1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 16024:2011Fertilizers Determinationof 1H-1,2,4-triazole in ureaand in fertilizers containingurea Method usinghigh-performance liquidchromatography (HPLC)BS EN 16024:2011 BR
2、ITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16024:2011.The UK participation in its preparation was entrusted to TechnicalCommittee CII/37, Fertilisers and related chemicals.A list of organizations represented on this committee can beobtained on request to its
3、secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 69223 9ICS 65.080Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was publis
4、hed under the authority of theStandards Policy and Strategy Committee on 31 May 2011.Amendments issued since publicationDate Text affectedBS EN 16024:2011EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16024 April 2011 ICS 65.080 English Version Fertilizers - Determination of 1H-1,2,4-triazole
5、in urea 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 Harns
6、toff 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
7、 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, F
8、rench, 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, Bulgar
9、ia, 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 S
10、TANDARDIZATION 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: EBS EN 16024:2011EN 16024:2011 (E) 2
11、 Contents Page Foreword 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 determinatio
12、n 79 Calculation and 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 . 11BS EN 16024:
13、2011EN 16024:2011 (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 identic
14、al text or by endorsement, 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 re
15、sponsible 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. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries
16、 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,
17、 Spain, Sweden, Switzerland and the United Kingdom. BS EN 16024:2011EN 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-perfor
18、mance liquid 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)
19、 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
20、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 Principle The sample of fer
21、tilizer is 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 deminera
22、lised, conductivity 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. BS EN 16024
23、:2011EN 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
24、mark 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/
25、l KCl. 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 acco
26、rdance 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 thi
27、s solution 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 st
28、andard solution (5.3) (each in a 100 ml measuring flask): BS EN 16024:2011EN 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
29、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 BS EN 16024:2011EN 16024:2011 (E) 7 Table 2 Detecto
30、r 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 10 l
31、 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, inject
32、 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 test s
33、olution. 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 the bas
34、is 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; BS EN 1
35、6024:2011EN 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-laboratory test has
36、 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 not be app
37、licable 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 equipment within
38、 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 using dif
39、ferent 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 0,019 5 BS
40、EN 16024:2011EN 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 of sampling and
41、 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 performing the meth
42、od, which may have influenced the test result(s). BS EN 16024:2011EN 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 participating and carried
43、 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 laboratories after eliminatin
44、g 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, sR(%) 0,002 68 0,0
45、07 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 BS EN 16024:2011EN 16024:2011 (E) 11 Bibliography 1 EN 1482-1, Fertilizers and liming materials Sampling and sample preparation Part 1: Sampling 2 EN 15360, Fertilizers Determ
46、ination of dicyandiamide Method using high-performance liquid chromatography (HPLC) 3 EN 15905, Fertilizers Determination of 3-methylpyrazole (MP) using high-performance liquid chromatography (HPLC) 4 ISO 5725-1, Accuracy (trueness and precision) of measurement methods and results Part 1: General pr
47、inciples and definitions 5 ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method 6 Regulation (EC) No 2003/2003 of the European Parliament and of the Council of
48、 13 October 2003 relating to fertilisers, Official Journal L 304, 21/11/2003 P. 0001-0194 This page deliberately left blankThis page deliberately left blankBSI is the independent national body responsible for preparing British Standardsand other standards-related publications, information and servic
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