1、March 2016 English price group 12No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 65.080!%M“2429958www.din.deDIN EN
2、16319Fertilizers and liming materials Determination of cadmium, chromium, lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution;English version EN 16319:2013+A1:2015,English translation of DIN EN 16319:2016-03Dngemittel und Kalkdnger Bestim
3、mung von Cadmium, Chrom, Blei und Nickel mit Atomemissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-AES) nach Knigswasseraufschluss;Englische Fassung EN 16319:2013+A1:2015,Englische bersetzung von DIN EN 16319:2016-03Engrais et amendements minraux basiques Dtermination du cadmium, chrome, p
4、lomb et nickel par spectromtrie dmission atomique avec plasma induit par haute frquence (ICP-AES) aprs digestion leau rgale;Version anglaise EN 16319:2013+A1:2015,Traduction anglaise de DIN EN 16319:2016-03SupersedesDIN EN 16319:2014-02www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt,
5、 the German-language original shall be considered authoritative.Document comprises 22 pages 03.16DIN EN 16319:2016-03 2 A comma is used as the decimal marker. National foreword This document (EN 16319:2013+A1:2015) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials
6、” (Secretariat: DIN, Germany) under the mandate M/418. The responsible German body involved in its preparation was DIN-Normenausschuss Lebensmittel und landwirtschaftliche Produkte (DIN Standards Committee Food and Agricultural Products), Working Committee NA 057-03-02 AA Dngemittel. The DIN Standar
7、ds corresponding to the International Standards referred to in this document are as follows: ISO 5725-1 DIN ISO 5725-1 ISO 5725-2 DIN ISO 5725-2 Amendments This standard differs from DIN EN 16319:2014-02 as follows: a) the title and scope have been extended to include liming materials; b) Clause 10
8、“Precision” has been extended to include liming materials; c) statistics for liming materials are now included in Annex A. Previous editions DIN CEN/TS 16319 (DIN SPEC 10789): 2012-06 DIN EN 16319: 2014-02 National Annex NA (informative) Bibliography DIN ISO 5725-1, Accuracy (trueness and precision)
9、 of measurement methods and results Part 1: General principles and definitions DIN ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method EUROPEAN STANDARD NORME
10、 EUROPENNE EUROPISCHE NORM EN 16319:2013+A1 December 2015 ICS 65.080 Supersedes EN 16319:2013English Version Fertilizers and liming materials - Determination of cadmium, chromium, lead and nickel by inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution Engrai
11、s et amendements minraux basiques - Dtermination du cadmium, chrome, plomb et nickel par spectromtrie dmission atomique avec plasma induit par haute frquence (ICP-AES) aprs digestion leau rgale This European Standard was approved by CEN on 15 September 2013 and includes Amendment 1 approved by CEN o
12、n 7 November 2015. 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 m
13、ay 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 language and notified
14、 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, Greece, Hungary, Icelan
15、d, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Manageme
16、nt Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16319:2013+A1:2015 EDngemittel und Kalkdnger BestimmungvonCadmium,Chrom,BleiundNickelmitAtomemissionsspektrometrie mit induktiv gekop
17、peltem Plasma (ICP-AES) nach KnigswasseraufschlussEN 16319:2013+A1:2015 (E) 2 Contents Page European 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 8.2 Prepara
18、tion of the test solution . 7 8.2.1 General 7 8.2.2 Preparation . 7 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 8 8.5 Preparation of the calibration solutions for the analysis of cadmium, chromium, nickel
19、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 results . 10 9.1 External calibration 10 9.2 Correction for spike recovery 10 9.3 Standard addition method 11 9.4 Calculation of th
20、e element content in the sample 11 10 Precision 12 10.1 Inter-laboratory tests . 12 10.2 Repeatability 12 10.3 Reproducibility . 12 11 Test report 13 Annex A (informative) Results of the inter-laboratory test . 15 A.1 Inter-laboratory tests . 15 A.2 Statistical results for the determination of cadmi
21、um, chromium, lead and nickel !for fertilizers“ . 15 A.3 Statistical results for the determination of cadmium, chromium, lead and nickel for liming materials 17 Bibliography . 20 DIN EN 16319:2016-03 EN 16319:2013+A1:2015 (E) 3 European foreword This document (EN 16319:2013+A1:2015) has been prepare
22、d 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 status of a national standard, either by publication of an identical text or by endorsement, at the latest by June 2016, and conflicting national
23、 standards shall be withdrawn at the latest by June 2016. 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 includes Amend
24、ment 1 approved by CEN on 2015-11-07. This document supersedes !EN 16319:2013“. The start and finish of text introduced or altered by amendment is indicated in the text by tags !“. !deleted text“ This document has been prepared under a mandate given to CEN by the European Commission and the European
25、 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, Former Yugoslav Republic
26、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. DIN EN 16319:2016-03 EN 16319:2013+A1:2015 (E) 4 1 Scope !This
27、 European Standard specifies a method for the determination of the content of cadmium, chromium, nickel and lead in fertilizers and liming materials using inductively coupled plasma-atomic emission spectrometry (ICP-AES) after aqua regia dissolution.“ Limits of quantification are dependent on the sa
28、mple 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 1“ Due to significant interference from Cu, Fe and Mn, no valid results can be reported using this method for fertilizer matrices containing high concentrations ( 10 %) o
29、f these micro-nutrients. !NOTE 2 The term fertilizer is used throughout the body of this European Standard and needs to be taken to include liming materials unless otherwise indicated.“ 2 Normative references The following documents, in whole or in part, are normatively referenced in this document a
30、nd 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 prepara
31、tion 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 12944-3:2001, Fertilizers and liming materials Vocabulary Part 3: Terms
32、 relating to liming materials“ 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, EN 12944-2:1999 and EN 12944-3:2001 apply.“ 4 Principle Cadmium, c
33、hromium, nickel and lead are extracted from the sample with aqua regia and conventional boiling. The concentrations in the extract 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
34、 the method 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 Use only reagents of recognized analytical grade. DIN EN 16319:2016-03 EN 16319:2013+A1:2015 (E) 5 Commercially avail
35、able 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, conforming to grade 2 according to EN ISO 3696. 6.2 Hydrochloric ac
36、id, 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. 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
37、 (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 the acid used and the prepara
38、tion 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 elemen
39、ts 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 so
40、lutions (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 Workin
41、g 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 cadmium, chromium, nickel and l
42、ead 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 standard solution I of cadmium
43、, 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
44、 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 suitable background correction.
45、 DIN EN 16319:2016-03 EN 16319:2013+A1:2015 (E) 6 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
46、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 ionisa
47、ble 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 c
48、orrect 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 standardization is also a good option, but the accuracy of the measurements after
49、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 589/21)or equivalent quality. 8 Procedure 8.1 General Calibrations by
