BRITISH STANDARD BS EN

15488:2007
BS
2000-556:2007

Ethanol as a blending
component for petrol —
Determination of
copper content —
Graphite furnace
atomic absorption
spectrometric method

The European Standard EN 15488:2007 has the status of a

British Standard

ICS 71.080.60

12&23<,1*:,7+287%6,3(50,66,21(;&(37$63(50,77('%<&23<5,*+7/$:
BS EN 15488:2007

National foreword

This British Standard is the UK implementation of EN 15488:2007.

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.
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
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Energy Institute, 61 New Cavendish Street, London W1G 7AR.
Tel: 020 7467 7100. Fax: 020 7255 1472.
This publication does not purport to include all the necessary provisions of a
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Compliance with a British Standard cannot confer immunity from
legal obligations.

This British Standard was Amendments issued since publication

published under the authority
of the Standards Policy and
Strategy Committee Amd. No. Date Comments
on 31 October 2007

© BSI and Energy Institute 2007

ISBN 978 0 580 56676 9

EUROPEAN STANDARD EN 15488
NORME EUROPÉENNE
EUROPÄISCHE NORM August 2007

ICS 71.080.60

English Version

Ethanol as a blending component for petrol - Determination of

copper content - Graphite furnace atomic absorption
spectrometric method

Éthanol comme base de mélange à l'essence - Ethanol zur Verwendung als Blendkomponente in
Détermination de la teneur en cuivre - Méthode par Ottokraftstoff - Bestimmung des Kupfergehaltes -
spectrométrie d'absorption atomique avec four en graphite Graphitrohr-Atomabsorptionsspektrometrie

This European Standard was approved by CEN on 30 June 2007.

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 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 Management Centre has the same status as the
official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, 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

COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: rue de Stassart, 36 B-1050 Brussels

© 2007 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15488:2007: E
worldwide for CEN national Members.
EN 15488:2007 (E)

Contents Page

Foreword..............................................................................................................................................................3
1 Scope ......................................................................................................................................................4
2 Normative reference ..............................................................................................................................4
3 Terms and definitions ...........................................................................................................................4
4 Principle..................................................................................................................................................5
5 Reagents and materials ........................................................................................................................5
6 Apparatus ...............................................................................................................................................5
6.1 Atomic absorption spectrometer .........................................................................................................5
7 Samples and sampling ..........................................................................................................................6
8 Preparation of blank and calibration solutions ..................................................................................6
8.1 Intermediate calibration solution .........................................................................................................6
8.2 Calibration solutions .............................................................................................................................6
9 Procedure ...............................................................................................................................................7
9.1 Instrument preparation .........................................................................................................................7
9.2 Calibration ..............................................................................................................................................7
10 Sample analysis .....................................................................................................................................8
11 Calculation..............................................................................................................................................8
12 Expression of results ............................................................................................................................8
13 Precision.................................................................................................................................................8
13.1 Repeatability...........................................................................................................................................8
13.2 Reproducibility.......................................................................................................................................9
14 Test report ..............................................................................................................................................9
Annex A (informative) Example of thermal program of the graphite furnace .............................................10
Bibliography ......................................................................................................................................................11

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 EN 15488:2007 (E)

Foreword
This document (EN 15488:2007) 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 February 2008, and conflicting national standards shall be withdrawn
at the latest by February 2008.

This document is based on IP 478 [1].

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, 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.

3
EN 15488:2007 (E)

1 Scope
This standard specifies a procedure for the determination of copper content in ethanol from 0,07 mg/kg to
0,20 mg/kg using graphite furnace atomic absorption spectrometry.

NOTE For the purpose of this document, the terms “% (m/m)” and "% (V/V)" are used to represent the mass fraction,
respectively the volume fraction of a material.

WARNING — Use of this standard may involve hazardous materials, operations and equipment. This
standard does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to use.

2 Normative reference
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 3170, Petroleum liquids — Manual sampling (ISO 3170:2004)

EN ISO 3696, Water for analytical laboratory use – Specification and test methods (ISO 3696:1987)

3 Terms and definitions

For the purposes of this document, the following terms and definitions apply.

3.1
radiant power
P
rate at which energy is transported in a beam of radiant energy

3.2
transmittance
T
ratio of the radiant power transmitted by a material to the radiant power incident upon it

3.3
absorbance
A
logarithm to the base 10 of the reciprocal of the transmittance

NOTE Can be derived by the following equation:

A = log (1/T) = -log (T) (1)

3.4
integrated absorbance
Ai
integrated area under the absorbance peak generated by the atomic absorption spectrometer

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 EN 15488:2007 (E)

4 Principle
The graphite furnace is aligned in the optical path of the atomic absorption spectrometer. A test portion is
pipetted onto the platform or at the wall of the graphite furnace. The furnace is heated in consecutive thermal
stages, firstly to dry the test portion completely without spattering, then to eliminate excess sample matrix, and
finally to volatilise the analyte of interest. During this final stage, the amount of light absorbed by the copper
atoms is measured over a specified period. The integrated absorbance Ai, produced by the copper in the test
portion, is compared to a calibration curve constructed from copper standards in ethanol solution.

