Designation: D6591 − 11

Designation: 548/06

Standard Test Method for

Determination of Aromatic Hydrocarbon Types in Middle
Distillates—High Performance Liquid Chromatography
Method with Refractive Index Detection1
This standard is issued under the fixed designation D6591; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

INTRODUCTION

This test method has the same title as IP 548-06 and is intended to be technically equivalent. The
ASTM format for test methods has been used, and where possible, equivalent ASTM test methods
have replaced the IP or ISO standards.
The test method is intended to be used as one of several possible alternative instrumental test
methods that are aimed at quantitative determination of hydrocarbon types in fuels. This does not
imply that a correlation necessarily exists between this and any other test method intended to give this
information, and it is the responsibility of the user to determine such correlation if necessary.

1. Scope* from 4 to 40 % (m/m) mono-aromatic hydrocarbons, 0 to 20 %

1.1 This test method covers a high performance liquid (m/m) di-aromatic hydrocarbons, 0 to 6 % (m/m) tri+-aromatic
chromatographic test method for the determination of mono- hydrocarbons, 0 to 26 % (m/m) polycyclic aromatic hydrocar-
aromatic, di-aromatic, tri+-aromatic, and polycyclic aromatic bons, and 4 to 65 % (m/m) total aromatic hydrocarbons.
hydrocarbon contents in diesel fuels and petroleum distillates 1.3 Compounds containing sulfur, nitrogen, and oxygen are
boiling in the range from 150 to 400°C. The total aromatic possible interferents. Mono-alkenes do not interfere, but con-
content in % m/m is calculated from the sum of the corre- jugated di- and poly-alkenes, if present, are possible interfer-
sponding individual aromatic hydrocarbon types.
ents.
NOTE 1—Aviation fuels and petroleum distillates with a boiling point
range from 50 to 300°C are not determined by this test method and should 1.4 By convention, this standard defines the aromatic hy-
be analyzed by Test Method, D6379 or other suitable equivalent test drocarbon types on the basis of their elution characteristics
methods. from the specified liquid chromatography column relative to
1.2 The precision of this test method has been established model aromatic compounds. Quantification is by external
for diesel fuels and their blending components, containing calibration using a single aromatic compound, which may or
may not be representative of the aromatics in the sample, for
1
This test method is under the jurisdiction of ASTM Committee D02 on each aromatic hydrocarbon type. Alternative techniques and
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee methods may classify and quantify individual aromatic hydro-
D02.04.0C on Liquid Chromatography. carbon types differently.
This test method is based on material published in IP Standard Methods for
Analysis and Testing of Petroleum and Related Products and British Standard 2000 1.5 Fatty Acid Methyl Esters (FAME), if present, interfere
Parts, copyright The Institute of Petroleum, 61 New Cavendish Street, London
W1M 8AR. Adapted with permission of The Institute of Petroleum. with tri+-aromatic hydrocarbons. If this method is used for
Current edition approved Dec. 1, 2011. Published February 2012. Originally diesel containing FAME, the amount of tri+-aromatics will be
approved in 2000. Last previous edition approved in 2006 as D6591–06. DOI: over estimated.
10.1520/D6591-11.

