Petroleum products - Determination of low concentration of sulfur in automotive fuels - Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012)

This European Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the determination of the sulfur content of automotive gasolines, including those containing up to 5 % (m/m) oxygen, and of automotive diesel fuels, including those containing up to 10 % (V/V) fatty acid methylester (FAME), having sulfur contents in the range 2 mg/kg to 50 mg/kg.
Other products may be analysed and other sulfur contents may be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this standard. For reasons of spectral overlap, this standard is not applicable to leaded automotive gasolines, lead replacement gasolines containing greater than 8 mg/kg lead, or to products and feedstocks containing lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.

Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen - Energiedispersives Röntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)

Diese Internationale Norm legt ein energiedispersives Röntgenfluoreszenzverfahren (edRFA) zur Bestimmung des Schwefelgehaltes im Bereich von 8 mg/kg bis 50 mg/kg in Ottokraftstoffen mit einem Sauerstoffgehalt von bis zu 3,7 % (m/m) (einschließlich von bis zu 10 % (V/V) Ethanol), sowie in Dieselkraftstoffen mit bis zu 10 % (V/V) Fettsäure-Methylester (FAME) fest. Andere Produkte auch mit anderen Schwefelgehalten können mit diesem Prüfverfahren ebenfalls untersucht werden; jedoch sind für andere als die hier genannten Kraftstoffe und Bereiche für den Schwefelgehalt keine Präzisionsangaben ermittelt worden. Wegen spektraler Überlagerungen ist das hier festgelegte Prüfverfahren nicht auf verbleite Ottokraftstoffe oder für Bleiersatzkraftstoffe mit Bleigehalten von mehr als 8 mg/kg einsetzbar. Das Prüfverfahren ist ebenfalls nicht auf Produkte oder Rohmaterialien anwendbar, die für die Elemente Blei, Silizium, Phosphor, Calcium, Kalium oder Halogenverbindungen Gehalte von mehr als 1/10 des gemessenen Schwefelgehaltes, oder aber mehr als 10 mg/kg aufweisen. ANMERKUNG Für die Zwecke dieser Internationalen Norm wird zur Angabe des Massenanteils einer Substanz der Ausdruck „% (m/m)“ und für den Volumenanteil einer Substanz der Ausdruck „% (V/V)“ verwendet.

Produits pétroliers - Détermination de la teneur en soufre en faible concentration dans les carburants pour automobiles - Méthode spectrométrique de fluorescence de rayons X dispersive en énergie (ISO 13032:2012)

L'ISO 13032:2012 spécifie une méthode d'essai par fluorescence de rayons X dispersive en énergie (FXDE) pour le dosage du soufre dans l'essence pour automobiles contenant jusqu'à 3,7 % (m/m) d'oxygène [y compris celle contenant de l'éthanol jusqu'à 10 % (V/V)], et dans les carburants diesels [y compris ceux contenant jusqu'à 10 % (V/V) d'esters méthyliques d'acide gras (EMAG)] ayant des teneurs en soufre comprises entre 8 mg/kg et 50 mg/kg.
D'autres produits peuvent être analysés et d'autres teneurs en soufre peuvent être déterminées suivant cette méthode; cependant, il n'a pas été établi de données de fidélité pour des produits autres que les carburants pour automobiles et pour des résultats en dehors du domaine spécifié pour l'ISO 13032:2012.
En raison de recouvrements spectraux, l'ISO 13032:2012 n'est pas applicable à l'essence pour automobiles contenant du plomb, ni à l'essence contenant un substitut de plomb dont la teneur en plomb est supérieure à 8 mg/kg, ni aux produits et charges contenant du plomb, du silicium, du phosphore, du calcium, du potassium ou des halogénures à des concentrations qui dépassent le dixième de la teneur en soufre mesurée, ou plus de 10 mg/kg, en choisissant la plus grande de ces valeurs.

