BS EN 16135:2011

BS 2000-588:2011

BSI Standards Publication

Automotive fuels —
Determination of manganese
content in unleaded petrol
— Flame atomic absorption
spectrometric method
(FAAS)
BS EN 16135:2011 BRITISH STANDARD

National foreword
This British Standard is the UK implementation of BS EN 16135:2011.
The UK participation in its preparation was entrusted to
Technical Committee PTI/13, Petroleum Testing and
Terminology.
A list of organizations represented on this committee can be
obtained on request to its secretary.
This publication does not purport to include all the
necessary provisions of a contract. Users are responsible for
its correct application.

Energy Institute, under the brand of IP, publishes and sells all
Parts of BS 2000, and all BS EN petroleum test methods that
would be Part of BS 2000, both in its annual publication
“Standard methods for analysis and testing of petroleum
and related products and British Standard 2000 Parts” and
individually.

Further information is available from:

Energy Institute, 61 New Cavendish Street, London W1G
7AR. Tel: 020 7467 7100. Fax: 020 7255 1472.
© The British Standards Institution
2012 ISBN 978 0 580 71641 6
ICS 75.160.20
Compliance with a British Standard cannot confer immunity from
legal obligations.
This British Standard was published under the authority of the
Standards Policy and Strategy Committee on 31 January 2012.
Amendments issued since publication
Date Text affected
 BS EN 16135:2011

EUROPEAN STANDARD EN 16135

NORME EUROPÉENNE
EUROPÄISCHE NORM
December 2011

ICS 75.160.20

English Version

Automotive fuels - Determination of manganese content in unleaded

petrol - Flame atomic absorption spectrometric method (FAAS)

Carburants pour automobiles - Détermination de la teneur en

Kraftstoffe für Kraftfahrzeuge - Bestimmung des
manganèse dans les essences sans plomb - Méthode par
Mangangehalts in unverbleitem Ottokraftstoff -
spectrométrie d'absorption atomique de flamme (FAAS)
Flammenatomabsorptionsspektrometrisches Verfahren
(FAAS)

This European Standard was approved by CEN on 29 October 2011.

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 and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION

C O M I TÉ EUR O P ÉEN DE NOR M A LI S A TI
ON EUR OP ÄIS C HES KOM ITEE FÜR NOR M
UNG

Management Centre: Avenue Marnix 17, B-1000 Brussels

© 2011 CEN All rights of exploitation in any form and by any means reserved
Ref. No. EN 16135:2011: E
worldwide for CEN national Members.
 BS EN 16135:2011
EN 16135:2011 (E)

Contents Page

Foreword........................................................................................................................................................... 3
1 Scope.................................................................................................................................................... 4
2 Normative references.......................................................................................................................... 4
3 Principle................................................................................................................................................ 4
4 Reagents............................................................................................................................................... 5
5 Apparatus............................................................................................................................................. 5
6 Sampling............................................................................................................................................... 6
7 Preparation of solutions...................................................................................................................... 6
General 6
Preparation of the calibration and quality control solution.................................................................................6
8 Calibration............................................................................................................................................ 7
Preparation of instrument....................................................................................................................................... 7
Preparation of the calibration................................................................................................................................. 7
Check of the calibration.......................................................................................................................................... 7
9 Sample analysis................................................................................................................................... 8
Sample solution preparation.................................................................................................................................. 8
Sample solution measurement............................................................................................................................... 8
10 Calculation............................................................................................................................................ 8
11 Expression of results.......................................................................................................................... 9
12 Precision............................................................................................................................................... 9
General 9
Repeatability, r...........................................................................................................................................................................9
Reproducibility, R......................................................................................................................................................................9
13 Test report............................................................................................................................................ 9
Bibliography.................................................................................................................................................... 10

2
 BS EN 16135:2011
EN 16135:2011 (E)

Foreword
This document (EN 16135:2011) 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.

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 June 2012, and conflicting national standards shall be withdrawn at the latest by June 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.

This document answers requirements originating from the amended Fuels Quality Directive [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, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United
Kingdom.

