ASTM D3326-90(2002)
(Practice)Standard Practice for Preparation of Samples for Identification of Waterborne Oils
Standard Practice for Preparation of Samples for Identification of Waterborne Oils
SCOPE
1.1 This practice covers the preparation for analysis of waterborne oils recovered from water. The identification is based upon the comparison of physical and chemical characteristics of the waterborne oils with oils from suspect sources. These oils may be of petroleum or vegetable/animal origin, or both. Seven procedures are given as follows:SectionsProcedure A (for samples of more than 50-mL volume containing significant quantities of hydrocarbons with boiling points above 280°C)8 to 12Procedure B (for samples containing significant quantities of hydrocarbons with boiling points above 280°C)13 to 17Procedure C (for waterborne oils containing significant amounts of components boiling below 280°C and to mixtures of these and higher boiling components)18 to 22Procedure D (for samples containing both petroleum and vegetable/animal derived oils)23 to 27Procedure E (for samples of light crudes and medium distillate fuels)28 to 34Procedure F (for thin films of oil-on-water)35 to 39Procedure G (for oil-soaked samples)40 to 44
1.2 Procedures for the analytical examination of the waterborne oil samples are described in Practice D 3415 and Test Methods D 3327, D 3328, D 3414, and D 3650. Refer to the individual oil identification test methods for the sample preparation method of choice. The deasphalting effects of the sample preparation method should be considered in selecting the best methods.
1.3 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. Specific caution statements are given in Sections 6 and 32.
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Designation: D 3326 – 90 (Reapproved 2002)
Standard Practice for
Preparation of Samples for Identification of Waterborne
Oils
This standard is issued under the fixed designation D 3326; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D95 Test Method for Water in Petroleum Products and
Bituminous Materials by Distillation
1.1 This practice covers the preparation for analysis of
D96 Test Method for Water and Sediment in Crude Oil by
waterborne oils recovered from water. The identification is
Centrifuge Method (Field Procedure)
based upon the comparison of physical and chemical charac-
D 1129 Terminology Relating to Water
teristics of the waterborne oils with oils from suspect sources.
D 1193 Specification for Reagent Water
These oils may be of petroleum or vegetable/animal origin, or
D 1959 Test Method for Iodine Value of Drying Oils and
both. Seven procedures are given as follows:
Fatty Acids
Sections
D 1983 Test Method for Fatty Acid Composition by Gas-
Procedure A (for samples of more than 50-mL volume
containing significant quantities of hydrocarbons
Liquid Chromatography of Methyl Esters
with boiling points above 280°C) 8 to 12
D 2800 Test Method for Preparation of Methyl Esters from
Procedure B (for samples containing significant quantities of
Oils for Determination of FattyAcid Composition by Gas
hydrocarbons with boiling points above 280°C) 13 to 17
Procedure C (for waterborne oils containing significant
Chromatography
amounts of components boiling below 280°C and
D 3325 Practice for Preservation of Waterborne Oil
to mixtures of these and higher boiling components) 18 to 22
Procedure D (for samples containing both petroleum and Samples
vegetable/animal derived oils) 23 to 27
D 3327 Test Methods forAnalysis of Selected Elements in
Procedure E (for samples of light crudes and medium distillate
Waterborne Oils
fuels) 28 to 34 D 3328 Test Methods for Comparison ofWaterborne Petro-
Procedure F (for thin films of oil-on-water) 35 to 39
leum Oils by Gas Chromatography
Procedure G (for oil-soaked samples) 40 to 44
D 3414 Test Method for Comparison of Waterborne Petro-
1.2 Procedures for the analytical examination of the water-
leum Oils by Infrared Spectroscopy
borne oil samples are described in Practice D3415 and Test
D 3415 Practice for Identification of Waterborne Oils
Methods D3327, D3328, D3414, and D3650. Refer to the
D 3650 Test Method for Comparison of Waterborne Petro-
individual oil identification test methods for the sample prepa-
leum Oils by Fluorescence Analysis
rationmethodofchoice.Thedeasphaltingeffectsofthesample
D 4489 Practices for Sampling of Waterborne Oils
preparation method should be considered in selecting the best
E1 Specification for ASTM Thermometers
methods.
E 133 Specification for Distillation Equipment
1.3 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.1 Definitions—For definitions of terms used in this prac-
priate safety and health practices and determine the applica-
tice, refer to Terminology D1129.
bility of regulatory limitations prior to use. Specific caution
3.2 Definitions of Terms Specific to This Standard:
statements are given in Sections 6 and 32.
2. Referenced Documents
2.1 ASTM Standards:
Annual Book of ASTM Standards, Vol 05.01.
Annual Book of ASTM Standards, Vol 11.01.
1 4
This practice is under the jurisdiction ofASTM Committee D19 on Water and Annual Book of ASTM Standards, Vol 06.03.
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Annual Book of ASTM Standards, Vol 11.02.
Organic Substances in Water. Discontinued; see 1993 Annual Book of ASTM Standards, Vol 11.02.
