ASTM D7845-13
(Test Method)Standard Test Method for Determination of Chemical Species in Marine Fuel Oil by Multidimensional Gas Chromatography – Mass Spectrometry
Standard Test Method for Determination of Chemical Species in Marine Fuel Oil by Multidimensional Gas Chromatography – Mass Spectrometry
SIGNIFICANCE AND USE
5.1 The test method allows the quantitation of chemical species at low levels in marine fuel oils and cutter stocks. A great many types and concentrations of chemical species are found in marine fuel oils. A root cause relationship between the presence of such species or their concentration in fuels and any failure modes allegedly induced by the use of these fuels has not been established. This method is necessary to establish test conditions required for future ISO 8217:2010 Petroleum products- Fuels (class F)-Specifications of marine fuel oils as defined in section 5.5 and Annex B item (d). Additional compounds may be determined by using the same conditions and by selecting required mass spectral selected ions, accordingly.
SCOPE
1.1 This test method covers the quantitative determination of a variety of chemical species in marine fuel oil (bunker fuel oil) by gas chromatography – mass spectrometry. By using the same conditions and by selecting required mass spectral selected ions, the test method may be used for the determination of other species than those for which precision statements and limits of detection have been established.
1.2 An example list of chemical species for which a limit of quantification has been determined by means of this test method is given in Table 1.TABLE 1 Component Table
Limit of Quantitation
mg/kg
n-butyl alcohol
10
Cyclohexanol
10
n-butyl ether
10
n-butyl acylate
10
Styrene
10
alpha-pinene
10
Phenol
20
alpha-methyl styrene
10
beta-pinene
10
4-methyl styrene
10
trans-B-methyl styrene
10
3-methyl styrene
10
2-methyl styrene
10
Dicyclopentadiene
10
Limonene
10
Indene
20
1-phenyl ethanol
20
para, alpha-Dimethyl styrene
20
2,5 dimethyl styrene
20
2,4 dimethyl styrene
20
2-phenyl ethanol (phenylethanol)
20
2-Ethyl Phenol
50
2,4 Dimethyl Phenol
20
4-Ethyl Phenol (co elutes with 3-ethylphenol)
20
2-Phenoxy-1-propanol
50
2-Phenoxy ethanol
50
4-isopropylphenol
50
1-Phenoxy-2-Propanol
20
Styrene Glycol
50
1.3 Other refinery hydrocarbon fractions and their mixtures may be tested using the same test method conditions. However, the precision of this test method reflects the compounds in Table 1.
1.4 Results are reported to the nearest 1.0 mg/kg.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Standards Content (Sample)
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Designation: D7845 − 13
StandardTest Method for
Determination of Chemical Species in Marine Fuel Oil by
Multidimensional Gas Chromatography – Mass
Spectrometry
This standard is issued under the fixed designation D7845; 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 and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
1.1 This test method covers the quantitative determination
of a variety of chemical species in marine fuel oil (bunker fuel
3. Terminology
oil) by gas chromatography – mass spectrometry. By using the
same conditions and by selecting required mass spectral
3.1 Definitions:
selected ions, the test method may be used for the determina-
3.1.1 direct or open split interface, n—anyGC/MSinterface
tion of other species than those for which precision statements
used to maintain atmospheric pressure at capillary column
and limits of detection have been established.
outlet.
1.2 An example list of chemical species for which a limit of
3.1.2 reconstructed ion chromatogram (RIC), n—a limited
quantification has been determined by means of this test
mass chromatogram representing the intensities of ion mass
method is given in Table 1.
spectrometric currents for only those ions having particular
1.3 Other refinery hydrocarbon fractions and their mixtures
mass to charge ratios used in this test method to selectively
maybetestedusingthesametestmethodconditions.However, extract and identify components in the presence of a complex
the precision of this test method reflects the compounds in
hydrocarbon matrix.
Table 1.
3.1.3 total ion chromatogram (TIC), n—mass spectrometer
1.4 Results are reported to the nearest 1.0 mg/kg.
computer output representing either the summed intensities of
all scanned ion currents or a sample of the current in the ion
1.5 The values stated in SI units are to be regarded as
beam for each spectrum scan plotted against the corresponding
standard. No other units of measurement are included in this
spectrum number.
standard.
