ASTM D3328-06(2013)
(Test Method)Standard Test Methods for Comparison of Waterborne Petroleum Oils by Gas Chromatography
Standard Test Methods for Comparison of Waterborne Petroleum Oils by Gas Chromatography
SIGNIFICANCE AND USE
4.1 Identification of a recovered oil is determined by comparison with known oils, selected because of their possible relationship to the particular recovered oil. The known oils are collected from suspected sources. Samples of such known oils must be collected and submitted along with the unknown for analysis. At present, identification of the source of an unknown oil by itself cannot be made (for example, from a library of known oils).
4.2 The use of a flame-photometric detector in addition to the flame-ionization detector provides a second, independent profile of the same oil, that is, significantly more information is available from a single analysis with dual detection.
4.3 Many close similarities (within uncertainties of sampling and analysis) will be needed to establish identity beyond a reasonable doubt. The analyses described will distinguish many, but not all samples. For cases in which this method does not clearly identify a pair of samples, and for important cases where additional comparisons are needed to strengthen conclusions, other analyses will be required (refer to Practice D3415). In particular, Practice D5739 is useful for such cases.
SCOPE
1.1 This test method covers the comparison of petroleum oils recovered from water or beaches with oils from suspect sources by means of gas chromatography (1, 2, 3).2 Such oils include distillate fuel, lubricating oil, and crude oil. The test method described is for capillary column analyses using either single detection (flame ionization) or dual detection (flame ionization and flame photometric) for sulfur containing species.
1.2 This test method provides high resolution for critical examination of fine structure that is resistant to weathering. The flame-photometric detection for sulfur components is an adjunct, not a substitute, for flame-ionization detection in the identification of waterborne petroleum oils (4-12). For this reason, flame photometric detection is optional.
1.3 This standard does not purport to address 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: D3328 − 06 (Reapproved 2013)
Standard Test Methods for
Comparison of Waterborne Petroleum Oils by Gas
Chromatography
This standard is issued under the fixed designation D3328; 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 D3415 Practice for Identification of Waterborne Oils
D4489 Practices for Sampling of Waterborne Oils
1.1 This test method covers the comparison of petroleum
D5739 Practice for Oil Spill Source Identification by Gas
oils recovered from water or beaches with oils from suspect
2 Chromatography and Positive Ion Electron Impact Low
sources by means of gas chromatography (1, 2, 3). Such oils
Resolution Mass Spectrometry
include distillate fuel, lubricating oil, and crude oil. The test
E355 Practice for Gas ChromatographyTerms and Relation-
method described is for capillary column analyses using either
ships
single detection (flame ionization) or dual detection (flame
ionization and flame photometric) for sulfur containing spe-
3. Terminology
cies.
3.1 Definitions—For definitions of terms used in this test
1.2 This test method provides high resolution for critical
method, refer to Practice D3415, Terminology D1129, and
examination of fine structure that is resistant to weathering.
Practice E355.
The flame-photometric detection for sulfur components is an
adjunct, not a substitute, for flame-ionization detection in the
4. Significance and Use
identification of waterborne petroleum oils (4-12). For this
4.1 Identification of a recovered oil is determined by com-
reason, flame photometric detection is optional.
parison with known oils, selected because of their possible
1.3 This standard does not purport to address the safety
relationship to the particular recovered oil. The known oils are
concerns, if any, associated with its use. It is the responsibility
collected from suspected sources. Samples of such known oils
of the user of this standard to establish appropriate safety and
must be collected and submitted along with the unknown for
health practices and determine the applicability of regulatory
analysis.At present, identification of the source of an unknown
limitations prior to use.
oil by itself cannot be made (for example, from a library of
known oils).
2. Referenced Documents
4.2 The use of a flame-photometric detector in addition to
2.1 ASTM Standards:
the flame-ionization detector provides a second, independent
D1129 Terminology Relating to Water
profileofthesameoil,thatis,significantlymoreinformationis
D1193 Specification for Reagent Water
available from a single analysis with dual detection.
D2549 Test Method for Separation of Representative Aro-
4.3 Many close similarities (within uncertainties of sam-
matics and Nonaromatics Fractions of High-Boiling Oils
pling and analysis) will be needed to establish identity beyond
by Elution Chromatography
a reasonable doubt. The analyses described will distinguish
D3325 Practice for Preservation of Waterborne Oil Samples
many, but not all samples. For cases in which this method does
D3326 Practice for Preparation of Samples for Identification
not clearly identify a pair of samples, and for important cases
of Waterborne Oils
where additional comparisons are needed to strengthen
conclusions, other analyses will be required (refer to Practice
These test methods are under the jurisdiction of ASTM Committee D19 on
D3415). In particular, Practice D5739 is useful for such cases.
Waterand are the direct responsibility of Subcommittee D19.06 on Methods for
Analysis for Organic Substances in Water.