3
BS EN 16135:2011
EN 16135:2011 (E)

1 Scope
This European Standard specifies a method based on flame atomic absorption spectrometry (FAAS) for the determination
of manganese content present as methylcyclopentadienyl manganese tricarbonyl (MMT 1)) in unleaded petrol from about
2 mg/l to about 8 mg/l. This test method is applicable to unleaded petrol containing up to 3,7 % (m/m) oxygen, including
those with ethanol up to 10 % (V/V).

NOTE 1 Manganese as MMT is added to petrol to increase antiknock properties.

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 establish appropriate
safety and health practices and to determine the applicability of regulatory limitations prior to use.

NOTE 2 Solutions of MMT in unleaded petrol are unstable when exposed to light. Low and erratic results are expected if samples
are exposed to light prior the analysis.

NOTE 3 Manganese contents higher than 8 mg/l can be measured after preliminary dilution of the sample with a suitable solvent.
However, the precision has not been established for such procedure.

NOTE 4 Application to the determination of other manganese compounds in unleaded petrol has not been tested.

NOTE 5 For the purposes of this European 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.

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 ISO 648, Laboratory glassware — Single-volume pipettes (ISO 648:2008)

EN ISO 1042, Laboratory glassware — One-mark volumetric flasks (ISO 1042:1998)

EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170:2004)

EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171:1988)

EN ISO 3675, Crude petroleum and liquid petroleum products — Laboratory determination of density —
Hydrometer method (ISO 3675:1998)

EN ISO 12185, Crude petroleum and petroleum products — Determination of density — Oscillating U-tube
method (ISO 12185:1996)

3 Principle
A portion of petrol sample is diluted with a hydrocarbon solvent. The solution is then aspirated into the air/acetylene
flame of an atomic absorption spectrometer. The absorbance is measured at 279,5 nm. Manganese content is calculated
by comparison with calibration solutions prepared from suitable manganese compounds.

1) MMT is a registered trademark of Ethyl Corporation.

4
 BS EN 16135:2011
EN 16135:2011 (E)

4 Reagents
Unless specified otherwise, only chemicals which are known to have a high degree of purity shall be used.

Kerosene, boiling range between 150 °C and 250 °C, analytical reagent grade.

NOTE Other grades of kerosene with analyte concentration below the detection limit of the instrument and screened by
performing a wavelength scan for analyte elements may be used.

2,2,4-trimethylpentane (iso-octane), analytical reagent grade.

Xylene (mixture of isomers), analytical reagent grade.

Solvent, add 25 ml iso-octane (4.2) and 25 ml xylene (4.3) to a 50 ml glass bottle (5.1.3) and mix thoroughly.

Manganese standard solution, dissolved in oil, c(Mn) = 1 000 mg/kg.

NOTE 1 A multi-element standard solution may also be used instead of the single element standard solution.

NOTE 2 Some element standard solutions are supplied with different element content on the market. These solutions may be
used instead of the required solutions, but an initial mass to mass dilution has to be done.

Manganese intermediate solution, c(Mn) = 20 mg/kg. Weigh 0,50 g  0,01 g of manganese standard
solution (4.5) into a 50 ml bottle (5.1.3). Add kerosene (4.1) to 25,00 g  0,01 g. Each mass shall be weighed to the
nearest 0,1 mg.

In case manganese standard solutions (4.5) with different manganese content are used, the mass of standard solution shall
be adjusted accordingly to achieve 20 mg/kg manganese content.

Air, oil free, under pressure in a steel cylinder, or compressed air.

Acetylene, 99,0 % min., under pressure in a steel cylinder.

5 Apparatus
Laboratory equipment

General

All glassware shall be cleaned carefully before use.

Glassware, usual laboratory glassware, together with the following:

Beakers, 50 ml.

Volumetric flasks, 20 ml, according to EN ISO 1042, with taper sleeve and plug.

Bottles, 50 ml, with screw caps, high-density polyethylene (HDPE).

Two-mark pipette, capacity 5 ml, conforming to class A of EN ISO 648, with suction ball, or alternatively
graduated pipettes or variable volume automatic pipettes, fitted with disposable polypropylene tips.

