ASTM D3326-07(2017)
(Practice)Standard Practice for Preparation of Samples for Identification of Waterborne Oils
Standard Practice for Preparation of Samples for Identification of Waterborne Oils
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, for example, suspected or questioned sources. Thus, samples of such known oils must be collected and submitted along with the unknown for analysis. It is unlikely that identification of the sources of an unknown oil by itself can be made without direct matching, that is, solely with a library of analyses.
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:
Sections
Procedure A (for samples of more than 50-mL volume containing significant quantities of hydrocarbons with boiling points above 280°C)
8 to 12
Procedure B (for samples containing significant quantities of hydrocarbons with boiling points above 280°C)
13 to 17
Procedure C (for waterborne oils containing significant amounts of components boiling below 280°C and to mixtures of these and higher boiling components)
18 to 22
Procedure D (for samples containing both petroleum and vegetable/animal derived oils)
23 to 27
Procedure E (for samples of light crudes and medium distillate fuels)
28 to 34
Procedure F (for thin films of oil-on-water)
35 to 39
Procedure G (for oil-soaked samples)
40 to 44
1.2 Procedures for the analytical examination of the waterborne oil samples are described in Practice D3415 and Test Methods D3328, D3414, and D3650. 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 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. Specific caution statements are given in Sections 6 and 32.
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.
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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:D3326 −07 (Reapproved 2017)
Standard Practice for
Preparation of Samples for Identification of Waterborne
Oils
This standard is issued under the fixed designation D3326; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
1.1 This practice covers the preparation for analysis of
mendations issued by the World Trade Organization Technical
waterborne oils recovered from water. The identification is
Barriers to Trade (TBT) Committee.
based upon the comparison of physical and chemical charac-
teristics of the waterborne oils with oils from suspect sources.
2. Referenced Documents
These oils may be of petroleum or vegetable/animal origin, or
both. Seven procedures are given as follows:
2.1 ASTM Standards:
Sections
D95Test Method for Water in Petroleum Products and
Procedure A (for samples of more than 50-mL volume
Bituminous Materials by Distillation
containing significant quantities of hydrocarbons with boiling
D1129Terminology Relating to Water
points above 280°C) 8 to 12
Procedure B (for samples containing significant quantities of
D1193Specification for Reagent Water
hydrocarbons with boiling points above 280°C) 13 to 17
D3325Practice for Preservation of Waterborne Oil Samples
Procedure C (for waterborne oils containing significant
D3328Test Methods for Comparison of Waterborne Petro-
amounts of components boiling below 280°C and to
mixtures of these and higher boiling components) 18 to 22
leum Oils by Gas Chromatography
Procedure D (for samples containing both petroleum and
D3414Test Method for Comparison of Waterborne Petro-
vegetable/animal derived oils) 23 to 27
leum Oils by Infrared Spectroscopy
Procedure E (for samples of light crudes and medium distillate
fuels) 28 to 34
D3415Practice for Identification of Waterborne Oils
Procedure F (for thin films of oil-on-water) 35 to 39
D3650Test Method for Comparison of Waterborne Petro-
Procedure G (for oil-soaked samples) 40 to 44
leum Oils By Fluorescence Analysis
1.2 Procedures for the analytical examination of the water-
D4489Practices for Sampling of Waterborne Oils
borne oil samples are described in Practice D3415 and Test
E1Specification for ASTM Liquid-in-Glass Thermometers
MethodsD3328,D3414,andD3650.Refertotheindividualoil
E133Specification for Distillation Equipment
identification test methods for the sample preparation method
of choice. The deasphalting effects of the sample preparation
3. Terminology
method should be considered in selecting the best methods.
3.1 Definitions:
1.3 The values stated in SI units are to be regarded as
3.1.1 For definitions of terms used in this standard, refer to
standard. No other units of measurement are included in this
Terminology D1129.
standard.
