You are on page 1of 12

IP 391/07 BS EN 12916 : 2006

BS 2000-391 : 2006

EUROPEAN STANDARD EN 12916

NORME EUROPENNE

EUROPISCHE NORM May 2006

ICS 75.080 Supersedes EN 12916:2000

English version

Petroleum products Determination of aromatic hydrocarbon


types in middle distillates High performance liquid
chromatography method with refractive index detection

Produits ptroliers - Dtermination des familles Minerallerzeugnisse - Bestimmung von


d'hydrocarbures aromatiques dans les distillats moyens - aromatischen Kohlenwasserstoffgruppen in
Mthode par chromatographie liquide haute Mitteldestillaten - HPLC Verfahren mit Brechzahl-
performance avec dtection par rfractomtrie Detektor
diffrentielle

This European Standard was approved by CEN on 20 April 2006.

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 Central
Secretariat 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 Central Secretariat has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark,
Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg,
Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Spain, Sweden, Switzerland and United
Kingdom.

European Committee for Standardization


Comit Europen de Normalisation
Europisches Komitee fr Normung

Central Secretariat: rue de Stassart, 36 B-1050 Brussels

2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 12916:2006 E
worldwide for CEN national Members.

391.1
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

Foreword

This document (EN 12916:2006) 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 November 2006, and conflicting national standards shall be
withdrawn at the latest by November 2006.

This document supersedes EN 12916:2000.

The method has been updated and improved in the sense that:

a method without back-flush is prescribed resulting in simplicity of the instrument;

the integration of aromatic hydrocarbon types has been better defined (definition of cut times);

fluorene is used as calibrant for the determination of aromatic hydrocarbons content instead of
1-methylnaphthalene in order to minimize the bias on the di-aromatic hydrocarbons content between
the former method and this version;

diesel fuels containing FAME up to 5 % (V/V) are included in the scope of the method and the
interferences between FAME and tri+-aromatic hydrocarbons do not exist any more;

The precision of the method has been re-calculated using data from a new inter-laboratory test
programme. The precision statement for % (m/m) PAHs, as defined by EN 590: 2004[1], is now
included.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, 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.

391.2
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

1 Scope 2 Normative references

This European Standard specifies a test method for The following referenced documents are
the determination of the content of mono-aromatic, indispensable for the application of this document.
di-aromatic and tri+-aromatic hydrocarbons in diesel For dated references, only the edition cited applies.
fuels that may contain fatty acid methyl esters
(FAME) up to 5 % (V/V) and petroleum distillates in For undated references, the latest edition of the
the boiling range from 150 C to 400 C. The referenced document (including any amendments)
polycyclic aromatic hydrocarbons content is applies.
calculated from the sum of di-aromatic and
tri+-aromatic hydrocarbons and the total content of EN 14214, Automotive fuels Fatty acid methyl
aromatic compounds is calculated from the sum of esters (FAME) for diesel engines Requirements
the individual aromatic hydrocarbon types. and test methods.

