1、April 2014 Translation by DIN-Sprachendienst.English price group 9No 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 6
2、5.080!%11U“2141450www.din.deDDIN EN 13368-1Fertilizers Determination of chelating agents in fertilizers by chromatography Part 1: Determination of EDTA, HEEDTA and DTPA by ionchromatography;English version EN 13368-1:2014,English translation of DIN EN 13368-1:2014-04Dngemittel Bestimmung von Chelatb
3、ildnern in Dngemitteln mit Chromatographie Teil 1: Bestimmung von EDTA, HEEDTA und DTPA mit Ionenchromatographie;Englische Fassung EN 13368-1:2014,Englische bersetzung von DIN EN 13368-1:2014-04Engrais Dtermination des agents chlatants dans les engrais par chromatographie Partie 1: Dtermination du E
4、DTA, HEEDTA et DTPA par chromatographie ionique;Version anglaise EN 13368-1:2014,Traduction anglaise de DIN EN 13368-1:2014-04SupersedesDIN EN 13368-1:2001-04www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 14 pages 03.14 DIN EN 13368-1:
5、2014-04 2 A comma is used as the decimal marker. National foreword This document (EN 13368-1:2014) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming materials” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the Normenausschuss Leben
6、smittel und landwirtschaftliche Produkte (Food and Agricultural Products Standards Committee), Working Committee NA 057-03-02 AA Dngemittel. DIN EN 13368 consists of the following parts, under the general title Fertilizers Determination of chelating agents in fertilizers by chromatography: Part 1: D
7、etermination of EDTA, HEEDTA and DTPA by ion chromatography Part 2: Determination of Fe chelated by o,o-EDDHA, o,o-EDDHMA and HBED by ion pair chromatography Amendments This standard differs from DIN EN 13368-1:2001-04 as follows: a) the title of the standard has been revised; b) referenced European
8、 Standards on vocabulary have been added to Clause 2 “Normative references”; c) Clause 3 “Terms and definitions” has been added; d) the sampling method is not part of the standard, an informative reference to EN 1482-1 has been added; e) Annex A “Complete names of chelating agents” has been technica
9、lly revised; f) the Bibliography has been revised. g) the standard has been editorially revised. Previous editions DIN EN 13368-1: 2001-04 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13368-1 January 2014 ICS 65.080 Supersedes EN 13368-1:2001English Version Fertilizers - Determination of che
10、lating agents in fertilizers by chromatography - Part 1: Determination of EDTA, HEEDTA and DTPA by ion chromatography Engrais - Dtermination des agents chlatants dans les engrais par chromatographie - Partie 1: Dtermination du EDTA, HEEDTA et DTPA par chromatographie ionique Dngemittel - Bestimmung
11、von Chelatbildnern in Dngemitteln mit Chromatographie - Teil 1: Bestimmung von EDTA, HEEDTA und DTPA mit IonenchromatographieThis European Standard was approved by CEN on 16 November 2013. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for gi
12、ving 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 application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three of
13、ficial 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 Management Centre has the same status as the official versions. CEN members are the national standards bodies
14、of 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, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain
15、, Sweden, Switzerland, Turkey 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 2014 CEN All rights of exploitation in any form and by any means reserved worldwide
16、for CEN national Members. Ref. No. EN 13368-1:2014 EEN 13368-1:2014 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Terms and definitions .4 4 Principle 4 5 Interferences 4 6 Reagents .5 7 Apparatus .6 8 Sampling and sample preparation .7 9 Procedure .7 9.1 Preparation of the tes
17、t solution 7 9.2 Preparation of the standard solutions .7 9.3 Chromatographic analysis 7 10 Expression of results 8 11 Precision .8 12 Test report 9 Annex A (informative) Complete names of chelating agents . 10 Annex B (informative) Chromatogram 11 Bibliography . 12 DIN EN 13368-1:2014-04EN 13368-1:
