DIN EN 16024-2011 Fertilizers - Determination of 1H-1 2 4-triazole in urea and in fertilizers containing urea - Method using high-performance liquid chromatography (HPLC) German ve.pdf

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1、June 2011 Translation by DIN-Sprachendienst.English price group 8No 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

2、.080!$s7A“1802030www.din.deDDIN EN 16024Fertilizers Determination of 1H-1,2,4-triazole in urea and in fertilizers containingurea Method using high-performance liquid chromatography (HPLC)English translation of DIN EN 16024:2011-06Dngemittel Bestimmung von 1H-1,2,4-Triazol in Harnstoff und harnstoffh

3、altigen Dngemitteln Verfahren mit Hochleistungs-Flssigchromatographie (HPLC)Englische bersetzung von DIN EN 16024:2011-06Engrais Dosage du 1H-1,2,4-triazole dans lure et les engrais contenant de lure Mthode par chromatographie liquide haute performance (HPLC)Traduction anglaise de DIN EN 16024:2011-

4、06www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.1306.11 DIN EN 16024:2011-06 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 260 “Fertilizers and liming mater

5、ials” (Secretariat: DIN, Germany) under the mandate M/418. The responsible German body involved in its preparation was the Normenausschuss Lebensmittel und landwirtschaftliche Produkte (Food and Agricultural Products Standards Committee), Working Committee NA 057-03-02 AA Dngemittel. The DIN Standar

6、ds corresponding to the International Standards referred to in this document are as follows, whereby EN ISO Standards are only listed below if these have not been published as DIN EN ISO Standards with the same number: EN ISO 3696 DIN ISO 3696 ISO 5725-1 DIN ISO 5725-1 ISO 5725-2 DIN ISO 5725-2 Nati

7、onal Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Specification and test methods 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)

8、of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method 2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16024 April 2011 ICS 65.080 English Version Fertilizers - Determination of 1H-1,2,4-triazole in u

9、rea and in fertilizers containing urea - Method using high-performance liquid chromatography (HPLC) Engrais - Dosage du 1H-1,2,4-triazole dans lure et les engrais contenant de lure - Mthode par chromatographie liquide haute performance (HPLC) Dngemittel - Bestimmung von 1H-1,2,4-Triazol in Harnstoff

10、 und harnstoffhaltigen Dngemitteln - Verfahren mit Hochleistungs-Flssigchromatographie (HPLC) This European Standard was approved by CEN on 26 February 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the

11、 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, Frenc

12、h, 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,

13、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 STAND

14、ARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16024:2011: EEN 16024:2011 (E) 2 Contents Page Forew

15、ord 31 Scope 42 Normative references 43 Terms and definitions .44 Principle 45 Reagents .46 Apparatus .57 Sampling and sample preparation .58 Procedure .58.1 Preparation of the test solution 58.2 Preparation of the calibration solutions 58.3 HPLC conditions 68.4 HPLC determination 79 Calculation and

16、 expression of the results 79.1 Calculation 79.2 Expression of results 810 Precision .810.1 Inter-laboratory test .810.2 Repeatability .810.3 Reproducibility .811 Test report 9Annex A (informative) Statistical results of the inter-laboratory test . 10Bibliography . 11DIN EN 16024:2011-06 EN 16024:20

17、11 (E) 3 Foreword This document (EN 16024:2011) 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 e

18、ndorsement, at the latest by October 2011, and conflicting national standards shall be withdrawn at the latest by October 2011. 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 i

19、dentifying 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. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to i

20、mplement 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,

21、 Switzerland and the United Kingdom. DIN EN 16024:2011-06 EN 16024:2011 (E) 4 1 Scope This European Standard specifies a method for the determination of triazole (TZ) in urea or in fertilizers containing urea in the presence of dicyandiamide or methylpyrazole respectively using high-performance liqu

22、id chromatography (HPLC). 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.