CAUTION — Attention shall be paid during the use of pipettes in the presence of volatile solvents or
petrol samples.

5
BS EN 16135:2011
EN 16135:2011 (E)

Analytical balance, capable of weighing to the nearest 0,1 mg.

Flame atomic absorption spectrometer, equipped with manganese hollow cathode lamp or lamp emitting
specific radiation of manganese, fitted with a burner head for acetylene and air flame, and suitable for use with organic
solutions.

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, samples 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

General

In order to avoid inhomogeneity, all calibration solutions shall be shaken vigorously before use. It is strongly advised to
use freshly prepared calibration solutions.

Preparation of the calibration and quality control solution

The calibration solutions and the Quality Control (QC) solution shall be prepared as indicated in Table 1. The mass of the
manganese intermediate solution (4.6) shall be weighed to the nearest 0,1 mg in a 20 ml volumetric flask (5.1.2.2). For
each calibration solution, add 5,0 ml of the solvent (4.4) and fill with kerosene (4.1) to the mark. Calibration solutions
shall be homogenized by shaking.

Table 1 — Concentration of manganese in calibration and quality control solutions

Calibration solutions Manganese Manganese

intermediate concentration
solution g mg/l
blank 0,0 0,00
1 0,2 0,2
2 0,5 0,5
3 1,0 1,0
4 1,5 1,5
5 2,0 2,0
QC 1,0 1,0

6
 BS EN 16135:2011
EN 16135:2011 (E)

8 Calibration

Preparation of instrument

Switch on the atomic absorption spectrometer (5.3) following the manufacturer instruction. Allow the
spectrometer and the lamp to obtain stability and adjust the instrumental conditions for manganese analysis. Set the
wavelength at 279,5 nm as described by the manufacturer.

Install the burner-head for acetylene-air and ignite the flame.

Adjust the flow rates of air (4.7) and acetylene (4.8) to obtain an oxidising flame, which should be fuel lean and
light blue in colour. Aspirate the kerosene (4.1) and adjust the flow rate of kerosene to keep the flame lean and blue.

NOTE A reduced flow rate of kerosene (4.1) is employed to avoid the formation of carbon residues that can affect the stability of the
flame.

Preparation of the calibration

Set the absorbance to zero while aspirating the kerosene (4.1).

Aspirate calibration solution 3 and adjust the burner position to get the maximum absorbance.

Set the absorbance to zero while aspirating the blank (7.2). Aspirate calibration solutions 1 to 5 (7.2) to check
for linearity.

Aspirate calibration solutions 1 to 5 (7.2) and record the absorbance values. For each calibration solution
perform three absorbance measurements with an integration time from 3 s to 5 s and calculate the mean absorbance
value.

The relative standard deviation (RSD) of the mean absorbance values shall be lower than 3 %. Higher RSD indicate the
presence of nebulisation problems and/or burner head dirt. In the latter case, nebulisation chamber and burner head shall
be cleaned and the procedure repeated from 8.1.2.

A calibration curve for manganese is constructed using a linear regression with concentration of the element in
the calibration solutions (7.2) as independent variable (X) and the corresponding absorbance values of manganese as
dependent variable (Y) according to Equation (1):

Y aX b (1)

where

a is the slope of the linear regression;

b is the intercept on Y-axis.

The construction of the calibration curve is done with use of built-in software of the spectrometer.

Check of the calibration

The calibration curves shall be checked in regular intervals. A Quality Control (QC) solution shall be prepared from
certified reference materials or from certified stock solutions to verify sensitivity and accuracy of the calibration curve
(7.2).

If the manganese content of the QC solution (7.2) differs from the reference value by more than R/1,41 (reproducibility
divided by 1,41), prepare a new QC solution as in 7.2. If the manganese content of the new QC solution still differs from
the reference value, a new calibration shall be established.

7
BS EN 16135:2011
EN 16135:2011 (E)

9 Sample analysis

Sample solution preparation

Homogenize the sample by vigorous shaking. Transfer 5 ml of sample portion into a 20 ml volumetric flask by means of
a pipette (5.1.4). Weigh the sample portion, mS, to the nearest 0,1 mg using the analytical balance (5.2) and fill to the
mark with kerosene (4.1).

