ASTM D5739-00

Standard Practice for Oil Spill Source Identification by Gas Chromatography and Positive Ion Electron Impact Low Resolution Mass Spectrometry

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.

General Information

• Status: Historical
• Publication Date: 09-Jun-2000
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaced By: ASTM D5739-06 - Standard Practice for Oil Spill Source Identification by Gas Chromatography and Positive Ion Electron Impact Low Resolution Mass Spectrometry
• Effective Date: 15-Aug-2006
• Referred By: ASTM E3163-18 - Standard Guide for Selection and Application of Analytical Methods and Procedures Used during Sediment Corrective Action
• Effective Date: 10-Jun-2000
• Referred By: ASTM D3328-06(2020) - Standard Test Methods for Comparison of Waterborne Petroleum Oils by Gas Chromatography
• Effective Date: 10-Jun-2000
• Referred By: ASTM D3415-98(2017) - Standard Practice for Identification of Waterborne Oils
• Effective Date: 10-Jun-2000

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D 5739 – 00
Standard Practice for
Oil Spill Source Identification by Gas Chromatography and
Positive Ion Electron Impact Low Resolution Mass
Spectrometry
This standard is issued under the fixed designation D 5739; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope* D 3328 Test Methods for Comparison of Waterborne Petro-
leum Oils by Gas Chromatography
1.1 This practice covers the use of gas chromatography and
D 3414 Test Method for Comparison of Waterborne Petro-
mass spectrometry to analyze and compare petroleum oil spills
leum Oils by Infrared Spectroscopy
and suspected sources.
D 3415 Practice for Identification of Waterborne Oils
1.2 The probable source for a spill can be ascertained by the
D 3650 Test Method for Comparison of Waterborne Petro-
examination of certain unique compound classes that also
leum Oils by Fluorescence Analysis
demonstrate the most weathering stability. To a greater or
D 5037 Test Method for Comparison of Waterborne Petro-
lesser degree, certain chemical classes can be anticipated to
leum Oils by High Performance Liquid Chromatography
chemically alter in proportion to the weathering exposure time
E 355 Practice for Gas Chromatography Terms and Rela-
and severity, and subsequent analytical changes can be pre-
tionships
dicted. This practice recommends various classes to be ana-
lyzed and also provides a guide to expected weathering—
3. Summary of Practice
induced analytical changes.
3.1 The recommended chromatography column is a capil-
1.3 This practice is applicable for moderately to severely
lary directly interfaced to the mass spectrometer (either qua-
degraded petroleum oils in the distillate range from diesel
drupole or magnetic).
through Bunker C; it is also applicable for all crude oils with
3.2 The low-resolution mass spectrometer is operated in the
comparable distillation ranges. This practice may have limited
positive ion electron impact mode, 70 eV nominal.
applicability for some kerosenes, but it is not useful for
3.3 Mass spectral data are acquired, stored, and processed
gasolines.
with the aid of commercially available computer-based data
1.4 The values stated in SI units are to be regarded as the
systems.
standard.
1.5 This standard does not purport to address all of the
4. Significance and Use
safety concerns, if any, associated with its use. It is the
4.1 This practice is useful for assessing the source for an oil
responsibility of the user of this standard to establish appro-
spill. Other less complex analytical procedures (Test Methods
priate safety and health practices and determine the applica-
D 3328, D 3414, D 3650, and D 5037) may provide all of the
bility of regulatory limitations prior to use.
necessary information for ascertaining an oil spill source;
2. Referenced Documents however, the use of a more complex analytical strategy may be
necessaryincertaindifficultcases,particularlyforsignificantly
2.1 ASTM Standards:
2 weathered oils. This practice provides the user with a means to
D 1129 Terminology Relating to Water
this end.
D 3325 Practice for Preservation of Waterborne Oil
4.1.1 This practice presumes that a “screening” of possible
Samples
suspect sources has already occurred using less intensive
D 3326 Practices for Preparation of Samples for Identifica-
techniques. As a result, this practice focuses directly on the
tion of Waterborne Oils
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
This practice is under the jurisdiction of ASTM Committee D19 on Water and
oils; they were chosen in order to develop a practice that is
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
universally applicable to petroleum oil identification in general
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.
Annual Book of ASTM Standards, Vol 11.01.
3 4
Annual Book of ASTM Standards, Vol 11.02. Annual Book of ASTM Standards, Vol 14.01.
*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.
D 5739 – 00
TABLE 1 Extracted Ion Chromatograms (EICs)
