ASTM D3328-06(2020)
(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 (1-3).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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D3328 − 06 (Reapproved 2020)
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 2. Referenced Documents
1.1 This test method covers the comparison of petroleum 2.1 ASTM Standards:
oils recovered from water or beaches with oils from suspect D1129 Terminology Relating to Water
sources by means of gas chromatography (1-3). Such oils D1193 Specification for Reagent Water
include distillate fuel, lubricating oil, and crude oil. The test D2549 Test Method for Separation of Representative Aro-
method described is for capillary column analyses using either matics and Nonaromatics Fractions of High-Boiling Oils
single detection (flame ionization) or dual detection (flame by Elution Chromatography
ionization and flame photometric) for sulfur containing spe- D3325 Practice for Preservation of Waterborne Oil Samples
cies. D3326 Practice for Preparation of Samples for Identification
of Waterborne Oils
1.2 This test method provides high resolution for critical
D3415 Practice for Identification of Waterborne Oils
examination of fine structure that is resistant to weathering.
D4489 Practices for Sampling of Waterborne Oils
The flame-photometric detection for sulfur components is an
D5739 Practice for Oil Spill Source Identification by Gas
adjunct, not a substitute, for flame-ionization detection in the
Chromatography and Positive Ion Electron Impact Low
identification of waterborne petroleum oils (4-12). For this
Resolution Mass Spectrometry
reason, flame photometric detection is optional.
E355 Practice for Gas ChromatographyTerms and Relation-
1.3 The values stated in SI units are to be regarded as
ships
standard. No other units of measurement are included in this
3. Terminology
standard.
1.4 This standard does not purport to address all of the
3.1 Definitions:
safety concerns, if any, associated with its use. It is the 3.1.1 For definitions of terms used in this standard, refer to
responsibility of the user of this standard to establish appro-
Practice D3415, Terminology D1129, and Practice E355.
priate safety, health, and environmental practices and deter-
4. Significance and Use
mine the applicability of regulatory limitations prior to use.
4.1 Identification of a recovered oil is determined by com-
1.5 This international standard was developed in accor-
dance with internationally recognized principles on standard- parison with known oils, selected because of their possible
relationship to the particular recovered oil. The known oils are
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom- collected from suspected sources. Samples of such known oils
must be collected and submitted along with the unknown for
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee. 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
These test methods are under the jurisdiction of ASTM Committee D19 on
Waterand are the direct responsibility of Subcommittee D19.06 on Methods for
the flame-ionization detector provides a second, independent
Analysis for Organic Substances in Water.
Current edition approved Jan. 1, 2020. Published January 2020. Originally
approved in 1974. Last previous edition approved in 2013 as D3328 – 06 (2013). For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/D3328-06R20. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
The boldface numbers in parentheses refer to a list of references at the end of Standards volume information, refer to the standard’s Document Summary page on
this standard. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3328 − 06 (2020)
profileofthesameoil,thatis,significantlymoreinformationis 7. Reference Standards
available from a single analysis with dual detection.
7.1 Normal Paraffınic Hydrocarbons—Prepared mixtures of
4.3 Many close similarities (within uncertainties of sam-
approximately decane to hexatriacontane, or selected indi-
pling and analysis) will be needed to establish identity beyond
vidual normal paraffins, are run under normal analysis condi-
a reasonable doubt. The analyses described will distinguish
tions to determine retention times of compounds.
many, but not all samples. For cases in which this method does
7.2 Resolution Mixture—Equal mixtures of n-heptadecane,
not clearly identify a pair of samples, and for important cases
n-octadecane, pristane and phytane in solution. See Annex A1
where additional comparisons are needed to strengthen
for details (A1.2.1).
conclusions, other analyses will be required (refer to Practice
D3415). In particular, Practice D5739 is useful for such cases.
8. Sampling
5. Interferences
8.1 Collect a representative sample in accordance with
Practices D4489.
5.1 Compounds that have the same retention time as petro-
leum hydrocarbons will interfere in the comparison of the
8.2 If the sample is not to be analyzed within 1 week, it
unknownwithknownoils.Thisisparticularlytrueifanimalfat
should be preserved in accordance with Practice D3325 be-
or vegetable oil, naturally occurring hydrocarbons, or spill-
cause of the possibility of bacterial decomposition of normal
treatment chemicals are present in relatively large amounts.
paraffins in the sample.
Independent analysis, for example, infrared spectroscopy, will
8.3 The sample should be prepared for analysis in accor-
establishthepresenceofthesecontaminantsiftheirpresenceis
dance with Practice D3326, because of the great variety of
suspected.Animal or vegetable oils can be removed effectively
materials and circumstances associated with collecting petro-
by Test Method D2549 or by Practice D3326 (Method D).
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 onAnalytical Reagents of theAmerican Chemical Society.
ionization detector, or it may be split (1 + 2) between a flame
6.2 Unless otherwise indicated references to water shall be
ionization and a flame-photometric detector. The flame photo-
understood to mean reagent water that meets the purity
metric detector is equipped with a narrow bandpass interfer-
specifications of Type I or Type II water presented in Specifi-
ence filter for spectral isolation of the sulfur emission at 394
cation D1193.
nm. The relative peak size of each component (as indicated by
6.3 Air—For use with the flame-ionization and flame- retention time) of recovered oil is compared visually with the
relative peak size of each component (of like retention time) of
photometricdetectors;maybeobtainedusingalaboratorypure
air generator, or from a zero grade tank supply. the suspected source.