3.2 Definitions of Terms Specific to 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
3.2.1 animal/vegetable-derived oils, n—a mixture made of
responsibility of the user of this standard to establish appro- mono-, di-, and triglyceride esters of fatty acids and other
priate safety, health, and environmental practices and deter-
substances of animal or vegetable origin, or both.
mine the applicability of regulatory limitations prior to use.
3.2.2 simulated weathering of waterborne oils by
Specific caution statements are given in Sections 6 and 32.
distillation, n—considers only the effect of evaporation, which
1.5 This international standard was developed in accor-
likelyisthemostsignificantshort-termweatheringeffectinthe
dance with internationally recognized principles on standard-
environment.
This practice is under the jurisdiction ofASTM Committee D19 on Water and
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published December 2017. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1974. Last previous edition approved in 2011 as D3326–07 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D3326-07R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3326−07 (2017)
3.2.3 simulated weathering of waterborne oils by PROCEDURE A—LARGE SAMPLES
evaporation, n—under ultraviolet light simulates the loss of
8. Scope
light components on weathering, as well as some oxidative
weathering.
8.1 This procedure covers the preparation for analysis of
samples in which the volumes of waterborne oil in the
4. Significance and Use
environmental and suspect source samples equal or exceed 50
4.1 Identification of a recovered oil is determined by com-
mLandinwhichtheoilportioncontainssignificantamountsof
parison with known oils selected because of their possible hydrocarbons with boiling points above 280°C.
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
oils must be collected and submitted along with the unknown
that of pentadecane on a nonpolar column.
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—Unless otherwise indicated, references
hydrocarbons with boiling points below 280°C (see Note 1), such as
to water shall be understood to mean reagent water that meets
gasoline and kerosene, can usually be obtained as neat samples without
thepurityspecificationsofTypeIorTypeIIwater,asspecified any sample preparation.
in Specification D1193.
9.2 The waterborne oil sample is dissolved in an equal
volume of chloroform or dichloromethane and centrifuged to
6. Caution
remove the free water, solids, and debris. The water layer, if
6.1 Solventsusedinthispracticearevolatile,flammable,or
present, is separated from the organic layer. Other debris, if
may cause the harm to the health of the user. Specifically,
present, is removed by filtration through glass wool.
benzene is a known carcinogen, while chloroform and carbon
NOTE 3—The use of spectrograde cyclohexane is required for the
tetrachloride are suspected carcinogens. Consequently, it is
extractionofsamplestobeanalyzedbyfluorescencespectrometrybyTest
important that extractions and separations utilizing these sub-
Method D3650. Separation of water may be accomplished by centrifuga-
stances must be carried out in a laboratory hood with a
tion or dying, or both, with anhydrous sodium sulfate.
minimum linear face velocity of 38 to 45 m/min (125 to 150
9.3 Whencentrifugationwillnotseparatethewaterfromthe
ft/min)locatedinaregulatedareapostedwithsignsbearingthe
chloroform solution of the sample, it is refluxed with an
legends: NO SMOKING or (if appropriate) DANGER-
aromaticorpetroleumdistillatesolventinaccordancewithTest
CHEMICAL CARCINOGEN-AUTHORIZED PERSONNEL
Method D95.
ONLY, or both.
NOTE 4—Pressure filtration has also been found useful for breaking
emulsions.
7. Sampling
9.4 Aportionofthesolvent/samplesolutionisretained.The
7.1 Collect representative samples in accordance with Prac-
solvent may be removed by evaporation. This portion of the
tices D4489.
sample may be used in the preliminary gas chromatographic
7.2 Preserve the waterborne oil samples in accordance with
analysis, Test Methods D3328 (Test Method A), and other
Practice D3325.
analyses in which the results are unaffected by weathering.