The solution shall be thoroughly homogenized by shaking and analyzed directly after preparation.

Sample solution measurement

The analysis of sample solution is carried out with the same instrumental parameters used for the calibration of the
spectrometer (8.1).

Aspirate the blank (7.2) and ensure that the absorbance has returned to zero. Aspirate the sample solution and perform
three absorbance measurements with the same integration time set for the calibration (8.2.4) and calculate the mean
absorbance value.

The relative standard deviation (RSD) of the mean absorbance values shall be lower than 3 %. Higher RSD indicate the
presence of nebulisation problems and/or burner head dirt. In the latter case, nebulisation chamber and burner head shall
be cleaned and the procedure repeated from 8.1.2.

Before starting the analysis of a new sample, aspirate the blank (7.2) and ensure that the absorbance has returned to zero.

NOTE A memory effect is observed when solutions containing MMT are aspirated into the flame, probably caused by a physical
interaction between the solutions and the nebulizer components.

The drift of the spectrometric system has to be checked before and at the end of the sample series or at least between
every 10 samples using the QC solution (8.3). If the manganese content of the QC solution still differs from the
reference values by more than R/1,41, proceed as indicated in 8.3.

10 Calculation
The content of manganese of the sample solution is calculated from the absorbance using Equation (1). This is done
with use of the appropriate software functions of the AA spectrometer.

The content of manganese of the petrol sample is calculated according to Equation (2):

CMn  S Mn    20 (2)
mS

where

CMn is the content of manganese of the petrol sample, expressed in mg/l;

SMn is the content of manganese of the sample solution, expressed in mg/l;

 is the density of the petrol sample (measured by EN ISO 12185 or EN ISO 3675 at 15 °C and corrected
to the temperature at which the analysis is done), expressed in g/ml;

20 is the volume of the sample solution in the flask (9.1), expressed in ml;

mS is the sample portion weight (9.1), expressed in g.

8
 BS EN 16135:2011
EN 16135:2011 (E)

11 Expression of results
Report the content of manganese in mg/l, rounded to the nearest 0,1 mg/l.

12 Precision

General

The precision given in 12.2 and 12.3 was determined by statistical examination of inter-laboratory test results in
accordance with EN ISO 4259 [1].

Repeatability, r

The difference between two test results, obtained by the same operator with the same apparatus under constant operating
conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed
the values calculated from Equation (3) only in one case in twenty.

r = 0,05 X + 0,28 (3)

where

X represents the mean of the two results expressed in mg/l.

Reproducibility, R

The difference between two single and independent test results, obtained by different operators working in different
laboratories on identical test material, would in the long run, in the normal and correct operation of the test method,
exceed the values calculated from Equation (4) only in one case in twenty.

R = 0,13 X + 0,75 (4)

where

X represents the mean of the two results expressed in mg/l.

13 Test report
The test report shall specify:

a) the reference to this European Standard, i.e. EN 16135;

b) all information necessary for the complete identification of the sample;

c) the sampling method used (see Clause 6);

d) all operating details not specified in this European Standard, or regarded as optional, together with details of any
incidents which may have influenced the test result;

e) the test result obtained (see Clause 11);

f) the date of the test.

9
BS EN 16135:2011
EN 16135:2011 (E)

Bibliography

[1] EN ISO 4259:2006, Petroleum products – Determination and application of precision data in relation to
methods of test (ISO 4259:2006)

[2] Directive 2009/30/EC of the European Parliament and of the Council of 23 April 2009 amending
Directive 98/70/EC as regards the specification of petrol, diesel and gas-oil and introducing a
mechanism to monitor and reduce greenhouse gas emissions and amending Council Directive
1999/32/EC as regards the specification of fuel used by inland waterway vessels and repealing
Directive 93/12/EEC, OJ L 140, 5.6.2009, p. 88-113

10
BS 2000 Series
Energy Institute
Buying Parts of BS 2000

Orders for BS 2000 publications should be addressed to either:

