Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA, o,o-EDDHMA and HBED by ion pair chromatography

This European Standard specifies a method for the chromatographic determination of the iron chelated by each individual ortho(hydroxy)-ortho(hydroxy) isomer of the chelating agents [o,o] EDDHA, [o,o] EDDHMA and by HBED in fertilizers containing one or more of these substances, except for [o,o] EDDHMA and HBED mixes. The method allows the identification and the determination of the total concentration of water soluble iron chelates of these chelating agents. It does not determine the free form of the chelating agents. This method is applicable to EC fertilizers covered by Regulation (EC) No 2003/2003 [4]. It is applicable to a mass fraction of the metal chelated of at least 0,625 %.

Düngemittel - Bestimmung von Chelatbildnern in Düngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o-EDDHA, o,o-EDDHMA und HBED mit lonen-Paarchromatographie

Dieses Dokument legt ein Verfahren zur chromatographischen Bestimmung des Ions, das mit jedem individuellen ortho(hydroxy)-ortho(hydroxy)-Isomer der Chelatbildner [o,o] EDDHA, [o,o] EDDHMA und mit HBED Chelate bildet, in Düngemitteln fest, die eine oder mehrere dieser Substanzen enthalten, mit Ausnahme von [o,o] EDDHMA- und HBED-Gemischen. Das Verfahren ermöglicht die Identifizierung und die Bestimmung der Gesamtkonzentration von wasserlöslichen Eisenchelaten dieser Chelatbildner. Es erlaubt nicht die Bestimmung der freien Form der Chelatbildner. Die vorliegende Verfahrensweise gilt für EG-Düngemittel, die in der Verordnung (EG) Nr. 2003/2003 [5] behandelt werden. Es gilt für einen Massenanteil an chelatisiertem Metall von mindestens 0,625 %. ANMERKUNG 1 Die Substanzen EDDHA (Ethylendiamin-N,N'-di(hydroxyphenyl)essigsäure) und EDDHMA (Ethylendiamin-N,N'-di(hydroxy-methylphenyl)essigsäure) existieren in mehreren unterschiedlichen isomeren Formen. Es sind sowohl Stellungsisomere (in Ortho-, Meta- und Parastellungen) als auch Stereoisomere (Meso- und dl-Racemformen) der Hydroxyl- oder Methylgruppen bekannt. Die Meso- und dl-Racemformen von ortho,ortho-EDDHA und ortho,ortho-EDDHMA sind Stellungsisomere der Hydroxylgruppen, die nach der Verordnung (EG) Nr. 2003/2003 zugelassen sind. Da Para-, Meta- und Orthomethyl-Stellungsisomere von EDDHMA eine ziemlich ähnliche Stabilität aufweisen, könnten sie in einer Gruppe zusammengefasst werden: in dem hier beschriebenen Verfahren werden die Para-, Meta- und Orthomethyl-Stellungsisomere von [o,o] EDDHMA zusammen betrachtet. HBED (N,N'-Bis(2-hydroxybenzyl)ethylendiamin-N,N'-diessigsäure) bildet keine isomeren Formen aus. ANMERKUNG 2 Gegenwärtig existieren analysenreine Standards nur für ortho,ortho-EDDHA, ortho,ortho-EDDHMA und HBED.

Engrais - Détermination des agents chélatants dans les engrais par chromatographie - Partie 2: Détermination du fer chélaté o,o-EDDHA, o,o-EDDHMA et HBED par chromatographie d’appariement d’ions

Le présent document spécifie une méthode de détermination par chromatographie du fer chélaté par chacun des isomères ortho(hydroxy)-ortho(hydroxy) des agents chélatants [o,o]-EDDHA et [o,o]-EDDHMA et par l'HBED dans les engrais contenant l'une ou plusieurs de ces substances, à l'exception des mélanges de [o,o]­EDDHMA et d'HBED. La méthode permet l'identification et la détermination de la concentration totale des chélates de fer solubles dans l’eau de ces agents chélatants. Elle ne permet pas de déterminer la forme libre de ces agents chélatants.
Le mode opératoire décrit concerne les engrais européens couverts par la Réglementation CE n°2003/2003 [5]. Il est applicable à une teneur en métal chélaté d'au moins 0,625 %.
NOTE 1   Les substances EDDHA (acide éthylènediamine-N,N'-di[(hydroxyphényl)acétique] et EDDHMA (acide éthylènediamine-N,N'-di(hydroxy-méthylphényl)acétique] existent sous plusieurs formes isomères différentes. Des isomères de position des groupes hydroxyl et méthyl (en position ortho, méta et para) sont connus , aussi bien que des stéréo-isomères (formes méso et dl-racémiques). Les deux formes méso et dl-racémiques de l'ortho-ortho-EDDHA et de l'ortho-ortho-EDDHMA sont des isomères de position des groupes hydroxyl autorisés par la réglementation (CE) n° 2003/2003. Dans la mesure où les isomères de position ortho, méta et para des groupes méthyl de l'EDDHMA présentent une stabilité tout à fait similaire, ils ont pu être regroupés. Dans la méthode décrite ici, les isomères de position ortho, méta et para des groupes méthyl de l'[o,o]-EDDHMA sont donc considérés conjointement. L'HBED (acide N,N´-bis(2-hydroxybenzyl)-éthylènediamine-N,N´-diacétique) ne présente pas de formes isomères.
NOTE 2   À l'heure actuelle, il n'existe de produit de référence pur pour analyse que pour l'ortho-ortho-EDDHA, l'ortho-ortho-EDDHMA et l'HBED.

