Chemical Species in Marine Fuel Oil: ASTM D7845-13

APPLICATION NOTE 227WA1114B
Chemical species in
Marine Fuel Oil ASTM D7845-13
INTRODUCTION
Bunker fuel is a type of liquid fuel which is fractionally distilled from crude oil. It gets its name from the tanks
on ships and ports in which it is stored. Also known as fuel oil, this material can be broken down into different
categories based on its chemical composition, intended purpose, and boiling temperature. In comparison with other
petroleum products, bunker fuel is highly viscous and potentially highly polluting in case of oil spills.
Emissions from bunker fuel burning in ships contribute to air pollution levels in many port cities. Analysing marine
bunker fuel helps owners meet marine fuel environmental regulatory compliance.
Figure 1. GC1300 with ISQ mass spectrometer and

configuration B described by ASTM D7845-13
ASTM D7845-13 is the standard test for determination of chemical The analyser has to meet the following specifications according to
species (see table 1 and 2) in marine fuel oil by multidimensional gas ASTM D7845:
chromatography-mass spectrometry. This application note describes
configuration B, which uses FID for setting the correct column switching ▲ Correlation r 2 value >0.90, using at least 5 calibration points. Table
time. SIM (Selected Ion Monitoring) acquisition mode is used for 2 demonstrates the r 2 factors for all components >0.99.
quantification. Six calibration standards, ranging from appr. 10 to 500 ▲ Demonstration of repeatability limits. The obtained
mg/kg are prepared to obtain the calibration curves. results (table 2) meet the requirents (table 1) easily.
▲ Sensitivity of 1 mg/kg styrene at mass 104 > 5:1. For the
Figure 2 shows the TIC chromatogram of a calibration standard, while described analyser a ratio of > 1000:1 is reported.
a fuel sample is shown in figure 3. Figure 4 gives an impression of the
TraceFinder software: a transparent overview of samples, Conclusion: the ASTM acceptance criteria are easily met by the
components, quantitation parameters and calibration data. presented analyser.
Results and chromatograms
Figure 2. TIC Chromatogram calibration standard
Figure 3. TIC Chromatogram oil sample
Figure 4. TraceFinder software workflow with selected ions and calibration curve for Indene (example)
Component Repeatability Limit Component Correlation Average St. Dev. Std. Dev.
(r2) (mg/kg) (n=10) x2,8
1-butanol 4.059 1-butanol 0.9988 19.04 0.427 1.28
butyl ether 7.444 butyl ether 1.0000 17.54 0.276 0.83
butyl acrylate 9.108 butyl acrylate 0.9999 17.82 0.210 0.63
cyclohexanol 7.860 cyclohexanol 0.9997 21.52 0.338 1.01
styrene 4.316 styrene 0.9999 17.97 0.330 0.99
beta-pinene 8.375 beta-pinene 0.9999 18.44 0.418 1.25
a-pinene 7.048 a-pinene 1.0000 17.76 0.364 1.09
alpha-methylstyrene 7.900 alpha-methylstyrene 0.9998 19.08 0.446 1.34
phenol 15.364 phenol 0.9989 41.91 0.925 2.77
trans-B-methylstyrene 12.137 trans-B-methylstyrene 0.9995 18.15 0.604 1.81
3-methylstyrene 5.940 3-methylstyrene 0.9998 19.14 0.590 1.77
limonene 13.246 limonene 0.9994 20.12 0.712 2.14
dicyclopentadiene 20.175 dicyclopentadiene 0.9993 19.57 0.540 1.62
indene 7.623 indene 0.9992 36.10 1.338 4.01
1-phenylethanol 12.117 1-phenylethanol 0.9985 41.67 1.530 4.59
para, alpha-dimethylstyrene 21.878 para, alpha-dimethylstyrene 0.9985 34.86 1.605 4.82
2,5-dimethylstyrene 19.383 2,5-dimethylstyrene 0.9991 34.14 1.657 4.97
2,4-dimethylstyrene 27.659 2,4-dimethylstyrene 0.9987 32.80 1.676 5.03
2-ethylphenol 41.320 2-ethylphenol 0.9943 71.19 4.708 14.12
2-phenylethanol 28.768 2-phenylethanol 0.9987 40.68 1.531 4.59
2,4-dimethylphenol 23.264 2,4-dimethylphenol 0.9995 37.73 1.606 4.82
4-ethylphenol 58.486 4-ethylphenol 0.9991 37.51 1.587 4.76
4-isopropylphenol 41.063 4-isopropylphenol 0.9943 72.26 5.005 15.02
2-Phenoxyethanol 48.527 2-Phenoxyethanol 0.9975 92.84 3.457 10.37
1-Phenoxy-2-propanol 21.462 1-Phenoxy-2-propanol 0.9979 39.56 1.717 5.15
Tabel 1. Repeatability Limits required by ASTM Table 2. Obtained results: r 2 > 0.9 and Standard Deviation * 2.8 < required repeatability limits of table 1.
Specifications
Application: Determination of various compounds in marine fuel oil by multidimensional GCMS
Configuration: Type B (additional FID for columns switching setting)
Injector: Modified PTV injector
Columns: Rxi-1ms, 0.25um, 30m * 0.25mm ID + Rxi-5ms, 0.5um, 60m * 0.32mm ID
Column switching: Deans column switching option
Detection: Thermo ISQ quadropole mass spectrometer
Software: Xcalibur with TraceFinder or Chromeleon
Analysis Time: Fast GC application
Correlation r 2: > 0.99
S/N ratio styrene > 1:1000
Repeatability see table 1 and 2
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APPLICATION NOTE 227WA1114B

Figure 1. GC1300 with ISQ mass spectrometer and

Figure 2. TIC Chromatogram calibration standard

Figure 3. TIC Chromatogram oil sample

For more information: G. A .S is an

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