ASTM D8276-19(2024)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D8276 − 19 (Reapproved 2024)
Standard Test Method for
Hydrocarbon Types in Middle Distillates, including Biodiesel
Blends by Gas Chromatography/Mass Spectrometry
This standard is issued under the fixed designation D8276; 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers an analytical scheme using the
D86 Test Method for Distillation of Petroleum Products and
gas chromatography/mass spectrometry (GC-MS) to determine
Liquid Fuels at Atmospheric Pressure
the hydrocarbon types present in middle distillates 170 °C to
D2425 Test Method for Hydrocarbon Types in Middle Dis-
365 °C boiling range, 5 % to 95 % by volume as determined by
tillates by Mass Spectrometry
Test Method D86, including biodiesel blends with up to 20 %
D4057 Practice for Manual Sampling of Petroleum and
by volume of fatty acid methyl ester (FAME). The detailed
Petroleum Products
hydrocarbon composition, total aromatic hydrocarbon and
D4177 Practice for Automatic Sampling of Petroleum and
polycyclic aromatic hydrocarbon contents can be determined.
Petroleum Products
The hydrocarbon types include: paraffins, noncondensed
D6299 Practice for Applying Statistical Quality Assurance
cycloparaffins, condensed dicycloparaffins, condensed
and Control Charting Techniques to Evaluate Analytical
tricycloparaffins, alkylbenzenes, indans or tetralins, or both,
Measurement System Performance
C H (indenes, etc.), naphthalenes, C H
n 2n-10 n 2n-14
D6300 Practice for Determination of Precision and Bias
(acenaphthenes, etc.), C H (acenaphthylenes, etc.), and
n 2n-16
Data for Use in Test Methods for Petroleum Products,
tricyclic aromatics. The content of FAME in biodiesel blends
Liquid Fuels, and Lubricants
can also be determined by GC.
D8144 Test Method for Separation and Determination of
Aromatics, Nonaromatics, and FAME Fractions in Middle
1.2 The values stated in acceptable SI units are to be
Distillates by Solid-Phase Extraction and Gas Chromatog-
regarded as the standard. No other units of measurement are
raphy
included in this standard.
1.3 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions of Terms Specific to This Standard:
responsibility of the user of this standard to establish appro-
3.1.1 The detailed definitions of the summation of charac-
priate safety, health, and environmental practices and deter-
teristic mass fragments can be found in Test Method D2425.
mine the applicability of regulatory limitations prior to use.
3.1.2 dual column GC-MS system, n—a gas
1.4 This international standard was developed in accor- chromatography/mass spectrometry system equipped with a
dance with internationally recognized principles on standard- hydrogen flame ionization detector (FID). Samples introduced
ization established in the Decision on Principles for the by the sample introduction system are split into two capillary
Development of International Standards, Guides and Recom- columns in parallel, in which one column connected to the FID
and the other one connected to the mass spectrometer.
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
3.1.3 polycyclic aromatic hydrocarbons, n—sum of the
concentrations of naphthalenes, C H (acenaphthenes, etc.),
n 2n-14
C H (acenaphthylenes, etc.) and tricyclic aromatics.
n 2n-16
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0M on Mass Spectrometry. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved March 15, 2024. Published April 2024. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2019. Last previous edition approved in 2019 as D8276 – 19. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D8276-19R24. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8276 − 19 (2024)
3.1.4 total aromatic hydrocarbons, n—sum of the concen- 5.3 Test Method D2425 is applicable to the determination of
trations of alkylbenzenes, indans, tetralins, C H (indenes, the detailed hydrocarbon composition in middle distillates,
n 2n-10
etc.) and polycyclic aromatics. however, the pre-separation procedure of elution chromatog-
raphy is time-consuming and not eco-friendly. By combining
4. Summary of Test Method
with the separation procedures described in Test Method
D8144, the dual column GC-MS system proposed in this
4.1 Samples are separated into saturate, aromatic, and/or
method can determine the total aromatic hydrocarbon contents,
FAME fractions by Test Method D8144. Aliquots of internal
polycyclic aromatic hydrocarbon contents and detailed hydro-
standards are added to these fractions and all of these fractions
carbon composition of diesel fuel/biodiesel blends simultane-
are analyzed by the dual column GC-MS system. The contents
ously. The content of FAME in biodiesel blends can also be
of the saturates, aromatic, and/or FAME fractions are calcu-
determined by GC. It is demonstrated to be time-saving and
lated based on the FID peak areas according to Test Method
eco-friendly for the quality control of diesel fuel and biodiesel
D8144 and the detailed hydrocarbon composition analysis can
blends.
