1、BSI Standards PublicationBS EN 16576:2014Automotive fuels Determination of manganeseand iron content in diesel Inductively coupled plasmaoptical emission spectrometry(ICP OES) methodBS EN 16576:2014 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 16576:2014.The
2、UK participation in its preparation was entrusted to TechnicalCommittee PTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. U
3、sers are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 81877 6ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of
4、 theStandards Policy and Strategy Committee on 31 December 2014.Amendments issued since publicationDate Text affectedBS EN 16576:2014EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16576 November 2014 ICS 75.160.20 English Version Automotive fuels - Determination of manganese and iron content i
5、n diesel - Inductively coupled plasma optical emission spectrometry (ICP OES) method Carburants pour automobiles - Dtermination des teneurs en manganse et en fer dans carburants diesel - Mthode spectromtrique optique par plasma couplage inductif (ICP OES) Kraftstoffe fr Kraftfahrzeuge - Bestimmung d
6、es Gehaltes an Mangan und Eisen in Dieselkraftstoff - Optische Emissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP OES) This European Standard was approved by CEN on 20 September 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions fo
7、r 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 thre
8、e 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 bod
9、ies 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, S
10、pain, 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 2014 CEN All rights of exploitation in any form and by any means reserved worldw
11、ide for CEN national Members. Ref. No. EN 16576:2014 EBS EN 16576:2014EN 16576:2014 (E) 2 Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents . 4 5 Apparatus . 5 6 Sampling . 6 7 Preparation of solutions . 6 7.1 General 6 7.2 Preparation of the Internal standard solu
12、tion for dilution . 6 7.3 Preparation of the manganese intermediate solution 7 7.4 Preparation of the iron intermediate solution . 7 7.5 Preparation of the calibration solutions 7 7.6 Preparation of manganese and iron quality control solution . 7 8 Calibration 8 8.1 General 8 8.2 Calibration of the
13、ICP OES spectrometer 8 8.3 Procedure A 8 8.4 Procedure B 8 8.5 Check of the calibration 9 9 Sample analysis . 9 9.1 Sample solution preparation 9 9.2 Sample solution measurement . 9 10 Calculation 10 11 Expression of results 10 12 Precision . 10 12.1 General 10 12.2 Repeatability, r . 11 12.3 Reprod
14、ucibility, R 11 13 Test report 11 Bibliography 12 BS EN 16576:2014EN 16576:2014 (E) 3 Foreword This document (EN 16576:2014) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat o
15、f which is held by NEN. 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 May 2015 and conflicting national standards shall be withdrawn at the latest by May 2015. Attention is drawn to the possibil
16、ity 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 answers requirements originating from the amended Fuels Quality Directive (FQD, 1). A similar technique fo
17、r unleaded petrol is described in EN 16136 2. 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, Form
18、er 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. BS EN 16576:2014EN 16576:2014 (E) 4 1 Sco
19、pe This European Standard specifies a method based on inductively coupled plasma optical emission spectrometry (ICP OES) for the determination of manganese content and of iron content, each from about 0,5 mg/l to about 7,0 mg/l in diesel fuels including those containing up to about 10 % (V/V) fatty
20、acid methylester (FAME). WARNING The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this European Standard to estab
21、lish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use. NOTE 1 Manganese and iron contents higher than 7,0 mg/l can be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been establ
22、ished for such a procedure. NOTE 2 For the purposes of this European Standard, the term “% (V/V)” is used to represent the volume fraction () of a material. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its
23、application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 1042, Laboratory glassware One -mark volumetric flasks (ISO 1042) EN ISO 3170, Petroleum liquids Manual sampling (ISO 31
24、70) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171) EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method (ISO 3675) EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U -tube meth
25、od (ISO 12185) 3 Principle A diesel fuel sample is diluted with a hydrocarbon solvent. The solution is introduced directly into the plasma of an ICP OES spectrometer. Iron and manganese contents are calculated by comparison with calibration solutions prepared from suitable iron and manganese compoun
26、ds. An internal standard is employed to correct viscosity effects. 4 Reagents Unless specified otherwise, only chemicals which are known to have a high degree of purity shall be used. 4.1 Kerosene, boiling range between 150 C and 250 C, analytical reagent grade. Other grades of kerosene with analyte
27、 concentrations below the detection limits for the two elements under investigation may be used. In this case, perform a wavelength check for absence of signals from the corresponding elements as well as for absence of spectral interference. 4.2 Manganese standard solution, dissolved in oil, (Mn) =
28、100 mg/kg. BS EN 16576:2014EN 16576:2014 (E) 5 A multi-element standard solution may also be used instead of the single element standard solution. Some element standard solutions are supplied with different element content on the market. These solutions may be used instead of the required solutions,
29、 but an initial mass to mass dilution has to be done. 4.3 Iron standard solution, dissolved in oil, (Fe) = 100 mg/kg. A multi-element standard solution may also be used instead of the single element standard solution. Some element standard solutions are supplied with different element content on the
