOMHQRSOD]PR
,&3$(6 SRUD]WDSOMDQMXY]ODWRWRSNL
Fertilizers - Determination of trace elements - Determination of cadmium, chromium,
lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES)
after aqua regia dissolution
Düngemittel und Calcium-/Magnesium-Bodenverbesserungsmittel - Bestimmung von
Elementspuren - Bestimmung von Cadmium, Chrom, Blei und Nickel mit
Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach
Königswasseraufschluss
Engrais - Dosage des éléments traces - Détermination du cadmium, chromium, plomb et
nickel par spectrométrie d'émission atomique avec plasma induit par haute fréquence
(ICP-AES) après digestion à l'eau régale
Ta slovenski standard je istoveten z: CEN/TS 16319:2012
ICS:
65.080 Gnojila Fertilizers
SIST-TS CEN/TS 16319:2012 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
SIST-TS CEN/TS 16319:2012
---------------------- Page: 2 ----------------------
SIST-TS CEN/TS 16319:2012
TECHNICAL SPECIFICATION
CEN/TS 16319
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
April 2012
ICS 65.080
English Version
Fertilizers - Determination of trace elements - Determination of
cadmium, chromium, lead and nickel by inductively coupled
plasma-atomic emission spectrometry (ICP-AES) after aqua
regia dissolution
Engrais - Dosage des éléments traces - Détermination du Düngemittel - Bestimmung von Elementspuren -
cadmium, chromium, plomb et nickel par spectrométrie Bestimmung von Cadmium, Chrom, Blei und Nickel mit
d'émission atomique avec plasma induit par haute Atomemissionsspektrometrie mit induktiv gekoppeltem
fréquence (ICP-AES) après digestion à l'eau régale Plasma (ICP-AES) nach Königswasseraufschluss
This Technical Specification (CEN/TS) was approved by CEN on 30 January 2012 for provisional application.
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, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 16319:2012: E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
Contents Page
Foreword .3
1 Scope .4
2 Normative references .4
3 Terms and definitions .4
4 Principle .4
5 Sampling and sample preparation .4
6 Reagents .4
7 Apparatus .5
8 Procedure .6
9 Calculation and expression of the results . 10
10 Precision . 12
11 Test report . 14
Annex A (informative) Results of the inter-laboratory test . 15
A.1 Inter-laboratory tests . 15
A.2 Statistical results for the determination of cadmium, chromium, lead and nickel . 15
Bibliography . 18
2
---------------------- Page: 4 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
Foreword
This document (CEN/TS 16319:2012) has been prepared by Technical Committee CEN/TC 260 “Fertilizers
and liming materials”, the secretariat of which is held by DIN.
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 has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this Technical Specification: 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, Romania, Slovakia, Slovenia,
Spain, Sweden, Switzerland, Turkey and the United Kingdom.
3
---------------------- Page: 5 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
1 Scope
This Technical Specification specifies a method for the determination of the content of cadmium, chromium,
nickel and lead in fertilizers with inductively coupled plasma-atomic emission spectrometry (ICP-AES) after
extraction with aqua regia. Limits of quantification are dependent on the sample matrix as well as on the
instrument, but can roughly be expected to be 0,3 mg/kg for Cd and 1 mg/kg for Cr, Ni and Pb.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.
EN 1482-2, Fertilizers and liming materials — Sampling and sample preparation — Part 2: Sample
preparation
EN 12944-1:1999, Fertilizers and liming materials and soil improvers — Vocabulary — Part 1: General terms
EN 12944-2:1999, Fertilizers and liming materials and soil improvers — Vocabulary — Part 2: Terms relating
to fertilizers
EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696)
3 Terms and definitions
For the purposes of this document, the terms and definitions given in EN 12944-1:1999 and EN 12944-2:1999
apply.
4 Principle
Cadmium, chromium, nickel and lead are extracted from the sample with aqua regia and conventional boiling.
The concentrations in the extract are measured by inductively coupled plasma–atomic emission spectrometry
(ICP-AES), with axial or radial viewing.