*A Summary of Changes section appears at the end of this standard

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 D6591 − 11
1.6 This standard does not purport to address all of the 3.1.6 tri+-aromatic hydrobons (T+AHs), n—in this test
safety concerns, if any, associated with its use. It is the method, compounds that have a longer retention time on the
responsibility of the user of this standard to establish appro- specified polar column than the majority of DAHs.
priate safety and health practices and determine the applica- [Link] Discussion—The elution characteristics of aromatic
bility of regulatory limitations prior to use. and non-aromatic compounds on the specified polar column
have not been specifically determined for this test method.
2. Referenced Documents Published and unpublished data indicate the major constituents
2.1 ASTM Standards:2 for each hydrocarbon type as follows: (1) non-aromatic hydro-
D1319 Test Method for Hydrocarbon Types in Liquid Petro- carbons: acyclic and cyclic alkanes (paraffins and naphthenes),
leum Products by Fluorescent Indicator Adsorption mono-alkenes (if present), (2) MAHs: benzenes, tetralins,
D2425 Test Method for Hydrocarbon Types in Middle Dis- indanes, thiophenes, and conjugated poly-alkenes, (3) DAHs:
tillates by Mass Spectrometry naphthalenes, biphenyls, indenes, fluorenes, acenaphthenes,
D4057 Practice for Manual Sampling of Petroleum and and benzothiophenes and dibenzothiophenes, (4) T+AHs:
Petroleum Products phenanthrenes, pyrenes, fluoranthenes, chrysenes, triph-
D4177 Practice for Automatic Sampling of Petroleum and enylenes, and benzanthracenes.
Petroleum Products
D5186 Test Method for Determination of the Aromatic 4. Summary of Test Method
Content and Polynuclear Aromatic Content of Diesel
Fuels and Aviation Turbine Fuels By Supercritical Fluid 4.1 A known mass of sample is diluted in the mobile phase,
Chromatography and a fixed volume of this solution is injected into a high
D6379 Test Method for Determination of Aromatic Hydro- performance liquid chromatograph, fitted with a polar column.
carbon Types in Aviation Fuels and Petroleum This column has little affinity for the non-aromatic hydrocar-
Distillates—High Performance Liquid Chromatography bons while exhibiting a pronounced selectivity for aromatic
Method with Refractive Index Detection hydrocarbons. As a result of this selectivity, the aromatic
hydrocarbons are separated from the non-aromatic hydrocar-
2.2 Energy Institute Standard:3
bons into distinct bands in accordance with their ring structure,
IP 548 Test Method for Determination of Aromatic Hydro-
that is, MAHs, DAHs, and T+AHs. At a predetermined time,
carbon Types in Middle Distillates – High Performance
after the elution of the DAHs, the column is backflushed to
Liquid Chromatography Method with Refractive Index
elute the T+AHs as a single sharp band.
Detection
4.2 The column is connected to a refractive index detector
3. Terminology that detects the components as they elute from the column. The
3.1 Definitions of Terms Specific to This Standard: electronic signal from the detector is continually monitored by
3.1.1 di-aromatic hydrocarbons (DAHs), n—in this test a data processor. The amplitudes of the signals (peak areas)
method, compounds that have a longer retention time on the from the sample aromatics are compared with those obtained
specified polar column than the majority of mono-aromatic from previously measured calibration standards in order to
hydrocarbons, but a shorter retention time than the majority of calculate percent m/m MAHs, DAHs, and T+AHs in the
tri+-aromatic hydrocarbons. sample. The sum of the percentages by mass of DAHs and
3.1.2 mono-aromatic hydrocarbons (MAHs), n—in this test T+AHs is reported as the percent m/m POLY-AH. The sum of
method, compounds that have a longer retention time on the MAHs, DAHs, and T+AHs is reported as the total aromatic
specified polar column than the majority of non-aromatic content (percent m/m) of the sample.
hydrocarbons but a shorter retention time than the majority of
DAHs. 5. Significance and Use
3.1.3 non-aromatic hydrocarbons, n—in this test method, 5.1 The aromatic hydrocarbon content of motor diesel fuel
compounds that have a shorter retention time on the specified is a factor that can affect exhaust emissions and fuel combus-
polar column than the majority of mono-aromatic hydrocar- tion characteristics, as measured by cetane number.
bons.
5.2 The United States Environmental Protection Agency
3.1.4 polycyclic aromatic hydrocarbons (POLY-AHs), n—in (US EPA) regulates the aromatic content of diesel fuels.
this test method, sum of the di-aromatic hydrocarbons and California Air Resources Board (CARB) regulations place
tri+-aromatic hydrocarbons. limits on the total aromatics content and polynuclear aromatic
3.1.5 total aromatic hydrocarbons, n—in this test method, hydrocarbon content of motor diesel fuel, thus requiring an
sum of the MAHs, DAHs, and T+AHs. appropriate analytical determination to ensure compliance with
the regulations.
2
For referenced ASTM standards, visit the ASTM website, [Link], or 5.3 This test method is applicable to materials in the same
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM boiling range as motor diesel fuels and is unaffected by fuel
Standards volume information, refer to the standard’s Document Summary page on
coloration. Test Method D1319, which has been mandated by
the ASTM website.
3
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR, the US EPA for the determination of aromatics in motor diesel
U.K., [Link] fuel, excludes materials with final boiling points greater than