23、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 r

24、elating 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 Principle The sample of fertilizer is

25、 dissolved in water or extracted with water. The triazole content is determined in the solution using reversed phase high-performance liquid chromatography with an electrochemical pulsed detector. 5 Reagents Use only reagents of recognized analytical grade. 5.1 Water, distilled or demineralised, con

26、ductivity less than 0,5 mS/m, according to EN ISO 3696:1995, grade 3. 5.2 1H-1,2,4-triazole. 5.3 Triazole standard solution, =1 g/l. Weigh 1 g of triazole to the nearest of 0,1 mg into a 1 000 ml measuring flask. Dissolve with water, make up to the mark with water and mix well. DIN EN 16024:2011-06

27、EN 16024:2011 (E) 5 5.4 Acetonitrile, gradient grade. 5.5 Buffer solution. Weigh 8,9 g of dipotassium hydrogen phosphate trihydrate and 35,93 g of potassium dihydrogen phosphate in a 1 000 ml measuring flask, add approximately 750 ml of water, dissolve in the ultrasonic bath and make up to the mark

28、with water. 6 Apparatus 6.1 Analytical balance, measuring accuracy 0,01 mg. 6.2 Ultrasonic bath. 6.3 Syringe filter, for aqueous solutions; pore size 0,25 m. 6.4 HPLC device. 6.5 Sampling issuing system. 6.6 Electrochemical detector. Working electrode: gold, Reference electrode: Ag+AgCl, 3 mol/l KCl

29、. 6.7 Reversed phase HPLC separator column, e. g. C8 10 m, 250 mm 4 mm. 6.8 Laboratory glassware. 7 Sampling and sample preparation Sampling is not part of the method specified in this document. A recommended sampling method is given in EN 1482-1. Sample preparation shall be carried out in accordanc

30、e with EN 1482-2. 8 Procedure 8.1 Preparation of the test solution Weigh approximately 0,2 g of the sample (m) in a 100 ml volumetric flask to the nearest 0,1 mg, add approximately 70 ml of water (5.1), dissolve in the ultrasonic bath (6.2) and make up to the mark with water (5.1). Filtrate this sol

31、ution straight into a vial through a syringe filter (6.3) to remove any conditioning agents. This solution is used for the determination. 8.2 Preparation of the calibration solutions To obtain the calibration curve, prepare the following dilution series according to Table 1 from the triazole standar

32、d solution (5.3) (each in a 100 ml measuring flask): DIN EN 16024:2011-06 EN 16024:2011 (E) 6 Table 1 Preparation of the dilution series Mass concentration of triazole mg/l Volume of standard solution (5.3) l 0,1 10 0,3 300,7 701,0 100 3,0 3005,0 500 7,0 70010,0 1 000 8.3 HPLC conditions Separation

33、column: filling for reversed phase HPLC (6.7) Column temperature: 20 C Elution agent: buffer solution (5.5) / acetonitrile (5.4) mixture 85 + 15 (volume fraction) Flow rate: 0,7 ml/min Injection volume: 10 l Detector programme: according to Table 2 DIN EN 16024:2011-06 EN 16024:2011 (E) 7 Table 2 De

34、tector programme waveform times potential integration0,00 0,25 V 0,30 0,25 V begin 0,60 0,25 V end 0,61 1,00 V 0,80 1,00 V 0,81 -0,60 V 1,00 -0,60 V The elution agent shall be degassed, e. g. in the ultrasonic bath (6.2). 8.4 HPLC determination To determine the calibration curve, inject an amount of

35、 10 l of each calibration solution (see 8.2) three times. The calibration curve may be used for the content determination when the correlation coefficient exceeds 0,99. NOTE The correlation coefficient is calculated in accordance with the method of smallest squares. To verify the equipment system, i

36、nject a calibration solution, prepared according to 8.2, with a content of 1 mg/l triazole and inject 10 l three times in succession. Once the determined content is within the tolerance of 0,05 mg/l (5 % rel.) , the equipment system satisfies the requirements for continuing the measurements on the t

