EN 13368-3-2017 en Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 3 Determination of [S S]-EDDS by ion pair chromatography.pdf

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1、BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06Fertilizers - Determination of chelating agents in fertilizers by chromatographyPart 3: Determination of S,S-EDDS by ion pair chromatographyBS EN 13368-3:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13368-3

2、December 2017 ICS 65.080 English Version Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 3: Determination of S,S-EDDS by ion pair chromatography Engrais - Dtermination des agents chlatants dans les engrais par chromatographie - Partie 3: Dtermination du S,S-ED

3、DS par chromatographie dappariement dions Dngemittel - Bestimmung von Chelatbildnern in Dngemitteln mit Chromatographie - Teil 3: Bestimmung von S,S-EDDS mit Ionen-Paarchromatographie This European Standard was approved by CEN on 25 September 2017. CEN members are bound to comply with the CEN/CENELE

4、C 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

5、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 offic

6、ial 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,

7、Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, 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 2017 CEN All rig

8、hts of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13368-3:2017 ENational forewordThis British Standard is the UK implementation of EN 133683:2017.The UK participation in its preparation was entrusted to Technical Committee CII/37, Fertilisers a

9、nd related chemicals.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2018 Pu

10、blished by BSI Standards Limited 2018ISBN 978 0 580 94825 1ICS 65.080Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2018.Amendments/corrigenda issued

11、 since publicationDate Text affectedBRITISH STANDARDBS EN 133683:2017EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13368-3 December 2017 ICS 65.080 English Version Fertilizers - Determination of chelating agents in fertilizers by chromatography - Part 3: Determination of S,S-EDDS by ion pair

12、chromatography Engrais - Dtermination des agents chlatants dans les engrais par chromatographie - Partie 3: Dtermination du S,S-EDDS par chromatographie dappariement dions Dngemittel - Bestimmung von Chelatbildnern in Dngemitteln mit Chromatographie - Teil 3: Bestimmung von S,S-EDDS mit Ionen-Paarch

13、romatographie This European Standard was approved by CEN on 25 September 2017. 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 bib

14、liographical 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 respo

15、nsibility 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 Rep

16、ublic 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 Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN

17、 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 13368-3:2017 EBS EN 133683:2017EN 13368-3:2017 (E) 2 Contents Pa

18、ge European foreword . 3 1 Scope 4 2 Normative references 4 3 Terms and definitions . 4 4 Principle . 4 5 Interferences 5 6 Reagents . 5 7 Apparatus . 6 8 Sampling and sample preparation 7 9 Procedure. 7 9.1 Preparation of the sample solution 7 9.2 Preparation of the calibration solutions 7 9.3 Chro

19、matographic analysis . 8 10 Expression of the results . 11 10.1 Mass fraction of the chelating agent S,S-EDDS 11 10.2 Fe chelated by S,S-EDDS (only for Fe-S,S-EDDS straight fertilizers) 12 11 Precision 12 11.1 Inter-laboratory test . 12 11.2 Repeatability 12 11.3 Reproducibility . 12 12 Test report

20、13 Annex A (informative) Statistical results of the inter-laboratory tests performed in 2016 14 A.1 Test samples 14 A.2 Inter-laboratory test procedure . 14 A.3 Results and statistical interpretation . 14 Annex B (informative) General procedure for the determination of the titrimetric purity of the

21、chelating agent using a photometric automatic titrator 16 Annex C (informative) Polarimetric evaluation of isomeric purity of the EDDS commercial fertilizers . 17 Annex D (informative) Complete names of chelating agents 19 Bibliography . 20 BS EN 133683:2017EN 13368-3:2017 (E) 3 European foreword Th

22、is document (EN 13368-3:2017) 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 publication of an identical text or by endorsement, at the

23、 latest by June 2018, and conflicting national standards shall be withdrawn at the latest by June 2018. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent right

24、s. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. The European Standard EN 13368 Fertilizers Determination of chelating agents in fertilizers by chromatography consists of the following parts: Part 1: Determination of

25、EDTA, HEEDTA and DTPA by ion chromatography Part 2: Determination of Fe chelated by o,o EDDHA, o,o EDDHMA and HBED, or the amount of chelating agents, by ion pair chromatography Part 3: Determination of S,S-EDDS by ion pair chromatography According to the CEN-CENELEC Internal Regulations, the nation

26、al 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, Lithu

27、ania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 133683:2017EN 13368-3:2017 (E) 4 1 Scope This European Standard specifies a method for the chromatographic determination of the chelat

28、ing agent S,S-EDDS in fertilizers. The method allows the identification and the determination of the total concentration of the water-soluble fraction of this chelating agent. It does not allow distinguishing between the free form and the metal bound form of the chelating agent. This method is appli

29、cable to EC fertilizers containing chelates of one or more of the following micro-nutrients: cobalt, copper, iron, manganese and zinc, covered by Regulation (EC) No 2003/2003 4. It is applicable to a mass fraction of the metal chelated of at least 0,35 %. NOTE The substance EDDS (ethylenediamine-N,N