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 D6591 − 11
315°C (600°F) from its scope. Test Method D2425 is appli- NOTE 5—Alternative forms of temperature control, for example,
cable to the determination of both total aromatics and poly- temperature-controlled laboratories, are permitted.
nuclear aromatic hydrocarbons in diesel fuel, but is much more 6.6 Backflush Valve—Any manual or automatic (air or
costly and time-consuming to perform. Test Method D5186, electrically actuated) flow-switching valve designed for use in
currently specified by CARB, is also applicable to the deter- HPLC systems that is capable of operating at pressures up to
mination of both total aromatics and polynuclear aromatic 2 × 104 kPa.
hydrocarbons in diesel fuel. Test Method D5186, however, 6.7 Refractive Index Detector—Any refractive index detec-
specifies the use of supercritical fluid chromatography equip- tor may be used provided it is capable of being operated over
ment that may not be readily available. the refractive index range from 1.3 to 1.6, meets the sensitivity
NOTE 2—Test Method D5186 was previously specified by CARB as an requirement specified in 9.4.2, gives a linear response over the
alternative to Test Method D1319. calibration range, and has a suitable output signal for the data
system.
6. Apparatus NOTE 6—If the refractive index detector has a facility for independent
6.1 High Performance Liquid Chromatograph (HPLC)— temperature control, it is recommended that this be set at the same
temperature as the column oven.
Any HPLC capable of pumping the mobile phase at flow rates
between 0.5 and 1.5 mL/min, with a precision better than 0.5 % 6.8 Computer or Computing Integrator—Any data system
and a pulsation of <1 % full scale deflection under the test can be used provided it is compatible with the refractive index
conditions described in Section 9. detector, has a minimum sampling rate of 1 Hz, and is capable
of peak area and retention time measurement. The data system
6.2 Sample Injection System, capable of injecting 10 µL
should also have minimum facilities for post-analysis data
(nominal) of sample solution with a repeatability better than
processing, such as baseline correction and reintegration. The
1 %.
ability to perform automatic peak detection and identification
6.2.1 An equal and constant volume of the calibration and
and to calculate sample concentrations from peak area mea-
sample solutions shall be injected into the chromatograph.
surements is recommended but not essential.
Both manual and automatic sample injection systems (using
either complete or partial filling of the sample loop) will, when 6.9 Volumetric Flasks, Grade B or better, of 10 and 100 mL
used correctly, meet the repeatability requirements laid down capacity.
in 6.2. When using the partial loop-filling mode, it is recom- 6.10 Analytical Balance, accurate to 60.0001 g.
mended that the injection volume should be less than half the
total loop volume. For complete filling of the loop, best results 7. Reagents
are obtained by overfilling the loop at least six times. 7.1 Cyclohexane, > 99 % pure.
NOTE 3—The repeatability of the injection system may be checked by NOTE 7—Cyclohexane may contain benzene as an impurity.
comparing peak areas from at least four injections of the system
performance standard (see 9.3). 7.2 Heptane, HPLC Grade. For use as HPLC mobile phase.
6.2.2 Sample and calibration injection volumes other than (Warning—Heptane is highly flammable and may cause
10 µL (typically in the range from 3 to 20 µL) may be used, irritation by inhalation, ingestion, or skin contact.)
provided they meet the requirements laid down for injection NOTE 8—Batch to batch variation of the solvent quality in terms of
repeatability (see 6.2), refractive index sensitivity and linearity water content, viscosity, refractive index and purity could cause unpre-
(see 9.4.2 and 10.1.5), and column resolution (see 9.4.3). dictable column behavior. Drying and filtering the mobile phase could
help to reduce the effect of the trace impurities in the solvent.
6.3 Sample Filter, if required (see 10.2.1)—A microfilter of NOTE 9—It is recommended practice to degas the HPLC mobile phase
porosity 0.45 µm or less, which is chemically-inert towards before use; this can be done conveniently, on-line, or off-line by helium
hydrocarbon solvents, is recommended for the removal of sparging, vacuum degassing or ultrasonic agitation. A failure to de-gas the
mobile phase may lead to negative peaks.
particulate matter from the sample solutions.
7.3 o-Xylene (1,2-Dimethylbenzene) , $ 98 % pure.
6.4 Column System—Any stainless steel HPLC column(s)
packed with an approved amino-bonded (or polar amino/ 7.4 1-Methylnaphthalene, $ 98 % pure.
cyano-bonded) silica stationary phase is suitable, provided it 7.5 Phenanthrene, $98 % pure.
meets the resolution requirements laid down in 9.4.3. See
7.6 Dibenzothiophene, $ 95 % pure.
Appendix X1 for guidance on the selection and use of suitable
column systems. 7.7 9-Methylanthracene, $ 95 % pure. (Warning—Gloves
should be worn when handling aromatic compounds (for
6.5 HPLC Column Oven—Any suitable HPLC column oven
example, disposable vinyl gloves).)
(block heating or air circulating) capable of maintaining a
constant temperature (6 1°C) within the range from 20 to NOTE 10—Purity is determined by gas chromatography with flame
40°C. ionization detection. The highest purity standards available should be
used.
NOTE 4—The refractive index detector is sensitive to both sudden and
gradual changes in the temperature of the eluent. All necessary precau- 8. Sampling
tions should be taken to establish constant temperature conditions
throughout the liquid chromatograph system. The temperature should be 8.1 Unless otherwise specified in the commodity specifica-
optimized depending on the stationary phase. tion, samples are taken by following Practice D4057 or D4177,

