Designation: D5186 − 15

Standard Test Method for

Determination of the Aromatic Content and Polynuclear
Aromatic Content of Diesel Fuels and Aviation Turbine Fuels
By Supercritical Fluid Chromatography1
This standard is issued under the fixed designation D5186; 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.

1. Scope* 3.1.1 critical pressure, n—that pressure needed to condense

1.1 This test method covers the determination of the total a gas at the critical temperature.
amounts of monoaromatic and polynuclear aromatic hydrocar- 3.1.2 critical temperature, n—the highest temperature at
bon compounds in motor diesel fuels, aviation turbine fuels, which a gaseous fluid may be converted to a liquid by means
and blend stocks by supercritical fluid chromatography (SFC). of compression.
The range of aromatics concentration to which this test method 3.1.3 mononuclear aromatic hydrocarbons,
is applicable is from 1 to 75 mass %. The range of polynuclear n—hydrocarbon compounds containing exactly one aromatic
aromatic hydrocarbon concentrations to which this test method ring. This group includes benzene, alkyl-substituted benzenes,
is applicable is from 0.5 to 50 mass %. indans, tetralins, alkyl-substituted indans, and alkyl-substituted
1.2 The values stated in SI units are to be regarded as tetralins.
standard. The values stated in inch-pound units are for infor- 3.1.4 polynuclear aromatic hydrocarbons, n—all hydrocar-
mation only. bon compounds containing two or more aromatic rings. These
1.3 This standard does not purport to address all of the rings may be fused as in naphthalene and phenanthrene, or
safety concerns, if any, associated with its use. It is the separate as in biphenyl.
responsibility of the user of this standard to establish appro- 3.1.5 restrictor, n—a device, attached to the outlet of a
priate safety and health practices and determine the applica- chromatographic column, to restrict the mobile phase flow
bility of regulatory limitations prior to use. such that the mobile phase is maintained in the supercritical
state throughout the chromatographic column.
2. Referenced Documents
3.1.6 supercritical fluid, n—a fluid maintained in a thermo-
2.1 ASTM Standards:2 dynamic state above its critical temperature and critical pres-
D1319 Test Method for Hydrocarbon Types in Liquid Petro- sure.
leum Products by Fluorescent Indicator Adsorption
3.1.7 supercritical fluid chromatography, n—a class of chro-
D1655 Specification for Aviation Turbine Fuels
matography that employs supercritical fluids as mobile phases.
D2425 Test Method for Hydrocarbon Types in Middle Dis-
tillates by Mass Spectrometry 4. Summary of Test Method
D6299 Practice for Applying Statistical Quality Assurance 4.1 A small aliquot of the fuel sample is injected onto a
and Control Charting Techniques to Evaluate Analytical packed silica adsorption column and eluted using supercritical
Measurement System Performance carbon dioxide mobile phase. Monoaromatics and polynuclear
3. Terminology aromatics in the sample are separated from nonaromatics and
detected using a flame ionization detector.
3.1 Definitions of Terms Specific to This Standard:
4.2 The detector response to hydrocarbons is recorded
throughout the analysis time. The chromatographic areas
1
This test method is under the jurisdiction of ASTM Committee D02 on corresponding to the monoaromatic, polynuclear aromatic, and
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0C on Liquid Chromatography.
nonaromatic components are determined and the mass %
Current edition approved April 1, 2015. Published June 2015. Originally content of each of these groups in the fuel is calculated by area
approved in 1991. Last previous edition approved in 2009 as D5186 – 03 (2009). normalization.
DOI: 10.1520/D5186-15.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 5. Significance and Use
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on 5.1 The aromatic hydrocarbon content of motor diesel fuels
the ASTM website. is a factor that can affect their cetane number and exhaust