Compounds containing sulfur, nitrogen and oxygen EN ISO 1042, Laboratory glassware One-mark
may interfere in the determination; mono-alkenes do volumetric flasks (ISO 1042:1998).
not interfere, but conjugated di-alkenes and
polyalkenes, if present, may do so. EN ISO 3170, Petroleum liquids Manual sampling
(ISO 3170:2004).
The precision statement of the test method has
been established for diesel fuels with and without EN ISO 3171, Petroleum liquids Automatic
FAME blending components, with a mono-aromatic pipeline sampling (ISO 3171:1988).
content in the range from 6 % (m/m) to 30 %
(m/m), a di-aromatic content from 1 % (m/m) to 3 Terms and definitions
10 % (m/m), a tri+-aromatic content from
0 % (m/m) to 2 % (m/m), a polycyclic aromatic For the purposes of this document, the following
content from 1 % (m/m) to 12 % (m/m), and a total terms and definitions apply.
aromatic content from 7 % (m/m) to 42 % (m/m).
3.1
NOTE 1 - For the purpose of this European Standard, the non-aromatic hydrocarbon
terms "% (m/m)" and "% (V/V)" are used to represent
compound having a shorter retention time on the
the mass fraction, and the volume fraction of a material
specified polar column than the majority of mono-
respectively.
aromatic hydrocarbons.
NOTE 2 - By convention, the aromatic hydrocarbon types
are defined on the basis of their elution characteristics 3.2
from the specified liquid chromatography column relative mono-aromatic hydrocarbon
to model aromatic compounds. Their quantification is MAH
performed using an external calibration with a single compound having a longer retention time on the
aromatic compound for each of them, which may or may specified polar column than the majority of non-
not be representative of the aromatics present in the aromatic hydrocarbons, but a shorter retention time
sample. Alternative techniques and test methods may than the majority of di-aromatic hydrocarbons.
classify and quantify individual aromatic hydrocarbon
types differently.
3.3
di-aromatic hydrocarbon
WARNING The use of this standard may involve
DAH
hazardous materials, operations and equipment. This
compound having a longer retention time on the
standard does not purport to address all of the
specified polar column than the majority of mono-
safety problems associated with its use. It is the
aromatic hydrocarbons, but a shorter retention time
responsibility of the user of this standard to
than the majority of tri+-aromatic hydrocarbons.
establish appropriate safety and health practices and
to determine the applicability of regulatory
limitations prior to use.

391.3
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

3.4 The column is connected to a refractive index


tri+-aromatic hydrocarbon detector which detects the components as they
T+AH elute from the column. The electronic signal from
compound having a longer retention time on the the detector is continually monitored by a data
specified polar column than the majority of di- processor. The amplitudes of the signals from the
aromatic hydrocarbons, but a shorter retention time aromatics in the sample are compared with those
than chrysene. obtained from calibration standards in order to
calculate the mass fraction of MAHs, DAHs and
3.5 T+AHs in the sample. The sum of the DAHs and
polycyclic aromatic hydrocarbon T+AHs mass fractions is reported as the mass
POLY-AH fraction of POLY-AH, and the sum of the MAHs,
sum of the di-aromatic hydrocarbons and tri+- DAHs and T+AHs mass fractions is reported as the
aromatic hydrocarbons mass fraction of total aromatic hydrocarbons.

3.6 5 Reagents and materials


total aromatic hydrocarbon
sum of the mono-aromatic hydrocarbons, di- NOTE - The highest purity reagents and materials
aromatic hydrocarbons and tri+-aromatic available should be used; those required to be of high
hydrocarbons performance liquid chromatography (HPLC) grade are
commercially available from major suppliers.
NOTE - Published and unpublished data indicate that the
major constituents for each hydrocarbon type may 5.1 Cyclohexane, of 99 % (m/m) minimum
include: purity.

a) non-aromatic hydrocarbons: acyclic and cyclic NOTE - Cyclohexane may contain benzene as an impurity.
alkanes (paraffins and naphthenes), mono-
alkenes (if present);
5.2 Heptane, HPLC analytical grade, as the
mobile phase.
b) MAHs: benzenes, tetralins, indanes and higher
naphthenobenzenes (e.g. octahydrophenan-
threnes), thiophenes, styrenes, conjugated NOTE 1 - Batch to batch variation of the solvent water
polyalkenes; content, viscosity, refractive index, and purity may cause
unpredictable column behaviour. Drying (for example, by
c) DAHs: naphthalenes, biphenyls, indenes, standing over activated molecular sieve type 5A) and
fluorenes, acenaphthenes, benzothiophenes and filtering the mobile phase may help reducing the effect of
dibenzothiophenes; trace impurities present in the solvent.

d) T+AHs: phenanthrenes, pyrenes, fluoranthenes, NOTE 2 - It is recommended practice to de-gas the mobile
chrysenes, triphenylenes, benzanthracenes. phase before use; this can be done conveniently on-line
or offline by helium sparging, vacuum degassing or
ultrasonic agitation. A failure to de-gas the mobile phase
3.7
may lead to negative peaks.
fatty acid methyl ester
FAME
5.3 1-Phenyldodecane, of 98 % (m/m) minimum
mixture of fatty acid methyl esters as specified in
purity.
EN 14214.
5.4 1,2-Dimethylbenzene (o-xylene), of 98 %
4 Principle (m/m) minimum purity.