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 D6591 − 11

FIG. 1 Diagrammatic Representation of Liquid Chromatograph

or a similar standard. In certain situations, sampling is done in NOTE 13—The flow rate may be adjusted (typically within the range
accordance with the requirements of national standards or from 0.8 to 1.2 mL/min) to an optimum value in order to meet the
resolution requirements specified in 9.4.3.
regulations for the sampling of the product under test.
9.3 Prepare a system performance standard (SPS) by weigh-
9. Apparatus Preparation ing cyclohexane (1.0 6 0.1 g), o-xylene (0.5 6 0.05 g),
9.1 Set up the chromatograph, injection system, column, dibenzothiophene (0.05 6 0.005 g) and 9-methylanthracene
backflush valve, column oven, refractive index detector, and (0.05 6 0.005 g) into a 100 mL volumetric flask and making up
computing integrator in accordance with the appropriate equip- to the mark with heptane. Ensure that the dibenzothiophene
ment manuals. Install the HPLC column and backflush valve in and 9-methylanthracene are dissolved in the o-xylene-
the column oven. Insert the backflush valve so that the detector cyclohexane mixture (for example, by using an ultrasonic bath)
is always connected independently of the direction of flow before adding heptane.
through the column (see Fig. 1). Maintain the sample injection NOTE 14—The SPS may be kept for up to one year if stored in a tightly
valve at the same temperature as the sample solution; in most stoppered bottle in a dark place between 5 and 25°C.
cases this will be at room temperature.
9.4 When operating conditions are steady, as indicated by a
NOTE 11—The column oven is optional if alternative arrangements are stable horizontal baseline, inject 10 µL of the SPS (see 9.3) and
made to maintain a constant temperature environment, for example, a record the chromatogram, using the data system. Ensure the
temperature-controlled laboratory (see 6.5). It is recommended to install
the backflush valve in the column oven and to install the apparatus away
baseline drift over the period of the HPLC analysis run is less
from drafts (that is, not near air-conditioning unit or fume cupboard). than 0.5 % of the peak height for cyclohexane.
Pipework and/or valving which is not temperature controlled should be
NOTE 15—A baseline drift greater than this indicates problems with the
insulated.
temperature control of the column/refractive index detector or polar
NOTE 12—Regular maintenance of the liquid chromatograph and its
material eluting from the column, or both. A period of up to 1 h may be
components is important to ensure consistent performance. Leakages and
required before the liquid chromatograph reaches steady state conditions.
partial blockage of filters, frits, injector needles and valve rotors can
produce flow rate inconsistencies and poor injector performance. 9.4.1 Ensure that baseline separation is obtained between all
9.2 Adjust the flow rate of the mobile phase to a constant four components of the SPS (see Fig. 2).
1.0 6 0.2 mL/min, and ensure the reference cell of the refrac- 9.4.2 Ensure that the data system can accurately measure the
tive index detector is full of mobile phase. Allow the tempera- peak areas of dibenzothiophene and 9-methylanthracene.
ture of the column oven (and refractive index detector, if NOTE 16—The S/N (signal to noise) ratio for dibenzothiophene and
equipped with temperature control) to stabilize. 9-methylanthracene should be 3:1 or greater.
9.2.1 To minimize drift, it is essential to make sure the
reference cell is full of solvent. The best way to accomplish this 9.4.3 Ensure that the resolution between cyclohexane and
is either (1) to flush the mobile phase through the reference cell o-xylene is not less than 5.0.
(then isolate the reference cell to prevent evaporation of the [Link] Column Resolution—Calculate the resolution be-
solvent) immediately prior to analysis, or (2) to continuously tween cyclohexane and o-xylene as follows:
make up for solvent evaporation by supplying a steady flow 2 3 ~ t 2 2 t 1!
Resolution 5 (1)
through the reference cell. The make-up flow is optimized so 1.699 3 ~ y 1 1y 2 !
that reference and analytical cell miss-match due to drying-out,
where:
temperature, or pressure gradients are minimized. Typically,
this can be accomplished with a make-up flow set at one tenth t1 = retention time of cyclohexane peak in seconds,
of the analytical flow. t2 = retention time of o-xylene peak in seconds,