Naftni proizvodi - Določevanje nizke koncentracije žvepla v gorivih za motorna vozila - Metoda z energijsko-disperzivno rentgensko fluorescenčno spektrometrijo (ISO 13032:2012)

Ta evropski standard določa preskusno metodo z energijsko-disperzivno rentgensko fluorescenčno spektrometrijo (EDXRF) za določanje vsebnosti žvepla v gorivih za motorna vozila, vključno s tistimi, ki vsebujejo do 5 % (m/m) kisika, in v dizelskih gorivih za motorna vozila, vključno s tistimi, ki vsebujejo do 10 % (V/V) metilnih estrov maščobnih kislin (FAME) in od 2 do 50 mg/kg žvepla.
Ta preskusna metoda se lahko uporablja za analizo drugih izdelkov in vsebnosti žvepla v drugih izdelkih, vendar za ta standard niso bili določeni podatki o natančnosti za izdelke, ki niso goriva za motorna vozila, in za rezultate zunaj določenega obsega. Zaradi prekrivanja spektra se ta standard ne uporablja za osvinčeni motorni bencin, bencin z nadomestkom svinca, ki vsebuje več kot 8 mg/kg svinca, ali za izdelke in surovine, ki vsebujejo svinec, silicij, fosfor, kalcij, kalij ali halide, katerih koncentracija je večja od ene desetine izmerjene koncentracije žvepla ali večja od 10 mg/kg, pri čemer se upošteva večja vrednost.

General Information

Status
Published
Public Enquiry End Date
19-Aug-2010
Publication Date
11-Apr-2012
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
29-Mar-2012
Due Date
03-Jun-2012
Completion Date
12-Apr-2012

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Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN ISO 13032:2012
01-maj-2012
1DIWQLSURL]YRGL'RORþHYDQMHQL]NHNRQFHQWUDFLMHåYHSODYJRULYLK]DPRWRUQD
YR]LOD0HWRGD]HQHUJLMVNRGLVSHU]LYQRUHQWJHQVNRIOXRUHVFHQþQRVSHNWURPHWULMR
,62
Petroleum products - Determination of low concentration of sulfur in automotive fuels -
Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012)
Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen -
Energiedispersives Röntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)
Produits pétroliers - Détermination de la teneur en soufre en faible concentration dans
les carburants pour automobiles - Méthode spectrométrique de fluorescence de rayons X
dispersive en énergie (ISO 13032:2012)
Ta slovenski standard je istoveten z: EN ISO 13032:2012
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
SIST EN ISO 13032:2012 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------

SIST EN ISO 13032:2012

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SIST EN ISO 13032:2012


EUROPEAN STANDARD
EN ISO 13032

NORME EUROPÉENNE

EUROPÄISCHE NORM
March 2012
ICS 75.160.20
English Version
Petroleum products - Determination of low concentration of
sulfur in automotive fuels - Energy-dispersive X-ray fluorescence
spectrometric method (ISO 13032:2012)
Produits pétroliers - Détermination de la teneur en soufre Mineralölerzeugnisse - Bestimmung niedriger
en faible concentration dans les carburants pour Schwefelgehalte in Kraftstoffen - Energiedispersives
automobiles - Méthode spectrométrique de fluorescence de Röntgenfluoreszenzspektrometrieverfahren (ISO
rayons X dispersive en énergie (ISO 13032:2012) 13032:2012)
This European Standard was approved by CEN on 29 February 2012.

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-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 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, 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, Turkey and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 13032:2012: E
worldwide for CEN national Members.

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SIST EN ISO 13032:2012
EN ISO 13032:2012 (E)
Contents Page
Foreword .3
2

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SIST EN ISO 13032:2012
EN ISO 13032:2012 (E)
Foreword
This document (EN ISO 13032:2012) 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 of
which is held by NEN, in collaboration with Technical Committee ISO/TC 28 " Petroleum products and
lubricants".
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 2012, and conflicting national standards shall be
withdrawn at the latest by September 2012.
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.
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, Turkey and the United Kingdom.
3

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SIST EN ISO 13032:2012

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SIST EN ISO 13032:2012
INTERNATIONAL ISO
STANDARD 13032
First edition
2012-03-01
Petroleum products — Determination of
low concentration of sulfur in automotive
fuels — Energy-dispersive X-ray
fluorescence spectrometric method
Produits pétroliers — Détermination de la teneur en soufre en faible
concentration dans les carburants pour automobiles — Méthode
spectrométrique de fluorescence de rayons X dispersive en énergie
Reference number
ISO 13032:2012(E)
©
ISO 2012

---------------------- Page: 7 ----------------------

SIST EN ISO 13032:2012
ISO 13032:2012(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2012
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO’s
member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2012 – All rights reserved

