D 5739 - 00 Rdu3mzk
D 5739 - 00 Rdu3mzk
D 5739 - 00 Rdu3mzk
Designation: D 5739 00
1. Scope*
1.1 This practice covers the use of gas chromatography and
mass spectrometry to analyze and compare petroleum oil spills
and suspected sources.
1.2 The probable source for a spill can be ascertained by the
examination of certain unique compound classes that also
demonstrate the most weathering stability. To a greater or
lesser degree, certain chemical classes can be anticipated to
chemically alter in proportion to the weathering exposure time
and severity, and subsequent analytical changes can be predicted. This practice recommends various classes to be analyzed and also provides a guide to expected weathering
induced analytical changes.
1.3 This practice is applicable for moderately to severely
degraded petroleum oils in the distillate range from diesel
through Bunker C; it is also applicable for all crude oils with
comparable distillation ranges. This practice may have limited
applicability for some kerosenes, but it is not useful for
gasolines.
1.4 The values stated in SI units are to be regarded as the
standard.
1.5 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.
D 3328 Test Methods for Comparison of Waterborne Petroleum Oils by Gas Chromatography3
D 3414 Test Method for Comparison of Waterborne Petroleum Oils by Infrared Spectroscopy3
D 3415 Practice for Identification of Waterborne Oils4
D 3650 Test Method for Comparison of Waterborne Petroleum Oils by Fluorescence Analysis3
D 5037 Test Method for Comparison of Waterborne Petroleum Oils by High Performance Liquid Chromatography3
E 355 Practice for Gas Chromatography Terms and Relationships4
3. Summary of Practice
3.1 The recommended chromatography column is a capillary directly interfaced to the mass spectrometer (either quadrupole or magnetic).
3.2 The low-resolution mass spectrometer is operated in the
positive ion electron impact mode, 70 eV nominal.
3.3 Mass spectral data are acquired, stored, and processed
with the aid of commercially available computer-based data
systems.
4. Significance and Use
4.1 This practice is useful for assessing the source for an oil
spill. Other less complex analytical procedures (Test Methods
D 3328, D 3414, D 3650, and D 5037) may provide all of the
necessary information for ascertaining an oil spill source;
however, the use of a more complex analytical strategy may be
necessary in certain difficult cases, particularly for significantly
weathered oils. This practice provides the user with a means to
this end.
4.1.1 This practice presumes that a screening of possible
suspect sources has already occurred using less intensive
techniques. As a result, this practice focuses directly on the
generation of data using preselected targeted compound
classes. These targets are both petrogenic and pyrogenic and
can constitute both major and minor fractions of petroleum
oils; they were chosen in order to develop a practice that is
universally applicable to petroleum oil identification in general
2. Referenced Documents
2.1 ASTM Standards:
D 1129 Terminology Relating to Water2
D 3325 Practice for Preservation of Waterborne Oil
Samples3
D 3326 Practices for Preparation of Samples for Identification of Waterborne Oils2
1
This practice is under the jurisdiction of ASTM Committee D19 on Water and
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved June 10, 2000. Published September 2000. Originally
published as D 5739 95. Last previous edition D 5739 95.
2
Annual Book of ASTM Standards, Vol 11.01.
3
Annual Book of ASTM Standards, Vol 11.02.
D 5739 00
TABLE 1 Extracted Ion Chromatograms (EICs)
Compound Type
C2
C3
C4
156
170
184A
18 to 23
20 to 25
22 to 27
Dibenzothiophenes
C0
C1
C2
C3
184A
198
212
226
23
27
29
31
to
to
to
to
28
32
34
35
Phenanthrenes/
anthracenes
C0
C1
C2
C3
178B
192
206
220
27
28
30
32
to
to
to
to
28
33
35
37
14a(H)
14b(H)
217
218
40 to 60
40 to 60
191
40 to 60
Alkanes
85
4 to 60
Alkanes
113
4 to 60
133
4 to 60
Benzonaphthothiophene
234
30 to 34
Tri-aromatic steranes
231
39 to 45
Norhopanes
177
33 to 47
Methylhopanes
205
41 to 46
Pyrene/fluoranthene
202
24 to 32
Methylpyrenes
216
30 to 32
Fluorenes
166
16 to 21
Bicyclonaphthalenes
208
15 to 22
Triterpanes
Approximate Time
Interval, min
Naphthalenes
Steranes
5. Apparatus
5.1 Gas Chromatograph Interfaced to a Mass Spectrometer,
with a 70-eV electron impact ionization source. The system
shall include a computer for the control of data acquisition and
reduction.
5.2 Capillary Column, with a high-resolution, 30 m by
0.25-mm or 0.32-mm inside diameter (0.25-m df) (such as J &
W DB-5 or Supelco PTE-5), interfaced directly to the mass
spectrometer.