and is also easy to handle and apply. This practice can
accommodate light oils and cracked products (exclusive of Approximate Time
Compound Type Ion
Interval, min
gasoline) on the one hand, as well as residual oils on the other.
Naphthalenes C 156 18 to 23
4.1.2 This practice provides analytical characterizations of 2
C 170 20 to 25
petroleum oils for comparison purposes. Certain classes of
A
C 184 22 to 27
source-specific chemical compounds are targeted in this quali-
A
Dibenzothiophenes C 184 23 to 28
tative comparison; these target compounds are both unique 0
C 198 27 to 32
descriptors of an oil and chemically resistant to environmental
C 212 29 to 34
degradation. Spilled oil can be assessed in this way as being
C 226 31 to 35
similar or different from potential source samples by the direct
B
Phenanthrenes/ C 178 27 to 28
visual comparison of specific extracted ion chromatograms
anthracenes C 192 28 to 33
(EICs). In addition, other, more weathering-sensitive chemical
C 206 30 to 35
C 220 32 to 37
compound classes can also be examined in order to crudely 3
assess the degree of weathering undergone by an oil spill
Steranes 14a(H) 217 40 to 60
sample.
14b(H) 218 40 to 60
4.2 This practice simply provides a means of making
Triterpanes 191 40 to 60
qualitative comparisons between petroleum samples; quantita-
tion of the various chemical components is not addressed.
Alkanes 85 4 to 60
Alkanes 113 4 to 60
5. Apparatus
Alkanes and Acyclic 133 4to60
5.1 Gas Chromatograph Interfaced to a Mass Spectrometer,
isoprenoids
with a 70-eV electron impact ionization source. The system
shall include a computer for the control of data acquisition and
Benzonaphthothiophene 234 30 to 34
reduction.
Tri-aromatic steranes 231 39 to 45
5.2 Capillary Column, with a high-resolution, 30 m by
0.25-mmor0.32-mminsidediameter(0.25-µmd)(suchasJ&
f Norhopanes 177 33 to 47
W DB-5 or Supelco PTE-5), interfaced directly to the mass
Methylhopanes 205 41 to 46
spectrometer.
Pyrene/fluoranthene 202 24 to 32
6. Reagents and Materials
Methylpyrenes 216 30 to 32
6.1 Purity of Reagents—Only pesticide grade, nanograde,
or distilled in glass grade solvents will be used.
Fluorenes 166 16 to 21
6.2 Purity of Reference Compounds—All must be certified
Bicyclonaphthalenes 208 15 to 22
to be at least 95 % pure.
A
An authentic standard of dibenzothiophene can be chromatographed to
6.3 Septa—Only high-temperature, low-bleed (such as
ascertain its actual retention time.
TM
B
Thermogreen ) shall be used.
Phenanthrene is both pyrogenic and petrogenic. Consequently, m/e 178 may
demonstrateanincreaserelativetoitssourceinspillcasesinwhicharsonorother
6.4 Vials, glass, polytetrafluorethylene-lined screw cap,
combustion processes have occurred. This can result in a significant distortion in
10-mL capacity.
the C anthracene/phenanthrene distribution, which is, generally speaking,
6.5 Syringes,10µL.
counter to expected weathering processes.
6.6 Perfluorotributylamine, used for tuning the mass spec-
trometer.
7. Preparation of Instrumentation
6.7 Resolution Mixture—Pristane, phytane, n-heptadecane,
and n-octadecane in equal concentration in cyclohexane (50 to 7.1 Set an initial head pressure of between 5 and 20 psi
150 ng/µL). using helium as the carrier at 250°C (for either a 30-m by
6.8 Mass Discrimination Mixture—Naphthalene, fluoran- 0.25-mm inside diameter column or a 30-m by 0.32-mm inside
thene, and benzo (g, h, i) perylene in equal concentration in diameter column). Adjust a final head pressure (for either
cyclohexane (50 to 150 ng/µL). column) such that the linear velocity is in the range from 30 to
6.9 Reference oil, possibly a crude oil, used for generation 40 cm/s.
oftheextractedionchromatograms(EICs)listedinTable1and 7.2 Mass Spectrometric Tuning:
validat of system performance for oil sample comparison 7.2.1 Tune the mass spectrometer to the following perfluo-
purposes. (See for representative EICs produced using the rotributylamine (PFTBA) specification, addressing both mass
conditions stated in section 8.) scale calibration and peak-to-peak ratios:
D 5739 – 00
8.2 Sample Preparation—Weigh 100 to 200 mg of oil into
(m/e 69 at 100 % of base peak)
A B
(m/e 219 at 35 to 40 % of base peak)
a screw-cap glass vial, and add 10 mLcyclohexane. Sonication
C
(m/e 502 at 1 to 2 % of base peak)
may be necessary, as well as centrifugation, to remove particu-
A
The sensitivity for almost all of the ions monitored (Table 1) can be improved
lates if the sample does not dissolve completely.
somewhat by adjusting this percentage to between 60 and 65; however, the
8.3 Instrumental Parameters:
resulting mass spectra may be distorted significantly so that MS computer search
routines for the identification of unknowns by comparison to conventionally 8.3.1 Gas Chromatograph—Use the following parameters:
acquired mass spectral libraries may be impaired significantly.
1-µL splitless injection for 45 s; an initial column temperature
B
Adjust the entrance lens voltage.