*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

1
 D5186 − 15
emissions. The aromatic hydrocarbon content and the naphtha- 0.05 µL to 0.50 µL liquid volume range. The inlet system
lenes content of aviation turbine fuels affect their combustion should be operated at between 25 °C and 30 °C. The sample
characteristics and smoke-forming tendencies. These proper- inlet system must be connected to the chromatographic column
ties represent specifications for aviation turbine fuels (see so that loss of chromatographic efficiency is avoided.
Specification D1655). 6.1.5 Post-column Restrictor—A device capable of main-
5.2 The United States Environmental Protection Agency taining mobile phase supercritical conditions within the col-
(USEPA) regulates the aromatic content of diesel fuels. Cali- umn and up to the detector inlet must be connected to the end
fornia Air Resources Board (CARB) regulations place limits on of the column.
the total aromatics content and polynuclear aromatic hydrocar- 6.1.6 Column—Any liquid or supercritical fluid chromato-
bon content of motor diesel fuel, thus requiring an appropriate graphic column may be used that provides separation of
analytical determination to ensure compliance with the regu- nonaromatic, monoaromatic, and polynuclear aromatic hydro-
lations. Producers of diesel fuels will require similar determi- carbons and meets the performance requirements of Section 8.
nations for process and quality control. This test method can be 6.1.7 Integrator—Means must be provided for the determi-
used to make such determinations. nation of both discrete chromatographic peak areas and the
accumulated area under the chromatogram. This can be done
5.3 This test method is applicable to materials in the boiling by means of a computer or electronic integrator. The computer
range of motor diesel fuels and is unaffected by fuel coloration. or integrator must have the capability of correcting for baseline
Test Method D1319, which has been mandated by the USEPA shifts during the run.
for the determination of aromatics in motor diesel fuel,
excludes materials with final boiling points greater than 315 °C 7. Reagents and Materials
(600 °F) from its scope. Test Method D2425 is applicable to
7.1 Purity of Reagents—Reagent grade chemicals shall be
the determination of both total aromatics and polynuclear
used in all tests. Unless otherwise indicated, it is intended that
aromatic hydrocarbons in diesel fuel, but is much more costly
all reagents conform to the specifications of the Committee on
and time-consuming to perform.
Analytical Reagents of the American Chemical Society where
5.4 Results obtained by this test method have been shown to such specifications are available.5 Other grades may be used,
be statistically more precise than those obtained from Test provided it is first ascertained that the reagent is of sufficiently
Method D1319 for typical diesel fuels, and this test method has high purity to permit its use without lessening the accuracy of
a shorter analysis time.3 Cooperative study data4 have found the determination.
this test method to be more precise than the published precision
7.2 Air—Zero grade (hydrocarbon-free) is used as the FID
of Test Method D1319 when applied to aviation turbine fuels
oxidant. (Warning—Air is usually supplied as a compressed
and diesel fuels. Results from this test method for total
gas under high pressure and supports combustion.)
polynuclear aromatic hydrocarbons are also expected to be at
least as precise as those of Test Method D2425. 7.3 Carbon Dioxide (CO2)— Supercritical fluid chromato-
graphic grade, 99.99 % minimum purity, supplied pressurized
6. Apparatus in a cylinder equipped with a dip tube for removal of liquid
6.1 Supercritical Fluid Chromatograph (SFC)—Any SFC CO2. (Warning—Liquid at high pressure. Release of pressure
instrumentation can be used that has the following capabilities results in production of extremely cold solid CO2 and gas,
and meets the performance requirements in Section 8. which can dilute available atmospheric oxygen.)
6.1.1 Pump—The SFC instrumentation must include a 7.4 Check Standard—A commercial standard reference
pump capable of delivering supercritical carbon dioxide to the material, which has accepted reference values, in accordance
column without pressure fluctuations and at constant flow. The with in Section 6 on Reference Materials in Practice D6299.
pump is typically a single-stroke-type (syringe) pump or a Alternatively, samples subjected to round robin may be used as
highly dampened reciprocating pump with pressure fluctua- check standards. It is important that the standard deviation of
tions not exceeding 60.3 % of the operating pressure. the values of the laboratory exchange program not be statisti-
6.1.2 Detector—This test method is limited to the use of the cally greater than the reproducibility for the test method.
flame ionization detector (FID). The detector must have
7.5 Hydrogen—Hydrogen of high quality (hydrocarbon-
sufficient sensitivity to detect 0.1 mass % toluene in hexade-
free) is used as the fuel for the flame ionization detector.
cane under instrument conditions employed in this test method.
(Warning—Hydrogen is usually supplied under high pressure
6.1.3 Column Temperature Control—The chromatograph
and is extremely flammable.)
must be capable of column temperature control of at least
60.5 °C (1 °F) at the operating temperature. 7.6 Performance Mixture—A quantitative mixture of ap-
6.1.4 Sample Inlet System—A liquid sample injection valve proximately 75 mass % hexadecane (n-C16), 20 mass %
is required, capable of reproducibly introducing samples in the
5
Reagent Chemicals, American Chemical Society Specifications, American
3
Supporting data (obtained in a comparison study of Test Methods D1319 and Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
D5186) have been filed at ASTM International Headquarters and may be obtained listed by the American Chemical Society, see Annual Standards for Laboratory
by requesting Research Report RR:D02-1276. Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
4
Supporting data have been filed at ASTM International Headquarters and may and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
be obtained by requesting Research Report RR:D02-1388. MD.