30、 market. These solutions may be used instead of the required solutions, but an initial mass to mass dilution has to be done. 4.4 Internal standard solutions (cobalt, scandium, yttrium), dissolved in oil, for example with 1 000 mg/kg per element, available as single element standards. NOTE The elemen
31、t standard solutions are commonly available as single element standards with various element content. 4.5 Argon, with a purity of 99,995 % (V/V). Small amounts of oxygen (purity O2 99,995 % (V/V) may be added, for instance in accordance with the operating instructions of the equipment manufacturer,
32、to the argon gas stream using a metering valve (30 ml/min to 100 ml/min) to prevent carbon deposits in the area of the plasma torch. 5 Apparatus 5.1 Laboratory equipment 5.1.1 General All glassware shall be cleaned carefully before use. 5.1.2 Glassware, usual laboratory glassware, together with the
33、following: 5.1.2.1 Beakers, 50 ml. 5.1.2.2 Volumetric flasks, 20 ml, 50 ml and 500 ml, according to EN ISO 1042, with taper sleeve and plug. 5.1.3 Bottles, 50 ml and 500 ml, with screw caps, high-density polyethylene (HDPE). 5.1.4 Graduated pipettes or variable volume automatic pipettes, fitted with
34、 disposable polypropylene tips. 5.2 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.3 ICP OES spectrometer 5.3.1 General ICP OES spectrometer equipped for the analysis of organic liquids, with a high-frequency generator and a nebulizer suitable for organic solvents. The use of a fee
35、d pump for sample introduction into the nebulizer is required. Both setup and operation of the ICP OES spectrometer shall be done in accordance with operating instructions of the manufacturer. 5.3.2 Wavelengths Table 1 gives the recommended wavelengths. As the magnitude of the background signal high
36、ly depends on spectral structures caused by the samples nature and origin, only net intensities are to be used for calculations. BS EN 16576:2014EN 16576:2014 (E) 6 Table 1 Recommended wavelengths Element Wavelength nm Manganese 257,610 259,372 260,569 279,482 279,827 293,931 Iron 234,350 238,204 24
37、0,488 259,940 261,187 Cobalt 238,892 Scandium 361,383 Yttrium 224,306 360,073 371,029 6 Sampling IMPORTANT The laboratory shall receive a sample which is truly representative and was not damaged or altered during transport or storage. Unless otherwise specified in the commodity specification, sample
38、s shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national regulations for the sampling of the product under test. The samples shall be filled into clean containers. 7 Preparation of solutions 7.1 General In order to avoid inhomogeneity, the el
39、ement standard solutions (4.2, 4.3 and 4.4) shall be shaken vigorously before use. It is strongly advised to use freshly prepared calibration solutions. 7.2 Preparation of the Internal standard solution for dilution Weigh 5 g of cobalt, scandium or yttrium stock solution (4.4) with a precision of 0,
40、1 g in a 500 ml volumetric flask (5.1.2.2). Fill up to 500 ml with kerosene solvent (4.1). The prepared solution shall be homogenized by vigorous shaking. BS EN 16576:2014EN 16576:2014 (E) 7 NOTE Experience from daily practice with yttrium used as internal standard has shown that internal standard s
41、olutions can be used for about two weeks. Internal standard solution with different element content may be used instead of the 1 000 mg/kg one. In that case, the mass has to be adjusted in order to get a minimum content of 10 mg/l in the internal standard solution for dilution. 7.3 Preparation of th
42、e manganese intermediate solution Weigh 3,00 g 0,01 g of manganese standard solution (4.2) into a 50 ml HDPE bottle (5.1.3). Add kerosene solvent (4.1) to 15,00 g 0,01 g. In case manganese standard solutions (4.2) with different manganese content are used, the mass of standard solution shall be adju
43、sted accordingly to achieve 20 mg/kg manganese content. 7.4 Preparation of the iron intermediate solution Weigh 3,00 g 0,01 g of iron standard solution (4.3) into a 50 ml HDPE bottle (5.1.3). Add kerosene solvent (4.1) to 15,00 g 0,01 g. In case iron standard solutions (4.3) with different iron cont
44、ent are used, the mass of standard solution shall be adjusted accordingly to achieve 20 mg/kg iron content. 7.5 Preparation of the calibration solutions The calibration solutions shall be prepared as indicated in Table 2. Each mass of manganese intermediate solution (7.3) and iron intermediate solut
45、ion (7.4) shall be weighed to the nearest 0,1 mg into a 20 ml volumetric flask (5.1.2.2). Fill with kerosene (4.1) to the mark. All solutions thus prepared shall be homogenized by shaking. Table 2 Concentration of iron and manganese in the calibration solutions Calibration solution Manganese interme
46、diate solution (7.3) g Iron intermediate solution (7.4) g Internal standard solution (7.2) ml Manganese concentration mg/l Iron concentration mg/l Blank 0,00 0,00 10 0,00 0,00 1 0,50 0,50 10 0,50 0,50 2 2,00 2,00 10 2,00 2,00 3 3,50 3,50 10 3,50 3,50 7.6 Preparation of manganese and iron quality con
47、trol solution A 1,0 mg/l quality control (QC) solution shall be prepared using independent manganese and iron standard solutions. The mass given is based on an element (Fe, Mn) content of 100 mg/kg. In case a standard solution with different element content is used, the mass shall be adjusted accord
48、ingly to obtain the specified element content. Weigh 0,5 g of manganese standard solution (4.2) and 0,5 g of iron standard solution (4.3) to the nearest 0,1 mg into a 50 ml volumetric flask (5.1.2.2), add 25 ml of the internal standard solution (7.2), and fill with kerosene (4.1) to the mark. All so
49、lutions thus prepared shall be homogenized by shaking. BS EN 16576:2014EN 16576:2014 (E) 8 8 Calibration 8.1 General The ICP OES spectrometer set up and instrument check are performed according to the instructions from the manufacturer. Follow the manufacturers instructions for setting up the instrument with organic solutions. The choice of the instrumental parameters is determined to obtain the best signal/background ratio for all elements. Net intensity of analytical lines shall be calculated by subtracting the intensity measur