1.6 This standard does not purport to address all of the 3.1.4 wall coated open tubular (WCOT), n—a type of
safety concerns, if any, associated with its use. It is the capillary column prepared by coating or bonding the inside
responsibility of the user of this standard to establish appro- wall of the capillary with a thin film of stationary phase.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. 4. Summary of Test Method
4.1 Asuitable internal standard, ethylbenzene d-10 is added
2. Referenced Documents
to the sample, which is then introduced into a gas chromato-
2.1 ASTM Standards:
graph equipped with two columns configured with a Deans
D4307 Practice for Preparation of Liquid Blends for Use as
switching system between the two columns. The sample first
Analytical Standards
passes through the polydimethylsiloxane (WCOT) pre-column
D6299 Practice for Applying Statistical Quality Assurance
which then performs a separation of the light hydrocarbon
fractionandeliminatesthehighboilinghydrocarbonfractionto
vent. The compounds of interest and internal standard are
This test method is under the jurisdiction of ASTM Committee D02 on
transferred to the high resolution polydimethylsiloxane
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
(WCOT) analytical column for chromatographic separation.
Subcommittee D02.04.0M on Mass Spectroscopy.
An auxiliary carrier gas is used to elute higher boiling
Current edition approved April 1, 2013. Published May 2013. DOI: 10.1520/
D7845-13.
hydrocarbons from the pre-column in back flush mode in order
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
to prepare for the next analysis cycle. The resulting chromato-
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
gram is then processed by mass spectral analysis based on
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. selected or extracted ion monitoring.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7845 − 13
TABLE 1 Component Table
6.1.2 Pre-Column Column—WCOT Column, 25 m long by
Limit of Quantitation 0.53-mm inside diameter fused silica WCOT column with a
mg/kg
1.0-micron film thickness of polydimethyl siloxane or any
n-butyl alcohol 10
column with suitable chromatographic resolution.
Cyclohexanol 10
n-butyl ether 10 6.1.3 Analytical Column—WCOT Column, 100 m by
n-butyl acylate 10
0.25-mm inside diameter fused silica WCOT column with a
Styrene 10
0.5-micron film thickness of polydimethyl siloxane or any
alpha-pinene 10
Phenol 20
column with suitable chromatographic resolution.
alpha-methyl styrene 10
6.1.4 Purged Packed Injector—Aninjectionportthatallows
beta-pinene 10
controlled injection of the sample at a temperature sufficient to
4-methyl styrene 10
trans-B-methyl styrene 10
pass the high boiling point fraction to the pre-column or any
3-methyl styrene 10
gas chromatographic injector system to perform the same
2-methyl styrene 10
function.
Dicyclopentadiene 10
Limonene 10
6.1.4.1 The injection port liner shall be replaced to remove
Indene 20
non-volatile materials.
1-phenyl ethanol 20
6.1.5 Electronic Pressure Control—Electronic pneumatic
para, alpha-Dimethyl styrene 20
2,5 dimethyl styrene 20
control of carrier gas flows. It can be flow or pressure
2,4 dimethyl styrene 20
programmed to speed up elution of components.
2-phenyl ethanol (phenylethanol) 20
6.1.6 Low-Volume Connector and Tees—A special union or
2-Ethyl Phenol 50
2,4 Dimethyl Phenol 20
tee for connecting two lengths of tubing 1.6-mm inside
4-Ethyl Phenol (co elutes with 3-ethylphenol) 20
diameter and smaller; sometimes referred to as a zero dead-
2-Phenoxy-1-propanol 50
volume union, tee, or an active splitting device.
2-Phenoxy ethanol 50
4-isopropylphenol 50
6.1.7 Pre-Column—ApolydimethylsiloxaneWCOTcolumn
1-Phenoxy-2-Propanol 20
used to isolate the light hydrocarbons to include methane to
Styrene Glycol 50
n-hexadecane from the higher boiling portion of the sample for
transfer to the analytical column for further separation and
quantification.