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 D6591 − 11

FIG. 2 Chromatogram of System Calibration Standard

y1 = half-height peak width of cyclohexane in seconds, and 10. Procedure

y2 = half-height peak width of o-xylene in seconds. 10.1 Calibration:
If the resolution is less than 5.0, check to see that all system 10.1.1 Prepare four calibration standards (A, B, C, and D), at
components are functioning correctly and that the chromato- the approximate concentrations given in Table 1, by weighing,
graphic dead volume has been minimized. Adjust the flow rate to the nearest 0.0001 g, the appropriate materials into 100-mL
to see if this improves the resolution, and make sure the mobile volumetric flasks and making up to the mark with heptane.
phase is of sufficiently high quality. Finally, regenerate or
NOTE 19—The recommended concentrations in Table 1 will cover most
replace the column. petroleum materials distilling in the diesel boiling range. Other standard
9.5 Measure the retention times of the dibenzothiophene concentrations may be used, provided they meet the requirements of the
test method (that is, linearity, detector sensitivity, and column resolution).
and 9-methylanthracene peaks, using the data system. NOTE 20—The calibration standard solutions should be stored in tightly
9.6 Calculate the backflush time, B, in seconds, using the stoppered bottles (for example, 10-mL volumetric flasks) in a dark place
following equation: between 5 and 25°C. Under these conditions, the solutions are viable for
at least six months.
B 5 t A 10.4~ t B 2 t A ! (2)
10.1.2 When operating conditions are steady (see 9.4),
where: inject 10 µL of calibration standard A. Record the chromato-
tA = retention time of dibenzothiophene in seconds, and gram, and measure the peak areas for each aromatic standard
tB = retention time of 9-methylanthracene in seconds. (see Fig. 3). Actuate the backflush valve at the predetermined
NOTE 17—The backflush time is the time after injection at which the time (see 9.6) to elute the T+AH standard as a single sharp
backflush valve will be actuated in order to elute T+AHs as a single sharp peak. When the analysis is finished, reverse the flow direction
peak. of the mobile phase (that is, return to forward flush) and allow
9.7 When operating conditions are steady, as indicated by a the baseline to stabilize before the next injection.
stable horizontal baseline, inject 10mL of the SPS (see 9.3) and 10.1.3 Repeat 10.1.2 using calibration standards B, C, and
record the chromatogram, using the data system. Actuate the D.
backflush valve at the predetermined time (see 9.6) to elute the 10.1.4 If the peak area for phenanthrene in calibration
T+AHs as a single sharp peak (see Fig. 3). When the analysis standard D is too small to measure accurately, prepare a new
is finished, reverse the flow direction of the middle phase (that calibration standard D with a higher concentration of phenan-
is, return to forward flush) and allow the baseline to stabilize threne (for example, 0.02 g/100 mL) and proceed in accor-
before the next injection. dance with 10.1.1.
9.8 Repeat 9.7, and ensure that the repeatabilities for peak 10.1.5 Plot percent m/v (g/100 mL) concentration against
area measurements of o-xylene, dibenzothiophene, and area counts for each aromatic standard, that is, o-xylene,
9-methylanthracene are within the precision of this test 1-methylnaphthalene, and phenanthrene. Calibration plots
method. shall be linear with a correlation coefficient greater than 0.999
and an intercept of less than 60.01 g/100 mL.
NOTE 18—If peak area repeatabilities are poor, check to see that the
injection system is working optimally and that the baseline is stable NOTE 21—A computer or a data system may be used to interpret these
(minimal drift) and noise-free. calibrations.