18、2014(E)3 Foreword This document (EN 13368-1:2014) 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 publication of an identical text or by
19、 endorsement, at the latest by July 2014, and conflicting national standards shall be withdrawn at the latest by July 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 ident
20、ifying any or all such patent rights. This document supersedes EN 13368-1:2001. The following modifications have been made: a) the title of the European Standard revised; b) referenced European Standards on vocabulary added to Clause 2; c) Clause 3 Terms and definitions added; d) the sampling method
21、 is not part of the standard, informative reference to EN 1482-1 added; e) Annex A: complete names of chelating agents technical revised; f) Bibliography revised; g) editorially revised. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countrie
22、s 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, Norway, Poland
23、, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 13368-1:2014-04EN 13368-1:2014(E)4 1 Scope This European Standard specifies a method for the chromatographic determination of the total amount of each of the individual chelating agents EDTA, H
24、EEDTA, and DTPA in fertilizers containing one or more of these substances. The method allows the identification and the determination of the total water soluble fraction of each of these chelating agents. It does not allow to distinguish between the free form and the metal bound form of the chelatin
25、g agents. NOTE EDTA, HEEDTA and DTPA are abbreviations used in this European Standard for the sake of simplicity. For complete names see Annex A. This method applies to fertilizers containing chelates of one or more of the following micro-nutrients: cobalt, copper, iron, manganese, zinc and with a m
26、ass fraction of at least 0,1 %. 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 referenc
27、ed document (including 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
28、 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 definitions For the purposes of this document, the terms and definitions given in EN 12944-1:1999 and EN 12944-2
29、:1999 apply. 4 Principle The micro-nutrients associated with the chelating agents present in an aqueous extract of the sample are replaced by iron(III). The iron chelates are separated and determined by ion chromatography. The separation is based on anion exchange, by elution with a nitrate acetate
30、solution. The detection is based on UV photometry at 330 nm, after post-column reaction with diluted perchloric acid. 5 Interferences Several substances can interfere, to a degree largely dependent on the type of column used. With the column described in 7.2, the following phenomena have been observ
31、ed. a) Injection of solutions having high concentrations of salts can cause shifts in the retention times, mostly decreasing the retention when compared to the standard solutions. In these cases, the identity of the peaks can be confirmed by standard addition. DIN EN 13368-1:2014-04EN 13368-1:2014(E
32、)5 b) Solutions having high concentrations of salts can also create a large signal at the void volume, poorly resolved from the HEEDTA peak. c) High concentrations of nitrate, carbonate, sulfate, and phosphate do not interfere. On the other hand, large amounts of chloride create a negative fronting
33、peak poorly resolved from the DTPA peak, and altering its peak shape. d) Compounds, related to the group of polyamino polycarboxylic acids can interfere. While signals for o,o EDDHA, o,o EDDHMA, and EDDHSA are not detected, relatively weak signals are observed for NTA and CDTA. Under some conditions
34、 NTA may coelute with HEEDTA or EDTA. NOTE EDDHA, EDDHMA, EDDHSA, NTA and CDTA are abbreviations used in this European Standard for the sake of simplicity. For complete names see Annex A. e) No signals have been detected for the following complexing agents: citrate, oxalate, tartrate, phthalate, and
35、 20 naturally occurring amino acids. 6 Reagents 6.1 Reagents of recognized analytical grade and water conforming to EN ISO 3696, degassed by boiling before use. 6.2 Nitric acid, c(HNO3) = 7,2 mol/l. Nitric acid, diluted 1 + 1 with water. 6.3 Sodium hydroxide solution, c(NaOH) = 0,5 mol/l. Dissolve 2