7.3 Theportionofthesampleusedmustberepresentativeof
9.5 Theremainderofthesolvent/samplesolutionisdistilled
the total sample. If the material is liquid, thoroughly stir the
using nitrogen purge to a liquid temperature of 280°C to
sampleasreceived,warmingifnecessarytoensureuniformity.
remove the solvent and simulate weathering conditions as
nearlyaspossible.Thedistillatemaybediscardedorsavedfor
characterization by gas chromatography (Test Methods
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
D3328). This simulated weathering treatment is necessary to
listed by the American Chemical Society, see Analar Standards for Laboratory
bring the unweathered suspect samples and the waterborne oil
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
sample to as nearly comparable physical condition for subse-
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. quent analysis as possible. Analyses requiring the use of this
D3326−07 (2017)
treated residue include elemental analysis; gas chromato- 10.7 Flowmeter, to regulate flow of nitrogen to distillation
graphicanalysis(TestMethodsD3328,TestMethodsAandB); flask. It should be calibrated and graduated for the range 10 to
aninfraredprocedure(TestMethodD3414);afluorescencetest 15 mL/min.
method (Test Method D3650); and any applicable test method
11. Reagents and Materials
or practice described in Practice D3415.
11.1 Filter Paper, medium retention, medium fast speed,
NOTE 5—The distillate might yield useful information but is discarded
in this practice. prewashed with solvent used.
11.2 Glass Wool, prewashed with solvent used.
10. Apparatus
11.3 Solvent—Chloroform (stabilized with ethanol) or di-
10.1 Centrifuge, capable of whirling two or more filled
chloromethane is used for dissolution of the waterborne oil
100-mLcentrifuge tubes at a speed that is controlled to give a
samples. If water is to be removed by distillation, an aromatic,
relative centrifugal force (rcf) between 500 and 800 at the tip
petroleum distillate, or volatile spirits solvent is required as
of the tubes.
specified in Test Method D95. The safety precautions associ-
ated with the use of the solvent selected should be considered
10.2 Centrifuge Tubes, cone shaped, 100 mL.
before it is used (see Note 3).
10.3 Distillation Apparatus for Water Determination, as
specified in Test Method D95.
12. Procedure
10.4 Distillation Apparatus for Simulated Weathering, as
12.1 Retention of Neat Samples:
described in Specification E133 except fitted with nitrogen-
12.1.1 Decantorsiphonoffaportionoftheneatwaterborne
stripping tubulation as illustrated in Fig. 1.
oil if possible.
10.5 Distillation Flask, 200 mL, as described in Specifica- 12.1.2 If not possible to obtain a neat sample, retain a
portion of the original oil.
tion E133.
10.6 Thermometer, ASTM high distillation, having a range 12.2 Removal of Water, Sediment, and Debris:
12.2.1 Transfer about 50 mLof original waterborne oil to a
from−2 to+400°C and conforming to the requirements for
thermometer 8C as prescribed in Specification E1. 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.
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
samplesshouldbedilutedwithanequalvolumeofchloroform
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-
ping tubulation are about 6 mm from the bottom of the flask.
Direct flow away from thermometer bulb to prevent local
cooling of thermometer (see Fig. 1).
12.3.2 Performdistillationusinganitrogenflowof10to15
FIG. 1 Adaptation of ASTM Distillation Flask for Topping Chloro-
form Solutions of Oil to Simulate Weathering mL/min. Terminate distillation at a liquid temperature of
D3326−07 (2017)
280°C. Shut off the nitrogen flow when the temperature of the 17.3 Centrifuge as described in 12.2.1.1 for 5 min.
liquid in the distillation flask cools below 175°C. Pour the hot
17.4
...
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: D3326 − 07 (Reapproved 2017)
Standard Practice for
Preparation of Samples for Identification of Waterborne
Oils
This standard is issued under the fixed designation D3326; 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 ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
1.1 This practice covers the preparation for analysis of
mendations issued by the World Trade Organization Technical
waterborne oils recovered from water. The identification is
Barriers to Trade (TBT) Committee.
based upon the comparison of physical and chemical charac-
teristics of the waterborne oils with oils from suspect sources.
