1、May 2017 English price group 11No 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!%e)o“2660676www.din.deDIN EN
2、16320Fertilizers and liming materials Determination of mercury by vapour generation (VG) after aqua regia dissolution;English version EN 16320:2013+A1:2017,English translation of DIN EN 16320:2017-05Dngemittel und Kalkdnger Bestimmung von Quecksilber mit Verdampfungstechnik (VG) nach Knigswasseraufs
3、chluss;Englische Fassung EN 16320:2013+A1:2017,Englische bersetzung von DIN EN 16320:2017-05Engrais et amendements minraux basiques Dtermination du mercure par gnration de vapeur (VG) aprs digestion leau rgale;Version anglaise EN 16320:2013+A1:2017,Traduction anglaise de DIN EN 16320:2017-05Supersed
4、esDIN EN 16320:201312www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.Document comprises 18 pages 04.17 2 A comma is used as the decimal marker. National foreword This document (EN 16320:2013+A1:2017) has been prepared by
5、 Technical Committee CEN/TC 260 “Fertilizers and liming materials” (Secretariat: DIN, Germany). 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
6、 057-03-02 AA “Fertilizers”. The DIN Standards 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 16320:2013-12 as follows: a) the title and scope have been extende
7、d to include liming materials; b) Clause 10 “Precision” has been extended to include liming materials; c) statistics of the interlaboratory test for liming materials have been included in Annex A; d) the standard has been revised and brought in line with the current rules of presentation. Previous e
8、ditions DIN CEN/TS 16320 (DIN SPEC 10790): 2012-06 DIN EN 16320: 2013-12 National Annex NA (informative) Bibliography DIN ISO 5725-1, Accuracy (trueness and precision) of measurement methods and results Part 1: General principles and definitions DIN ISO 5725-2, Accuracy (trueness and precision) of m
9、easurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method DIN EN 16320:2017-05 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16320:2013+A1 February 2017 ICS 65.080 English Version Fertilizers and liming mate
10、rials - Determination of mercury by vapour generation (VG) after aqua regia dissolution Engrais et amendements minraux basiques - Dtermination du mercure par gnration de vapeur (VG) aprs digestion leau rgale Dngemittel und Kalkdnger - Bestimmung von Quecksilber mit Verdampfungstechnik (VG) nach Knig
11、swasseraufschluss This European Standard was approved by CEN on 29 August 2013 and includes Amendment 1 approved by CEN on 11 December 2016. 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 nati
12、onal 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, French, German). A ver
13、sion 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, Bulgaria, Croatia, Cyprus,
14、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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
15、 Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16
16、320:2013+A1:2017 EEN 16320:2013+A1:2017 (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 . 5 7 Apparatus . 6 8 Procedure. 7 8.1 General 7 8.2 Preparation of the test solution . 7 8.
17、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 . 8 8.4 Preparation of the blank test solution 8 8.5 Preparation of the calibration solutions 8 8.5.1 Calibration solutions for the analysis of mercury . 8 8.5.2 Calibratio
18、n standards 9 8.6 Determination of mercury . 9 8.6.1 General 9 8.6.2 Determination by VG-AAS 9 8.6.3 Spectrometer settings of VG-AAS . 9 8.6.4 Determination by VG-ICP-AES . 10 9 Calculation and expression of the results . 11 9.1 External calibration 11 9.2 Correction for spike recovery 11 9.3 Standa
19、rd addition method 12 9.4 Calculation of the element content in the sample 12 10 Precision 13 10.1 Inter laboratory tests 13 10.2 Repeatability 13 10.3 Reproducibility . 13 11 Test report 14 Annex A (informative) Results of the inter-laboratory test . 15 Bibliography . 16 DIN EN 16320:2017-05 EN 163
20、20:2013+A1:2017 (E) 3 European foreword This document (EN 16320:2013+A1:2017) 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 status of a national standard, either by publicatio
21、n of an identical text or by endorsement, at the latest by August 2017, and conflicting national standards shall be withdrawn at the latest by August 2017. This document includes Amendment 1 approved by CEN on 11 December 2016. This document supersedes !EN 16320:2013“. The start and finish of text i
22、ntroduced or altered by amendment is indicated in the text by tags ! “. 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
23、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 following countries are bound to implement this European Standard: Austria, Belgium, Bulga
24、ria, 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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerl
25、and, Turkey and the United Kingdom. DIN EN 16320:2017-05 EN 16320:2013+A1:2017 (E) 4 1 Scope This European Standard specifies a method for the determination of the content of mercury in fertilizers !and liming materials“ after extraction with aqua regia and the detection of mercury by vapour generat
26、ion (VG) coupled to an atomic absorption spectrometer or an inductively coupled plasma-atomic emission spectrometer. A limit of quantification of 0,01 mg/kg is to be expected. !NOTE The term fertilizer is used throughout the body of this European Standard and includes liming materials unless otherwi