37、est solution. Inject 10 l of the test solution three times in succession. Special care has to be taken to obtain good peak separation in order to avoid interference from other substances present in the sample. 9 Calculation and expression of the results 9.1 Calculation Carry out the evaluation on th

38、e basis of the calibration curve over the peak areas. Calculate the mass fraction of 1H-1,2,4-triazole, wTZ, in percent according to the following equation: maFbAw=100)(dpkTZ(1) where Apkis the peak area; b is the ordinate section of the calibration curve; a is the slope of the calibration curve; DI

39、N EN 16024:2011-06 EN 16024:2011 (E) 8 Fdis the dilution factor; m is the mass of the test portion, in milligrams. 9.2 Expression of results Calculate the arithmetic mean from both values obtained. Indicate the result to the nearest 0,001 %. 10 Precision 10.1 Inter-laboratory test An inter-laborator

40、y test has been carried out in 2009 with 8 participating laboratories and 4 different samples of fertilizers. This test yielded the data given in Annex A. Repeatability and reproducibility were calculated according to ISO 5725-1 and ISO 5725-2. The values derived from this inter-laboratory test may

41、not be applicable to concentration ranges and matrices other than those given in Annex A. 10.2 Repeatability The absolute difference between two independent single test results, obtained with the same method on identical test material in the same laboratory by the same operator using the same equipm

42、ent within a short interval of time, will in not more than 5 % of the cases exceed the values of r given in Table 3. 10.3 Reproducibility The absolute difference between two single test results, obtained with the same method on identical test material in different laboratories by different operators

43、 using different equipment, will in not more than 5 % of the cases exceed the values of R given in Table 3. Table 3 Mean values, repeatability and reproducibility limits Sample x r R UAN 1 0,057 6 0,002 4 0,007 4 UAN 2 0,071 8 0,00 40 0,021 1 Urea 1 0,063 6 0,004 83 0,020 9 Urea 2 0,070 1 0,005 68 0

44、,019 5 DIN EN 16024:2011-06 EN 16024:2011 (E) 9 11 Test report The test report shall contain at least the following information: a) all information necessary for the complete identification of the sample; b) the test method used with reference to this document; c) the test results obtained; d) date

45、of sampling and sampling procedure (if known); e) date when the analysis was finished; f) whether the requirement of the repeatability limit has been fulfilled; g) all operating details not specified in this document, or regarded as optional, together with details of any incidents occurred when perf

46、orming the method, which may have influenced the test result(s). DIN EN 16024:2011-06 EN 16024:2011 (E) 10 Annex A (informative) Statistical results of the inter-laboratory test The precision of the method has been determined in the year 2009 in an inter-laboratory test with eight laboratories parti

47、cipating and carried out on four samples of fertilizer. The statistical results are given in Table A.1. Table A.1 Statistical results of the inter-laboratory test Parameter UAN 1 UAN 2 Urea 1 Urea 2 Year of the test 2009 2009 2009 2009 Number of participating laboratories 8 8 8 8 Number of laborator

48、ies after eliminating outliers 7 7 5 5 mean value, x , (%) 0,057 6 0,071 8 0,063 6 0,070 1 Repeatability standard deviation sr, (%) 0,000 88 0,001 45 0,001 74 0,002 05 RSDr(%) 1,52 2,02 2,74 2,92 Repeatability limit r (2,77 sr) (%) 0,002 4 0,004 0 0,004 83 0,005 68 Reproducibility standard deviation

49、, sR(%) 0,002 68 0,007 61 0,007 55 0,007 02 RSDR(%) 4,66 10,60 11,87 10,02 Reproducibility limit R (2,77 sR) (%) 0,007 4 0,021 1 0,020 9 0,019 5 DIN EN 16024:2011-06 EN 16024:2011 (E) 11 Bibliography 1 EN 1482-1, Fertilizers and liming materials Sampling and sample preparation Part 1: Sampling 2 EN 15360, Fertilizers Determination of dicyandiamide Method using high-performance liquid chromatography (HPLC