Gnojila - Določevanje kelatov v gnojilih s kromatografijo - 2. del: Določevanje železovih kelatov z o,o-EDDHA, o,o-EDDHMA in HBED s kromatografijo ionskih parov

Ta evropski standard določa metodo za kromatografsko določevanje železovih kelatov z vsakim posameznim orto(hidroksi)-orto(hidroksi) izomerom kelatov [o,o] EDDHA, [o,o] EDDHMA in HBED v gnojilih, ki vsebujejo eno ali več teh snovi, razen mešanic [o,o] EDDHMA in HBED. Metoda omogoča opredelitev in določevanje skupne koncentracije v vodi topnih železovih kelatov teh kelatov. Z metodo ni mogoče določiti proste oblike kelatov. Ta metoda se uporablja za gnojila ES, navedena v Uredbi (ES) št. 2003/2003 [4]. Uporablja se za masni delež kovinskih kelatov najmanj 0,625 %.

General Information

Status
Withdrawn
Public Enquiry End Date
14-Jun-2011
Publication Date
21-Apr-2013
Withdrawal Date
07-Nov-2017
Technical Committee
Current Stage
9900 - Withdrawal (Adopted Project)
Start Date
17-Oct-2017
Due Date
09-Nov-2017
Completion Date
08-Nov-2017

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.SDURYDüngemittel - Bestimmung von Chelatbildnern in Düngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o-EDDHA, o,o-EDDHMA und HBED mit lonen-PaarchromatographieEngrais - Détermination des agents chélatants dans les engrais par chromatographie - Partie 2: Détermination du fer chélaté o,o-EDDHA, o,o-EDDHMA et HBED par chromatographie d’appariement d’ionsFertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA, o,o-EDDHMA and HBED by ion pair chromatography65.080GnojilaFertilizersICS:Ta slovenski standard je istoveten z:EN 13368-2:2012SIST EN 13368-2:2013en,fr,de01-maj-2013SIST EN 13368-2:2013SLOVENSKI
STANDARDSIST EN 13368-2:20071DGRPHãþD



SIST EN 13368-2:2013



EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 13368-2
August 2012 ICS 65.080 Supersedes EN 13368-2:2007English Version
Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 2: Determination of Fe chelated by o,o-EDDHA, o,o-EDDHMA and HBED by ion pair chromatography
Engrais - Détermination des agents chélatants dans les engrais par chromatographie - Partie 2 : Détermination du fer chélaté o,o-EDDHA, o,o-EDDHMA et HBED par chromatographie d'appariement d'ions
Düngemittel - Bestimmung von Chelatbildnern in Düngemitteln mit Chromatographie - Teil 2: Bestimmung von Fe chelatisiertem o,o-EDDHA, o,o-EDDHMA und HBED mit lonen-Paarchromatographie This European Standard was approved by CEN on 6 July 2012.
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 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 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, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,
B-1000 Brussels © 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13368-2:2012: ESIST EN 13368-2:2013



EN 13368-2:2012 (E) 2 Contents Page Foreword .31Scope .42Normative references .43Terms and definitions .44Principle .45Interferences .56Reagents .57Apparatus .68Sampling and sample preparation .79Procedure .79.1Preparation of the sample solution .79.2Preparation of the calibration solutions .79.3Chromatographic analysis .810Expression of the results (Fe in Fe-chelates) . 1310.1Fe chelated by [o,o] EDDHA or [o,o] EDDHMA . 1310.2Fe chelated by HBED . 1311Precision . 1311.1Inter-laboratory test . 1311.2Repeatability . 1411.3Reproducibility . 1412Test report . 14Annex A (informative)
Statistical results of the inter-laboratory tests . 16A.1Statistical results of the inter-laboratory test performed in 2003 . 16A.1.1Test samples . 16A.1.2Inter-laboratory test procedure . 16A.1.3Results and statistical interpretation. 16A.2Results of the inter-laboratory test performed in 2010 . 17A.2.1Test samples . 17A.2.2Inter-laboratory test procedure . 17A.2.3Results and statistical interpretation. 18Annex B (informative)
General procedure for the determination of the titrimetric purity of the chelating agents using a photometric automatic titrator . 19Annex C (informative)
Complete names of chelating agents . 20Bibliography . 21 SIST EN 13368-2:2013