2. Referenced Documents
These oils may be of petroleum or vegetable/animal origin, or
both. Seven procedures are given as follows:
2.1 ASTM Standards:
Sections D95 Test Method for Water in Petroleum Products and
Procedure A (for samples of more than 50-mL volume
Bituminous Materials by Distillation
containing significant quantities of hydrocarbons with boiling
D1129 Terminology Relating to Water
points above 280°C) 8 to 12
Procedure B (for samples containing significant quantities of
D1193 Specification for Reagent Water
hydrocarbons with boiling points above 280°C) 13 to 17
D3325 Practice for Preservation of Waterborne Oil Samples
Procedure C (for waterborne oils containing significant
D3328 Test Methods for Comparison of Waterborne Petro-
amounts of components boiling below 280°C and to
mixtures of these and higher boiling components) 18 to 22
leum Oils by Gas Chromatography
Procedure D (for samples containing both petroleum and
D3414 Test Method for Comparison of Waterborne Petro-
vegetable/animal derived oils) 23 to 27
leum Oils by Infrared Spectroscopy
Procedure E (for samples of light crudes and medium distillate
fuels) 28 to 34
D3415 Practice for Identification of Waterborne Oils
Procedure F (for thin films of oil-on-water) 35 to 39
D3650 Test Method for Comparison of Waterborne Petro-
Procedure G (for oil-soaked samples) 40 to 44
leum Oils By Fluorescence Analysis
1.2 Procedures for the analytical examination of the water-
D4489 Practices for Sampling of Waterborne Oils
borne oil samples are described in Practice D3415 and Test
E1 Specification for ASTM Liquid-in-Glass Thermometers
Methods D3328, D3414, and D3650. Refer to the individual oil
E133 Specification for Distillation Equipment
identification test methods for the sample preparation method
of choice. The deasphalting effects of the sample preparation
3. Terminology
method should be considered in selecting the best methods.
3.1 Definitions:
1.3 The values stated in SI units are to be regarded as
3.1.1 For definitions of terms used in this standard, refer to
standard. No other units of measurement are included in this
Terminology D1129.
standard.
3.2 Definitions of Terms Specific to 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 3.2.1 animal/vegetable-derived oils, n—a mixture made of
responsibility of the user of this standard to establish appro-
mono-, di-, and triglyceride esters of fatty acids and other
priate safety, health, and environmental practices and deter- substances of animal or vegetable origin, or both.
mine the applicability of regulatory limitations prior to use.
3.2.2 simulated weathering of waterborne oils by
Specific caution statements are given in Sections 6 and 32.
distillation, n—considers only the effect of evaporation, which
1.5 This international standard was developed in accor-
likely is the most significant short-term weathering effect in the
dance with internationally recognized principles on standard-
environment.
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. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2017. Published December 2017. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1974. Last previous edition approved in 2011 as D3326 – 07 (2011). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D3326-07R17. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3326 − 07 (2017)
3.2.3 simulated weathering of waterborne oils by PROCEDURE A—LARGE SAMPLES
evaporation, n—under ultraviolet light simulates the loss of
8. Scope
light components on weathering, as well as some oxidative
weathering.
8.1 This procedure covers the preparation for analysis of
samples in which the volumes of waterborne oil in the
4. Significance and Use
environmental and suspect source samples equal or exceed 50
4.1 Identification of a recovered oil is determined by com- mL and in which the oil portion contains significant amounts of
parison with known oils selected because of their possible
hydrocarbons with boiling points above 280°C.
relationship to the particular recovered oil, for example,
NOTE 1—The boiling point may be ascertained by injecting the neat
suspected or questioned sources. Thus, samples of such known
samples into the gas chromatograph and checking the elution times above
oils must be collected and submitted along with the unknown
that of pentadecane on a nonpolar column.
for analysis. It is unlikely that identification of the sources of
8.2 The preparation of samples containing mostly hydrocar-
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
tee on Analytical Reagents of the American Chemical Society.