A known mass of sample is diluted with heptane 5.5 Hexamethylbenzene, of 98 % (m/m)


and a fixed volume of this solution injected into a minimum purity.
high performance liquid chromatograph fitted with
a polar column. This column has little affinity for 5.6 Naphthalene, of 98 % (m/m) minimum
non-aromatic hydrocarbons, whilst exhibiting a purity.
strong selectivity for aromatic hydrocarbons. As a
result of this selectivity, the aromatic hydrocarbons 5.7 Fluorene, of 98 % (m/m) minimum purity.
are separated from the non-aromatic hydrocarbons
and into distinct bands according to their ring 5.8 Phenanthrene, of 98 % (m/m) minimum
structure, i.e. MAH, DAH and T+AH compounds. purity.

391.4
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

5.9 Dibenzothiophene, of 95 % (m/m) minimum cyano-bonded) silica stationary phase meeting the
purity. resolution requirements given in 8.6, 8.7 and 8.9.
See Annex A for guidance on the selection and use
5.10 9-Methylanthracene, of 95 % (m/m) of suitable column systems.
minimum purity.
6.5 Temperature control, consisting of either a
5.11 Chrysene, of 95 % (m/m) minimum purity. heating block, or an air-circulating HPLC column
oven or an alternative form of temperature control,
5.12 FAME (see 3.7). such as a temperature-controlled laboratory, capable
of maintaining a constant temperature in the range
WARNING Protective gloves should be worn 20 C 1 C to 40 C 1 C.
when handling aromatic compounds.
NOTE - The refractive index detector is sensitive to both
6 Apparatus sudden and gradual changes in the temperature of the
eluent. All necessary precautions should be taken to
establish constant temperature conditions throughout the
6.1 Liquid chromatograph, consisting of a high liquid chromatograph system. The temperature should be
performance instrument capable of pumping the optimised depending on the stationary phase.
mobile phase at flow rates from 0,5 ml/min to
1,5 ml/min, with a precision better than 0,5 % and 6.6 Refractive index detector, capable of being
a pulsation of < 1 % full scale deflection under the operated over the refractive index range 1,3 to 1,6
test conditions described in Clause 8. and giving a linear response over the calibration
range with a suitable output signal for the data
6.2 Sample injection system, capable of system.
nominally injecting 10 :l of sample solution with a
repeatability better than 1 %. NOTE - If the detector is equipped with a device for
independent temperature control, it is recommended that
NOTE 1 - Equal and constant volumes of the calibration it is set at the same temperature as the column oven.
and sample solutions are injected into the chromatograph.
Both manual and automatic sample injection systems, 6.7 Computer or computing integrator,
using either complete or partial filling of the sample loop, compatible with the refractive index detector,
can meet these repeatability requirements when used
having a minimum sampling rate of 1 Hz and
correctly. When using the partial filling mode, it is
capable of peak area and retention time
recommended that the injection volume is less than half
the total loop volume. For complete filling of the loop, measurements. It shall also have minimum
best results are obtained by overfilling the loop at least capabilities for post-analysis data processing such
six times. as baseline correction and re-integration.

The repeatability of the injection system may be checked NOTE - The ability to perform automatic peak detection
by comparing peak areas from at least four injections of and identification and to calculate sample concentrations
the system calibration standard (see 8.3). from peak area measurements is recommended, but is not
essential.
NOTE 2 - Sample and calibration injection volumes
different from 10 :l (typically in the range 3 :l to 20 :l) 6.8 Volumetric flasks, 10 ml and 100 ml
may be used provided they meet the requirements for capacity, conforming to grade A of EN ISO 1042.
injection repeatability, refractive index sensitivity and
linearity (see 9.4), and column resolution (see 8.9). 6.9 Analytical balance, capable of weighing to
the nearest 0,000 1 g.
6.3 Sample filter, if required (see 10.1),
consisting of a microfilter of porosity 0,45 :m or
less, chemically inert towards hydrocarbon solvents,
7 Sampling
for the removal of particulate matter from the
Unless otherwise specified in the commodity
sample solutions.
specification, samples shall be taken as described in
NOTE - PTFE filters have been found to be suitable. EN ISO 3170 or EN ISO 3171 and/or in accordance
with the requirements of national standards or
6.4 Column system, consisting of a stainless regulations for the sampling of the product under
steel HPLC column(s) packed with a commercial test.
3 :m, 5 :m or 10 :m amino-bonded (or amino/