6.4 Carrier Gas—High-purity grade helium is used as
NOTE 2—This duel detector method is based on the early work done by
carrier gas. Kahn (13), Garza (4), and Adlard (7).
6.5 Cyclohexane—High-purity (HPLC-grade). For sample
9.2 In this test method, elution of characteristic hydrocar-
preparation and for use in reference standards.
bons occurs generally in order of increasing boiling point.
6.6 Hydrogen—Forusewiththeflame-ionizationandflame-
10. Apparatus
photometric detectors; may be obtained using a hydrogen
generator, or from a prepurified grade tank supply.
10.1 Chromatographic Column—Fused silica capillary col-
umnwithbondedphaseSE-30orequivalent,30mby0.32mm
6.7 Methylene Chloride—For use in reference standards and
inside diameter (0.1 µm film thickness).
glassware cleaning.
6.8 Normal Alkane Standards—Normal alkanes, decane
NOTE 3—Other columns, providing equivalent or better resolution may
besubstituted(seeAnnexA1),buttheanalysistimewillbeincreasedwith
through hexatriacontane, for use as reference compounds.
longer columns.
6.9 Thiophene—For use in optimization of flame-
10.2 Gas Chromatograph—A commercial or custom de-
photometric detector.
signed gas chromatograph with heated injection and detector
zones and a column oven capable of being programmed from
75°C to at least 325°C for heavier oils (higher boiling than
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington, gasolines, jet fuels, etc.).
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
10.2.1 For light distillate fuels, the chromatograph must be
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
capable of programming from 50°C and also be capable of
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. maintaining isothermal control at 50°C.
D3328 − 06 (2020)
TABLE 1 Operating Conditions for Chromatographic Columns
10.2.2 Carrier Gas Pressure Regulator is substituted pres-
(11-13)
sure regulator for the mass flow controllers to give more
Column 30mby0.32mmIDby0.1µmfilm
precise rates in the low flow ranges (1 to 5 mL/mm).
thickness, fused capillary
10.2.3 Injection Port—The use of glass injector inserts that
Packing bonded phase SE-30, or equivalent
Carrier gas: helium
can be replaced or cleaned frequently, or both, will prolong the
Flow, mL/min:
useful life of the column (3).
Column 1 to 2
10.2.4 Detectors—A hydrogen-flame ionization detector is Makeup gas 40
Temperature, °C:
always used for analyses.Aflame-photometric detector with a
Injection port 250
394 nm bandpass filter is used for dual detection (9-12).
Column:
Heavier oils:
10.2.5 Carrier Gas Makeup is required at the effluent of the
Initial 60 hold 4 min
column with a temperature independent mass flow controller.
Final 280 (FID) 250 (FID/FPD) hold 30 min
10.2.6 Effluent Splitter—Aneffluentsplitterwithasplitratio Lighter oils:
Initial 40 hold 10 min
of 1 + 2 (FID⁄FPD) is required for dual detection.
Final 280 hold 10 min
10.2.7 Bleeder for Reference Compound—A device for Detector 300 (FID) 250 (FID/FPD)
A A
Program Rate, °C/min 3–8
in-line bleed of a reference compound (thiophene and cyclo-
Chart speed, in/min (mm/min) 2.5 (10)
hexane) into the carrier flow for detector optimization is
Sensitivity, mV 1
A
required, when using a flame-photometric detector. Sample size, µL 1.0 (cyclohexane solution)
Effluent split ration (FPD procedures) 1 + 2 (FID/FPD)
10.2.8 Recorder, or an integrator or computer data handling
A
The precise rate is dictated by the design of the gas chromatograph.
system capable of acquiring data at a rate compatible with the
high resolution of the capillary column. Alternatively, a strip-
chart recorder is required to measure detector response at
full-scale range of 1 mV with a response time of 1 s (or less). 11.3.4 Adjust the hydrogen and air flow, and the air/
A second recorder, or dual-pen recorder, is required for dual hydrogen flow ratio to the detector(s), as specified for the
detection. instrument being used. Ignite the flame(s) (see 11.4 for
optimization).
10.3 Syringe—A microsyringe of 0.5 to 1 µL capacity.
11.3.5 Adjust the carrier gas flow as indicated in Table 1.
10.4 Gas Traps—Any commerically available gas filter 11.3.6 Program the column temperature as indicated in
traps to be placed in line to remove trace hydrocarbon and Table 1, and hold at the maximum temperature while monitor-
water impurities from the helium, hydrogen, nitrogen, and air ing the effluent. If there are no peaks in the chromatogram and
gas supplies. there is minimal baseline shift at high temperatures, then the
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
10.6 Glass Insert, packed with glass wool (optional). and seal the ends of the column. When the column is to be
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
cyclohexane for FID optimization and thiophene for the FDP
in the manufacturer’s instructions.
optimization.
11.2 Shut off the downstream end of the system and
12. Operating Conditions for Analysis (Notes 6-8)
pressurize the carrier gas supply to a gage pressure of approxi-
NOTE 6—One of the problems frequently encountered with the flame
mately 15 psi (103 kPa) above the operating pressure. Shut off
photometric detector is “flameout” when large amounts of solvent are
the cylinder valve and observe the pressure gage. Consider the
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-
tion has been suggested (8) which consists of reversing the hydrogen gas
Do not use the soap solution near the ionization detector.
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
h
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