Fertilizers - Determination of urea condensates using high-performance liquid chromatography (HPLC) - Isobutylidenediurea and crotonylidenediurea (method A) and methylen-urea oligomers (method B)

Fertilizers containing the condensates of urea and specified aldehydes (with crotonaldehyde called crotonyliden diurea or CDU, with isobutyraldehyde called isobutylidene diurea or IBDU, with formaldehyde called urea formaldehyde or methylene urea or MU) are covered by Annex I of the Regulation (EC) 2003/2003 [1] as nitrogenous fertilizers. The methods described in this European Standard enable the quantitative determination of these condensates and the determination of the solubility of the MU-oligomers according to the Regulation.

Düngemittel - Bestimmung von Harnstoffkondensaten mit Hochleistungs-Flüssigchromatographie (HPLC) - Isobutylidendiharnstoff und Crotonylidendiharnstoff (Verfahren A) und Methylenharnstoff-Oligomere (Verfahren B)

Diese Europäische Norm legt Verfahren für die Bestimmung von Isobutylidendiharnstoff (IBDU), Crotony-lidendiharnstoff (CDU) (Verfahren A) und Methylenharnstoff-Oligomere (MU) (Verfahren B) in Düngemitteln mit Hochleistungs-Flüssigchromatographie (HPLC) fest.
Das Verfahren gilt für alle Düngemittel, die keine störenden organischen Verbindungen enthalten.

Engrais - Dosage des condensats d'urée par chromatographie liquide haute performance (HPLC) - Isobutylidène diurée et crotonylidène diurée (méthode A) et oligomères de méthylène-urée (méthode B)

La présente Norme européenne spécifie les méthodes de dosage de l’isobutylidène diurée (IBDU), de la
crotonylidène diurée (CDU) (méthode A) et des oligomères de méthylène-urée (MU) (méthode B) dans les
engrais par chromatographie liquide haute performance (HPLC).
La méthode est applicable à tous les engrais qui ne contiennent pas de composés organiques interférents.

Gnojila - Določevanje kondenzatov sečnine s tekočinsko kromatografijo visoke ločljivosti (HPLC) - Izobutilidendiurea in krotonilidendiurea (metoda A) in oligomeri metilenuree (metoda B)

Ta evropski standard določa metode za določevanje izobutilidendiura(IBDU), krotonilidendiurea(CDU) (metoda A) ter oligomeri metilenuree (MU) (metoda B) v gnojilih s tekočinsko kromatografijo visoke ločljivosti (HPLC). Metoda se uporablja za vsa gnojila, ki ne vsebujejo motečih organskih spojin.

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Düngemittel - Bestimmung von Harnstoffkondensaten mit Hochleistungs-Flüssigchromatographie (HPLC) - Isobutylidendiharnstoff und Crotonylidendiharnstoff (Verfahren A) und Methylenharnstoff-Oligomere (Verfahren B)Engrais - Dosage des condensats d'urée par chromatographie liquide haute performance (HPLC) - Isobutylidène diurée et crotonylidène diurée (méthode A) et oligomères de méthylene-urée (méthode B)Fertilizers - Determination of urea condensates using high-performance liquid chromatography (HPLC) - Isobutylidenediurea and crotonylidenediurea (method A) and methylene-urea oligomers (method B)65.080GnojilaFertilizersICS:Ta slovenski standard je istoveten z:EN 15705:2010SIST EN 15705:2010en,fr,de01-oktober-2010SIST EN 15705:2010SLOVENSKI

STANDARDSIST-TS CEN/TS 15705:20091DGRPHãþD
SIST EN 15705:2010
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 15705
March 2010 ICS 65.080 Supersedes CEN/TS 15705:2009English Version

Fertilizers - Determination of urea condensates using high-performance liquid chromatography (HPLC) - Isobutylidenediurea and crotonylidenediurea (method A) and methylen-urea oligomers (method B)

Engrais - Dosage des condensats d'urée par chromatographie liquide haute performance (HPLC) - Isobutylidène diurée et crotonylidène diurée (méthode A) et oligomères de méthylène-urée (méthode B)

Düngemittel - Bestimmung von Harnstoffkondensaten mit Hochleistungs-Flüssigchromatographie (HPLC) - Isobutylidendiharnstoff und Crotonylidendiharnstoff (Verfahren A) und Methylenharnstoff-Oligomere (Verfahren B) This European Standard was approved by CEN on 21 February 2010.