27、se indicated.“ 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 (incl
28、uding 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 so
29、il improvers - Vocabulary - Part 2: Terms relating to fertilizers !EN 12944-3:2001, Fertilizers and liming materials and soil improvers Vocabulary Part 3: Terms relating to liming materials “ EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) 3 Terms and defin
30、itions For the purposes of this document, the terms and definitions given in EN 12944-1:1999 and EN 12944-2:1999 and !EN 12944-3:2001“apply. 4 Principle Mercury is extracted from the sample with aqua regia and conventional boiling. The concentration of mercury in the extract is measured by (cold) va
31、pour generation (VG) coupled to a suitable detector, such as an atomic absorption spectrometer (AAS) or an inductively coupled plasma-atomic emission spectrometer (ICP-AES). 5 Sampling and sample preparation Sampling is not part of the method specified in this European Standard. A recommended sampli
32、ng method is given in EN 1482-1. Sample preparation shall be carried out in accordance with EN 1482-2. DIN EN 16320:2017-05 EN 16320:2013+A1:2017 (E) 5 6 Reagents Use only reagents of recognized analytical grade. Commercially available stock solutions shall be replaced according to the specification
33、s 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 of EN ISO 3696. 6.2 Hydrochloric acid, c(HCl) = 12 mol/l; 37 % volume fraction; approximately 1,18 g/ml. 6.3 Nitri
34、c acid, c(HNO3) = 16 mol/l; not less than 65 % volume fraction, approximately 1,42 g/ml. 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 solution, mercury s
35、tandard stock solution, e.g. = 1 000 mg/l. 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 commercially available standard stock solutions for mercury. 6.
36、6 Working standard solutions. Depending on the scope, different working standard solutions may be necessary. In general, the stability of mercury working standard solutions should be checked. 6.6.1 Working standard solution I, = 10 mg/l for mercury. Dilute 1,00 ml of the standard stock solution for
37、mercury (6.5) to 100,0 ml with the mixed acid solution (6.4). This solution is used to prepare 200 g/l mercury working standard solution. 6.6.2 Working standard solution II, = 200 g/l for mercury. Dilute 2,00 ml of the 10 mg/l mercury working standard solution I (6.6.1) to 100,0 ml with the mixed ac
38、id solution (6.4). This solution is used to prepare spiked test solutions and calibration solutions. 6.7 Reducing agents. 6.7.1 General. Tin(II) chloride or sodium borohydride may be used as the reducing agent, but it is not advisable to use the two reagents alternately. Observe the instructions of
39、the manufacturers of the apparatus. The concentration by mass of the reducing agent solutions may be varied to suit the system, and the relevant information provided by the manufacturer of the apparatus shall be observed. 6.7.2 Tin(II) chloride solution, (SnCl22H2O) = 100 g/l. Dissolve 50 g of tin(I
40、I) chloride in approximately 100 ml of hydrochloric acid (6.2) in a 500 ml volumetric flask and dilute to the mark. Prepare a fresh solution daily. DIN EN 16320:2017-05 EN 16320:2013+A1:2017 (E) 6 6.7.3 Sodium borohydride solution, e.g. = 2 g/l. Dissolve 2 g of sodium hydroxide pellets in water, add
41、 2 g of sodium borohydride and dilute to 1 000 ml with water (6.1). Prepare a fresh solution daily and, when necessary, filter before use. When the analysis procedure is of a longer time, it is recommended to cool the sodium borohydride solution (i.e. with ice around the flask) during its use in the
42、 vapour generation ICP-AES or AAS measurement. WARNING It is essential to observe the safety instructions for working with sodium borohydride. Sodium borohydride forms hydrogen with acids and this can result in an explosive air/hydrogen mixture. A permanent extraction system shall be provided at the
43、 point where measurements are carried out. 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.
44、 The settings of the working conditions (e.g. gas flows, RF or plasma power, sample uptake rate, integration time, number of replicates) shall be optimized according the manufacturers instructions. Radial viewing of the plasma may be used if it can be shown that the limit of quantification for mercu
45、ry is below the required legal limit value. 7.4 Atomic absorption spectrometer, equipped with a heated quartz cuvette or a mercury absorption cell, or optionally with an amalgamation system. 7.5 Vapour generation equipment. 7.5.1 Continuous flow or flow-injection cold-vapour system. 7.5.2 Element-sp
46、ecific lamp for mercury. 7.6 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 an
47、d documented regularly. 7.7 Ash-free filter paper, i.e. Whatman 589/21) or equivalent quality. 1) Whatman 589/2is an example of a suitable product available commercially. This Information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of
48、 this product. Equivalent products may be used if they can be shown to lead to the same results. DIN EN 16320:2017-05 EN 16320:2013+A1:2017 (E) 7 8 Procedure 8.1 General Calibrations by standard additions with several standards or by matrix matching are very powerful calibration techniques and can b
49、e 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
