1、BSI Standards PublicationBS EN 16317:2013Fertilizers Determinationof trace elements Determination of arsenic byinductively coupled plasma-atomic emission spectrometry(ICP-AES) after aqua regiadissolutionBS EN 16317:2013 BRITISH STANDARDNational forewordThis British Standard is the UK implementation
2、of EN 16317:2013. Itsupersedes PD CEN/TS 16317:2012 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can beobtained on request to its secretary.This publicati
3、on does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 81509 6ICS 65.080Compliance with a British Standard cannot confer immunity fromlega
4、l obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 October 2013.Amendments issued since publicationDate Text affectedBS EN 16317:2013EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16317 October 2013 ICS 65.080 Supersedes CE
5、N/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 larsenic par spectromtrie dmission atomique a
6、vec 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 was approved by CEN on 29 August 2013.
7、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 a
8、pplication 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 to the CEN-CENELEC
9、 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, Iceland, Ireland, Italy,
10、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 NORMUNG Management Centre: Avenue Marnix 17, B
11、-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: EBS 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
12、 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 . 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
13、solution . 7 8.5 Preparation of the calibration solutions for the analysis of arsenic 8 8.6 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 St
14、andard addition method . 10 9.4 Calculation of the element content in the sample 11 10 Precision . 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 S
15、tatistical results for the determination of arsenic by ICP-AES 13 Bibliography 14 BS EN 16317:2013EN 16317:2013 (E) 3 Foreword This document (EN 16317:2013) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials”, the secretariat of which is held by DIN. This European
16、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 April 2014. Attention is drawn to the possibility that some of the elements of
17、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 been made to the former edition: a) the CEN Technical Specification has been adopt
18、ed 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 CEN-CENELEC Internal Regulations, the national standards organisations of the fol
19、lowing 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, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands,
20、 Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. 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-ato
21、mic emission spectrometry (ICP-AES) after aqua regia 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 referen
22、ced 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
23、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 Spec
24、ification 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 Arsenic is extracted from the sample with aqua regia and conventional boiling. The concentration in the extract i
25、s 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 methods specified in this European Standard. A recommended sampling method is given in EN 1482-1. Sample preparation shall be car
26、ried out in accordance with EN 1482-2. 6 Reagents 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 shal
27、l be renewed monthly as a general rule. 6.1 Water, 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. BS EN 16317:2013EN 16317:2013 (E) 5 6.4 Mixed acid solu
28、tion 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 solution arsenic standard stock solution, e.g. = 1 000 mg/l in arsenic. Use suitable stock solutions. Single-element stock solu
29、tions with adequate specification stating the acid used and the preparation technique are commercially available. It is recommended to use a commercially available standard stock solution for arsenic. 6.6 Working standard solutions. Depending on the scope, different working standard solutions may be
30、 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 same 100 ml flask. This solution is used to prepare spiked test solutions and standard and calibration solutions. 6.6.2 W
31、orking 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 solution is used to prepare spiked test solutions and calibration solutions. 7 Apparatus 7.1 Common laboratory glasswar
32、e. 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. The settings of the working conditions (e.g. gas flows, RF or plasma power, sample u
33、ptake 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 the limit of quantification for arsenic is below the required legal limit values. The use of axial orientation of the v
34、iewing 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
35、). 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 f
36、or 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
37、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. BS EN 16317:2013EN 16317:2013 (E) 6 7.5 Ash-free filter paper, i.
38、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 (multiplicative matrix effec
39、ts). 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
40、 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 rout
41、ine 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
42、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 fertilizers with unknown matrix composition or with a matrix that
43、cannot be 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 ra
44、nge 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 calibrat
45、ion 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
46、linear working range of the ICP-AES. 8.2 Preparation of the test solution 8.2.1 General The following extraction procedure leads, in most cases for mineral fertilizers, to trace element results which correspond to the total contents of these elements. Calibration with several standard additions and
47、external calibration after matrix matching or by correction for matrix effects with internal standardization 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
48、 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
49、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 further with 10 ml of water (6.1) (action 3). 1) Whatman 589/2is an example of a suitable product available commercially. This Information is given for the convenience of users of this European Standa