2
 D5186 − 15
toluene, 3 mass % tetralin (1,2,3,4-tetrahydronaphthalene), and TABLE 1 Theoretical Response Factors
2 mass % naphthalene is used for performance checks. Component Carbon Number Molecular Mass RRFtheo
Toluene 7 92.13 1.075
7.7 Quality Control Sample—A homogeneous material hav- Tetralin 10 132.2 1.070
ing similar physical and chemical properties to the samples to Naphthalene 10 128.2 1.104
be analyzed. The choice of such material should be guided by
Section 6 on Reference Materials in Practice D6299. Examples
of such material can be motor diesel fuel, aviation turbine fuel RF i
or other typical samples containing aromatics and polynuclear RRFi 5
RFC16
(4)
aromatics similar to the samples to be analyzed.
where:
8. Preparation of Apparatus Ai = Component i in performance mix, area %,
8.1 Install the SFC instrumentation in accordance with the Mi = Component i in performance mix, known mass %,
RFi = response factor of Component i,
manufacturer’s instructions. System operating conditions will
RFC16 = response factor of hexadecane in performance mix,
depend upon the column used and optimization of perfor-
and
mance. If the performance characteristics in terms of retention RRFi = relative response factor of Component i.
and resolution, specified in 8.2, are not achieved, modify the
temperature, pressure, or mobile phase flow rate to achieve These values can then be compared to the theoretical
compliance. A column of low activity may be reactivated by response factor for each component in the performance mix as
solvent rinsing using established liquid chromatography acti- calculated by the following equation:
vation techniques.
NOTE 1—This temperature can be increased (up to 40 °C) if the
RRFtheo 5 S 12.01 3 n
MW D S
3
226.4
12.01 3 16 D (5)

resolution between the monoaromatics and polynuclear aromatics is not where:

satisfactory. Lower temperatures are suggested to improve resolution
between nonaromatics and monoaromatics. 12.01 = atomic mass of carbon,
n = number of carbon atoms in component molecule,
8.2 System Performance: MW = molecular mass of component,
8.2.1 Resolution—Analyze the performance mixture pre- 226.4 = molecular mass of hexadecane, and
pared in 7.6. The resolution between the nonaromatics and 16 = number of carbon atoms in hexadecane molecule.
monoaromatics (RNM) must be at least four and resolution
The measured RRF for each component in the test mixture
between the monoaromatics and polynuclear aromatics (RMD)
must be within 610 % of the theoretical value as calculated
must be at least two when calculated in accordance with the
with Eq 5 or summarized in Table 1. If this is not attained, it
following equations:
will be necessary to vary the injection volume, restrictor
2 3 ~ t 2 2 t 1! position, or detector gas flows, or combination thereof, until
R NM 5 (1)
1.699 3 ~ y 2 1y 1 ! agreement is attained.
2 3 ~ t 4 2 t 3! 8.2.4 Detector Linearity Check:
R MD 5 (2) 8.2.4.1 The following procedure has been found to be useful
1.699 3 ~ y 4 1y 3 !
for verifying detector linearity. It is recommended that the
where: range of aromatics covers at least the samples to be analyzed.
t1 = time for the n-C16 peak apex, s, However, the size of the hexadecane (n-C16) diluent peak tends
t2 = time for the toluene peak apex, s, to exceed the linear range of the FID. Should this occur, the
t3 = time for the tetralin peak apex, s, detector accuracy test (see 8.2.3) provides one indication of
t4 = time for the naphthalene peak apex, s, linear performance.
y1 = peak width at half height of n-C16 peak, s, 8.2.4.2 Select a motor diesel or aviation turbine fuel that has
y2 = peak width at half height of toluene, s, an aromatics content equal to or greater than the maximum
y3 = peak width at half height of tetralin, s, and concentration to be analyzed. Accurately prepare two weighed
y4 = peak width at half height of naphthalene, s. blends of this fuel in n-C16. The mass dilutions should
8.2.2 Retention Time Reproducibility —Repeated injections nominally contain fuel and n-C16 in proportions of 1:1 and 1:3.
of the performance mixture must show a retention time 8.2.4.3 Analyze the fuel and two blends by the procedure in
repeatability (maximum difference between duplicate runs) of Section 9. Determine the measured mass % aromatics present
not more than 0.5 % for n-C16 and toluene peaks. in the neat fuel and each blend as described in Section 10.
8.2.3 Detector Accuracy Test—This test method assumes 8.2.4.4 Calculate the expected concentration of aromatics in
that the FID response approximates the theoretical unit carbon the two blends using the following equation:
response. To verify this assumption, analyze the performance D
mixture and calculate the response factors, relative to hexade- B5A3 (6)
C1D
cane ( RRFi), for each of the components in the performance
mix, using the following equations: where:
Ai A = aromatics in the original fuel, mass %,
RFi 5 (3) B = expected aromatics in the diluted fuel, mass %,
Mi

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 D5186 − 15
TABLE 2 Precision Estimate—Total Aromatics
Total Aromatics, Repeatability, Reproducibility,
mass % mass % mass %
1 0.2 0.8
5 0.2 1.1
10 0.3 1.3
15 0.3 1.4
20 0.3 1.5
25 0.3 1.6
35 0.4 1.7
50 0.4 1.8
75 0.4 2.0