Ion
7. Preparation of Instrumentation
7.1 Set an initial head pressure of between 5 and 20 psi
using helium as the carrier at 250C (for either a 30-m by
0.25-mm inside diameter column or a 30-m by 0.32-mm inside
diameter column). Adjust a final head pressure (for either
column) such that the linear velocity is in the range from 30 to
40 cm/s.
7.2 Mass Spectrometric Tuning:
7.2.1 Tune the mass spectrometer to the following perfluorotributylamine (PFTBA) specification, addressing both mass
scale calibration and peak-to-peak ratios:
D 5739 00
8.2 Sample PreparationWeigh 100 to 200 mg of oil into
a screw-cap glass vial, and add 10 mL cyclohexane. Sonication
may be necessary, as well as centrifugation, to remove particulates if the sample does not dissolve completely.
8.3 Instrumental Parameters:
8.3.1 Gas ChromatographUse the following parameters:
1-L splitless injection for 45 s; an initial column temperature
of 55C for 2 min; a temperature ramp at 6C/min to 270C; a
temperature ramp of 3C/min to 300C; a final column
temperature of 300C for 17 min; an injection temperature of
290C; and a mass spectrometer (MS) interface temperature of
300C. A total run time of approximately 65 min will be
achieved using these parameters.
8.3.2 Mass Spectrometer Data Acquisition Parameters
Operate the mass spectrometer in selected ion monitoring
(SIM) for the 24 ions listed in Table 2. Since all of the ions will
be scanned every second, the dwell time for each is 70 ms.
Allow a solvent delay time of 4 min before the start of MS
scanning.
8. Procedure
8.1 Refer to Terminology D 1129 for terms relating to water
and Practice D 3415 for identification of waterborne oils. Refer
to Practice D 3325 for the preservation of oil samples and
Practice D 3326 for preparation of the neat oil sample. (Practice D 3326 includes Procedure F for recovering oil from thin
films on water and Procedure G for recovering oil from sand
and debris.) It is the responsibility of the user to validate this
method for use with these types of matrices since oil recovered
from them may contain contamination derived from the substrate material.
3
m/e
Dwell/ms
85
113
156
166
170
177
178
183
184
191
192
198
202
205
206
208
212
216
217
218
220
226
231
234
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
70
Elution range/min
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
to
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
D 5739 00
Dibenzothiophene and anthracene/phenanthrene are therefore
inherently more resistant than naphthalenes.
9.1.3.3 Steranes and triterpanes are relatively water insoluble and are extraordinarily resistant to biodegradation.
9.1.3.4 The most stable EICs should be examined first,
progressing toward the less stable ones. This order from more
weathering stable to less weathering stable is shown in Fig. 1.
9.1.4 Susceptibility of the Various Compound Classes to
Weathering ExposureIt may be best to first examine the
highest molecular weight homologous series with the greatest
degree of substitution, since weathering results in progressive
losses greatest for the lowest molecular weight homologous
series with the least degree of substitution, progressing toward
the highest molecular weight series with the greatest degree of
substitution. In those cases in which weathering has not
progressed sufficiently to eradicate an entire substituted series
completely, the remnants will continue to reflect the original
ratios of the unweathered oil. The EICs for a weathered oil
versus its unweathered source will thus remain qualitatively the
same, that is, the EICs will not change.
9.1.4.1 m/e 85This m/e serves to provide a chromatographic trace for the alkanes. It is included to assess gross
weathering effects since this compound class is very weathering sensitive. Losses in the rapidly eluting, early part of the
spill EIC relative to the source are to be expected due to
various weathering phenomena (evaporation, dissolution, and
biodegradation). An example of how pronounced this is, is
shown in Fig. 2.
NOTE 3Differences in the amounts of oil injected cause differences in
the full-scale y axis, as indicated in Fig. 2 and discussed in 9.1.2.
9.1.4.2 m/e 113This m/e serves to provide a chromatographic trace for the saturated alkanes as does m/e 85, but more
pronounce if the sample is weathered.
9.1.4.3 m/e 183This m/e serves to provide a chromatographic trace for the alkanes and acyclic isoprenoids as does
m/e 85, but accentuates the acyclic isoprenoids (i.e. pristane
and phytane) in the sample.
D 5739 00
FIG. 2 EIC (m/e 85) for a Slightly Weathered (Upper) and Heavily
Weathered (Lower) Oil Sample
FIG. 3 EIC (m/e 206) for a Slightly Weathered (Upper) and Heavily
Weathered (Lower) Oil Sample
9.1.4.4 m/e 156 and 170These m/es represent the homologous series of C2 and C3 substituted naphthalenes, respectively. These are included since they are important components
in low-boiling oil products and cracked oils, although they are
generally inferior choices for examination since the entire
naphthenic series is relatively weathering sensitive. (Naphthalene and C1-substituted naphthalenes are not included due to
their extremely poor weathering stabilities.)