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—Unless otherwise indicated, references
hydrocarbons with boiling points below 280°C (see Note 1), such as
to water shall be understood to mean reagent water that meets
gasoline and kerosene, can usually be obtained as neat samples without
the purity specifications of Type I or Type II water, as specified any sample preparation.
in Specification D1193.
9.2 The waterborne oil sample is dissolved in an equal
volume of chloroform or dichloromethane and centrifuged to
6. Caution
remove the free water, solids, and debris. The water layer, if
6.1 Solvents used in this practice are volatile, flammable, or
present, is separated from the organic layer. Other debris, if
may cause the harm to the health of the user. Specifically,
present, is removed by filtration through glass wool.
benzene is a known carcinogen, while chloroform and carbon
NOTE 3—The use of spectrograde cyclohexane is required for the
tetrachloride are suspected carcinogens. Consequently, it is
extraction of samples to be analyzed by fluorescence spectrometry by Test
important that extractions and separations utilizing these sub-
Method D3650. Separation of water may be accomplished by centrifuga-
stances must be carried out in a laboratory hood with a
tion or dying, or both, with anhydrous sodium sulfate.
minimum linear face velocity of 38 to 45 m/min (125 to 150
9.3 When centrifugation will not separate the water from the
ft/min) located in a regulated area posted with signs bearing the
chloroform solution of the sample, it is refluxed with an
legends: NO SMOKING or (if appropriate) DANGER-
aromatic or petroleum distillate solvent in accordance with Test
CHEMICAL CARCINOGEN-AUTHORIZED PERSONNEL
Method D95.
ONLY, or both.
NOTE 4—Pressure filtration has also been found useful for breaking
emulsions.
7. Sampling
9.4 A portion of the solvent/sample solution is retained. The
7.1 Collect representative samples in accordance with Prac-
solvent may be removed by evaporation. This portion of the
tices D4489.
sample may be used in the preliminary gas chromatographic
7.2 Preserve the waterborne oil samples in accordance with
analysis, Test Methods D3328 (Test Method A), and other
Practice D3325.
analyses in which the results are unaffected by weathering.
7.3 The portion of the sample used must be representative of
9.5 The remainder of the solvent/sample solution is distilled
the total sample. If the material is liquid, thoroughly stir the
using nitrogen purge to a liquid temperature of 280°C to
sample as received, warming if necessary to ensure uniformity.
remove the solvent and simulate weathering conditions as
nearly as possible. The distillate may be discarded or saved for
characterization by gas chromatography (Test Methods
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
D3328). This simulated weathering treatment is necessary to
listed by the American Chemical Society, see Analar Standards for Laboratory
bring the unweathered suspect samples and the waterborne oil
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
sample to as nearly comparable physical condition for subse-
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. quent analysis as possible. Analyses requiring the use of this
D3326 − 07 (2017)
treated residue include elemental analysis; gas chromato- 10.7 Flowmeter, to regulate flow of nitrogen to distillation
graphic analysis (Test Methods D3328, Test Methods A and B); flask. It should be calibrated and graduated for the range 10 to
an infrared procedure (Test Method D3414); a fluorescence test 15 mL/min.
method (Test Method D3650); and any applicable test method
11. Reagents and Materials
or practice described in Practice D3415.
11.1 Filter Paper, medium retention, medium fast speed,
NOTE 5—The distillate might yield useful information but is discarded
prewashed with solvent used.
in this practice.
11.2 Glass Wool, prewashed with solvent used.
10. Apparatus
11.3 Solvent—Chloroform (stabilized with ethanol) or di-
10.1 Centrifuge, capable of whirling two or more filled
chloromethane is used for dissolution of the waterborne oil
100-mL centrifuge tubes at a speed that is controlled to give a
samples. If water is to be removed by distillation, an aromatic,
relative centrifugal force (rcf) between 500 and 800 at the tip
petroleum distillate, or volatile spirits solvent is required as
of the tubes.
specified in Test Method D95. The safety precautions associ-
ated with the use of the solvent selected should be considered
10.2 Centrifuge Tubes, cone shaped, 100 mL.
before it is used (see Note 3).