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 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 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, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,

B-1000 Brussels © 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15705:2010: ESIST EN 15705:2010

EN 15705:2010 (E) 2 Contents Page Foreword ..............................................................................................................................................................3Introduction .........................................................................................................................................................41Scope ......................................................................................................................................................52Normative references ............................................................................................................................53Terms and definitions ...........................................................................................................................54Sampling and sample preparation .......................................................................................................55Method A: Determination of CDU and IBDU .......................................................................................56Method B: Determination of methylen-urea oligomers (MU) ............................................................87Precision method A and method B ................................................................................................... 138Test report ........................................................................................................................................... 14Annex A (informative)

Results of the inter-laboratory tests ........................................................................ 15Annex B (informative)

Chromatogram and calibration curves method A .................................................. 17Annex C (informative)

Chromatogram and calibration curves method B .................................................. 19Bibliography ..................................................................................................................................................... 22 SIST EN 15705:2010

EN 15705:2010 (E) 3 Foreword This document (EN 15705:2010) 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 latest by September 2010, and conflicting national standards shall be withdrawn at the latest by September 2010. This document supersedes CEN/TS 15705:2009. 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 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 of the European Standard: a) introduction; b) information concerning the preparation of the standard substances MDU and DMTU. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. SIST EN 15705:2010

EN 15705:2010 (E) 4 Introduction Fertilizers containing the condensates of urea and specified aldehydes (with crotonaldehyde called crotonyliden diurea or CDU, with isobutyraldehyde called isobutylidene diurea or IBDU, with formaldehyde called urea formaldehyde or methylene urea or MU) are covered by Annex I of the Regulation (EC) 2003/2003 [1] as nitrogenous fertilizers. The methods described in this European Standard enable the quantitative determination of these condensates and the determination of the solubility of the MU-oligomers according to the Regulation. SIST EN 15705:2010

EN 15705:2010 (E) 5

1 Scope This European Standard specifies methods for the determination of isobutylidenediurea (IBDU), crotonylidenediurea (CDU) (method A) and methylene-urea oligomers (MU) (method B) in fertilizers using high-performance liquid chromatography (HPLC). The method is applicable to all fertilizers which do not contain interfering organic compounds. 2 Normative references The following referenced documents are indispensable for the application of this document. 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, 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 3696:1995, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987) 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 Sampling and sample preparation Sampling is not part of the method specified in this European Standard. A recommended sampling method is given in EN 1482-1. Sample preparation shall be carried out in accordance with EN 1482-2. 5 Method A: Determination of CDU and IBDU 5.1 Principle The sample is extracted with water and, after appropriate dilution, analyzed using a suitable HPLC system. 5.2 Reagents 5.2.1 Reagents of recognized analytical grade and distilled or demineralized water (grade 3 according to EN ISO 3696:1995). 5.2.2 Acetonitrile, p.a., HPLC-grade. SIST EN 15705:2010

EN 15705:2010 (E) 6 5.2.3 Isobutylidenediurea and crotonylidenediurea, in their pure form. 5.3 Apparatus 5.3.1 Laboratory equipment and glassware, for preparation of solutions and dilutions. 5.3.2 Analytical balance, capable of weighing to an accuracy of ± 0,1 mg. 5.3.3 HPLC-system, with UV-detector. 5.3.4 Ultrasonic bath 5.3.5 Magnetic stirrer 5.3.6 Disposable filter, 0,45 µm. 5.4 Procedure 5.4.1 System parameters of HPLC Analytical/separating column: silica column with C18 reverse phase 1) Detection wavelength: 200 nm Eluent: acetonitrile/water: 10/90 (volume fraction) Flow rate: 1 ml/min Temperature: ambient temperature Injection volume: 20 µl 5.4.2 Calibration 5.4.2.1 Stock solution IBDU (IBDU) = 100 mg/l Weigh 100/R mg of IBDU (5.2.3), where R is the purity of IBDU, into a 1 000 ml flask and add about 900 ml of water (5.2.1). Dissolve in an ultrasonic bath (5.3.4) for about 10 min, followed by stirring on a magnetic stirrer (5.3.5) for about 1 h. Make up to volume. Filtration is not necessary. 5.4.2.2 Stock solution CDU (CDU) = 100 mg/l Weigh 100/R mg of CDU (5.2.3) , where R is the purity of CDU, into a 1 000 ml flask and add about 900 ml of water (5.2.1). Dissolve in an ultrasonic bath (5.3.4) for about 10 min, followed by stirring on a magnetic stirrer (5.3.5) for about 1 h. Make up to volume. Filtration is not necessary. 5.4.2.3 Calibration solution For calibration, prepare three solutions according to Table 1 using one-mark (bulb) pipettes and dilute to the mark with water (5.2.1).