EN 13368-2:2012 (E) 3 Foreword This document (EN 13368-2:2012) has been prepared by Technical Committee CEN/TC 260 “Fertilizers and lliming 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 February 2013, and conflicting national standards shall be withdrawn at the latest by February 2013. 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 supersedes EN 13368-2:2007. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. The following has been added to the former edition (EN 13368-2:2007) of this European Standard: a) new substance Fe-HBED added to the scope and to the title; b) requirements concerning the use of different columns in order to avoid overlapping of the meso isomer of Fe-[o,o] EDDHMA and Fe-HBED peaks added in Clause 5, Interferences; c) iron-nitrate solution and Fe-HBED solution added in Clause 6, Reagents; d) the sampling method is not part of the standard; informative reference to EN 1482-1 added; e) Table 1 enlarged by a column for total chelate; f) typical chromatogram of a commercial Fe-HBED sample added (Figure 4); g) Formula (2) on calculation of Fe-HBED added; h) Table 2 enlarged by the precision data concerning determination of Fe-HBED; i) A.2: Results of the inter-laboratory test performed in 2010 added; j) Annex C: Complete names of chelating agents technical revised; k) Bibliography revised. This European Standard "Fertilizers — Determination of chelating agents in fertilizers by ion chromatography" consists of the following parts: Part 1: Determination 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 According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following 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, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. SIST EN 13368-2:2013



EN 13368-2:2012 (E) 4 1 Scope This European Standard specifies a method for the chromatographic determination of the iron chelated by each individual ortho(hydroxy)-ortho(hydroxy) isomer of the chelating agents [o,o] EDDHA, [o,o] EDDHMA and by HBED in fertilizers containing one or more of these substances, except for [o,o] EDDHMA and HBED mixes. The method allows the identification and the determination of the total concentration of water soluble iron chelates of these chelating agents. It does not determine the free form of the chelating agents. This method is applicable to EC fertilizers covered by Regulation (EC) No 2003/2003 [4]. It is applicable to a mass fraction of the metal chelated of at least 0,625 %. NOTE 1 The substances EDDHA (ethylenediamine-N,N’-di[(hydroxyphenyl)acetic acid] and EDDHMA (ethylenediamine-N,N’-di[(hydroxymethylphenyl)acetic acid] exist as several different isomeric forms. Positional isomers for the hydroxyl or methyl groups (in ortho, meta, and para positions) as well as stereo isomers (meso and dl-racemic forms) are known. Both meso and dl-racemic forms of the ortho,ortho-EDDHA and ortho,ortho-EDDHMA are positional isomers for the hydroxyl groups allowed by the Regulation (EC) No 2003/2003. Since para, meta and ortho methyl positional isomers of the EDDHMA present quite similar stability, they could be grouped: in the method here described the para, meta and ortho methyl positional isomers of the [o,o] EDDHMA are considered together. HBED (N,N´-bis(2-hydroxybenzyl)-ethylenediamine-N,N´-diacetic acid) does not present isomeric forms. NOTE 2 At present, analytically pure standards only exist for ortho,ortho-EDDHA, ortho,ortho-EDDHMA and HBED. All other substances being unavailable as a standard, the influence of their eventual presence in the samples (with respect to the sensitivity and the selectivity of this method) has not been studied. NOTE 3 The meso and the dl-racemic forms of [o,o] EDDHA and [o,o] EDDHMA can be determined separately by this method. 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 (including any amendments) applies. 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 1482-2, Fertilizers and liming materials — Sampling and sample preparation — Part 2: Sample preparation 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 12944-2:1999 apply. 4 Principle The iron chelates are separated and determined by isocratic ion-pair high-performance liquid chromatography. When an iron chelate (anion) is added to a polar fluid (eluent), containing a large cation, an ion pair is formed. This ion pair is retained by an apolar solid phase (stationary phase). The strength of the retention depends on the molecular size and its acidity. Then, each iron chelate presents a characteristic retention time depending on the chelating agent, and it is separated from the other substances present in the sample. The separation is carried out on a reverse phase silica column and an aqueous solution of TBA+ (tetrabutylammonium) and acetonitrile as eluent. The detection is based on photometry at 280 nm. NOTE For additional information, see [5], [6] and [7]. SIST EN 13368-2:2013