5 Sampling and sample preparation
Sampling is not part of the methods specified in this Technical Specification. A recommended sampling
method is given in EN 1482-1.
Sample preparation shall be carried out in accordance with EN 1482-2.
6 Reagents
Use only reagents of recognized analytical grade.
Commercially available stock solutions shall be replaced according to the specifications from the supplier or
after one year if prepared in the laboratory from available salts. Standard solutions shall be renewed monthly
as a general rule.
4
---------------------- Page: 6 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
6.1 Water conforming to grade 2 according to EN ISO 3696.
6.2 Hydrochloric acid c(HCl) = 12 mol/l; 37 % volume fraction; ρ ≈ 1,18 g/ml.
6.3 Nitric acid c(HNO ) = 16 mol/l; not less than 65 % volume fraction, ρ ≈ 1,42 g/ml.
3
6.4 Mixed solution of 0,8 mol/l nitric acid and 1,8 mol/l hydrochloric acid
Mix 150 ml of hydrochloric acid (6.2) and 50 ml nitric acid (6.3) to 1,0 l of water (6.1).
6.5 Standard stock solutions cadmium, chromium, nickel and lead standard stock solutions, e.g.
ρ = 1 000 mg/l for each element.
Use suitable stock solutions. Both single-element stock solutions and multi-element stock solutions with
adequate specification stating the acid used and the preparation technique are commercially available. It is
recommended to use commercially available standard stock solutions for cadmium, chromium, nickel and
lead.
6.6 Working standard solutions
Depending on the scope, different working standard solutions may be necessary.
In general, when combining elements in working standard solutions, their chemical compatibility shall be
regarded. Spectral interferences from other elements present in working standard solutions also need to be
considered. Various combinations of elements at different concentrations may be used, provided that the
standard stock solutions (6.5) are diluted with the same acid and in equal concentration as the acid in the test
solution.
NOTE In equal concentrations (in mg/l), cadmium, chromium, nickel and lead are compatible in a multi-element
standard solution for the determination by ICP-AES for this application.
6.6.1 Working standard solution I ρ = 100 mg/l for cadmium, chromium, nickel and lead.
Dilute 10,0 ml of each standard stock solution of cadmium, chromium, nickel and lead (6.5) to 100,0 ml with
the mixed acid solution (6.4) in the same 100 ml flask. If non-equal concentrations of cadmium, chromium,
nickel and lead are needed, dilute the required volumes into 100,0 ml. This solution is used to prepare spiked
test solutions and standard and calibration solutions.
6.6.2 Working standard solution II ρ = 10 mg/l for cadmium, chromium, nickel and lead.
Dilute 10,0 ml of the working standard solution I of cadmium, chromium, nickel and lead (6.6.1) to 100,0 ml
with the mixed acid solution (6.4) in a 100 ml flask. If non-equal concentrations of cadmium, chromium, nickel
and lead are needed, dilute the require volume from the standard stock solutions (6.5) into 100,0 ml. This
solution is used to prepare spiked test solutions and calibration solutions.
7 Apparatus
7.1 Common laboratory glassware
7.2 Analytical balance capable of weighing to an accuracy of 1 mg.
5
---------------------- Page: 7 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
7.3 Inductively coupled plasma-atomic emission spectrometer with axial or radial viewing of the
plasma and with suitable background correction.
The settings of the working conditions (e.g. gas flows, RF or plasma power, sample uptake rate, integration
time and number of replicates) shall be optimised according the manufacturer’s instructions. Radial viewing of
the plasma may be used if it can be shown that the limits of quantification for cadmium, chromium, nickel and
lead are below the required legal limit values.
The use of axial orientation of the viewing optics requires good control of the matrix effects coming from
"easily ionisable elements" (i.e. the influence of easily ionisable elements in varying concentrations on the
signal intensities of the analytes). For alkali-elements, this can be achieved by adding caesium-chloride
solution (CsCl). In general, matrix matching of calibration solutions or calibration by standard additions with
several calibration standards will correct accurately for these matrix effects. Spike recovery of one known
standard combined with external calibration can, if used properly, also correct sufficiently for matrix effects
(see 8.1). Correction by internal standardisation is also a good option, but the accuracy of the measurements
after internal standard correction should be validated properly prior to use on unknown fertilizer samples.