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 D6591 − 11

FIG. 3 Chromatogram of Calibration Standard A

TABLE 1 Concentrations of Calibration Components 10.2.4 Draw a baseline from just before the beginning of the
Calibration Cyclohexane o-Xylene 1-Methyl- Phenanthrene non-aromatics peak (A in Fig. 5) to a point on the chromato-
Standard naphthalene gram immediately before the backflush point (D in Fig. 5).
g/100 mL g/100 mL g/100mL g/100mL
10.2.5 Drop a vertical line from the valley (B in Fig. 5)
A 5.0 4.0 4.0 0.4
B 2.0 1.0 1.0 0.2 between non-aromatics and MAHs to the baseline.
C 0.5 0.25 0.25 0.05 10.2.6 Drop a vertical line from the valley (C in Fig. 5)
D 0.1 0.05 0.02 0.01 between MAHs and DAHs to the baseline.
10.2.7 Draw a baseline from just before the T+AH peak (E
in Fig. 5) to a point just after the T+AH compounds elute (F in
NOTE 22—It should only be necessary to calibrate the refractive index Fig. 5). As some baseline disturbance is to be expected
detector on a daily basis. following actuation of the backflush valve, wait for the
NOTE 23—It is recommended that a reference diesel or one of the four baseline to stabilize before drawing the baseline after the
calibration standards be run after every five samples to check the stability
of the system.
backflush point.
10.2.8 Integrate the area due to MAHs from points B to C
10.2 Analysis of Samples: (see Fig. 5).
10.2.1 Weigh, to the nearest 0.001 g, between 0.9 and 1.1 g 10.2.9 Integrate the area due to DAHs from points C to D
of sample into a 10-mL volumetric flask, and make up to the (see Fig. 5).
mark with heptane. Shake thoroughly to mix. Allow the 10.2.10 Integrate the area due to T+AHs from points E to F
solution to stand for 10 min, and filter (see 6.3), if necessary, (see Fig. 5).
to remove insoluble material.
[Link] For samples in which the concentration of one or NOTE 25—If the chromatographic data have been processed automati-
cally, visually check to see that the integration parameters have correctly
more aromatic hydrocarbon types falls outside the calibration identified and integrated the peaks.
range, prepare a more concentrated (for example, 2 g/10 mL)
or more dilute (0.5 g/10 mL) sample solution as appropriate. 11. Calculation
NOTE 24—If another dilution factor than the one suggested is used, it 11.1 Percent m/m Aromatic Hydrocarbon Type Contents—
could modify the retention time and the amount calculated. Calculate the percent m/m contents for MAHs, DAHs, and
10.2.2 When operating conditions are steady (see 9.4) and T+AHs, using the following equation:
identical to those used for obtaining the calibration data (see @ ~ A 3 S ! 1I # 3 V
10.1), inject 10 µL of the sample solution (see 10.2.1) and start % m/m MAHs or DAHs or T1AHs 5 (3)
M
data collection. Actuate the backflush valve at the predeter-
mined time (see 9.6) to elute the T+AHs as a single sharp peak where:
(see Fig. 4). When the analysis is finished, reverse the flow A = MAH or DAH or T+AH peak area for the sample,
direction of the mobile phase (that is, return to forward flush) S = slope of the MAH or DAH or T+AH calibration plot (%
and allow the baseline to stabilize before injecting the next m/v versus peak area),
sample. I = intercept of MAH or DAH or T+AH % m/v calibration