9.1.4.5 m/e 184This m/e represents both the C4substituted naphthalene series and dibenzothiophene, and it is
more weathering stable than m/e 156 and 170.
9.1.4.6 m/e 177, 191, and 205These m/e serve to provide
a chromatographic trace for the basic structures for three
variants of hopanes (i.e. m/e 177 norhopanes, m/e 191 sterioisomers of hopane A and B and m/e 205 methylhopanes)
present in the sample and are important due to their resistivity
to weathering.
9.1.4.7 m/e 178, 192, 206, 220m/e 178 represents the
anthracene/phenanthrene content of an oil; their C1, C2, and C3
homologous series are represented by m/e 192, 206, and 220,
respectively. The C2 and C3-substituted phenanthrenes/
anthracenes provide the most weathering impervious chromatographic patterns. Fig. 3 shows the 206 EIC for the same
oil sample slightly weathered (less than 5 % depletion) and
heavily weathered (40 to 60 % depletion). Virtual overlays of
these EICs demonstrate the very good stability to degradation
for these compounds. Consequent examination of the most
highly substituted members would be a prudent analytical
choice.
D 5739 00
from the first to the last peak in each homologous series. (This
results in the summation of all peak areas between 33 and 36
min for the case of the 206 EIC shown in Fig. 3.)
9.2.2.1 The total integrated areas of the EICs from the spill
(weathered) and its source are then normalized to the most
weathering-stable homologous series and plotted graphically in
the form of a histogram. This results in the graphic plot shown
in Fig. 5 for the relative distributions for an unweathered and
severely weathered Iranian crude oil, which had spent over six
months on a rocky shore and had lost over 40 % by weight.
This results in normalizing the less weathering stable to the
most weathering stable because the various distributions are
normalized to C3 dibenzothiophenes. Expected weatheringinduced differences can be tracked in this way for an environmental sample relative to its unweathered source by examination of the relative area count differences as reflected in readily
apparent graphic differences.
9.2.2.2 This process simply results in a relative comparison
of the various analyte distributions between two samples since
only the area counts are compared. Minor differences between
injection amounts will then have no consequences because this
procedure involves normalizing.
9.2.3 Expected Changes in the Relative Distributions Resulting from WeatheringThe bacterial degradation rate
within a homologous series and degree of water solubility are
inversely proportional to the degree of alkylation. This results
in the more highly substituted homologs being depleted more
slowly than the less highly substituted ones (as mentioned in
9.1.4). The severity of weathering is reflected in the normalized
area differences for the less highly substituted members within
each homologous series; the relative loss increases with
decreasing alkylation. The expected weathering trends are
indicated in Fig. 5, as shown by a progressively greater loss
with decreasing alkylation within each series in addition to a
greater overall loss for the naphthalenes (two fused rings)
relative to phenanthrenes/anthracenes (three fused rings). The
relative losses of the various homologous series can be
estimated by displaying the weathering data in a manner
similar to that shown in Fig. 5. For the naphthalene series, C2
shows the greatest relative loss with only approximately 7 %
remaining; approximately 15 % C3 remains; and approximately 20 % C4 remains. For the phenanthrene/anthracene
series, approximately 40 % C1 remains; approximately 80 %
C2 remains; and approximately 100 % C3 remains. In a similar
fashion, approximately 25 % dibenzothiophene remains; approximately 50 % C1 remains; and approximately 75 % C2
remains.
9.2.3.1 Data such as that shown in Fig. 5 and previously
enumerated shall be discovered for any weathered oil sample.
That is, the least substituted members within a given homologous series must display the greatest loss; intermediate substitution must display intermediate loss; and the most highly
substituted must display the least loss.
FIG. 4 EIC (m/e 191) for a Slightly Weathered (Upper) and Heavily
Weathered (Lower) Oil Sample
9.1.4.12 m/e 231This m/e indicates the tri-aromatic sterane content present in the sample. These make good supplementary ions useful for evaluating the maturation process for
the oil sample, since these ions are transitional in the formation
of phenanthranes.
9.1.4.13 m/e 234This m/e serves to provide a chromatographic trace for the benzonaphthiophene content present in the
sample. This is a good supplementary ion useful for evaluating
sulfur content for a more weathered oil sample.
9.2 Assessment of the Degree of Weathering Undergone by
an Environmental Sample:
9.2.1 IntroductionIn addition to qualitative assessment of
the EICs discussed previously, spill oil samples may also be
assessed for the degree of weathering they have undergone by
examining the relative changes in distributions of the various
homologous series. Furthermore, environmental samples are
affected by weathering phenomena in certain predictable ways,
and the extent of these changes is a gross measure of the
weathering severity.