---------------------- Page: 8 ----------------------

SIST EN ISO 13032:2012
ISO 13032:2012(E)
Contents Page
Foreword .iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Principle . 1
4 Reagents and materials . 1
4.1 Diluent oil . 1
4.2 Sulfur compounds . 2
4.3 Reference materials (CRMs) . 2
4.4 Quality control samples . 2
5 Apparatus . 2
5.1 Energy-dispersive X-ray fluorescence instrument . 2
6 Sampling and sample handling . 3
7 Apparatus preparation . 4
7.1 Analyser . 4
7.2 Sample cups . 4
8 Calibration . 4
8.1 General . 4
8.2 Preparation of primary standards . 4
8.3 Calibration standards . 5
8.4 Calibration procedure . 6
9 Procedure . 7
10 Calculation . 7
11 Expression of results . 7
12 Precision . 8
12.1 General . 8
12.2 Repeatability, r . 8
12.3 Reproducibility, R . 8
13 Test report . 8
Annex A (informative) Matrix effects . 9
Annex B (normative) Guidelines for measuring low sulfur concentrations . 11
Bibliography .12
© ISO 2012 – All rights reserved iii

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SIST EN ISO 13032:2012
ISO 13032:2012(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International
Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 13032 was prepared by the European Committee for Standardization (CEN) Technical Committee
CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological
origin, in collaboration with ISO Technical Committee TC 28, Petroleum products and lubricants, in accordance
with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).
iv © ISO 2012 – All rights reserved

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SIST EN ISO 13032:2012
ISO 13032:2012(E)
Introduction
This International Standard is directed specifically at the lower end of the concentration range covered in
[2]
ISO 20847 . By selecting the instrument type, a better signal-to-background ratio for sulfur K-L emission is
2,3
assured. A knowledge of the general composition of the sample for analysis is advantageous in obtaining the
best test result.
NOTE IUPAC X-ray line notation (S K-L ) is used in this International Standard; the corresponding Siegbahn X-ray
2,3
line notation (S-Ka) is being phased out.
Where matrix matching is not used and where the C:H mass ratio of the test sample is known or can be
determined, accuracy can be improved by the use of Equation (A.1) (see A.2.3) to correct the result to the
C:H mass ratio of the calibration standards, i.e. the reference diluent oil (see 4.1).
Some instruments include the capability for instrument-based matrix correction; notes on the use of this
approach to compensate for matrix effects in the test sample are provided in A.3 for information.
[3]
This International Standard is based on IP test method PM DU developed by the Energy Institute.
© ISO 2012 – All rights reserved v

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SIST EN ISO 13032:2012

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SIST EN ISO 13032:2012
INTERNATIONAL STANDARD ISO 13032:2012(E)
Petroleum products — Determination of low concentration
of sulfur in automotive fuels — Energy-dispersive X-ray
fluorescence spectrometric method
WARNING — The use of this International Standard may involve hazardous materials, operations and
equipment. This International Standard does not purport to address all of the safety problems associated
with its use. It is the responsibility of the user of this International Standard to establish appropriate
safety and health practices and determine the applicability of regulatory limitations prior to use.
1 Scope
This International Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the
determination of sulfur content in automotive gasoline containing up to 3,7 % (m/m) oxygen [including those
blended with ethanol up to 10 % (V/V)], and in diesel fuels [including those containing up to about 10 % (V/V)
fatty acid methylester (FAME)] having sulfur contents in the range 8 mg/kg to 50 mg/kg.
Other products can be analysed and other sulfur contents can be determined according to this test method;
however, no precision data for products other than automotive fuels and for results outside the specified range
have been established for this International Standard.
For reasons of spectral overlap, this International Standard is not applicable to leaded automotive gasoline,
gasoline having a content of greater than 8 mg/kg lead replacement or to product and feedstock containing
lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the
concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.
NOTE For the purposes of this International Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the
mass fraction, m, and the volume fraction, f, of a material respectively.
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.
ISO 3170:2004, Petroleum liquids — Manual sampling
ISO 3171:1988, Petroleum liquids — Automatic pipeline sampling
3 Principle
The test portion, in a cup fitted with an X-ray transparent window, is placed in a beam of exciting radiation from
an X-ray tube. The intensity of the sulfur K-L characteristic X-radiation is measured and the accumulated
2,3
count is compared with a calibration curve constructed from sulfur standards covering the range of sulfur
contents under examination.
NOTE The exciting radiation can be either direct or indirect via a polarizing or secondary target.
4 Reagents and materials
4.1 Diluent oil
The reference diluent oil is white oil (light paraffin oil) of high purity grade, with a maximum sulfur content of
0,5 mg/kg. However, if only one type of matrix is to be analysed (e.g. motor gasoline), the accuracy of results
© ISO 2012 – All rights reserved 1