10.2.3 With reference to Fig. 5, devise a suitable method to plot,
find and identify correctly the MAHs, DAHs, and T+AHs. Fig. M = mass (g) of sample taken (see 10.2.1), and
5 shows a typical chromatogram for a sample of diesel fuel. V = total volume (mL) of sample solution (see 10.2.1).

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 D6591 − 11

FIG. 4 Chromatogram of Sample of Diesel Fuel

FIG. 5 Chromatogram with Peaks Identified and Showing Baseline

NOTE 26—This calculation may be performed directly by the data

system.

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 D6591 − 11
11.2 Percent m/m Polycyclic Aromatic Hydrocarbon Type TABLE 2 Precision Values
Content—Calculate the percent m/m content for POLY-AH Range
using the following equation: Aromatic Type % Repeatability Reproducibility
(m/m)
%m/m POLY 2 AH 5 %m/m DAHs1%m/m T1AHs (4) Mono-aromatic 4-40 0.026(XA + 0.063(X + 17.3)
hydrocarbons 14.7)
11.3 Total Aromatic Hydrocarbon Content—Calculate the (MAH)
total aromatic hydrocarbon content of the sample (percent Di-aromatic hydrocarbons 0-20 0.10(X + 2.6) 0.32(X + 1.8)
m/m) as the sum of the concentrations of the individual (DAH)
Tri+-aromatic hydrocarbons 0-6 0.12(X + 0.6) 0.64(X + 0.3)
hydrocarbon types (that is, MAHs + DAHs + T+AHs). (T+AH)
Polycyclic aromatic 0-26 0.13(X + 2.5) 0.29(X + 2.5)
12. Report hydrocarbons
(POLY-AH)
12.1 Report MAH, DAH, T+AH, POLY-AH and total aro- Total aromatic hydrocarbons 4-65 0.036(X + 1.5) 0.116(X + 6.3)
matic hydrocarbon contents to the nearest 0.1 % m/m. A
X = Average of results being compared
12.2 Report the following information in the test report:
12.2.1 A reference to Test Method D6591;
12.2.2 The type and identification of the product tested;
12.2.3 The result of the test (see Section 11);
13.1.2 Reproducibility—The difference between two single
12.2.4 Any deviation, by agreement or otherwise, from the
and independent results obtained by different operators work-
procedure specified; and
ing in different laboratories on identical test materials would, in
12.2.5 The date of the test.
the long run, in the normal and correct operation of the test
13. Precision and Bias4 method, exceed the following values given in Table 2 only in
13.1 Precision—The following criteria should be used for one case in twenty.
judging the acceptability of results (95 % probability): 13.1.3 Bias—No information can be presented on the bias of
13.1.1 Repeatability—The difference between two results the procedure in Test Method D6591 for measuring aromatic
obtained by the same operator on the same apparatus under hydrocarbon types in middle distillates because no material
constant operating conditions on identical test material would, having an accepted reference value is available.
in the long run, in the normal and correct operation of the test
14. Keywords
method, exceed the following values given in Table 2 only in
one case in twenty. 14.1 aromatic hydrocarbons; aromatics; diesel fuel; high
performance liquid chromatography; hydrocarbon types; petro-
4
Supporting data have been filed at ASTM International Headquarters and may leum distillates; refractive index detection; total aromatics in
be obtained by requesting Research Report RR:D02-1503. fuel