10.3 Distillation Apparatus for Water Determination, as
specified in Test Method D95.
12. Procedure
10.4 Distillation Apparatus for Simulated Weathering, as
12.1 Retention of Neat Samples:
described in Specification E133 except fitted with nitrogen-
12.1.1 Decant or siphon off a portion of the neat waterborne
stripping tubulation as illustrated in Fig. 1.
oil if possible.
12.1.2 If not possible to obtain a neat sample, retain a
10.5 Distillation Flask, 200 mL, as described in Specifica-
tion E133. portion of the original oil.
12.2 Removal of Water, Sediment, and Debris:
10.6 Thermometer, ASTM high distillation, having a range
from −2 to +400°C and conforming to the requirements for 12.2.1 Transfer about 50 mL of original waterborne oil to a
100-mL centrifuge tube. Add about 50 mL of chloroform or
thermometer 8C as prescribed in Specification E1.
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.
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 Starting at 12.1, treat all reference or suspect samples
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-
ping tubulation are about 6 mm from the bottom of the flask.
Direct flow away from thermometer bulb to prevent local
cooling of thermometer (see Fig. 1).
12.3.2 Perform distillation using a nitrogen flow of 10 to 15
FIG. 1 Adaptation of ASTM Distillation Flask for Topping Chloro-
form Solutions of Oil to Simulate Weathering mL/min. Terminate distillation at a liquid temperature of
D3326 − 07 (2017)
280°C. Shut off the nitrogen flow when the temperatur
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D3326 − 07 (Reapproved 2011) D3326 − 07 (Reapproved 2017)
Standard Practice for
Preparation of Samples for Identification of Waterborne
Oils
This standard is issued under the fixed designation D3326; 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
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:
Sections
Procedure A (for samples of more than 50-mL volume
containing significant quantities of hydrocarbons with boiling
points above 280°C) 8 to 12
Procedure B (for samples containing significant quantities of
hydrocarbons with boiling points above 280°C) 13 to 17
Procedure C (for waterborne oils containing significant
amounts of components boiling below 280°C and to
mixtures of these and higher boiling components) 18 to 22
Procedure D (for samples containing both petroleum and
vegetable/animal derived oils) 23 to 27
Procedure E (for samples of light crudes and medium distillate
fuels) 28 to 34
Procedure F (for thin films of oil-on-water) 35 to 39
Procedure G (for oil-soaked samples) 40 to 44
Sections
Procedure A (for samples of more than 50-mL volume
containing significant quantities of hydrocarbons
with boiling points above 280°C) 8 to 12
Procedure B (for samples containing significant quantities of
hydrocarbons with boiling points above 280°C) 13 to 17
Procedure C (for waterborne oils containing significant
amounts of components boiling below 280°C and
to mixtures of these and higher boiling components) 18 to 22
Procedure D (for samples containing both petroleum and
vegetable/animal derived oils) 23 to 27
Procedure E (for samples of light crudes and medium distillate
fuels) 28 to 34
Procedure F (for thin films of oil-on-water) 35 to 39
Procedure G (for oil-soaked samples) 40 to 44
1.2 Procedures for the analytical examination of the waterborne oil samples are described in Practice D3415, and Test Methods
D3328, D3414, and D3650. 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 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. Specific caution statements are given in Sections 6 and 32.
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.