---------------------- Page: 13 ----------------------

SIST EN ISO 13032:2012
ISO 13032:2012(E)
may be improved by using a matrix-matched diluent. These should match, approximately, the aromatic and
oxygen contents of the material to be analysed and should consist of high-purity components of less than
0,5 mg/kg sulfur content.
NOTE 1 Suitable components for the matched matrix diluent include n-heptane, 2,2,4-trimethylpentane, toluene,
xylenes, ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME).
NOTE 2 For the analysis of diesel fuels containing FAME, the accuracy of results can be improved by use of a matched
matrix diluent oil of the white oil with FAME.
4.2 Sulfur compounds
4.2.1 General
Sulfur compounds of known sulfur content shall be used for the preparation of the primary standards. The
compounds given in 4.2.2 to 4.2.5 are suitable and their nominal sulfur contents are given. Where the purity of
these compounds is less than 99 % (m/m), either the concentrations and nature of all impurities are to be known
or certified reference materials (CRMs) shall be used instead.
4.2.2 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m), or
4.2.3 Dibutylsulfide (DBS), with a nominal sulfur content of 21,915 % (m/m), or
4.2.4 Thionaphthene (Benzothiophene) (TNA), with a nominal sulfur content of 23,890 % (m/m), or
4.2.5 Dibutyldisulfide (DBDS), with a nominal sulfur content of 35,950 % (m/m).
4.3 Reference materials (CRMs)
CRMs from accredited suppliers, containing a range of sulfur concentrations, are suitable alternatives to the
compounds listed in 4.2.2 to 4.2.5 for use as calibration standards.
4.4 Quality control samples
Stable samples representative of the materials being analysed, which have a sulfur content that is known by
this test method over a substantial period of time, or are supplied commercially with a certified value. Ensure,
before use, that the material is within its shelf-life.
5 Apparatus
5.1 Energy-dispersive X-ray fluorescence instrument
5.1.1 Performance characteristics.
For a 10 mg/kg sulfur standard (see 8.3), the instrument shall be capable of meeting the following performance
characteristics:
RR− R ≥ 1,3 (1)
()
sb b
and
CR() < 5% (2)
V s
where
2 © ISO 2012 – All rights reserved

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SIST EN ISO 13032:2012
ISO 13032:2012(E)
R is the gross count rate (counts per second) for the sulfur region of interest for a 10 mg/kg sulfur
s
standard;
R is the gross count rate (counts per second) for the same region of interest for a blank sample
b
[diluent oil (4.1)];
C is the coefficient of variation (relative standard deviation) based on 10 individual measurements of
V
the calibration standard.
The 10 mg/kg sulfur standard shall be a CRM (4.3) or shall be prepared from one of the compounds given in
4.2.2 to 4.2.5 following the procedures described in Clause 8.
5.1.2 Source of X-ray excitation, with significant flux at X-ray energies above 2,5 keV.
For X-ray detectors with a resolution greater than 200 eV at 2,3 keV, all characteristic X-ray lines originating
from the X-ray tube anode shall have an energy above 3,3 keV to ensure minimal background variation due to
scatter from the X-ray tube anode lines.
5.1.3 Removable sample cup, providing a sample depth of at least 5 mm and equipped with replaceable
X-ray transparent film.
NOTE The transparent film is normally polyester or polycarbonate film with a thickness of between 2 µm and 6 µm.
Polyester film is the preferred choice as samples of very high aromatic content can dissolve polycarbonate film. There are
possibly trace amounts of silicon, calcium and sulfur in some types of film. However, the effects are normally cancelled
out where samples and standards are analysed using the same batch of film. It is important that samples, standards and
blanks be measured using the same batch of film to avoid bias.
5.1.4 X-ray detector, with a resolution not exceeding 800 eV at 2,3 keV.
5.1.5 Means of discriminating between sulfur K-L characteri
...