of 55°C for 2 min; a temperature ramp at 6°C/min to 270°C; a
C
Adjust the ion focus voltage.
temperature ramp of 3°C/min to 300°C; a final column
7.2.2 Retune every 12 h of mass spectrometer operation.
temperature of 300°C for 17 min; an injection temperature of
7.3 Resolution Check—Under the instrumental conditions
290°C; and a mass spectrometer (MS) interface temperature of
listed (7.1), pristane and phytane usually display 80 % or
300°C. A total run time of approximately 65 min will be
greater resolution from C and C , respectively. If the
17 18 achieved using these parameters.
resolution is less than 50 %, take corrective action such as
8.3.2 Mass Spectrometer Data Acquisition Parameters—
replacement of the injector liner and seals and removal of the
Operate the mass spectrometer in selected ion monitoring
front of the analytical column. Report the degree of resolution
(SIM)forthe24ionslistedinTable2.Sincealloftheionswill
in Section 10. Refer to Practice E 355 for calculation of
be scanned every second, the dwell time for each is 70 ms.
resolution values.
Allow a solvent delay time of 4 min before the start of MS
7.4 Mass Discrimination Check:
scanning.
7.4.1 Use the gas chromatographic instrumental parameters
NOTE 1—It is recognized that the different monitored classes of
enumerated in 8.3.1; operate the mass spectrometer, but in the
analytes elute only in certain regions of the chromatogram; consequently,
linear scan mode from m/e 45 to 360 in 1 s.
not all ions need be monitored continuously. However, no effort has been
made to segment the chromatogram by using different SIM masses at
7.4.2 Inject a 1-µL solution of naphthalene, fluoranthene,
different times for the sake of maintaining simplicity. It is also recognized
and benzo (g,h,i) perylene in equal concentrations (from 50 to
that the signal-to-noise ratio is improved by an increase in the dwell time;
150 ng/µL) in cyclohexane.
however, this improvement is directly proportional to the square root of
7.4.3 Integrate the total ion chromatogram (TIC).
the proportional dwell time increase. A signal-to-noise ratio increase of
only two would thus result from a four-fold increase in the dwell (from 70
7.4.4 Calculate the following ratios:
to 280 ms). This increased dwell time would permit only 3 ions/s to be
(1) Area of naphthalene to area of fluoranthene, and
monitored. Nevertheless, the experienced analyst who is working with a
(2) Area of benzo (g,h,i) perylene to area of fluoranthene.
well-characterized oil source, such as monitoring degradation over time,
maychoosetomonitorfewerionsinordertomaximizethesignal-to-noise
7.4.5 Theratioof(1)mustbelessthanorequalto2,andthe
ratios and consequently improve the sensitivity for a subset of the ions
ratio of (2) must be greater than or equal to 0.2. Report this
listed in the table. Similarly, users of certain older model mass spectrom-
value in Section 10.
etersmayalsochoosetomodifySIMacquisitionbymonitoringfewerions
7.4.6 A high molecular weight response can sometimes be
simultaneously in order to offset lowered MS sensitivity.
improved by changing the penetration of the chromatographic
8.4 Sample Analysis Batching Requirements—Every time
column into the injector body or using silanized glass wool or
the mass spectrometer is used, bracket all samples by a
quartz as injector packing material, or both. Electronic flow
control (instead of constant column head pressure) has recently
TABLE 2 SIM Acquisition
become available for Capillary GC. It can be used to provide a
m/e Dwell/ms Elution range/min
high molecular weight response by increased flow during
85 70 4 to 60
splitless injection.
113 70 4 to 60
7.5 Retention Time Check—The absolute retention times for
156 70 4 to 60
166 70 4 to 60
the mass discrimination check compounds (7.4.1) must be
170 70 4 to 60
recorded.The batch-to-batch retention time reproducibility can
177 70 4 to 60
be documented in this way. Report these retention times in 178 70 4 to 60
183 70 4 to 60
Section 10.
184 70 4 to 60
191 70 4 to 60
8. Procedure 192 70 4 to 60
198 70 4 to 60
8.1 Refer toTerminology D 1129 for terms relating to water 202 70 4 to 60
205 70 4 to 60
andPracticeD 3415foridentificationofwaterborneoils.Refer
206 70 4 to 60
to Practice D 3325 for the preservation of oil samples and
208 70 4 to 60
Practice D 3326 for preparation of the neat oil sample. (Prac- 212 70 4 to 60
216 70 4 to 60
tice D 3326 includes Procedure F for recovering oil from thin
217 70 4 to 60
films on water and Procedure G for recovering oil from sand
218 70 4 to 60
and debris.) It is the responsibility of the user to validate this 220 70 4 to 60
226 70 4 to 60
method for use with these types of matrices since oil recovered
231 70 4 to 60
from them may contain contamination derived from the sub-
234 70 4 to 60
strate material.
D 5739 – 00
duplicate analysis, and specifically prepare an oil sample in Dibenzothiophene and anthracene/phenanthrene are therefore
duplicate (8.2). Also, the first and last samples to be analyzed inherently more
...