391.5
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

Key
1 pump 4 column
2 injection device 5 refractive index detector
3 oven 6 data acquisition system

Figure 1 Diagrammatic representation of liquid chromatograph

8 Apparatus preparation 1-phenyldodecane (5.3), 0,5 g 0,05 g 1,2


dimethylbenzene (5.4), 0,1 g 0,01 g
8.1 Set up the liquid chromatograph (6.1), hexamethylbenzene (5.5), 0,1 g 0,01 g
sample injection system (6.2), column (6.4), naphthalene (5.6), 0,05 g 0,005 g
refractive index detector (6.6) and computing dibenzothiophene (5.9) and 0,05 g 0,005 g
integrator (6.7) in accordance with the 9-methylanthracene (5.10) into a 100 ml volumetric
manufacturers manuals. If a column oven is used flask. Place the flask and its contents into an
(6.5), install the HPLC column in the column oven. ultrasonic bath until a visual examination shows that
Maintain the sample injection system at the same all the components have dissolved into the 1,2
temperature as the sample solution; in most cases dimethylbenzene/cyclohexane mixture. Remove from
this should be at room temperature. the ultrasonic bath and make up to the mark with
heptane.
NOTE - Regular maintenance of the liquid chromatograph
and its components is important to ensure consistent NOTE - The SCS1 may be kept for at least one year if
performance. Leakages and partial blockage of filters, stored in a tightly stoppered bottle in a cool dark place
frits, injector needles and valve rotors can produce flow (for example in a refrigerator).
rate inconsistencies and poor injector repeatability.
8.4 Prepare a system calibration standard
8.2 Adjust the flow rate of the mobile phase to 2 (SCS2) by weighing, to the nearest 0,000 1 g,
a constant between 0,8 ml/min and 1,2 ml/min and 0,4 g 0,1 g FAME (5.12) and 0,04 g 0,01 g
ensure the reference cell of the refractive index chrysene (5.11) into a 100 ml volumetric flask and
detector is full of mobile phase (see NOTE). Allow making up to the mark with heptane (5.2). Keep the
the temperature of the column and of the refractive solution into an ultrasonic bath at 35 C.
index detector, if it is equipped with temperature
control, to stabilize. Ensure the appearance is homogeneous without
deposits of chrysene on the bottom.
NOTE - In order to minimize instrument drift, the
reference cell of the detector should be filled with mobile NOTE 1 - 25 min has been found to be a suitable time for
phase, either by flushing mobile phase through the all the components to become dissolved.
reference cell immediately prior to the analysis, and then
isolating the reference cell to prevent evaporation, or by NOTE 2 - The SCS2 may be kept for at least one year if
compensating for evaporation by supplying a steady flow stored in a tightly stoppered bottle in a dark place (for
of mobile phase through the reference cell. The flow example in a refrigerator).
should be optimized so that cell mismatch due to drying-
out (reference cell) or temperature or pressure gradients 8.5 When operating conditions are steady, as
(reference or analysis cells, depending the type of
indicated by a stable horizontal baseline, inject 10 :l
detector) are minimized; with some detectors this can be
accomplished using a mobile phase flow through the
of the SCS1 (8.3). Ensure the baseline drift over the
reference cell of one tenth of that through the analysis period of the HPLC analysis run is less than 1 % of
cell. the peak height for cyclohexane.

8.3 Prepare a system calibration standard NOTE - A baseline drift greater than this indicates
1 (SCS1) by weighing, to the nearest 0,000 1 g, problems with the temperature control of the
column/refractive index detector and/or material eluting
1,0 g 0,1 g cyclohexane (5.1), 0,1 g 0,01 g
from the column.