7.4 Dilutor
Instrument used for automated volumetric dilutions or other appropriate equipment (e.g. pipettes and
volumetric glassware) to perform dilutions. The precision and accuracy of this type of equipment for volumetric
dilutions shall be established, and controlled and documented regularly.
7.5 Ash-free filter paper i.e. Whatman 589/2 or equivalent quality.
8 Procedure
8.1 General
Calibrations by standard additions with several standards or by matrix matching are very powerful calibration
techniques and can be used to accurately correct for matrix effects from easy-ionisable elements
(multiplicative matrix effects). Additive matrix effects (i.e. spectral interferences) are not corrected for with
standard additions calibration. For matrix matching, additive matrix effects will be corrected for when the
added matrix is the cause of the matrix effect. The main drawback of calibration by standard addition with
several standards is the requirement for a calibration function for each sample type, which is a time
consuming process. For matrix matching a profound knowledge of the sample matrix is needed, which is not
always necessarily available. These two techniques may thus not be practical to use in routine fertilizer
laboratories.
Correction by internal standardisation is also a good option, but the accuracy of the measurements after
internal standard correction should be validated properly prior to use on unknown fertilizer samples.
It is therefore suggested that calibrations are to be performed by means of external calibration and correction
of matrix effects by addition of one known spike of a standard solution (spike recovery). The method of
external calibration and correction for spike recovery allows for the analysis of fertilisers with unknown matrix
composition or with a matrix that cannot be synthetically imitated easily. This calibration technique may not be
as precise as calibration by standard additions with several standards but the increased uncertainty is small
compared to the total uncertainty of the method, if the total analyte concentration is in the linear working range
after the spike and the added spike corresponds to at least a doubling of the analyte concentration. Many
matrix errors can be compensated for by this procedure, if they are not additive (e.g. spectral interferences).
Aliquots of the sample solution are analysed by the means of external calibration and then one aliquot is
spiked with known concentrations of the analytes without changing the matrix of the sample solution. The
calculated spike recovery is then used to correct the concentration calculated from the external calibration
function. The concentration of the spikes shall be in the linear working range of the ICP-AES.
6
---------------------- Page: 8 ----------------------
SIST-TS CEN/TS 16319:2012
CEN/TS 16319:2012 (E)
8.2 Preparation of the test solution
8.2.1 General
The following extraction procedure leads, in most cases for mineral fertilisers, to trace element results which
correspond to the total contents of these elements.
Calibration with several standard additions and external calibration after matrix matching or by correction for
matrix effects with internal standardisation may also be used.
8.2.2 Preparation
8.2.2.1 Weigh (3 ± 0,003) g of the prepared sample and transfer to a suitable reaction vessel (action 1).
8.2.2.2 Moisten the sample with about 0,5 ml to 1,0 ml of water (6.1) and add, whilst mixing, (21 ± 0,1) ml
of hydrochloric acid (6.2) followed by (7 ± 0,1) ml of nitric acid (6.3) drop by drop if necessary to reduce
foaming. Connect a condenser to the reaction vessel and let the mixture stand at room temperature until any
effervescence almost ceases to allow for slow oxidation of any organic mass in the sample (action 2).
8.2.2.3 Transfer to the heating device and raise the temperature of the reaction mixture slowly to reflux
conditions. Maintain for 2 h, ensuring that the condensation zone is lower than 1/3 of the height of the
condenser, then allow to cool. Rinse the condenser a further with 10 ml of water (6.1) (action 3).
If the digested sample contains particulates which can clog nebulisers or interfere with the injection of the
sample, the sample should be centrifuged and allowed to settle, or filtered before transferring into a suitable
sized volumetric flask. For exa
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.