5. Interferences
Current edition approved Feb. 15, 2013. Published March 2013. Originally
approved in 1974. Last previous edition approved in 2006 as D3328 – 06. DOI:
5.1 Compounds that have the same retention time as petro-
10.1520/D3328-06R13.
leum hydrocarbons will interfere in the comparison of the
The boldface numbers in parentheses refer to the references at the end of these
test methods.
unknownwithknownoils.Thisisparticularlytrueifanimalfat
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
or vegetable oil, naturally occurring hydrocarbons, or spill-
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
treatment chemicals are present in relatively large amounts.
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. Independent analysis, for example, infrared spectroscopy, will
*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
D3328 − 06 (2013)
establishthepresenceofthesecontaminantsiftheirpresenceis 8.3 The sample should be prepared for analysis in accor-
suspected.Animal or vegetable oils can be removed effectively dance with Practices D3326, because of the great variety of
by Test Method D2549 or by Practices D3326 (Method D). materials and circumstances associated with collecting petro-
leum oils from the environment. For heavier oils, a procedure
NOTE 1—Test Method D2549 will also remove the aromatic fraction.
to deasphalt the oil may be necessary.
6. Reagents and Materials
9. Summary of Test Method
6.1 Purity of Reagents—Reagent grade chemicals shall be
9.1 This test method uses a gas chromatographic capillary
used in all tests. Unless otherwise indicated it is intended that
column system for the separation of petroleum hydrocarbons.
all reagents shall conform to the specifications of the Commit-
The effluent of the column may be detected with a flame-
tee on Analytical Reagents of the American Chemical Soci-
ionization detector, or it may be split (1 + 2) between a flame
ety.
ionization and a flame-photometric detector. The flame photo-
6.2 Unless otherwise indicated references to water shall be
metric detector is equipped with a narrow bandpass interfer-
understood to mean reagent water that meets the purity
ence filter for spectral isolation of the sulfur emission at 394
specifications of Type I or Type II water presented in Specifi-
nm. The relative peak size of each component (as indicated by
cation D1193.
retention time) of recovered oil is compared visually with the
6.3 Air—For use with the flame-ionization and flame- relative peak size of each component (of like retention time) of
photometricdetectors;maybeobtainedusingalaboratorypure
the suspected source.
air generator, or from a zero grade tank supply.
NOTE 2—This duel detector method is based on the early work done by
6.4 Carrier Gas—High-purity grade helium is used as Kahn (13), Garza (4), and Adlard (7).
carrier gas.
9.2 In this test method, elution of characteristic hydrocar-
bons occurs generally in order of increasing boiling point.
6.5 Cyclohexane—High-purity (HPLC-grade). For sample
preparation and for use in reference standards.
10. Apparatus
6.6 Hydrogen—Forusewiththeflame-ionizationandflame-
photometric detectors; may be obtained using a hydrogen 10.1 Chromatographic Column—Fused silica capillary col-
generator, or from a prepurified grade tank supply. umnwithbondedphaseSE-30orequivalent,30mby0.32mm
inside diameter (0.1 µm film thickness).
6.7 Methylene Chloride—For use in reference standards and
glassware cleaning.
NOTE 3—Other columns, providing equivalent or better resolution may
besubstituted(seeAnnexA1),buttheanalysistimewillbeincreasedwith
6.8 Normal Alkane Standards—Normal alkanes, decane
longer columns.
through hexatriacontane, for use as reference compounds.
10.2 Gas Chromatograph—A commercial or custom de-
6.9 Thiophene—For use in optimization of flame-
signed gas chromatograph with heated injection and detector
photometric detector.
zones and a column oven capable of being programmed from
75°C to at least 325°C for heavier oils (higher boiling than
7. Reference Standards
gasolines, jet fuels, etc.).
7.1 Normal Paraffınic Hydrocarbons—Prepared mixtures of
10.2.1 For light distillate fuels, the chromatograph must be
approximately decane to hexatriacontane, or selected indi- capable of programming from 50°C and also be capable of
vidual normal paraffins, are run under normal analysis condi-
maintaining isothermal control at 50°C.
tions to determine retention times of compounds. 10.2.2 Carrier Gas Pressure Regulator is substituted pres-
sure regulator for the mass flow controllers to give more
7.2 Resolution Mixture—Equal mixtures of n-heptadecane,
precise rates in the low flow ranges (1 to 5 mL/mm).
n-octadecane, pristane and phytane in solution. See Annex A1
10.2.3 Injection Port—The use of glass injector inserts that
for details (A1.2.1).
can be replaced or cleaned frequently, or both, will prolong the
useful life of the column (3).
8. Sampling
10.2.4 Detectors—A hydrogen-flame ionization detector is
8.1 Collect a representative sample in accordance with
always used for analyses.Aflame-photometric detector with a
Practice D4489.
394nmbandpassfilterisusedfordualdetection (9, 10, 11, 12).
8.2 If the sample is not to be analyzed within 1 week, it
10.2.5 Carrier Gas Makeup is required at the effluent of the
should be preserved in accordance with Practice D3325 be-
column with a temperature independent mass flow controller.
cause of the possibility of bacterial decomposition of normal
10.2.6 Effluent Splitter—Aneffluentsplitterwithasplitratio
paraffins in the sample.
of 1 + 2 (FID⁄FPD) is required for dual detection.