be determined by the summation of characteristic mass frag-
ments in the saturate and aromatic fractions. Calculations are
6. Apparatus
performed as the procedures described in Test Method D2425
and the concentration of hydrocarbon types in each fraction are
6.1 Dual Column GC-MS System—The dual column
mathematically combined according to their mass percents.
GC-MS system shall be equipped with sample introduction
The contents of total aromatics and polycyclic aromatics can be
system, capillary column, column temperature programmer,
calculated by summing up the concentrations of corresponding
FID, mass spectrometer, and data acquisition system. Samples
hydrocarbon types. The content of FAME in biodiesel blends
are introduced into the dual column GC-MS system and split
can be determined by GC-FID. Results are expressed in mass
into two capillary columns in parallel, then analyzed by the
percent.
FID and mass spectrometer, respectively. The schematic rep-
resentation of dual column GC-MS system is shown in Fig. 1.
5. Significance and Use
Recommended GC-MS operating conditions are given in Table
5.1 A knowledge of the hydrocarbon composition of the
1. The GC-MS system and operating conditions shall ensure
middle distillates, including the biodiesel blends is useful in
baseline separation of the solvent, sample and internal standard
following the effect of changes in process variables, diagnosing
as shown in Fig. 2 and Fig. 3. Any other GC-MS system and
the source of plant upsets, and in evaluating the effect of
operating conditions capable of yielding equivalent results may
changes in composition on product performance properties.
be used.
The total aromatics content and polycyclic aromatics content
6.1.1 Sample Introduction System—Manual or recom-
are also important to evaluate the quality of diesel fuels/
mended automated liquid syringe injection into a splitting inlet
biodiesel blends. It requires an appropriate analytical method
may be employed. An inlet adaptor and two-hole ferrule are
to make such determinations for diesel fuel/biodiesel blends
required for connecting two capillary columns in parallel to the
production process and quality control.
inlet of GC. The sample amount reaching the column (combi-
5.2 This test method provides a comprehensive analytical nation of injection volume and split ratio) should meet the
requirement of separation efficiency of column and linear
strategy for the determination of the total aromatics contents,
response calibration range.
polycyclic aromatics contents and the detail hydrocarbon
composition of diesel fuel/biodiesel blends to ensure compli- 6.1.2 Capillary Column—Two identical non-polar silica
ance with certain specifications or regulations. capillary columns are recommended in this test method. One
FIG. 1 Schematic Representation of Dual Column GC-MS System
D8276 − 19 (2024)
A
TABLE 1 Recommended Operating Conditions of GC-MS
7. Reagents and Materials
Gas Chromatograph:
7.1 Purity of Reagents—Reagent grade chemicals shall be
Column Fused silica WCOT capillary column
Size 30 m × 0.25 mm ID, film thickness used in all tests. Unless otherwise indicated, it is intended that
0.25 μm
all reagents shall conform to the specifications of the commit-
Stationary phase Non-polar, such as 100 % dimethyl
tee on Analytical Reagents of the American Chemical Society,
polysiloxane or 5 % phenyl-methyl
polysiloxane
where such specifications are available. Other grades may be
Oven Temperature Program 60 °C for 2 min, then 40 °C /min to
used, provided it is pure enough to be used without lessening
300 °C for 5 min
the accuracy of the determination.
Inlet
Temperature 300 °C
7.2 n-hexane, reagent grade. (Warning—Flammable.)
Split ratio 30:1
Sample size 1.0 μL
7.3 n-triacontane, reagent grade.
Carrier gas
Type Helium
7.4 Internal Standard Solution, triacontane dissolved in
Constant Flow Mode 1 mL/min
n-hexane solvent to obtain the mass concentrations of
Detector
0.001 g ⁄mL to 0.005 g ⁄mL.
