1、BSI Standards PublicationBS EN 16317:2013Fertilizers Determinationof trace elements Determination of arsenic byinductively coupled plasma-atomic emission spectrometry(ICP-AES) after aqua regiadissolutionCopyright European Committee for Standardization Provided by IHS under license with CENNot for Re
2、saleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16317:2013. Itsupersedes PD CEN/TS 16317:2012 which is withdrawn.The UK participation in its preparation was entrusted to Te
3、chnicalCommittee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The Br
4、itish Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 81509 6ICS 65.080Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 October
5、2013.Amendments issued since publicationDate Text affectedCopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 163
6、17 October 2013 ICS 65.080 Supersedes CEN/TS 16317:2012English Version Fertilizers - Determination of trace elements - Determination of arsenic by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution Engrais - Dosage des lments traces - Dtermination de larse
7、nic par spectromtrie dmission atomique avec plasma induit par haute frquence (ICP-AES) aprs digestion leau rgale Dngemittel - Bestimmung von Elementspuren - Bestimmung von Arsen mit Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach Knigswasseraufschluss This European Standard
8、 was approved by CEN on 29 August 2013. 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
9、 national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own
10、language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Gr
11、eece, 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 COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUN
12、G Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16317:2013: ECopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reprod
13、uction or networking permitted without license from IHS-,-,-BS EN 16317:2013EN 16317:2013 (E) 2 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 8.1 General . 6 8
14、.2 Preparation of the test solution . 6 8.2.1 General . 6 8.2.2 Preparation . 6 8.3 Preparation of the test solution for the correction of matrix effects by spike recovery . 7 8.4 Preparation of the blank test solution . 7 8.5 Preparation of the calibration solutions for the analysis of arsenic 8 8.
15、6 Determination of arsenic by ICP-AES . 8 8.6.1 General . 8 8.6.2 Determination by ICP-AES . 8 9 Calculation and expression of the results 9 9.1 External calibration 9 9.2 Correction for spike recovery 9 9.3 Standard addition method . 10 9.4 Calculation of the element content in the sample 11 10 Pre
16、cision . 11 10.1 Inter laboratory tests 11 10.2 Repeatability . 11 10.3 Reproducibility . 11 11 Test report 12 Annex A (informative) Results of the inter-laboratory test 13 A.1 Inter-laboratory tests . 13 A.2 Statistical results for the determination of arsenic by ICP-AES 13 Bibliography 14 Copyrigh
17、t European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013EN 16317:2013 (E) 3 Foreword This document (EN 16317:2013) has been prepared by Technical Committee CEN/TC 260 “Fertilizer
18、s and liming materials”, 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 April 2014, and conflicting national standards shall be withdrawn at the latest by
19、 April 2014. 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 CEN/TS 16317:2012. The following changes have be
20、en made to the former edition: a) the CEN Technical Specification has been adopted as a European Standard; b) the document has been editorially revised. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. According to the C
21、EN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hung
22、ary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo r
23、eproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013EN 16317:2013 (E) 4 1 Scope This European Standard specifies a method for the determination of the content of arsenic in fertilizers using inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua reg
24、ia dissolution. Limits of quantification are dependent on the sample matrix as well as on the instrument, but can roughly be expected to be 1,5 mg/kg for As. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its
25、 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, Fertil
26、izers 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
27、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 Arsenic is extracted from the sample with aqua regia and conventional boiling. The concentration in the extract is measured by inductively coupled plasmaatomic emi
28、ssion spectrometry (ICP-AES) with axial or radial viewing. 5 Sampling and sample preparation Sampling is not part of the methods specified in this European Standard. A recommended sampling method is given in EN 1482-1. Sample preparation shall be carried out in accordance with EN 1482-2. 6 Reagents
29、Use only reagents of recognised 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. 6.1 Water,
30、 according to EN ISO 3696, grade 2. 6.2 Hydrochloric acid, c(HCl) = 12 mol/l; 37 % volume fraction; 1,18 g/ml. 6.3 Nitric acid, c(HNO3) = 16 mol/l; not less than 65 % volume fraction, 1,42 g/ml. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo r
31、eproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013EN 16317:2013 (E) 5 6.4 Mixed acid 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 solutio
32、n arsenic standard stock solution, e.g. = 1 000 mg/l in arsenic. Use suitable stock solutions. Single-element stock solutions with adequate specification stating the acid used and the preparation technique are commercially available. It is recommended to use a commercially available standard stock s
33、olution for arsenic. 6.6 Working standard solutions. Depending on the scope, different working standard solutions may be necessary. 6.6.1 Working standard solution I, = 100 mg/l for arsenic. Dilute 10,0 ml of the stock solution of arsenic (6.5) to 100,0 ml with the mixed acid solution (6.4) in the s
34、ame 100 ml flask. This solution is used to prepare spiked test solutions and standard and calibration solutions. 6.6.2 Working standard solution II, = 10 mg/l for arsenic. Dilute 10,0 ml of the working standard solution I (6.6.1) to 100,0 ml with the mixed acid solution (6.4) in a 100 ml flask. This
35、 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. 7.3 Inductively coupled plasma-atomic emission spectrometer, with axial or radial viewing of the plasma and w
36、ith suitable background correction. The settings of the working conditions (e.g. gas flows, RF or plasma power, sample uptake rate, integration time, number of replicates) shall be optimised according to the manufacturers instructions. Radial viewing of the plasma may be used if it can be shown that
37、 the limit of quantification for arsenic is 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
38、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. Sp
39、ike 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 validat
40、ed 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
41、 established, and controlled and documented regularly. Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16317:2013EN 16317:2013 (E) 6 7.5 Ash-free filter paper, i.e. Whatman
42、 589/21)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). Addit
43、ive 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 s
44、tandards 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 fertil
45、izer 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 o
46、f 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 fertilizers with unknown matrix composition or with a matrix that cannot be
47、easily imitated synthetically. 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
48、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 th
49、en 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. 8.2 Prepar