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 May 1, 2011Dec. 15, 2017. Published June 2011December 2017. Originally approved in 1974. Last previous edition approved in 20072011 as
D3326 – 07.D3326 – 07 (2011). DOI: 10.1520/D3326-07R11.10.1520/D3326-07R17.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3326 − 07 (2017)
2. Referenced Documents
2.1 ASTM Standards:
D95 Test Method for Water in Petroleum Products and Bituminous Materials by Distillation
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D3325 Practice for Preservation of Waterborne Oil Samples
D3328 Test Methods for Comparison of Waterborne Petroleum Oils by Gas Chromatography
D3414 Test Method for Comparison of Waterborne Petroleum Oils by Infrared Spectroscopy
D3415 Practice for Identification of Waterborne Oils
D3650 Test Method for Comparison of Waterborne Petroleum Oils By Fluorescence Analysis
D4489 Practices for Sampling of Waterborne Oils
E1 Specification for ASTM Liquid-in-Glass Thermometers
E133 Specification for Distillation Equipment
3. Terminology
3.1 Definitions—Definitions: For definitions of terms used in this practice, refer to Terminology D1129.
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 animal/vegetable-derived oils—oils, n—a mixture made of mono-, di-, and triglyceride esters of fatty acids and other
substances of animal or vegetable origin, or both.
3.2.2 Simulated weathering of waterborne oils by distillation considers only the effect of evaporation, which likely is the most
significant short-term weathering effect in the environment.
3.2.2 simulated weathering of waterborne oils by distillation, n—considers only the effect of evaporation, which likely is the
most significant short-term weathering effect in the environment.
3.2.3 Simulated weathering of waterborne oils by evaporation under ultraviolet light simulates the loss of light components on
weathering, as well as some oxidative weathering.
3.2.3 simulated weathering of waterborne oils by evaporation, n—under ultraviolet light simulates the loss of light components
on weathering, as well as some oxidative weathering.
4. 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, for example, suspected or questioned sources. Thus, samples of such known oils must be collected
and submitted along with the unknown for analysis. It is unlikely that identification of the sources of an unknown oil by itself can
be made without direct matching, that is, solely with a library of analyses.
5. Reagents and Materials
5.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society. Special
ancillary procedures such as fluorescence may require higher purity grades of solvents. Other grades may be used provided it is
first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination.
5.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water that meets the
purity specifications of Type I or Type II water, as specified in Specification D1193.
6. Caution
6.1 Solvents used in this practice are volatile, flammable, or may cause the harm to the health of the user. Specifically, benzene
is a known carcinogen, while chloroform and carbon tetrachloride are suspected carcinogens. Consequently, it is important that
extractions and separations utilizing these substances must be carried out in a laboratory hood with a minimum linear face velocity
of 38 to 45 m/min (125 to 150 ft/min) located in a regulated area posted with signs bearing the legends: NO SMOKING or (if
appropriate) DANGER-CHEMICAL CARCINOGEN-AUTHORIZED PERSONNEL ONLY, or both.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D3326 − 07 (2017)
7. Sampling
7.1 Collect representative samples in accordance with Practices D4489.
7.2 Preserve the waterborne oil samples in accordance with Practice D3325.
7.3 The portion of the sample used must be representative of the total sample. If the material is liquid, thoroughly stir the sample
as received, warming if necessary to ensure uniformity.
PROCEDURE A—LARGE SAMPLES
8. Scope
8.1 This procedure covers the preparation for analysis of samples in which the volumes of waterborne oil in the environmental
and suspect source samples equal or exceed 50 mL and in which the oil portion contains significant amounts of hydrocarbons with
boiling points above 280°C.
NOTE 1—The boiling point may be ascertained by injecting the neat samples into the gas chromatograph and checking the elution times above that
of pentadecane on a nonpolar column.
8.2 The preparation of samples containing mostly hydrocarbons of boiling points below 280°C, such as petroleum distillate
fuels, is beyond the scope of this procedure (see Procedure C or E).
9. Summary of Procedure
9.1 A neat portion of the waterborne oil is retained. If not possible to obtain a neat portion, then retain a portion of the
waterborne oil as received. This is to be used in those analyses performed on samples containing significant quantities of
hydrocarbons with boiling points below 280°C. Preparation of these samples is beyond the scope of this procedure, but are covered
in Procedure C.