Current edition approved May 25, 1990. Published October 1990. Originally Annual Book of ASTM Standards, Vol 14.03.
e1 8
published as D3326–74T. Last previous edition D 3326–90 (1996) . Annual Book of ASTM Standards, Vol 14.04.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 3326 – 90 (2002)
3.2.1 animal/vegetable-derived oils—a mixture made of 7.2 Preserve the waterborne oil samples in accordance with
mono-, di-, and triglyceride esters of fatty acids and other Practice D3325.
substances of animal or vegetable origin, or both. 7.3 Theportionofthesampleusedmustberepresentativeof
3.2.2 Simulated weathering of waterborne oils by distilla- the total sample. If the material is liquid, thoroughly stir the
tion considers only the effect of evaporation, which likely is sampleasreceived,warmingifnecessarytoensureuniformity.
the most significant short-term weathering effect in the envi-
PROCEDURE A—LARGE SAMPLES
ronment.
3.2.3 Simulated weathering of waterborne oils by evapora-
8. Scope
tion under ultraviolet light simulates the loss of light compo-
8.1 This procedure covers the preparation for analysis of
nents on weathering, as well as some oxidative weathering.
samples in which the volumes of waterborne oil in the
4. Significance and Use
environmental and suspect source samples equal or exceed 50
mLandinwhichtheoilportioncontainssignificantamountsof
4.1 Identification of a recovered oil is determined by com-
hydrocarbons with boiling points above 280°C.
parison with known oils selected because of their possible
relationship to the particular recovered oil, for example,
NOTE 1—The boiling point may be ascertained by injecting the neat
suspectedorquestionedsources.Thus,samplesofsuchknown
samples into the gas chromatograph and checking the elution times above
that of pentadecane on a nonpolar column.
oils must be collected and submitted along with the unknown
for analysis. It is unlikely that identification of the sources of
8.2 Thepreparationofsamplescontainingmostlyhydrocar-
an unknown oil by itself can be made without direct matching,
bons of boiling points below 280°C, such as petroleum
that is, solely with a library of analyses.
distillate fuels, is beyond the scope of this procedure (see
Procedure C or E).
5. Reagents and Materials
5.1 Purity of Reagents—Reagent grade chemicals shall be 9. Summary of Procedure
used in all tests. Unless otherwise indicated, it is intended that
9.1 A neat portion of the waterborne oil is retained. If not
all reagents shall conform to the specifications of the Commit-
possible to obtain a neat portion, then retain a portion of the
teeonAnalyticalReagentsoftheAmericanChemicalSociety.
waterborne oil as received.This is to be used in those analyses
Special ancillary procedures such as fluorescence may require
performed on samples containing significant quantities of
higher purity grades of solvents. Other grades may be used
hydrocarbons with boiling points below 280°C. Preparation of
provided it is first ascertained that the reagent is of sufficiently
these samples is beyond the scope of this procedure, but are
high purity to permit its use without lessening the accuracy of
covered in Procedure C.
the determination.
NOTE 2—Waterborne oil samples containing significant quantities of
5.2 Purity of Water—Unlessotherwiseindicated,references
hydrocarbons with boiling points below 280°C (see Note 1), such as
to water shall be understood to mean reagent Type II water
gasoline and kerosene, can usually be obtained as neat samples without
conforming to Specification D1193.
any sample preparation.
9.2 The waterborne oil sample is dissolved in an equal
6. Caution
volume of chloroform or dichloromethane and centrifuged to
6.1 Solventsusedinthispracticearevolatile,flammable,or
remove the free water, solids, and debris in accordance with
may cause the harm to the health of the user. Specifically,
Test Method D96. The water layer, if present, is separated
benzene is a known carcinogen, while chloroform and carbon
from the organic layer. Other debris, if present, is removed by
tetrachloride are suspected carcinogens. Consequently, it is
filtration through glass wool.
important that extractions and separations utilizing these sub-
NOTE 3—The use of spectrograde cyclohexane is required for the
stances must be carried out in a laboratory hood with a
extractionofsamplestobeanalyzedbyfluorescencespectrometrybyTest
minimum linear face velocity of 38 to 45 m/min (125 to 150
Method D3650. Separation of water may be accomplished by centrifu-
ft/min)locatedinaregulatedareapostedwithsignsbearingthe
gation or dying, or both, with anhydrous sodium sulfate.
legends: NO SMOKING or (if appropriate) DANGER-
9.3 Whencentrifugationwillnotseparatethewaterfromthe
CHEMICAL CARCINOGEN-AUTHORIZED PERSONNEL
chloroform solution of the sample, it is refluxed with an
ONLY, or both.
aromaticorpetroleumdistillatesolventinaccordancewithTest
MethodD95.
7. Sampling
7.1 Collect representative samples in accordance with Prac- NOTE 4—Pressure filtration has also been found useful for breaking
emulsions.
tices D4489.