NOTE The second heating stage is used to eliminate as much of the sample matrix as possible before the
atomization step, as non-dissociated molecular species are the most common form of interference. Spectrometers are
equipped with background correction capabilities to control further possibilities of erroneous results due to molecular
absorption.

5 Reagents and materials

5.1 General
All reagents shall be of analytical reagent grade or of higher purity.

5.2 Ethanol, 99,8 % (m/m) minimum purity.

5.3 Copper standard, aqueous solution containing 1 000 mg/l of copper as inorganic salt (e.g. nitrate), or
a multi-element aqueous standard containing 1 000 mg/l of copper.

5.4 Water, for analytical laboratory use, conforming to grade 3 of EN ISO 3696.

5.5 Argon, regulated compressed gas of 99,999 % minimum purity for the graphite furnace gas flow system.

5.6 Nitric acid (HNO3), c(HNO3) ≈ 0,5 mol/l

Cautiously add 50 ml ± 2 ml of nitric acid (ρ = 1,40 g/ml) to 500 ml ± 10 ml water (5.4).
Mix and allow to cool to room temperature.
Make up to 1 000 ml with water (5.4).

6 Apparatus

6.1 Atomic absorption spectrometer

6.1.1 Capable of setting the wavelength at 324,8 nm or 327,4 nm, with the appropriate slit, e.g. as specified
by the manufacturer, and using peak area integration for the signal and background readings. It shall be
equipped with the features described in 6.1.2 to 6.1.4.

NOTE The wavelength of 327,4 nm can be used for the measurements, however, the precision for results measured
at this wavelength was not determined.

6.1.2 Copper hollow cathode lamp

6.1.3 Background correction system, capable to cover the 324,8 nm or 327,4 nm wavelength.

6.1.4 Graphite furnace accessory, which uses pyrolytically coated graphite tubes with or without
integrated platforms.

6.2 Autosampler, capable of reproducibly delivering 10 µl ± 0,1 µl aliquots to the graphite furnace.

6.3 Micropipette, capable of reproducibly delivering volumes in the range 20 µl to 100 µl with an accuracy
of ± 0,4 µl at 50 µl.

5
EN 15488:2007 (E)

6.4 Polyethylene containers, 25 ml volume.

Rinse the containers with water (5.4).

6.5 Analytical balance, capacity of 100 g and capable of weighing to the nearest 0,01 g.

6.6 Ultrasonic bath

7 Samples and sampling

Unless otherwise specified, laboratory samples shall be obtained by the procedures described in
EN ISO 3170. High density polyethylene containers shall be used. The containers should be carefully cleaned
and rinsed with pure water to avoid contamination.

Samples should be analysed as soon as possible after removal from bulk supplies, to prevent loss of copper.

NOTE High density polyethylene containers are used to prevent losses of copper by wall adsorption.

8 Preparation of blank and calibration solutions

8.1 Intermediate calibration solution

Weigh a polyethylene container (6.4) and transfer with a micropipette (6.3) 100 µl of copper standard (5.3).
Add water (5.4) to the container to bring the mass up to approximately 10,0 g and re-weigh to the nearest
0,01 g.

Seal the container, mix well and mark with the copper content calculated as following:

Vc
S= (2)
mw

where

S is the copper content of the intermediate calibration solution in mg/kg;

Vc is the volume of copper standard (5.3) in µl;

mw is the mass of water (5.4) in g.

NOTE This procedure leads to intermediate calibration solution with nominal copper content corresponding to
10 mg/kg. The intermediate solution is stable for up to one week.

8.2 Calibration solutions

The calibration solutions shall be prepared daily.

Weigh five polyethylene containers (6.4), add about 5 g ethanol (5.2) to each container and then respectively
20 µl, 40 µl, 60 µl, 80 µl and 100 µl of intermediate calibration solution (8.1). Reserve a sixth container for the
preparation of the blank.

Add ethanol (5.2) to each of the six containers to bring the mass up to approximately 10,0 g and re-weigh to
the nearest 0,01 g.

Seal each container, mix well and mark with the copper content (including the blank) calculated as following:

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 EN 15488:2007 (E)

Vi ⋅ S
C= (3)
me

where

C is the copper content of the calibration solution in µg/kg;

S is the copper content of the intermediate calibration solution (8.1) in mg/kg;

Vi is the volume of intermediate calibration solution (8.1) in µl;

me is the mass of ethanol (5.2) in g.

NOTE This procedure leads to calibration solutions with nominal copper contents corresponding to 0 µg/kg, 20 µg/kg,
40 µg/kg, 60 µg/kg, 80 µg/kg and 100 µg/kg respectively.

9 Procedure

9.1 Instrument preparation

9.1.1 Set the spectrometer (6.1) at a wavelength of 324,8 nm or 327,4 nm, and the appropriate slit width.

9.1.2 Condition new (or re-installed) graphite tube assemblies with the temperature program provided by
the spectrometer manufacturer.