EN 13368-2:2012 (E) 5 5 Interferences No interferences have been detected. Iron chelates with HBEP, EDDHSA, EDTA, DTPA, CDTA, HEEDTA, p,p-EDDHA, o,p-EDDHA, as well as the chelating agents do not interfere since they are separated from Fe-[o,o] EDDHA, Fe-[o,o] EDDHMA or Fe-HBED. Fe-[o,o] EDDHA does not interfere with Fe-[o,o] EDDHMA or Fe-HBED. In the case that Fe-[o,o] EDDHMA and Fe-HBED are present in the same sample, an overlapping of the meso isomer of the Fe-[o,o] EDDHMA and Fe-HBED peaks may occur with some equipment depending on the column used. The use of a different column of the same type can solve this problem. NOTE For the complete names of the abbreviations of chelating agents used in this document, see Annex C. 6 Reagents 6.1 General All reagents shall be of recognised analytical grade. All water used for the preparation of eluents, standards, and sample solutions shall conform to EN ISO 3696, grade 1 and shall be degassed, and free of organic contaminants. If products with a declared purity of less than 99 % are used for the preparation of standard solutions, a correction should be made in order to obtain exactly the required concentration in the solution. If there is any doubt of the purity of the standard, it is necessary to determine it. NOTE For this determination, a titrimetric method can be used. See Annex B for a general method using an automatic titrator. Manual titration could also be adequate. 6.2 Sodium hydroxide solution, c(NaOH) = 0,1 mol/l. Dissolve 4 g of NaOH in pellet form in a 1 l volumetric flask with water (6.1). Dilute to the mark and homogenise. NOTE The incorporation of CO2 from the atmosphere should be carefully avoided. Otherwise the dissolution of chelating agents (see 6.6, 6.7 and 6.8) can be incomplete. 6.3 Hydrochloric acid solution, c(HCl) = 1,0 mol/l. Dilute 88 ml of hydrochloric acid (mass fraction 35 % HCl) to 1 000 ml with water. 6.4 Hydrochloric acid solution, c(HCl) = 0,1 mol/l. Dilute 50 ml of hydrochloric acid 1,0 mol/l (6.3) to 500 ml with water. 6.5 Iron-nitrate solution, ρ(Fe) = 1 050 mg/l. Dissolve 0,759 4 g of ferric nitrate 9-hydrate (Fe(NO3)3·9H2O) in 100 ml of water. Check (for example by AAS) that the Fe concentration in this solution is 1 050 mg ± 30 mg/l. NOTE As the Fe(NO3)3·9H2O is deliquescent it will be added in solution of a known concentration. 6.6 Fe-[o,o] EDDHA solution, ρ(Fe) = 100 mg/l. Dissolve 0,322 1 g (see 6.1) of ethylenediamine-N,N-di[(ortho-hydroxyphenyl)acetic acid] in 350 ml of water and 27 ml of NaOH (6.2) in a 500 ml beaker. Add 50 ml of the Fe solution (6.5) to the chelating agent solution, stirring for about 5 min. SIST EN 13368-2:2013



EN 13368-2:2012 (E) 6 Adjust the solution to pH 7,0 with NaOH solution (6.2). Let the solution stand overnight in darkness to allow excess Fe to precipitate as oxide. Filter quantitatively through a cellulose filter and make up to volume (500 ml) in a volumetric flask with water. The standard obtained in this way can be stored in darkness for one year. 6.7 Fe-[o,o] EDDHMA solution, ρ(Fe) = 100 mg/l. Dissolve 0,347 1 g (see 6.1) of ethylenediamine-N,N’-di[(ortho-hydroxy-para-methylphenyl)acetic acid] [the paramethyl isomer of [o,o] EDDHMA, (see Note 1 in Clause 1)] in 350 ml of water and 27 ml of NaOH (6.2) in a 500 ml beaker. Add 50 ml of the Fe solution (6.5) to the chelating agent solution, stirring for about 5 min. Adjust the solution to pH 7,0 with NaOH solution (6.2). Let the solution stand overnight in darkness to allow excess Fe to precipitate as oxide. Filter quantitatively through a cellulose filter and make up to volume (500 ml) in a volumetric flask with water. The standard obtained in this way can be stored in darkness for one year. 6.8 Fe-HBED solution, ρ(Fe) = 100 mg/l. Dissolve 0,347 1 g (see 6.1) of N,N’-bis(2-hydroxybenzyl)-ethylenediamine-N,N’-diacetic acid (HBED) or 0,379 7 g if HBED·HCI is used in 350 ml of water and 27 ml of NaOH (6.2) in a 500 ml beaker. Add 50 ml of the Fe solution (6.5) to the chelating agent solution, stirring for about 5 min. Adjust the solution to pH 5,0 with HCI solution (6.4) or NaOH solution (6.2). Let the solution stand overnight in darkness to allow excess Fe to precipitate as oxide. Filter quantitatively through a cellulose filter and make up to volume (500 ml) in a volumetric flask w
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