SLOVENSKI STANDARD
oSIST prEN ISO 13032:2010
01-julij-2010
1DIWQLSURL]YRGL'RORþHYDQMHQL]NHYVHEQRVWLåYHSODYJRULYLK]DPRWRUQDYR]LOD
0HWRGD]HQHUJLMVNRGLVSHU]LYQRUHQWJHQVNRIOXRUHVFHQþQRVSHNWURPHWULMR
,62',6
Petroleum products - Determination of low sulfur content of automotive fuels - Energy-
dispersive X-ray fluorescence spectrometry (ISO/DIS 13032:2010)
Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen -
Energiedispersive Röntgenfluoreszenzspektrometrie (ISO/DIS 13032:2010)
Produits pétroliers - Détermination de la basse teneur en soufre des carburants pour
automobiles - Spectrométrie de fluorescence de rayons X dispersive en énergie
(ISO/DIS 13032:2010)
Ta slovenski standard je istoveten z: prEN ISO 13032
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
oSIST prEN ISO 13032:2010 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
oSIST prEN ISO 13032:2010

---------------------- Page: 2 ----------------------
oSIST prEN ISO 13032:2010


EUROPEAN STANDARD
DRAFT
prEN ISO 13032
NORME EUROPÉENNE

EUROPÄISCHE NORM

May 2010
ICS 75.160.20
English Version
Petroleum products - Determination of low sulfur content of
automotive fuels - Energy-dispersive X-ray fluorescence
spectrometry (ISO/DIS 13032:2010)
Produits pétroliers - Détermination de la basse teneur en Mineralölerzeugnisse - Bestimmung niedriger
soufre des carburants pour automobiles - Spectrométrie de Schwefelgehalte in Kraftstoffen - Energiedispersive
fluorescence de rayons X dispersive en énergie (ISO/DIS Röntgenfluoreszenzspektrometrie (ISO/DIS 13032:2010)
13032:2010)
This draft European Standard is submitted to CEN members for parallel enquiry. It has been drawn up by the Technical Committee
CEN/TC 19.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to
provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a European Standard.


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 Ref. No. prEN ISO 13032:2010: E
worldwide for CEN national Members.

---------------------- Page: 3 ----------------------
oSIST prEN ISO 13032:2010
prEN ISO 13032:2010 (E)
Contents Page
Foreword .3

2

---------------------- Page: 4 ----------------------
oSIST prEN ISO 13032:2010
prEN ISO 13032:2010 (E)
Foreword
This document (prEN ISO 13032:2010) has been prepared by Technical Committee CEN/TC 19 “Water in
diesel fuel emulsion for use in internal combustion engines” the secretariat of which is held by NEN, in
collaboration with Technical Committee ISO/TC 28 " Petroleum products and lubricants".
This document is currently submitted to the parallel Enquiry.
3

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oSIST prEN ISO 13032:2010

---------------------- Page: 6 ----------------------
oSIST prEN ISO 13032:2010
DRAFT INTERNATIONAL STANDARD ISO/DIS 13032
ISO/TC 28 Secretariat: ANSI
Voting begins on: Voting terminates on:
2010-05-20 2010-10-20
INTERNATIONAL ORGANIZATION FOR STANDARDIZATION • МЕЖДУНАРОДНАЯ ОРГАНИЗАЦИЯ ПО СТАНДАРТИЗАЦИИ • ORGANISATION INTERNATIONALE DE NORMALISATION
Petroleum products — Determination of low sulfur content of
automotive fuels — Energy-dispersive X-ray fluorescence
spectrometry
Produits pétroliers — Détermination de la basse teneur en soufre des carburants pour automobiles —
Spectrométrie de fluorescence de rayons X dispersive en énergie
ICS 75.160.20

ISO/CEN PARALLEL PROCESSING
This draft has been developed within the European Committee for Standardization (CEN), and processed
under the CEN-lead mode of collaboration as defined in the Vienna Agreement.
This draft is hereby submitted to the ISO member bodies and to the CEN member bodies for a parallel
five-month enquiry.
Should this draft be accepted, a final draft, established on the basis of comments received, will be
submitted to a parallel two-month approval vote in ISO and formal vote in CEN.
In accordance with the provisions of Council Resolution 15/1993 this document is circulated in
the English language only.
Conformément aux dispositions de la Résolution du Conseil 15/1993, ce document est distribué
en version anglaise seulement.
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©
International Organization for Standardization, 2010