1) LiChrosorb RP-18 7 µm 250/4 mm is 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 or CENELEC of this product. SIST EN 15705:2010

EN 15705:2010 (E) 7 For the determination of the retention time, dilute 10 ml of the stock solution 5.4.2.1 or respectively 5.4.2.2 into two 100 ml flasks and make up to volume with water (5.2.1). The evaluation of calibration is carried out manually or by means of a suitable PC-aided (computerized) calculation method. Table 1 — Preparation of calibration solutions Parameter Amount of stock solution IBDU/CDU ml (to be added to the 100 ml flask) Content of IBDU mg/l Content of CDU mg/l Standard 1 10 10,0 10,0 Standard 2 25 25,0 25,0 Standard 3 50 50,0 50,0

5.4.3 Preparation of the test portion Weigh 1 g of the sample grounded to < 0,2 mm to the nearest 0,1 mg and flush into a 1 000 ml volumetric flask with water (5.2.1). Fill the flask to an amount of approximately 900 ml and treat it for 10 min in the ultrasonic bath (5.3.4). Then make up to the mark and stir for 1 h at room temperature on a magnetic stirrer (5.3.5). Dilute 10 ml of the solution in a 100 ml volumetric flask and filter into the HPLC injection vial through a disposable filter (5.3.6). 5.4.4 Measurement Measurement is performed manually or by means of an automatic sample loading system (autosampler). 5.4.5 Important annotations IBDU is able to form urea in aqueous solution. Therefore, the measurement of the calibration and sample solutions shall be completed within one working day. The concentrations of CDU and IBDU in the sample solutions shall be kept within the calibration limits (5.4.2) to ensure sufficient reproducibility. 5.5 Calculation The calculation can be performed manually or by means of a PC using the calibration parameters in respect to the amount used. In the case of PC-aided (computerized) calculation and application of Table 1 regarding the amounts of stock solution, the content of IBDU/CDU in milligrams per litre will be calculated by the system. The calculated values are equal to the percentage mass concentration of IBDU/CDU in the analysed sample of fertilizer. Following general rules for declaration in regulations to declare the content of the compounds as percentage mass fraction of nitrogen, calculate the contents, wN(IBDU)/wN(CDU) in percent (g/100 g), according to the following equations: 322,0IBDU(IBDU)N×=ww (1) SIST EN 15705:2010

EN 15705:2010 (E) 8 0,326CDUN(CDU)×=ww (2) where 0,322 is the conversion factor for the content of IBDU in the fertilizer into nitrogen content; 0,326 is the conversion factor for the content of CDU in the fertilizer into nitrogen content. 6 Method B: Determination of methylen-urea oligomers (MU) NOTE By the condensation of urea and formaldehyde several oligomers like methylen–diurea (MDU), dimethylen-triurea (DMTU), trimethylen-tetraurea (TMTU) and higher oligomers are formed. These three molecules are the most soluble in water, the higher compounds are insoluble in hot water, but their nitrogen is available for plants by microbiological decomposition. Also urea is always a companion of MU – oligomers. 6.1 Principle The sample is extracted with boiling water and analyzed using a suitable HPLC system. The methylen-urea soluble oligomers are measured and detected by the HPLC-method. In the HPLC-diagram methylen-urea oligomers are represented by different peaks: urea, methylen-diurea, dimethylen-triurea; trimethylen-tetraurea are, in the mean time, the most soluble and important. 6.2 Reagents 6.2.1 Reagents of recognized analytical grade and distilled or demineralized water (grade 3 according to EN ISO 3696:1995). 6.2.2 Acetonitrile, p.a., HPLC-grade. 6.2.3 Urea, p.a., 46,6 % of total nitrogen. 6.2.4 Methylen-diurea (MDU), synthesized and purified by a special laboratory, 42,4 % of total nitrogen. 2) 6.2.5 Dimethylen-triurea (DMTU), synthesized and purified by a special laboratory, 41,2 % of total nitrogen. 2) 6.2.6 Trimethylen-tetraurea (TMTU), synthesized and purified by a special laboratory, 40,6 % of total nitrogen. 6.3 Apparatus 6.3.1 Laboratory equipment and glassware, for preparation of solutions and dilutions. 6.3.2 Analytical balance, capable of weighing to an accuracy of ± 0,1 mg. 6.3.3 Technical balance, capable of weighing to an accuracy of ± 0,01 g. 6.3.4 HPLC-system, equipped with an UV-detector.

2) The standard substances MDU and DMTU can be prepared according to the method given in Official Methods of Analysis of AOAC International, AOAC Official Method 983.01, JAOAC 66, 769 (1983). SIST EN 15705:2010

EN 15705:2010 (E) 9
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