36、0 g of NaOH in pellet form in a 1 l volumetric flask with water. Dilute to the mark and homogenize. 6.4 EDTA stock solution, c(EDTA) = 2 mmol/l. Dissolve 372 mg of the disodium dihydrogen salt of ethylene diamine tetraacetic acid dihydrate in 400 ml of water in a 500 ml volumetric flask. After disso
37、lution, dilute to the mark with water and homogenize. Store the solution in a plastic bottle. 6.5 HEEDTA stock solution, c(HEEDTA) = 2 mmol/l. Dissolve 380 mg of the trisodium salt of hydroxyethyl ethylene diamine triacetic acid dihydrate in 400 ml of water in a 500 ml volumetric flask. After dissol
38、ution, dilute to the mark with water and homogenize. Store the solution in a plastic bottle. 6.6 DTPA stock solution, c(DTPA) = 2 mmol/l. Dissolve 393 mg of diethylene triamine pentaacetic acid in 10 ml of NaOH (6.3) in a 50 ml beaker. After dissolution, transfer quantitatively into a 500 ml volumet
39、ric flask, dilute to the mark with water and homogenize. Store the solution in a plastic bottle. 6.7 EDTA/HEEDTA/DTPA standard mixtures. Into a set of three volumetric flasks of 100 ml, pipette respectively 2,5 ml, 5 ml and 10 ml of each stock solution of 2 mmol/l (6.4, 6.5 and 6.6). Dilute to the m
40、ark with water and homogenize. These solutions contain a mixture of EDTA, HEEDTA and DTPA, in concentrations of respectively 0,05 mmol/l, 0,1 mmol/l and 0,2 mmol/l. They should be used within two days. DIN EN 13368-1:2014-04EN 13368-1:2014 (E) 6 6.8 Eluent nitrate (50 mmol/l) and acetate (50 mmol/l)
41、. Dissolve 4,10 g of anhydrous sodium acetate (NaCH3COO) in a mixture of 800 ml of water and 6,95 ml of nitric acid (6.2) in a 1 l volumetric flask. Dilute to the mark with water and homogenize. Adjust the pH of the eluent to 2,75 0,20. Before use, filter the solution through a 0,45 m membrane filte
42、r (7.3). NOTE The concentration of the eluent influences the speed and the efficiency of the separation, which can be carried out with eluent concentrations varying between 25 mmol/l and 75 mmol/l of nitrate and acetate. At low concentrations, an improved separation between the void signal, the HEED
43、TA and the EDTA peaks can be obtained, while at high concentrations a better DTPA peak shape is observed. 6.9 Iron(III) nitrate solution. Dissolve 5 g of ferric nitrate nonahydrate (Fe(NO3)3.9H2O) in a mixture of 800 ml of water and 21 ml of nitric acid (6.2) in a 1 l volumetric flask. Dilute to the
44、 mark with water and homogenize. Store the solution in a plastic bottle. NOTE Nitric acid is added in order to stabilize the solution and to allow the complete replacement of other chelated micro-nutrients by iron(III). 6.10 Perchloric acid solution, 2 %. Dilute 29 ml of perchloric acid (70 % HClO4,
45、 = 1,67 g/ml) to 1 l with water. 7 Apparatus Usual laboratory equipment, glassware, and the following: 7.1 Rotary shaker, capable of operating at a rotational speed of about 35 min1to 45 min1. 7.2 Chromatograph, equipped with: a) an isocratic pump delivering the eluent (6.8) at a flow rate of 0,5 ml
46、/min; b) an injection valve with an injection loop of about 50 l; c) an anion exchange separator column 10 m particles 2 % substrate x linking 100 mmolccapacity (per column) alkyl quaternary ammonium medium high (hydrophobic)1); NOTE 1 The column mentioned in c) is not exclusive. Any anion exchange
47、column with comparable capacity, hydrophobicity, and selectivity can probably be used. NOTE 2 Columns can, in their native state, exhibit some sensitivity towards various anions (e.g. nitrate, sulfate, phosphate) which can disappear after treatment with excess iron. It can be necessary to preconditi
48、on the column prior to its use by repeated injections, at least 10, of the iron(III) solution (6.9), followed by equilibration under eluent flow for at least 6 h. After many injections, especially of products having complex matrices, the column may lose some of the capacity and the separating efficiency. Substances like phenolic compounds (e.g. o,o EDDHA, humic acids) can be strongly adsorbed on the column particles. Suspended and colloidal matter can block the column entrance and disturb the eluent flow. The column