6.1.8 Deans Switching Backflush Configuration (Fig.
1)—Acolumn backflush configuration utilizing dynamic pres-
5. Significance and Use
sure differential which provides suitable means to remove the
5.1 The test method allows the quantitation of chemical
heavier hydrocarbon fraction from the pre-column or any
species at low levels in marine fuel oils and cutter stocks. A
similar configuration that allows for controlled chromato-
great many types and concentrations of chemical species are
graphic separation of components of interest and heavier
foundinmarinefueloils.Arootcauserelationshipbetweenthe
hydrocarbon fraction. An alternative Deans switching back-
presence of such species or their concentration in fuels and any
flush configuration is shown on Fig. 2.
failure modes allegedly induced by the use of these fuels has
6.2 Mass Spectrometry:
not been established. This method is necessary to establish test
conditions required for future ISO 8217:2010 Petroleum 6.2.1 Mass Spectrometer, capable of producing electron
ionization spectra at 70 electron volts or higher, and capable of
products- Fuels (class F)-Specifications of marine fuel oils as
scanning the range of the specified quantitation masses or
defined in section 5.5 and Annex B item (d). Additional
(m/e). The mass scan range shall cover the masses of interest
compounds may be determined by using the same conditions
for quantitation and should yield at least 5 scans across the
and by selecting required mass spectral selected ions, accord-
ingly. peak width at half peak width fora1to3 mg/kg ethylbenzene
d10 peak and cover the masses of interest for quantitation. A
6. Apparatus scan range set for specific ions is defined in Table 2.
6.2.1.1 The mass spectrometer shall be capable of being
6.1 Gas Chromatography:
interfaced to a gas chromatograph and WCOT columns. The
6.1.1 Gas Chromatograph—Any gas chromatograph
interface shall be at a high enough temperature to prevent
equipped with a flame ionization detector (FID) and having
condensation of components boiling up to 350°C. Usually,
sensitivity of 0.01 mg/kg. The gas chromatograph must be
20°C above the final column temperature is adequate. Direct
capable of linear temperature control from 50 to 320°C for the
column interface to the mass spectrometer may be used. An
capillary column oven. The gas chromatograph must be ca-
open split interface with computer controlled programmable
pable of controlling multiple valve events. Carrier gas flow
flowcontroller(s)mayalsobeused,tomaintainallcomponents
controllers and or electronic pressure control modules shall be
within the linearity of the mass spectrometer and at the same
capable of precise control where the required flow rates are
time maintain detectability of lower concentration chemical
low. Pressure control devices and gauges shall be capable of
components.
precise control for the typical pressures required.The tempera-
ture program rate must repeat to within 0.1°C and provide
retention time repeatability of 0.05 min throughout the tem-
perature program. Deans, David R., Chromatographia, Vol 1, 18-22, 1968.
D7845 − 13
FIG. 1 Deans Switching Backflush, Configuration A
FIG. 2 Deans Switching Backflush, Configuration B
6.2.1.2 Acquistion mode selected ion monitoring (SIM) provided it is first ascertained that the reagent is of sufficiently
extractedionmodeorfullscanmodeusingthequantitativeand high purity to permit its use without lessening the accuracy of
qualitative ions referenced in Table 2. Additional compounds
the determination.
may be added by selecting and collecting data in full scan
7.2 Carrier Gas—Helium and hydrogen have been used
mode.
successfully. The recommended minimum purity of the carrier
6.2.1.3 Tuning shall be performed for low mass resolution
gas used is 99.999 mol %. Additional purification using
using perfluorotributylamine mass fragment ions at m/z 69,
commercially available scrubbing reagents may be necessary
131 and 219 amu. The mass spectrometer is tuned either
to remove trace oxygen, which may deteriorate the perfor-
automatically or manually for optimum performance.
mance of the GC WCOT.