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oSIST prEN ISO 13032:2010
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Contents Page
Foreword. iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Principle. 1
4 Chemicals and materials. 2
4.1 Diluent oil. 2
4.2 Sulfur compounds . 2
4.3 Reference materials. 2
4.4 Quality control samples . 2
5 Apparatus . 2
6 Sampling and sample handling. 3
7 Apparatus preparation . 4
7.1 Analyser. 4
7.2 Sample cups. 4
8 Calibration . 4
8.1 General. 4
8.2 Preparation of primary standards . 4
8.3 Calibration standards. 5
8.4 Calibration procedure. 6
9 Procedure . 7
10 Calculation. 7
11 Expression of results . 7
12 Precision. 7
12.1 General. 7
12.2 Repeatability, r . 7
12.3 Reproducibility, R . 7
13 Test report . 8
Annex A (informative) Matrix effects . 9
A.1 General. 9
A.2 Diluent selection . 9
A.3 Instrument based matrix correction . 10
Annex B (normative) Guidelines for measuring low sulfur concentrations . 11
B.1 Sample preparation . 11
B.2 Sample measurement. 11
B.3 Calibration validation . 11
Bibliography . 12

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oSIST prEN ISO 13032:2010
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Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 13032 was prepared by the European Committee for Standardization (CEN) Technical Committee
CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological
origin, in collaboration with Technical Committee ISO/TC 28, Petroleum products and lubricants, in
accordance with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).
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oSIST prEN ISO 13032:2010
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Introduction
This International Standard is directed specifically at the lower end of the concentration range covered in
ISO 20847 [1]. By restriction of instrument type, a better signal to background ratio for sulfur K emission is
assured.
Knowledge before analysis of the general composition of the sample is advantageous in obtaining the best
test result.
Where matrix matching is not used and where the C:H mass ratio of the test sample is known or can be
determined, accuracy may be improved by the use of the equation given in A.2.3 to correct the result to the
C:H mass ratio of the calibration standards i.e. the reference diluent oil (4.1).
Some instruments include the capability for instrument based matrix correction, and notes for information are
provided in A.3 on the use of this approach for compensating for matrix effects in the test sample.

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oSIST prEN ISO 13032:2010
DRAFT INTERNATIONAL STANDARD ISO/DIS 13032

