1、BSI Standards PublicationBS EN 16319:2013Fertilizers Determinationof trace elements Determination of cadmium,chromium, lead and nickel byinductively coupled plasma-atomic emission spectrometry(ICP-AES) after aqua regiadissolutionCopyright European Committee for Standardization Provided by IHS under
2、license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16319:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16319:2013. It supersedes PD CEN/TS 16319:2012 which is withdrawn.The UK participation in its prep
3、aration was entrusted to Technical Committee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for
4、its correct application. The British Standards Institution 2013. Published by BSI Standards Limited 2013ISBN 978 0 580 81715 1ICS 65.080Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and
5、 Strategy Committee on 31 October 2013.Amendments/corrigenda 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 16319:2013EUROPEAN ST
6、ANDARD NORME EUROPENNE EUROPISCHE NORM EN 16319 October 2013 ICS 65.080 Supersedes CEN/TS 16319:2012English Version Fertilizers - Determination of trace elements - Determination of cadmium, chromium, lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regi
7、a dissolution Engrais - Dosage des lments trace - Dtermination du cadmium, chrome, plomb et nickel par spectromtrie dmission atomique avec plasma induit par haute frquence (ICP-AES) aprs digestion leau rgale Dngemittel - Bestimmung von Elementspuren - Bestimmung von Cadmium, Chrom, Blei und Nickel m
8、it Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach Knigswasseraufschluss This European Standard was approved by CEN on 15 September 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standa
9、rd the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English,
10、 French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulg
11、aria, 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, Slovakia, Slovenia, Spain, Sweden, Switzerland, Tu
12、rkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC 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.
13、 Ref. No. EN 16319:2013: ECopyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16319:2013EN 16319:2013 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Terms
14、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 8.2 Preparation of the test solution 6 8.2.1 General 6 8.2.2 Preparation .7 8.3 Preparation of the test solution for the correction of matrix effects by spike recovery 7 8.
15、4 Preparation of the blank test solution .8 8.5 Preparation of the calibration solutions for the analysis of cadmium, chromium, nickel and lead 8 8.6 Determination of cadmium, chromium, nickel and lead by ICP-AES .8 8.6.1 General 8 8.6.2 Determination by ICP-AES 8 9 Calculation and expression of the
16、 results . 10 9.1 External calibration. 10 9.2 Correction for spike recovery 10 9.3 Standard addition method . 11 9.4 Calculation of the element content in the sample . 12 10 Precision 12 10.1 Inter-laboratory tests 12 10.2 Repeatability 12 10.3 Reproducibility 12 11 Test report . 14 Annex A (inform
17、ative) 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 . 17 Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction o
18、r networking permitted without license from IHS-,-,-BS EN 16319:2013EN 16319:2013 (E) 3 Foreword This document (EN 16319:2013) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials”, the secretariat of which is held by DIN. This European Standard shall be given the st
19、atus 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 April 2014. Attention is drawn to the possibility that some of the elements of this document may be the subje
20、ct 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 16319:2012. The following changes have been made to the former edition: the CEN Technical Specification has been adopted as a European Standard; an exp
21、lanation concerning possible interferences when using this method for the determination of Cd, Cr, Ni and Pb in micro-nutrient fertilizers has been added as a NOTE to Clause 1; the document has been editorially revised. This document has been prepared under a mandate given to CEN by the European Com
22、mission and the European Free Trade Association. 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, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, F
23、ormer Yugoslav Republic of Macedonia, 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. Copyright European Committee for Stand
24、ardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16319:2013EN 16319:2013 (E) 4 1 Scope This European Standard specifies a method for the determination of the content of cadmium, chromium, nickel and lead in fert
25、ilizers 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. NOTE Due to sig
26、nificant interference from Cu, Fe and Mn, no valid results can be reported using this method for fertilizer matrices containing high concentrations ( 10 %) of these micro-nutrients. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and a
27、re 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
28、 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
29、 (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 extrac
30、t are measured by inductively coupled plasmaatomic emission spectrometry (ICP-AES), with axial or radial viewing. 5 Sampling and sample preparation Sampling is not part of the method specified in this European Standard. A recommended sampling method is given in EN 1482-1. Sample preparation shall be
31、 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
32、shall be renewed monthly as a general rule. 6.1 Water, conforming to grade 2 according to EN ISO 3696. 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 Stand
33、ardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16319:2013EN 16319:2013 (E) 5 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
34、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. = 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 t
35、he 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 ge
36、neral, 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, provide
37、d 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 th
38、is application. 6.6.1 Working standard solution I, = 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 cad
39、mium, 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, = 10 mg/l for cadmium, chromium, nickel and lead. Dilute 10,0 ml of the working st
40、andard 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 soluti
41、on 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 with sui
42、table 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 optimized according to the manufacturers instructions. Radial viewing of the plasma may be used if it can be shown that the
43、 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 varyi
44、ng concentrations on the signal intensities of the analytes). Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-BS EN 16319:2013EN 16319:2013 (E) 6 For alkali-elements, this can be
45、 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
46、 can, if used properly, also correct sufficiently for matrix effects (see 8.1). Correction by internal standardization 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.
47、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 f
48、ilter paper, i.e. Whatman 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 (multiplicati
49、ve 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 standar