391.6
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

Key
1 cyclohexane 5 naphthalene
2 phenyldodecane 6 dibenzothiophene
3 1,2 dimethylbenzene 7 9-methylanthracene
4 hexamethylbenzene

Figure 2 Chromatogram of the system calibration standard SCS1

8.6 Ensure the components of the SCS1 are Ensure the retention time of chrysene peak be
eluted in the order: cyclohexane, phenyldodecane, higher than the retention time of 9-
1,2 dimethylbenzene, hexamethylbenzene, methylanthracene peak.
naphthalene, dibenzothiophene and 9-methylan-
thracene. NOTE - Test the column with the SCS2 to verify its
performances when starting the method with a new
8.7 Ensure that baseline separation is obtained column, after a period of time of inactivity or when
between all components of the SCS1 (see Figure 2). samples with FAME should be run.

8.8 Measure the retention times of the 9 Calibration


cyclohexane, phenyldodecane, 1,2 dimethyl-
benzene, hexamethylbenzene, dibenzothiophene and 9.1 Prepare four calibration standards referenced
9-methylanthracene peaks using the data system. A, B, C and D at the approximate (but accurately
known) concentrations given in Table 1, by
8.9 Ensure that the resolution between weighing the appropriate materials to the nearest
cyclohexane and 1,2 dimethylbenzene is between 0,000 1 g into 100 ml volumetric flasks and making
5,7 and 10 (see 11.2). up to the mark with heptane (5.2).

8.10 Calculate the cut times using the equations NOTE - The calibration standards are viable for at least six
given in 11.3. months if stored in tightly stoppered containers (e.g.
100 ml volumetric flasks) in a cool dark place (for
example, in a refrigerator).
8.11 Ensure the appearance of SCS 2 is
homogeneous (8.4) and then, inject 10 :l of the
9.2 When operating conditions are steady (see
SCS2 and check the chrysene peak elutes just
8.4), inject 10 :l of calibration standard A. Record
before or together with the first peak of FAME.
the chromatogram and measure the peak areas for
each aromatic standard (see Figure 3).

391.7
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

Table 1 Concentrations of calibration standard components

Calibration 1,2 Dimethylbenzene Fluorene Phenanthrene


standard g/100 ml g/100 ml g/100 ml
A 4,0 2 0,4
B 1,0 1,0 0,2
C 0,25 0,25 0,05
D 0,05 0,02 0,01

Key
1 1,2 dimethylbenzene
2 fluorene
3 phenanthrene

Figure 3 Chromatogram of calibration standard A

9.3 Repeat 9.2 for each of the other calibration 10 Procedure


standards B, C and D. If the peak area for
phenanthrene in calibration standard D is too small 10.1 Weigh between 0,9 g and 1,1 g of sample
to be accurately measured, prepare a new to the nearest 0,001 g into a 10 ml volumetric flask
calibration standard, D+, with a higher concentration and make up to the mark with heptane (5.2). Shake
of phenanthrene, e.g. 0,02 g/100 ml, and repeat thoroughly to mix. Allow the solution to stand for
9.2. 10 min and, if necessary,use a filter to remove
insoluble material (6.3).
9.4 Plot concentration in g/100 ml against area
counts for each aromatic standard, i.e. 1,2 For samples where the concentration of one or more
dimethylbenzene, fluorene and phenanthrene. aromatic hydrocarbon types falls outside the
Calibration plots shall be linear with a correlation
coefficient greater than 0,999 and an intercept calibration range, prepare a more concentrated
between 0,01 g/100 ml. (2 g/10 ml) or more dilute (0,5 g/10 ml) sample
solution, as appropriate.
NOTE - A computer or data system may be used to
perform these calibrations. NOTE - If another dilution factor than the one suggested

391.8
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

is used, it may modify the retention time and the amount retention time provided the signal has returned to its
calculated. baseline value (i.e. the signal at point A after
allowance has been made for any baseline drift,
10.2 When operating conditions are steady (see 8.5).
8.4) and identical to those used for obtaining the
calibration data (Clause 9), inject 10 :l of the 10.5 Drop a vertical line from the valley between
sample solution (10.1) and start data collection. the non-aromatics and MAHs (point B, tb , in Figure
4) to the baseline (10.4). If several valleys are
10.3 Identify correctly the MAHs, DAHs and present, use the nearest-one from the time tb (see
T+AHs: 11.3).