9.4 Aportionofthesolvent/samplesolutionisretained.The
solvent may be removed by evaporation. This portion of the
sample may be used in the preliminary gas chromatographic
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
analysis, Test Methods D3328 (Test Method A), and other
listed by the American Chemical Society, see Analar Standards for Laboratory
analyses in which the results are unaffected by weathering.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
9.5 Theremainderofthesolvent/samplesolutionisdistilled
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. using nitrogen purge to a liquid temperature of 280°C to
D 3326 – 90 (2002)
remove the solvent and simulate weathering conditions as 10.5 Distillation Flask, 200 mL, as described in Specifica-
nearlyaspossible.Thedistillatemaybediscardedorsavedfor tion E133.
characterization by gas chromatography (Test Methods 10.6 Thermometer, ASTM high distillation, having a range
D3328). This simulated weathering treatment is necessary to from−2 to+400°C and conforming to the requirements for
bring the unweathered suspect samples and the waterborne oil thermometer 8C as prescribed in SpecificationE1.
sample to as nearly comparable physical condition for subse- 10.7 Flowmeter, to regulate flow of nitrogen to distillation
quent analysis as possible. Analyses requiring the use of this flask. It should be calibrated and graduated for the range 10 to
treated residue include elemental analysis (Test Methods 15 mL/min.
D3327); gas chromatographic analysis (Test MethodsD3328,
11. Reagents and Materials
Test Methods A and B); an infrared procedure (Test Method
11.1 Filter Paper, medium retention, medium fast speed,
D3414); a fluorescence test method (Test Method D3650);
prewashed with solvent used.
andanyapplicabletestmethodorpracticedescribedinPractice
11.2 Glass Wool, prewashed with solvent used.
D3415.
11.3 Solvent—Chloroform (stabilized with ethanol) or
NOTE 5—The distillate might yield useful information but is discarded
dichloromethane is used for dissolution of the waterborne oil
in this practice.
samples. If water is to be removed by distillation, an aromatic,
10. Apparatus petroleum distillate, or volatile spirits solvent is required as
specified in Test MethodD95. The safety precautions associ-
10.1 Centrifuge, capable of whirling two or more filled
ated with the use of the solvent selected should be considered
100-mLcentrifuge tubes at a speed that is controlled to give a
before it is used (see Note 3).
relative centrifugal force (rcf) between 500 and 800 at the tip
of the tubes, as specified in Test MethodD96.
12. Procedure
10.2 Centrifuge Tubes,coneshaped,100mL,asspecifiedin
12.1 Retention of Neat Samples:
Test MethodD96.
12.1.1 Decantorsiphonoffaportionoftheneatwaterborne
10.3 Distillation Apparatus for Water Determination,as
oil if possible.
specified in Test MethodD95.
12.1.2 If not possible to obtain a neat sample, retain a
10.4 Distillation Apparatus for Simulated Weathering,as
portion of the original oil.
described in Specification E133 except fitted with nitrogen-
12.2 Removal of Water, Sediment, and Debris:
stripping tubulation as illustrated in Fig. 1.
12.2.1 Transfer about 50 mLof original waterborne oil to a
100-mL centrifuge tube. Add about 50 mL of chloroform or
dichloromethane to the tube and mix thoroughly. For waxy
samples, use chloroform. Warm solutions to 50°C to prevent
precipitation (see Note 3).
12.2.1.1 Centrifuge the mixture at 500 to 800 rcf (relative
centrifugal force) for 10 min to separate free water and solids
as specified in Test Method D96. For waxy samples, use
chloroform. Warm solutions to 50°C to prevent precipitation
(see Note 3).
12.2.1.2 Withdraw the water layer if present. Decant the
chloroform or dichloromethane solution to a sample bottle.
Filter through a glass wool plug, if necessary, to afford a clean
separation.
12.2.2 Process those samples from which water cannot be
separated by centrifugation by Test Method D95 distillation
procedure. Filter the dry solution through medium retention
filter paper. Rinse filter paper with solvent to remove oil. For
waxy samples, use chloroform and keep filter funnel and
contents at 50°C during filtration (see Note 3).
12.2.3 Startingat12.1,treatallreferenceorsuspectsamples
in an identical fashion. If it is apparent that the reference or
suspect samples contain less than 1% water and sediment,
centrifugation may be eliminated and the reference or suspect
samples should be diluted with an equal volume of chloroform
or dichloromethane before proceeding.
12.3 Removal of Solvent and Simulated Weathering:
12.3.1 Transfer approximately 100 mL of the solution to a
chemically clean 200-mL flask. Assemble apparatus so the
ASTM high distillation thermometer (8C) and nitrogen strip-
FIG. 1 Adaptation of ASTM Distillation Flask for Topping
Chloroform Solutions of Oil to Simulate Weathering ping tubulation are about 6 mm from the bottom of the flask.
D 3326 – 90 (2002)
Direct flow away from thermometer bulb to prevent local 17.3 Centrifuge as described in 12.2.1.1 for 5 min.
cooling of thermometer (see Fig. 1). 17.4 Decant supernatant liquid into a 250-mL beaker and
12.3.2 Performdistillationusinganitrogenflowof10to15 evaporate the solvent and volatiles initially at 25 to 35°C and
mL/min. Terminate distillation at a liquid
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