7. Reagents and Materials
7.3 Calibration Standard—This standard shall be prepared
7.1 Purity of Reagents—Reagent grade chemicals should be
by adding the chemicals to include those in Table 1 prepared
used in all tests. Unless otherwise indicated, it is intended that
from high (99+ %) purity reagent grade materials.
all reagents conform to the specifications of the Committee on
7.4 Standards for Calibration and Identification—Chemical
Analytical Reagents of the American Chemical Society where
compounds used to prepare standards should be 99 % or
such specifications are available. Other grades may be used,
greater purity (see Table 1). If reagents of high purity are not
available, an accurate assay of the reagent shall be performed
using a properly calibrated GC or other techniques. The
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not concentration of the impurities that overlap the other calibra-
listed by the American Chemical Society, see Annual Standards for Laboratory
tion components shall be known and used to correct the
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
concentration of the calibration components. The use of only
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. high purity reagents is strongly recommended because of the
D7845 − 13
TABLE 2 Mass Spectrometer Compound Quantitation Ions (Retention Time Data Based on Configuration A)
Retention Compound CAS # Quantifying Qualifier 1 Qualifier 2 Qualifier 3
Time
21.55 Ethylbenzene-d10 25837-05-2 116 115
13.55 n-butyl alcohol 71-36-3 56 74
22.58 Cyclohexanol 108-93-0 82 100 44
22.61 n-butyl ether 142-96-1 87 101 130
22.78 n-butyl acylate 141-32-2 55 128 73
23.23 Styrene 100-42-5 104
26.03 alpha-pinene 80-56-8 93 136 121
26.66 Phenol 108-95-2 94 66
27.79 alpha-methyl styrene 98-83-9 118 103
28.21 beta-pinene 19902-08-0 93 136 121
28.46 4-methyl styrene 622-97-9 117 118 116 103
28.57 trans-B-methyl styrene 873-66-5 117 118 103 77
28.66 3-methyl styrene 100-80-1 117 118 116 103
29.95 2-methyl styrene 611-15-4 117 118 103 77
30.11 Dicyclopentadiene 77-73-6 66 132
30.43 Limonene 5989-27-5 68 93 136 121
31.11 Indene 95-13-6 116 115 63 89
31.16 1-phenyl ethanol 98-85-1 107 122 79
32.93 para, alpha-Dimethyl styrene 1195-32-0 132 117 102
33.29 2,5 dimethyl styrene 2039-89-6 132 117 77
33.47 2,4 dimethyl styrene 2234-20-0 132 117 77
33.57 2-phenyl ethanol (phenylethanol) 60-12-8 122 103 77
34.05 2-Ethyl Phenol 90-00-6 107 122 77
34.55 2,4 Dimethyl Phenol 105-67-9 122 107 77
35.13 4-Ethyl Phenol (co elutes with 3-ethylphenol) 123-07-9 107 122 77
3-ethylphenol (co elution) 620-17-7
35.86 2-Phenoxy-1-propanol 4169-04-4 105 136 77
37.43 2-Phenoxy ethanol 122-99-6 94 138 77
37.51 4-isopropylphenol 99-89-8 121 136 94 77
38.53 1-Phenoxy-2-Propanol 770-35-4 94 152 108 77
40.53 Styrene Glycol 25779-13-9 107 138 79
error that may be introduced from impurity corrections. Stan- analytical column and potentially interfering with the determi-
dards are used for calibration as well as for establishing the nation of compounds of interest.
identification by retention time in conjunction with mass
8.4 Setting the Backflush Time for Configuration A—The
spectral match.
pre-column connected to the analytical column and the mass
7.5 n-hexadecane—99+ % purity or better. spectrometer as shown in Fig. 1 inject the calibration standard
andrecordthechromatogram.Identifythepeaks.Theretention
7.6 Dilution Solvents—Reagent grade toluene, 99.9 % (or
time data are used to set the valve on time to assure the
suitable dilution solvent).
compound peaks are not backflushed. The retention times
7.7 Internal Standards—Deuteratedanalogofethylbenzene,
should be incorporated into the software timed events before
as specified, shall be used as internal standard because of the
continuing with sample analysis. Assure all of the compounds
similar chromatographic characteristics as the components
of interest are
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