APPENDIX

(Nonmandatory Information)

X1. RECOMMENDATIONS FOR SELECTION AND USE OF CHROMATOGRAPHIC COLUMNS

X1.1 Column lengths of 150 to 300 mm with an internal two hours conditioning at 1 mL/min is recommended but
diameter of 4 to 5 mm have been found to be satisfactory. It is longer periods of up to two days are sometimes necessary.
good practice to protect the analytical column by using a guard Alternatively, a reduced flow rate (for example, 0.25 mL/min)
column (for example, 30 mm by 4.6 mm ID packed with silica for a minimum of 12 h (for example, overnight) may be used.
or amino-silica) and replacing it regularly.
X1.4 Most of the columns used in the round robin precision
X1.2 Batch to batch variations, in terms of resolution and study have exhibited long-term stability and column lifetimes
aromatic hydrocarbon type selectivity, have been noted for up to two or more years. However, small changes in column
some commercial stationary phases. Laboratories are advised performance may go undetected by an operator in the absence
to test individual columns prior to purchase to ensure they meet of appropriate quality control measures. Laboratories are
the minimum resolution and selectivity requirements of this advised to record, on a regular basis, the column head pressure
standard. and calibrant retention times as a simple diagnostic tool for
monitoring system and column performance. Participation in
X1.3 New columns will typically be shipped in a solvent interlaboratory precision monitoring schemes and the regular
different from the mobile phase used in this standard and use of validated and/or internal reference gas oils as part of the
should be conditioned by purging the column with the mobile test procedure and column evaluation are strongly recom-
phase (heptane) prior to use in routine analysis. A minimum of mended.

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 D6591 − 11
X1.5 Used columns, which do not meet the requirements of and selectivity requirements of this test method:
this standard, may be regenerated by flushing the column in
X1.6.1 Waters Spherisorb 3 NH2.
backflush mode with a polar solvent (for example, dichlo-
romethane, 1 mL/min for 2 h) and then re-conditioning as for X1.6.2 Waters Spherisorb 5 NH2.
a new column. Before discarding a used column, it is recom-
mended to check carefully all other system components for X1.6.3 UBondapak 10 µm NH2.
leaks, dead volumes or partial blockage of filters, or both, X1.6.4 Whatman 5 PAC.
column frits, tubing, injector needles/seats and valve rotors
which may also be contributing to poor column performance. X1.6.5 Lichrosphere 100 NH2, 5 µm.

X1.6 In the round robin precision study, the following

columns/stationary phases were found to meet the resolution

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D6591–06) that may impact the use of this standard.

(1) Revised 6.2.

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Copyright by ASTM Int'l (all rights reserved); 9