Petroleum products — Determination of low sulfur content of
automotive fuels — Energy-dispersive X-ray fluorescence
spectrometry
WARNING — The use of this International Standard may involve hazardous materials, operations and
equipment. This International Standard does not purport to address all of the safety problems
associated with its use. It is the responsibility of the user of this International Standard to establish
appropriate safety and health practices and determine the applicability of regulatory limitations prior
to use.
1 Scope
This European Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the
determination of sulfur content of automotive gasolines containing up to 3,7 % (m/m) oxygen (including those
blended with ethanol up to 10 % (V/V)), and of diesel fuels, including those containing up to about 10 % (V/V)
fatty acid methylester (FAME), having sulfur contents in the range 8 mg/kg to 50 mg/kg.
NOTE For the purposes of this standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass
fraction (µ) and the volume fraction (φ) of a material respectively.
Other products may be analysed and other sulfur contents may be determined according to this test method,
however, no precision data for products other than automotive fuels and for results outside the specified range
have been established for this standard.
For reasons of spectral overlap, this standard is not applicable to leaded automotive gasolines, lead
replacement gasolines containing greater than 8 mg/kg of lead, or to products and feedstocks containing lead,
silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the
concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.
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.
ISO 3170:2004, Petroleum liquids — Manual sampling
ISO 3171:1999, Petroleum liquids — Automatic pipeline sampling
3 Principle
A test portion of the sample, in a cup fitted with an X-ray transparent window, is placed in a beam of exciting
radiation from an X-ray tube. The intensity of the sulfur K characteristic X-radiation is measured, and the
accumulated count is compared with a calibration curve constructed from sulfur standards covering the range
of sulfur contents under examination.
NOTE The exciting radiation may be either direct, or indirect via a polarising or secondary target.
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4 Chemicals and materials
4.1 Diluent oil
The reference diluent oil is white oil (light paraffin oil) of high purity grade, with a sulfur content of 0,5 mg/kg
maximum. However, if only one type of matrix is to be analysed (e.g. motor gasoline), accuracy of results may
be improved by using a matrix matched diluent. These should match approximately the aromatic and oxygen
content of the material to be analysed, and should consist of high purity components of less than 0,5 mg/kg
sulfur content.
NOTE 1 Suitable components for the matched matrix diluent include n-heptane, 2,2,4-trimethylpentane, toluene,
xylenes, ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether
(TAME).
NOTE 2 For the analysis of diesel fuels containing FAME, accuracy of results may be improved by use of a matched
matrix diluent oil of the white oil with FAME.
4.2 Sulfur compounds
4.2.1 General
Sulfur compounds of known sulfur content shall be used for the preparation of the primary standards. The
compounds given in 4.2.2 to 4.2.5 are suitable, and their nominal sulfur contents are given. Where the purity
of these compounds is less than 99 % (m/m), either the concentrations and nature of all impurities are to be
known or certified reference materials shall be used instead.
4.2.2 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m).
4.2.3 Dibutylsulfide (DBS), with a nominal sulfur content of 21,915 % (m/m).
4.2.4 Thionaphthene (Benzothiophene) (TNA), with a nominal sulfur content of 23,890 % (m/m).
4.2.5 Dibutyldisulfide (DBDS), with a nominal sulfur content of 35,950 % (m/m).
4.3 Reference materials
Certified reference materials (CRMs) from accredited suppliers, containing a range of sulfur concentrations,
are suitable alternatives to the compounds listed in 4.2 for use as calibration standards.
4.4 Quality control samples
Stable samples representative of the materials being analysed, that have a sulfur content that is known by this
test method over a substantial period of time, or supplied commercially with a certified value. Ensure before
use, that the material is within its shelf life.
5 Apparatus
5.1 Energy-dispersive X-ray fluorescence instrument
5.1.1 Performance characteristics
For a 10 mg/kg sulfur standard, the instrument shall be capable of meeting the following performance
characteristics:
(R −R )/ R ≥ 1,3 (1)
s b b
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and
RSD(R )< 5% (2)
s
where
R is the gross count rate (counts per second) for the sulfur region of interest for a 10 mg/kg sulfur standard;
s
R is the gross count rate (counts per second) for the same region of interest for a blank sample (diluent oil);
b
RSD is the relative standard deviation based on 10 individual measurements of the standard.
5.1.2 Source of X-ray excitation, with significant flux at X-ray energies above 2,5 keV.
For X-ray detectors with a resolution greater than 200 eV at 2,3 keV, all characteristic X-ray lines originating
from the X-ray tube anode shall have an energy above 3,3 keV to ensure minimal background variation due to
scatter from the X-ray tube anode lines.
5.1.3 Removable sample cup, providing a sample depth of at least 5 mm, and equipped with replaceable
X-ray transparent film.
NOTE The transparent film is normally polyester or polycarbonate film with a thickness between 2 μm and 6 μm.