NOTE 2—Waterborne oil samples containing significant quantities of hydrocarbons with boiling points below 280°C (see Note 1), such as gasoline and
kerosene, can usually be obtained as neat samples without any sample preparation.
9.2 The waterborne oil sample is dissolved in an equal volume of chloroform or dichloromethane and centrifuged to remove
the free water, solids, and debris. The water layer, if present, is separated from the organic layer. Other debris, if present, is removed
by filtration through glass wool.
NOTE 3—The use of spectrograde cyclohexane is required for the extraction of samples to be analyzed by fluorescence spectrometry by Test Method
D3650. Separation of water may be accomplished by centrifugation or dying, or both, with anhydrous sodium sulfate.
9.3 When centrifugation will not separate the water from the chloroform solution of the sample, it is refluxed with an aromatic
or petroleum distillate solvent in accordance with Test Method D95.
NOTE 4—Pressure filtration has also been found useful for breaking emulsions.
9.4 A portion of the solvent/sample solution is retained. The solvent may be removed by evaporation. This portion of the sample
may be used in the preliminary gas chromatographic analysis, Test Methods D3328 (Test Method A), and other analyses in which
the results are unaffected by weathering.
9.5 The remainder of the solvent/sample solution is distilled using nitrogen purge to a liquid temperature of 280°C to remove
the solvent and simulate weathering conditions as nearly as possible. The distillate may be discarded or saved for characterization
by gas chromatography (Test Methods D3328). This simulated weathering treatment is necessary to bring the unweathered suspect
samples and the waterborne oil sample to as nearly comparable physical condition for subsequent analysis as possible. Analyses
requiring the use of this treated residue include elemental analysis; gas chromatographic analysis (Test Methods D3328, Test
Methods A and B); an infrared procedure (Test Method D3414); a fluorescence test method (Test Method D3650); and any
applicable test method or practice described in Practice D3415.
NOTE 5—The distillate might yield useful information but is discarded in this practice.
10. Apparatus
10.1 Centrifuge, capable of whirling two or more filled 100-mL centrifuge tubes at a speed that is controlled to give a relative
centrifugal force (rcf) between 500 and 800 at the tip of the tubes.
10.2 Centrifuge Tubes, cone shaped, 100 mL.
10.3 Distillation Apparatus for Water Determination, as specified in Test Method D95.
10.4 Distillation Apparatus for Simulated Weathering, as described in Specification E133 except fitted with nitrogen-stripping
tubulation as illustrated in Fig. 1.
10.5 Distillation Flask, 200 mL, as described in Specification E133.
D3326 − 07 (2017)
FIG. 1 Adaptation of ASTM Distillation Flask for Topping Chloroform Solutions of Oil to Simulate Weathering
10.6 Thermometer, ASTM high distillation, having a range from − 2 to + 400°Cfrom −2 to +400°C and conforming to the
requirements for thermometer 8C as prescribed in Specification E1.
10.7 Flowmeter, to regulate flow of nitrogen to distillation flask. It should be calibrated and graduated for the range 10 to 15
mL/min.
11. Reagents and Materials
11.1 Filter Paper, medium retention, medium fast speed, prewashed with solvent used.
11.2 Glass Wool, prewashed with solvent used.
11.3 Solvent—Chloroform (stabilized with ethanol) or dichloromethane is used for dissolution of the waterborne oil samples.
If water is to be removed by distillation, an aromatic, petroleum distillate, or volatile spirits solvent is required as specified in Test
Method D95. The safety precautions associated with the use of the solvent selected should be considered before it is used (see Note
3).
12. Procedure
12.1 Retention of Neat Samples:
12.1.1 Decant or siphon off a portion of the neat waterborne oil if possible.
12.1.2 If not possible to obtain a neat sample, retain a portion of the original oil.
12.2 Removal of Water, Sediment, and Debris:
12.2.1 Transfer about 50 mL of 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. For
waxy samples, use chloroform. Warm solutions to 50°C to prevent precipi
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