Energy Institute – Library and Information Service

61 New Cavendish Street
London
W1G 7AR

Tel: +44 (0)20 7467 7100

Fax: +44 (0)20 7255 1472
www.energyinst.org.uk

Order standards securely via:

www.energyinstpubs.org.uk

or:

British Standards Institution – Customer Services

389 Chiswick High Road
London
W4 4AL

Tel: +44 (0)20 8996 9001

Fax: +44 (0)20 8996 7001
www.bsi-global.com

Order hard copy standards securely via:

www.bsi-global.com/bsonline

Copyright

Copyright exists in all BS 2000 publications. No part of this publication may

be reproduced in any form without the prior permission in writing of BSI and
the Energy Institute. Enquiries about copyright should be made to the
Secretary of PTI/13 at the Energy Institute.

PTI/13
This page deliberately left blank
This page deliberately left blank
 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW

British Standards Institution (BSI)

BSI is the national body responsible for preparing British Standards and other standards-re
BSI is incorporated by Royal Charter. British Standards and other standardization products a

About us
We bring together business, industry, government, consumers, innovators
and others to shape their combined experience and expertise into standards
-based solutions.
The knowledge embodied in our standards has been carefully assembled
in a dependable format and refined through our open consultation
process. Organizations of all sizes and across all sectors choose standards
to help them achieve their goals.
Information on standards
We can provide you with the knowledge that your organization needs
to succeed. Find out more about British Standards by visiting our website at
bsigroup.com/standards or contacting our Customer Services team or
Knowledge Centre.
Buying standards
You can buy and download PDF versions of BSI publications, including British
and adopted European and international standards, through our website at
bsigroup.com/shop, where hard copies can also be purchased.
If you need international and foreign standards from other Standards
Development Organizations, hard copies can be ordered from our Customer
Services team.
Revisions
Our British Standards and other publications are updated by amendment or revision.
We continually improve the quality of our products and services to benefit your
business. If you find an inaccuracy or ambiguity within a British Standard or other
BSI publication please inform the Knowledge Centre.
Copyright
All the data, software and documentation set out in all British Standards and
other BSI publications are the property of and copyrighted by BSI, or some person
or entity that owns copyright in the information used (such as the international
standardization bodies) and has formally licensed such information to BSI for
commercial publication and use. Except as permitted under the Copyright, Designs
and Patents Act 1988 no extract may be reproduced, stored in a retrieval system
or transmitted in any form or by any means – electronic, photocopying, recording
or otherwise – without prior written permission from BSI. Details and advice can
be obtained from the Copyright & Licensing Department.
Useful Contacts:
Customer Services
Tel: +44 845 086 9001
Email (orders): orders@bsigroup.com
Email (enquiries): cservices@bsigroup.com

Subscriptions Subscriptions
Our range of subscription services are designed to make using standards Tel: +44 845 086 9001
easier for you. For further information on our subscription products go Email: subscriptions@bsigroup.com
to bsigroup.com/subscriptions.
Knowledge Centre
With British Standards Online (BSOL) you’ll have instant access to over 55,000
Tel: +44 20 8996
British and adopted European and international standards from your desktop.
It’s available 24/7 and is refreshed daily so you’ll always be up to date. 7004
Email: knowledgecentre@bsigroup.com
You can keep in touch with standards developments and receive substantial
discounts on the purchase price of standards, both in single copy and subscription Copyright & Licensing
format, by becoming a BSI Subscribing Member. Tel: +44 20 8996 7070
PLUS is an updating service exclusive to BSI Subscribing Members. You will Email: copyright@bsigroup.com
automatically receive the latest hard copy of your standards when they’re
revised or replaced.
To find out more about becoming a BSI Subscribing Member and the benefits
of membership, please visit bsigroup.com/shop.
With a Multi-User Network Licence (MUNL) you are able to host standards
publications on your intranet. Licences can cover as few or as many users as you
wish. With updates supplied as soon as they’re available, you can be sure your
documentation is current. For further information, email bsmusales@bsigroup.com.

BSI Group Headquarters

389 Chiswick High Road London W4 4AL UK