Polyester film is the preferred choice as samples of very high aromatic content may dissolve polycarbonate film. There are
possibly trace amounts of silicon, calcium and sulfur in some types of film. However, the effects should be cancelled out
when samples and standards are analysed using the same batch of film. It is important that samples, standards and
blanks are measured using the same batch of film to avoid bias.
5.1.4 X-ray detector, with a resolution not exceeding 800 eV at 2,3 keV.
5.1.5 Means of discriminating between sulfur K characteristic X-radiation and other X-rays of higher
energy (if required, e.g. filters)
5.1.6 Signal conditioning and data handling electronics, including the functions of pulse counting and
an energy region for the S peak as a minimum.
5.2 Analytical balance, capable of weighing to the nearest 0,1 mg.
5.3 Mixer, magnetic stirrer with PTFE-coated stirring rods.
5.4 Flasks, of 100 ml capacity, narrow-necked, conical, and made of borosilicate glass.
6 Sampling and sample handling
6.1 Unless otherwise specified, samples shall be taken by the procedures described in ISO 3170 or
ISO 3171.
6.2 Store samples which contain light fractions (e.g. motor gasoline and naphtha) in a refrigerator.
6.3 Mix samples by gentle hand shaking prior to the removal of the test portion.
6.4 Allow test portions to attain ambient temperature prior to analysis.
NOTE Further sample handling recommendations are given in IP 558 (ASTM D 7343) [2].
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7 Apparatus preparation
7.1 Analyser
7.1.1 Set up the analyser (5.1) in accordance with the manufacturer’s instructions. Wherever possible, the
instrument shall be continuously switched on to maintain optimum stability.
7.1.2 If required, purge the optical system with helium (minimum 99 % purity) following the manufacturer's
guidelines on flush time and flow rate to ensure stability of measurements.
7.2 Sample cups
It is recommended that disposable sample cups are used. If disposable cups are not used, thoroughly clean
the sample cups with an appropriate solvent and dry before use.
Do not re-use disposable cups.
Use the same batch of window material for each run of verification and sampling analysis (see NOTE to
5.1.3).
Keep handling of window material to the absolute minimum. Follow the guidelines given in annex B.
NOTE Differences in window material thickness between batches, or the presence of even partial finger marks, are
sufficient to affect results.
8 Calibration
8.1 General
Use either certified reference materials (4.3) or primary standards prepared from sulfur compounds (4.2)
dissolved in diluent oil (4.1) as a basis for the preparation of the two primary calibration standards. Always
validate your calibration with certified reference materials (CRMs) with matching matrices to your samples.
NOTE Recommendations on selection of diluent oil are provided in Annex A. Accuracy may be improved by utilising
manufacturers’ recommended instrument based matrix correction (see Annex A). Refer to the manufacturer’s
recommended corrections for this method.
8.2 Preparation of primary standards
8.2.1 Prepare two primary standards with sulfur contents of approximately 500 mg/kg and 1 000 mg/kg.
8.2.2 Weigh, to the nearest 0,1 mg, the appropriate quantity of diluent oil (4.1) (see Table 1), into a flask
(5.4) and add the appropriate quantity of the selected sulfur compound (4.2) or certified reference material
(4.3), weighed to the nearest 0,1 mg.
Mix the contents of the flask thoroughly at room temperature using the mixer (5.3).
Table 1 — Composition of primary standards based on nominal sulfur contents
DBT DBS TNA
Approximate sulfur content White oil
(4.2.2) (4.2.3) (4.2.4)
mg/kg g
g g g
1 000 50,0 0,29 0,23 0,21
500 50,0 0,144 0,114 0,105
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8.2.3 Calculate the sulfur content, S, in milligrams per kilogram to one decimal place in each case, from the
amounts of diluent oil and sulfur compound used as follows:
⎛⎞
mc +m c
ss d d (3)
S=×10 000
⎜⎟
mm+
⎝⎠sd
where
m is the mass of sulfur compound, expressed in grams (g);
s
m is the mass of diluent oil, expressed in grams (g);
d
c is the sulfur content of the sulfur compound, expressed in percent mass, % (m/m);
s
c is the sulfur content of the diluent oil, expressed in percent mass, % (m/m).
d
8.2.4 Store primary standards in tightly closed glass containers in a dark cool place, preferably in a
refrigerator. Before use, examine for any phase separation or discoloration, shake vigorously, and let stand to
allow for removal of air bubbles. Discard any standard that shows sediment, phase separation or
discoloration.
NOTE Stability trials have shown that primary standards are stable for up to six months when stored in a refrigerator.
8.3 Calibration standards
8.3.1. Prepare calibration standards of nominal concentrations as shown in Table 2, from the primary
standards (8.2) in the selected diluent oil (4.1), and calculate the exact sulfur content of the calibration
standard using the equation given in 8.2.3.
Prepare calibration standards of nominal sulfur content of 100 mg/kg, 70 mg/kg and 30 mg/kg from the
1 000 mg/kg primary standard, and calibration standards of nominal sulfur content of 5 mg/kg, 10 mg/kg and
50 mg/kg from the 500 mg/kg primary standard.
Use the reference diluent oil (4.1) as the nominal zero mg/kg point for the calibration. Calibration standards, of
certified sulfur content in a specified diluent oil (e.g. diesel), are suitable for use for analysis of known similar
materials.
Table 2 – Nominal composition of calibration standards
Sulfur content Mass of diluent oil Primary standard Mass of Primary standard
mg/kg
...

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