MAH are compounds having a retention 10.6 Drop a vertical line from the valley between
time between tb and tc (see 11.3); the MAHs and DAHs (point C, tc in Figure 4) to the
baseline (10.4). If several valleys are present, use
DAH are compounds having a retention time the nearest-one from the time tc (see 11.3).
between tc and td (see 11.3);
10.7 Drop a vertical line from the valley between
T+AH are compounds having a retention the DAHs and T+AHs (point D, td, in Figure 4) to
time between td and te (see 11.3). the baseline (10.4). If several valleys are present,
use the nearest-one from the time td (see 11.3). If
10.4 Draw a line from just before the beginning of no valley is present, use td.
the non-aromatics peak (point A, ta, in Figure 4) to
a point on the chromatogram immediately after the 10.8 Integrate the area due to MAHs from points
T+AHs (point E, te, in Figure 4), where the signal B to C.
has returned to its baseline value (i.e. the signal at
point A after allowance has been made for any 10.9 Integrate the area due to DAHs from points
baseline drift, 8.5). C to D.

If DAHs and/or T+AHs are not present in the 10.10 Integrate the area due to T+AHs from
sample then point E shall be selected at an earlier points D to E.

Key
1 mono-aromatic hydrocarbons
2 di-aromatic hydrocarbons
3 tri+-aromatic hydrocarbons

Figure 4 Chromatogram with the peaks identified and showing the integration

391.9
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

10.11 If the chromatographic data have been TAH+ have been eluted.
processed automatically, check visually that the
integration parameters have correctly identified and 11.4 Aromatic hydrocarbons type content
integrated the peaks.
Determine the content, C, as mass fraction, of
11 Calculation MAHs, DAHs and T+AHs, either directly from the
data system, or calculated using the following
11.1 Reference times equation:

Retention times to be measured from the [( A x S ) + I ] xV


C= (2)
chromatogram of SCS1 (8.7) are: M

the retention time of cyclohexane (t1), in where


seconds;
the retention time of phenyldodecane (t2), in A is the MAH or DAH or T+AH peak
seconds; area of the sample;
the retention time of 1,2 dimethylbenzene
(t3), in seconds; S is the slope of the MAH or DAH or
the retention time of hexamethylbenzene T+AH calibration plot (concen-
(t4), in seconds; tration in g/100 ml versus peak
the retention time of dibenzothiophene (t6), area);
in seconds;
the retention time of 9-methylanthracene I is the intercept of the MAH or DAH
(t7), in seconds. or T+AH calibration plot;

11.2 Column resolution M is the mass of sample taken, in


grams (10.1);
Calculate the resolution, R, between cyclohexane
and 1,2 dimethylbenzene using the following V is the volume of sample solution, in
equation. millilitres (10.1).

2 (t 3 t 1 ) 11.5 Polycyclic and total aromatic hydrocarbons


R= (1) content
1,699 ( y1 + y 3 )
Calculate the polycyclic aromatic hydrocarbons
where content of the sample, as a mass fraction, from the
y1 is the width at half-height of the sum of the di and tri+-hydrocarbons types contents
cyclohexane peak, in seconds; (i.e. DAHs and T+AHs), and the total aromatic
hydrocarbons content of the sample, as a mass
y3 is the width at half-height of the 1,2 fraction, from the sum of the individual
dimethylbenzene peak, in seconds. hydrocarbons types (i.e. MAHs, DAHs and T+AHs).
11.3 Cut times
12 Expression of results
Determine the cut times, ta, tb, tc, td, and te, in
seconds, using the following: Report the MAH, DAH, T+AH, POLY-AH and total
aromatic hydrocarbons content to the nearest 0,1 %
ta is a point on the baseline just before (m/m).
the non-aromatic peak;
13 Precision
tb is 0,5 (t1 + t2);
13.1 General
tc is t4;
The precision as determined by statistical
td is t6 + 0,4 (t7 ! t6); examination of inter-laboratory test results in
accordance with EN ISO 4259[2] is given in 13.2
te is a point on the baseline when all and 13.3.