10.2.7 Bleeder for Reference Compound—A device for
in-line bleed of a reference compound (thiophene and cyclo-
“Reagent Chemicals,American Chemical Society Specifications,”Am. Chemi-
hexane) into the carrier flow for detector optimization is
cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
required, when using a flame-photometric detector.
theAmerican Chemical Society, see “Reagent Chemicals and Standards,” by Joseph
10.2.8 Recorder, or an integrator or computer data handling
Rosin, D. Van Nostrand Co., Inc., New York, NY, and the “United States
Pharmacopeia.” system capable of acquiring data at a rate compatible with the
D3328 − 06 (2013)
high resolution of the capillary column. Alternatively, a strip- 11.3.3 Adjust the carrier gas flow as indicated in Table 1.
chart recorder is required to measure detector response at 11.3.4 Adjust the hydrogen and air flow, and the air/
full-scale range of 1 mV with a response time of 1 s (or less).
hydrogen flow ratio to the detector(s), as specified for the
A second recorder, or dual-pen recorder, is required for dual instrument being used. Ignite the flame(s) (see 11.4 for
detection.
optimization).
11.3.5 Adjust the carrier gas flow as indicated in Table 1.
10.3 Syringe—A microsyringe of 0.5 to 1 µL capacity.
11.3.6 Program the column temperature as indicated in
10.4 Gas Traps—Any commerically available gas filter
Table 1, and hold at the maximum temperature while monitor-
traps to be placed in line to remove trace hydrocarbon and
ing the effluent. If there are no peaks in the chromatogram and
water impurities from the helium, hydrogen, nitrogen, and air
there is minimal baseline shift at high temperatures, then the
gas supplies.
column is ready for use; otherwise, recondition it.
10.5 FPD Linearizer—Optional accessory to facilitate com-
11.3.7 Return the oven temperature to 75°C.
parison of FPD chromatograms.
11.3.8 If the column is to be moved or stored, disconnect
and seal the ends of the column. When the column is to be
10.6 Glass Insert, packed with glass wool (optional).
reused, even after conditioning, it is always necessary to cycle
NOTE4—Forinstrumentsthatcanusethisinstrument,splitlessinjection
through the temperature program to remove any accumulated
of an oil in cyclohexane solution simplifies the analysis by eliminating the
volatiles.
need to deasphalt most oil samples.
11.4 Optimization of Detectors—Adjust hydrogen and air
11. Preparation of Chromatograph
flows to give optimal detector responses for a given signal
provided by the reference compound bleeder (10.2.7). Use
11.1 Install the column in the chromatograph, as described
in the manufacturer’s instructions. cyclohexane for FID optimization and thiophene for the FDP
optimization.
11.2 Shut off the downstream end of the system and
pressurize the carrier gas supply to a gage pressure of approxi-
12. Operating Conditions for Analysis (Notes 6-8)
mately 15 psi (103 kPa) above the operating pressure. Shut off
NOTE 6—One of the problems frequently encountered with the flame
the cylinder valve and observe the pressure gage. Consider the
photometric detector is “flameout” when large amounts of solvent are
injectedwiththesample.Therecommendedsamplepreparationprocedure
system tight if no pressure drop is noted in 10 to 15 min. Use
avoids this problem at the same time that it permits the use of small
a small amount of aqueous soap solution to locate minor leaks.
samples. For those who may encounter this problem, a simple modifica-
Do not use the soap solution near the ionization detector.
tion has been suggested (8) which consists of reversing the hydrogen gas
and air/oxygen gas inlets to the detector.
11.3 Column Conditioning for New Columns:
NOTE 7—For oil identification under the recommended procedure, air
NOTE 5—For previously conditioned columns, proceed to 11.3.4.
has been found satisfactory for combustion for the FPD, that is, oxygen is
not necessary.
11.3.1 During conditioning, disconnect the column at the
NOTE 8—See the manufacturer’s manual for maintenance information
detector end to avoid deposition of volatiles on the detector(s).
for the FPD. Present flame photometric units should not be heated above
11.3.2 For new columns, follow the manufacturer’s instruc-
250°C, unless the photometer is removed from the heated zone by fiber
tions for column conditioning. optics.
TABLE 1 Operating Conditions for Chromatographic Columns (11, 12, 13)
Column 30mby0.32mmIDby0.1µmfilm
thickness,
fused capillary
Packing bonded phase SE-30, or equivalent
Carrier gas: helium
Flow, mL/min:
Column 1to2
Makeup gas 40
Temperature, °C:
Injection port 250
Column:
Heavier oils:
Initial 60 hold 4 min
Final 280 (FID) 250 (FID/FPD) hold 30 min
Lighter oils:
Initial 40 hold 10 min
Final 280 hold 10 min
Detector 300 (FID) 250 (FID/FPD)
A A
Program Rate, °C/min 3–8
Chart speed, in/min (mm/min) 2.5 (10)
Sensitivity, mV 1
A
Sample size, µL 1.0 (cyclohexane solution)
Effluent split ration (FPD procedures) 1 + 2 (FID/FPD)
A
The precise rate is dictated by the design of the gas chromatograph.
...
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