Type Flame ionization detector (FID)
Temperature 350 °C
7.5 Carrier Gas, Helium, 99.99 % pure. (Warning—
Fuel gas Hydrogen (~30 mL/min)
Oxidizing gas Air (~300 mL/min) Compressed gas under high pressure.)
Make-up gas Helium (~25 mL/min)
7.6 Hydrogen, 99.9 % pure. (Warning—Extremely flam-
GC-MS Interface:
GC-MS interface type Direct
mable gas under high pressure.)
GC-MS interface temperature 300 °C
7.7 Air, compressed, 99.9% pure. (Warning—Compressed
Mass Spectrometer:
Type Quadrupole
gas under high pressure that supports combustion.)
MS data acquisition mode Full scan
Scan rate (amu/s) ~1500 7.8 Quality Control Sample, used to routinely monitor the
Mass scan range m/z 50~300
stability and performance of the GC-MS system. The quality
Ionization voltage 70 eV
control (QC) sample is a saturate or an aromatic fraction of
MS source temperature 220 °C
Solvent delay 2 min (adjust according to the
middle distillates separated by Test Method D8144. The
retention time of solvent in TIC
composition of QC sample shall be similar with that in test
chromatogram)
sample.
A
The ILS study was performed under these typical operating conditions given in
this table. The operating condition may vary. The length of the WCOT (wall-coated
7.9 Check Standard, saturate and aromatic fractions sepa-
open tubular) column can be 15 m to 30 m; the inner diameter can be 0.15 mm to
rated by Test Method D8144 with known hydrocarbon com-
0.32 mm. The suitable oven program can be selected to ensure baseline
position. The accepted reference value (ARV) of this check
separation of the solvent, sample, and internal standard. See Fig. 2 and Fig. 3 for
examples of suitable resolution.
standard is determined by collaborative experimental work
using Test Method D2425 according to the requirement of
Practice D6299. If check standards are easily available, they
end of these two columns is connected in parallel to the inlet of
can be also used as QC samples to monitor both stability and
GC and the other one end of them is connected to the FID and
accuracy simultaneously.
the mass spectrometer, respectively. The column and condi-
NOTE 1—Any commercially available check standard with known
tions must provide separation of typical petroleum hydrocar- hydrocarbon composition and uncertainties acceptable for the intended
application can also be used.
bons in order of increasing boiling point. See Fig. 2 and Fig. 3
for examples of acceptable separation.
8. Sampling
6.1.3 FID—This test method requires a flame ionization
8.1 Unless otherwise specified, samples shall be obtained in
detector (FID). The detector shall have enough sensitivity,
accordance with Practices D4057, D4177, or other comparable
linearity, and stability to meet performance requirements.
practices. Samples should be stored in sealed containers.
6.1.4 Mass Spectrometry—The mass spectrometer shall be
capable of producing electron ionization spectra at 70 eV or
9. Calibration and Preparation of Apparatus
higher, and capable of acquiring mass spectra from 50 amu to
300 amu with unit resolution or better. The mass spectrometer 9.1 Prepare the GC-MS system according to manufacturer’s
shall be capable of being interfaced to a gas chromatograph and
instructions and set analysis operating conditions as suggested
capillary column. The interface shall be at a high enough
by Table 1.
temperature to prevent condensation of components boiling up
9.2 Calibrate and tune the mass spectrometer as following
to 350 °C.
every two weeks or when the overall performance of the mass
6.1.5 Data Acquisition System—A computerized data acqui-
spectrometry is not satisfied.
sition system shall be capable of acquiring of total ion
chromatogram (TIC) and FID chromatogram simultaneously
during the sample runs. The average mass spectrum for the
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington,
duration of the chromatographic program shall be obtained for
DC. For suggestions on the testing of reagents not listed by the American Chemical
the summation of characteristic mass fragments. And the areas
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
of FID chromatogram shall be integrated manually or auto-
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
matically. copeial Convention, Inc. (USPC), Rockville, MD.
D8276 − 19 (2024)
FIG. 2 Total Ion Chromatograms (TIC) and Flame Ionization Detector (FID) Chromatograms of Saturate and Aromatic Fractions in Diesel
Fuel
9.2.1 Mass calibration for the mass spectrometer is per- MNL7. The QC sample precision should be periodically
formed using perfluorotributylamine (PFTBA) w
...