30、-disuccinic acid) exists as several different stereo isomeric forms. S,S (with CAS Number 20846917), R,R and R,S optical isomers are possible. S,S and R,R are mirror images with equal chemical characteristics. However only the S,S isomer is biodegradable. When both are present, they form the racemic

31、 mixture. The R,S isomer (the meso isomer) is only slowly biodegradable. Only the S,S-EDDS isomer is allowed by the Regulation (EC) No 2003/2003. Since the Cu chelate of the R,R-EDDS isomer presents the same stability as the S,S-EDDS, both should coelute. The absence of R,S-EDDS indicates that only

32、a pure isomer (S,S or R,R) exists. An additional test based on polarimetry can be used to ascertain the isomeric characteristic of the sample, or the standard. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for i

33、ts 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 preparation EN 12944-1:1999,

34、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 - Specification and test methods (ISO 36

35、96) 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 micronutrients associated with the S,S-EDDS present in an aqueous extract of the sample are replaced by Cu(II). The Cu(II) chelates are separat

36、ed and determined by isocratic ion-pair high-performance liquid chromatography. When a copper 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 dep

37、ends on the molecular size and its acidity. Then, each copper 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

38、 of TBA+(tetrabutylammonium) and copper acetate and methanol as eluent. The detection is based on photometry at 254 nm. A derivatization method should be used to form the Cu chelates, so the chelating agent is determined by BS EN 133683:2017EN 13368-3:2017 (E) 5 the isocratic ion-pair high-performan

39、ce liquid chromatography here specified. 5 Interferences No interferences have been detected. Metal chelates with o,o EDDHA, o,o EDDHMA, HBED, EDDHSA, EDTA, DTPA, HEEDTA, IDHA, o,p EDDHA, lignosulfonates and heptagluconate as well as the chelating agents do not interfere since after the Cu derivatiz

40、ation they are separated from Cu-S,S-EDDS. Since retention times depend on the column type, any interference should be checked if a mixture with other chelating or complexing agents is suspected. For the complete names of the abbreviations of chelating agents used in this document, see Annex D. 6 Re

41、agents 6.1 General. All reagents shall be of recognized 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 %

42、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 on the purity of the standard substances, it is necessary to determine it. For the determination of its concentration, a titrim

43、etric method can be used. See Annex B for a photometric method using an automatic titrator. Manual titration can also be adequate. The isomeric purity can be checked using the method indicated in Annex C. 6.2 Sodium hydroxide solution, c(NaOH) = 0,15 mol/l. Dissolve 3,0 g of NaOH in pellet form in a

44、 500 ml volumetric flask with water (6.1). Dilute to the mark and homogenize. The incorporation of CO2from the atmosphere should be carefully avoided. Otherwise, the dissolution of the chelating agent (see 6.6) can be incomplete. 6.3 Phosphoric acid solution, c(H3PO4) = 1,0 mol/l. Dilute 68 ml of ph

45、osphoric acid (mass fraction 85 % H3PO4) to 1 000 ml with water. 6.4 Phosphoric acid solution, c(H3PO4) = 0,1 mol/l. Dilute 50 ml of phosphoric acid 1,0 mol/l (6.3) to 500 ml with water. 6.5 Cu acetate solution (for derivatization), c(Cu) approximately 0,02 mol/l. Dissolve 4,00 g of copper acetate m

46、onohydrate (Cu(CH3-COO)2H2O) in 1 l of water. 6.6 S,S-EDDS solution, c(EDDS) = 8,95 mmol/l. If the EDDS acid form is used (CAS# 20846-91-7), dissolve 26,16/P g (where P is the purity of the solid standard in percentage of EDDS acid form), in 50 ml of water and 20 ml of NaOH (6.2) in a 100 ml beaker

47、and make up to 100 ml in a volumetric flask with water. The standard obtained in this way may be stored in darkness in a fridge (at about 5 C) for 6 months. If a significant yellowing appears (due to photodecomposition) a fresh standard should be prepared. BS EN 133683:2017EN 13368-3:2017 (E) 6 If E

48、DDS trisodium salt solution is used instead of the acid form then dissolve 32,07/P g (where P is the purity of the standard in percentage of EDDS trisodium salt) in 50 ml of water in a 100 ml beaker and make up to 100 ml in a volumetric flask with water. NOTE This concentration is equivalent to (Fe)

49、 = 500 mg/l. Since most commercial samples are Fe chelates, equivalent Fe concentration is given to simplify final calculations. 6.7 Eluent for the determination. Dissolve 1,00 g of copper acetate monohydrate (Cu(CH3-COO)2H2O) (5,00 mmol) in 900 ml of water. Add 2 ml of TBAOH (mass fraction 40 % Tetrabutylammonium hydroxide solution in water). Adjust to pH 2,8 with phosphoric acid solution (6.3 and 6.4). Add 40 ml of methanol (HPLC grade) and make up to volume in a 1 l vol