NOTE 4Examination of the relative distributions of the various
homologous series described as follows is meant only to assist in
ascertaining the identity of a spill oil sample relative to its unweathered
source. By careful examination of the EICs, using visual overlay as
specified in 9.1, the identity or nonidentity should have been established
previously. Comparison of the various distributions provides only additional confirmatory data by verification of weathering-expected losses.
10. Report
10.1 Data generated by this practice will assist the analyst in
reporting the results as either similar, inconclusive, or dissimilar. Supporting documentation should generally be included in
the full report, consisting of the EICs and histograms, and a
D 5739 00
5
The boldface numbers in parentheses refer to the list of references at the end of
this standard.
D 5739 00
12. Keywords
12.1 anthracenes; dibenzothiophenes; extracted ion chromatogram; fused-ring aromatics; gas chromatography; identi-
fication; mass spectrometry; naphthalenes; oil spill; phenanthrenes; selected ion monitoring; steranes; triterpanes;
weathering
APPENDIXES
(Nonmandatory Information)
X1. RELATIONSHIP BETWEEN SUBSTITUTION AND RETENTION TIME WITHIN A
HOMOLOGOUS SERIES
D 5739 00
D 5739 00
FIG. X1.2 Comparison of Extracted Ion Chromatograms Corresponding to C2, C3, and C4-Substituted Naphthalenes
10
D 5739 00
FIG. X1.3 Comparison of Extracted Ion Chromatograms Corresponding to Phenanthrene/Anthracene and the
C1, C2, and C3-Substituted Series
11
D 5739 00
X2. RELATIVE RETENTION TIME AND REPRESENTATIVE EICs FOR THE REMAINING m/e RATIOS EXAMINED USING
THIS PROCEDURE
X2.1.3 Triterpanes/HopanesFigure X2.3 plots approximately the 35 through 50 min portions of the three basic
hopane structures (biomarkers) for an oil sample (that is, EICs
177, 191 and 205).
X2.1.4 Pyrenes/FluoranthenesFigure X2.4 plots approximately the 25 through 35 min portions of the pyrene, fluoranthene and the C1 substituted structures for an oil sample (that
is, EICs 202 and 216).
X2.1.5 FluorenesFigure X2.5 plots approximately the 19
through 22.5 min portions of the fluorene structures for an oil
sample (that is EIC 166).
X2.1.6 BicyclonaphthalenesFigure X2.6 plots approximately the 15 through 22.5 min portions of the bicyclonaphthalene structures for an oil sample (that is, EIC 208).
X2.1.7 BenzonaphthothiophenesFigure X2.7 plots approximately the 27 through 35 min portions of the bicyclonaphthalene structures for an oil sample (that is, EIC 234).
REFERENCES
(1) Henry, C. B. Jr., Overton, E. B., and Robinson, J., Standard Method:
SourceFingerprint Analysis of Moderate to Heavily Contaminated
Samples Associated with the Exxon Valdez Oil Spill, Technical
Report, National Oceanic and Atmospheric Administration, Grant
#50ABNC-9-00002.
(2) Wrang, P., and Adamsen, D., Oil Identification by GC/MS II, Fingerprinting of Bio-MarkersGeneral Principles and Description of
Method, Chapter 5, Ministry of the Environment, National Environmental Research Institute, Soborg, Denmark, Journal No. 0-7001, Oct.
5, 1990.
(3) Wrang, P., and Cederberg, T., Storr-Hansen, E., Adamsen, D., and
Worsoe, I. M., Oil Identification by GC/MS III, Weathering, Chapter
6, Ministry of the Environment, National Environmental Research
Institute, Soborg, Denmark, Journal No. 0-7001, Oct. 5, 1990.
(4) Douglas, G. S., McCarthy, K. T., Dahlen, D. T., Seavey, J. A.,
Steinhauer, W. G., Prince, R. C., and Elmendorf, D. L., The Use of
Hydrocarbon Analyses for Environmental Assessment and Remediation, Chapter 1, Contaminated SoilsDiesel Fuel Contamination,
Lewis Publishers, Chelsea, MI, 1992.
(5) Butler, E. L., Douglas, G. S., Steinhauer, W. G., Prince, R. C., Aczel,
T., Hsu, C. S., Bronson, M. T., Clark, J. R., Lindstrom, J. E., Hopane,
a New Chemical Tool for Measuring Oil Biodegration, Proceedings
from In Situ and On-Site Bioreclamation, Hinchee, R. E., and
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D 5739 00
SUMMARY OF CHANGES
The reason for the changes to the current method is to increase conformity with the European Union method.
Section 8.3.1: Documentation of changes to the GC parameters
for oil analysis.
Sections 8 and 9: Tables 1 and 2, respectively includes
additional compounds added to the method.
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13