9.1.3 Adjust the autosampler (6.2) tip as near as possible to the graphite platform surface but avoid contact
between tip and surface. Use the blank solution (8.2) to evaluate the correct delivery of ethanol solutions. The
delivered aliquot should distribute evenly onto the platform. Autosampler cups made of polyethylene,
polypropylene or polytetra-fluorethylene (PTFE) can be used. Use nitric acid (5.6) as the rinse solution of the
autosampler.

Due to the high volatility and surface tension of ethanol, the positioning of the tip and the correct delivery of
sample aliquots should be checked periodically, as uneven delivery leads to erroneous measurements. Check
the correct delivery of aliquots when the integrated absorbance of two repeated injections differ by more than
15 %.

9.2 Calibration

9.2.1 Apply the thermal program for copper analysis as given in the instrument manufacturer’s instructions.
Due to the different design of graphite furnace atomizers, the thermal program shall be developed according
to the atomizer characteristics. Refer to the instrument manual to set the best temperatures for copper
pyrolisis and atomization steps. A thermal program is given as an example in Annex A.

9.2.2 Temperatures, ramp and hold times of drying steps shall be optimised so that the sample dries
completely without spattering.

9.2.3 The ramp time for the pyrolisis step may be lengthened if it appears that an excess amount of smoke
from the sample matrix is generated very quickly as the furnace heats from the second drying step (Drying 2)
to the pyrolisis. Also, all smoke shall be evolved at least 5 s before the end of the pyrolisis step. If smoke still
evolves at the end of the pyrolisis step, the hold time shall be lengthened.

9.2.4 For the spectrometer trace of absorbance versus atomization hold time, the absorbance at the end of
the atomization hold time should return to the initial baseline absorbance. If this is not observed, increase the
atomization hold time until this is attained.

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EN 15488:2007 (E)

9.2.5 On each day of analysis, or together with each set of samples, prepare a calibration curve from the six
calibration solutions (8.2). For each calibration solution, pipette 10 µl onto the platform of the graphite tube.
Apply the copper thermal program. Perform three runs for each calibration solution and average the recorded
integrated absorbances, Ai.

9.2.6 Plot the average of integrated absorbances (on y-axis) against the copper content in µg/kg (on x-axis).
Construct the best fit curve from the data.

The correlation coefficient should be not lower than 0,990. Otherwise repeat the procedure in Clause 8.

NOTE Many spectrometers have the capability of constructing the calibration curve, internally, or via computer
software. Experience has shown that the curve is linear up to approximately 100 µg/kg. If curve fitting software is
unavailable, the calibration solutions may be diluted with ethanol to bring them into the linear calibration region.

10 Sample analysis
Vigorously shake the sample container and homogenise using the ultrasonic bath (6.6) for 1 min prior to
withdrawal of the test portions.

For each test portion, pipette a known volume, from 5 µl to 25 µl onto the platform of the graphite tube. Apply
the copper thermal program to the furnace. Perform three runs for each test portion and average the
measured integrated absorbance, Ai.

If the integrated absorbance exceeds that of the highest calibration solution dilute the sample.

11 Calculation
Enter the averaged Ai of the test portion in the calibration curve produced concurrently or on the same day.
Read off the copper content of the sample, taking into account the pipetted volume or dilution.

12 Expression of results
Report the copper content in mg/kg, rounded to the nearest 0,002 mg/kg.

13 Precision
NOTE The precision given was determined by statistical examination of interlaboratory test results using
EN ISO 4259 [2].

13.1 Repeatability

The difference between two successive test results obtained by the same operator with the same apparatus
under constant operating conditions on identical test material would, in the normal and correct operation of the
test method, exceed the value given below only in one case in twenty:

r = 0,065 X + 0,003 (4)

where

X is the average of the two results being compared, in mg/kg.

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 EN 15488:2007 (E)

13.2 Reproducibility

The difference between two single and independent results obtained by different operators working in different
laboratories on nominally identical test material would, in the normal and correct operation of the test method,
exceed the value given below only in one case in twenty:

R = 0,316 X + 0,013 (5)

where

X is the average of the two results being compared, in mg/kg.

14 Test report
The test report shall contain at least the following information:

a) type and identification of the product under test;

b) reference to this European standard, i.e. EN 15488;

c) result of the test (see clause 12);

d) any deviation from the procedure described;

e) date of the test.

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EN 15488:2007 (E)

Annex A
(informative)

Example of thermal program of the graphite furnace

Table A.1 shows an example of a thermal program that can be used for the determination described in this
method.

Table A.1 — Example of a thermal program for the graphite furnace

Step Drying 1 Drying 2 Pyrolisis Atomization Cleaning

a
a b c

Temperature, °C 70 150 1 000 1 900 2 450

Ramp, s 1 10 15 0 1
Hold, s 30 20 35 5 5
Gas flow, ml/min 300 250 300 0 300
Read - - - ON -
a see 9.2.2.
b see 9.2.3.
c see 9.2.4.

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 EN 15488:2007 (E)

Bibliography

[1] IP 478:2004, Standard Test Method for Determination of Copper in Jet Fuels by Graphite Furnace
Atomic Absorption Spectrometry.

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

11
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