10. Calculation
10.1 Determine the mass % for monoaromatics, polynuclear
FIG. 1 Typical Chromatogram aromatic hydrocarbons, and total aromatics content as follows:
AM
M % 5 100 3 (7)
AN1AM1AP
AP
P % 5 100 3 (8)
C = mass of hexadecane in the dilution, and AN1AM1AP
D = mass of original diesel fuel in the dilution. A % 5 M %1P % (9)
8.2.4.5 Compare the measured results obtained for mass % where:
aromatics in the two dilutions with their corresponding ex-
M % = monoaromatics in sample, mass %,
pected aromatics results. These values should agree to within P % = polynuclear aromatic hydrocarbons in sample, mass
the repeatability limits stated in 13.1.1. If agreement is not %,
obtained, it may be necessary to adjust restrictor position or A % = total aromatics in sample, mass %,
FID gas flows, clean the FID, or decrease the injection volume. AM = area of monoaromatics in sample,
AN = area of nonaromatics in sample, and
9. Procedure AP = area of polynuclear aromatic hydrocarbons in
9.1 Using the same conditions as determined and used in sample.
Section 8, analyze the samples. Record the chromatographic
data, stopping only when the sample has been completely 11. Determination of Accuracy and Precision
eluted from the column. This is observed, at the end of the run, 11.1 Routinely assess the precision and accuracy of the
by the detector signal returning to baseline and remaining analytical system as follows:
there. This will generally occur after the elution of the tricyclic 11.1.1 Accuracy—Analyze a check standard monthly as
aromatics. described in Section 9. The results obtained for total aromatics
and polynuclear aromatics shall agree within the accepted
9.2 Integrate the total chromatographic area from the begin-
reference values. Alternatively, exchange samples circulated as
ning of the first peak to the return to baseline at the end of the
part of an interlaboratory program can be used as described in
chromatogram (see Fig. 1).
Section 6 on Reference Materials in Practice D6299. In this
9.2.1 The chromatogram consists of one peak for the case, the analysis obtained shall not exceed the reproducibility
nonaromatics and one or more peaks for the aromatics. limits given in Tables 2 and 3. Failure to attain the conditions
9.2.1.1 Assign the area corresponding to the first peak described shall be followed by corrective action and subse-
(terminating at the bottom of the lowest valley between the quent verification of the accuracy assessment, prior to the
retention times of hexadecane and toluene from the analysis of analysis of samples.
the performance mix) to the nonaromatics. 11.1.2 Precision—At least once in a 24-h period, when
9.2.1.2 All of the integrated area eluting after the bottom of performing the test method, analyze successively in duplicate a
this valley but prior to the time corresponding to the start (not typical sample selected as a quality control (QC) sample as
the apex) of the napthalene peak (determined in the analysis of described in Section 6 on Reference Materials in Practice
the performance mixture) is assigned to the monoaromatics. D6299. The sample is subjected to the procedures of Section 9.
Use area summing to determine the total area of this region in The results shall not exceed the repeatability values described
the chromatogram. in 13.1.1. Failure to achieve precision shall lead to corrective
9.2.1.3 All of the integrated area occurring after the start action and subsequent reevaluation of the precision. The record
time of the naphthalene peak through the final return to keeping of the analysis of this sample over time can be used to
baseline is assigned to the polynuclear aromatic hydrocarbons. determine if the analytical system is under statistical control as
Use area summing to determine the total area of this region in described in Annex A1 on Statistical Quality Control Tools in
the chromatogram. Practice D6299.

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 D5186 − 15
TABLE 3 Precision Estimate—Polynuclear Aromatics the test method, exceed the following values only in one case
Polynuclear Aromatics, Repeatability, Reproducibility, in twenty (see Tables 2 and 3).
mass % mass % mass %
0.5 0.1 0.3 Repeatability = 0.16 (X)0.23 mass % for total aromatics,
1 0.2 0.5 = 0.16 (X) 0.16 mass % for polynuclear aromat-
2 0.2 0.6
3 0.2 0.8
ics where X is less than 5 mass %,
5 0.2 1.0 = 0.36 ( X)0.13 mass % for polynuclear aromat-
10 0.5 5.6 ics where X is greater than 10 mass %.
15 0.5 6.9
25 0.5 8.9 13.1.2 Reproducibility—The difference between two single
50 0.6 12.5 and independent results obtained by different operators work-
ing in different laboratories on identical test material would, in
the long run, exceed the following values only in one case in
twenty (see Tables 2 and 3).
12. Report
Reproducibility = 0.75 (X)0.23 mass % for total aromatics,
12.1 Report the mass percent of monoaromatics, poly- = 0.47 (X) 0.45 mass % for polynuclear
nuclear aromatic hydrocarbons, and total aromatics to the aromatics where X is less than 5 mass %,
nearest one tenth of a percent (0.1 %). = 1.77 ( X)0.50 mass % for polynuclear
aromatics where X is greater than 10 mass
13. Precision and Bias %.
13.1 The precision of the procedure in this test method as 13.2 Bias—Reference materials for this test method which
determined by the statistical examination of interlaboratory test can be used as a measure of the test method’s bias, are being
results is as follows.4 developed.
13.1.1 Repeatability—The difference between successive
results obtained by the same operator with the same apparatus 14. Keywords
under constant operating conditions on identical test material 14.1 aromatic hydrocarbons; aromatics; diesel fuel; mono-
would, in the long run, in the normal and correct operation of aromatics; polynuclear; supercritical fluid chromatography

SUMMARY OF CHANGES

Subcommittee D02.04 has identified the location of selected changes to this standard since the last issue
(D5186 – 03 (2009)) that may impact the use of this standard. (Approved April 1, 2015.)

(1) Deleted former Table 1 and references to it within the text.

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