391.10
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

13.2 Repeatability 14 Test report


The difference between two test results, obtained The test report shall include at least the following
by the same operator with the same apparatus information:
under constant operating conditions on identical test
material, in the normal and correct operation of the a) type and identification of the product under
test method, would in the long run exceed the test;
values given in Table 2 only in one case in twenty.
b) reference to this European Standard;
13.3 Reproducibility
c) result of the test (see Clause 12);
The difference between two single and independent
results, obtained by different operators working in d) deviation from the procedure described;
different laboratories on nominally identical test
material, in the normal and correct operation of the e) date of the test.
test method, would in the long run exceed the
values given in Table 2 only in one case in twenty.

Table 2 Precision values

Aromatic type Range Repeatability Reproducibility


% (m/m)
Mono-aromatic hydrocarbons 6 - 30 0,032 X ! 0,161 0,144 X ! 0,344
(MAH)
Di-aromatic hydrocarbons 1 - 10 0,151 X ! 0,036 0,363 X ! 0,087
(DAH)
Tri+-aromatic hydrocarbons 0-2 0,092 X + 0,098 0,442 X + 0,471
(T+AH)
Polycyclic aromatic hydrocarbons 1 - 12 0,074 X + 0,186 0,185 X + 0,465
(POLY-AH)
Total aromatic hydrocarbons 7 - 42 0,040 X ! 0,070 0,172 X ! 1,094
NOTE - X is the mean of two results being compared.

391.11
AROMATICS IN MIDDLE DISTILLATES HPLC RI DETECTION, IP 391

Annex A
(informative)

Column selection and use


Column lengths of 150 mm to 300 mm with an Most of the columns used in the round robin
internal diameter of 4 mm to 5 mm have been found precision study have exhibited long-term stability
to be satisfactory. It is good practice to protect the and column lifetimes may be two or more years.
analytical column by using a guard column (e.g. However, small changes in column performance
30 mm by 4,6 mm ID packed with amino-silica) and may go undetected by an operator in the absence of
replacing it regularly. appropriate quality control measures. Laboratories
are advised to record, on a regular basis, the column
Batch to batch variations, in terms of resolution and head pressure and calibrant retention times as a
aromatic hydrocarbon type selectivity, have been simple diagnostic tool for monitoring system and
noted for some commercial stationary phases. column performance. Participation in inter-laboratory
Laboratories are advised to test individual columns precision monitoring schemes and the regular use of
prior to purchase to ensure they meet the minimum validated and/or internal reference gas oils as part of
resolution and selectivity requirements of this the test procedure and column evaluation are
standard. strongly recommended.

New columns will typically be shipped in a solvent Used columns, which do not meet the requirements
different from the mobile phase used in this of this standard, may be regenerated by flushing the
standard and should be conditioned by purging the column in backflush mode with a polar solvent (e.g.
column with the mobile phase (heptane). A dichloromethane, 1 ml/min for two hours) and then
minimum of two hours conditioning at 1 ml/min is reconditioning as for a new column. Before
recommended but longer periods of up to two days discarding a used column, it is recommended to
are sometimes necessary. Alternatively, a reduced carefully check all other system components for
flow rate (e.g. 0,25 ml/min) for a minimum of 12 h leaks, dead volumes and/or partial blockage of
(e.g. overnight) may be used. filters, column frits, tubing, injector needles/seals
and valve rotors which may also be contributing to
poor column performance.

Bibliography
[1] EN 590:2004/AC 2005, Automotive fuels [2] EN ISO 4259:1995, Petroleum products
Diesel Requirements and test methods Determination and application of precision
data in relation to methods of test (ISO
4259:1992/Cor 1:1993).

391.12