ASTM D3326-90(1996)e1
(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: Sections Procedure A (for samples of more than 50-mL volume con- taining significant quantities of hydrocarbons with boiling points above 280[deg]C) 8 to 12 Procedure B (for samples containing significant quantities of hydrocarbons with boiling points above 280[deg]C) 13 to 17 Procedure C (for waterborne oils containing significant amounts of components boiling below 280[deg]C and to mix- tures of these and higher boiling components) 18 to 22 Procedure D (for samples containing both petroleum and vege- table/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 D3327, 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 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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e1
Designation: D 3326 – 90 (Reapproved 1996)
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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
e NOTE—Keywords were added editorially in December 1996.
1. Scope Bituminous Materials by Distillation
D 96 Test Method for Water and Sediment in Crude Oil by
1.1 This practice covers the preparation for analysis of
Centrifuge Method (Field Procedure)
waterborne oils recovered from water. The identification is
D 1129 Terminology Relating to Water
based upon the comparison of physical and chemical charac-
D 1193 Specification for Reagent Water
teristics of the waterborne oils with oils from suspect sources.
D 1959 Test Method for Iodine Value of Drying Oils and
These oils may be of petroleum or vegetable/animal origin, or
Fatty Acids
both. Seven procedures are given as follows:
D 1983 Test Method for Fatty Acid Composition by Gas-
Sections
Liquid Chromatography of Methyl Esters
Procedure A (for samples of more than 50-mL volume
containing significant quantities of hydrocarbons
D 2800 Test Method for Preparation of Methyl Esters from
with boiling points above 280°C) 8 to 12
Oils for Determination of Fatty Acid Composition by Gas
Procedure B (for samples containing significant quantities of
Chromatography
hydrocarbons with boiling points above 280°C) 13 to 17
Procedure C (for waterborne oils containing significant
D 3325 Practice for Preservation of Waterborne Oil
amounts of components boiling below 280°C and
Samples
to mixtures of these and higher boiling components) 18 to 22
D 3327 Test Methods for Analysis of Selected Elements in
Procedure D (for samples containing both petroleum and
vegetable/animal derived oils) 23 to 27
Waterborne Oils
Procedure E (for samples of light crudes and medium distillate
D 3328 Test Methods for Comparison of Waterborne Petro-
fuels) 28 to 34 leum Oils by Gas Chromatography
Procedure F (for thin films of oil-on-water) 35 to 39
D 3414 Test Method for Comparison of Waterborne Petro-
Procedure G (for oil-soaked samples) 40 to 44
leum Oils by Infrared Spectroscopy
1.2 Procedures for the analytical examination of the water-
D 3415 Practice for Identification of Waterborne Oils
borne oil samples are described in Practice D 3415 and Test
D 3650 Test Method for Comparison of Waterborne Petro-
Methods D 3327, D 3328, D 3414, and D 3650. Refer to the
leum Oils by Fluorescence Analysis
individual oil identification test methods for the sample prepa-
D 4489 Practices for Sampling of Waterborne Oils
ration method of choice. The deasphalting effects of the sample
E 1 Specification for ASTM Thermometers
preparation method should be considered in selecting the best
E 133 Specification for Distillation Equipment
methods.
3. Terminology
1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
3.1 Definitions—For definitions of terms used in this prac-
responsibility of the user of this standard to establish appro-
tice, refer to Terminology D 1129.
priate safety and health practices and determine the applica-
3.2 Definitions of Terms Specific to This Standard:
bility of regulatory limitations prior to use. Specific caution
3.2.1 animal/vegetable-derived oils—a mixture made of
statements are given in Sections 6 and 32.
mono-, di-, and triglyceride esters of fatty acids and other
substances of animal or vegetable origin, or both.
2. Referenced Documents
3.2.2 Simulated weathering of waterborne oils by distilla-
2.1 ASTM Standards:
tion considers only the effect of evaporation, which likely is
D 95 Test Method for Water in Petroleum Products and
Annual Book of ASTM Standards, Vol 05.01.
Annual Book of ASTM Standards, Vol 11.01.
This practice is under the jurisdiction of ASTM Committee D19 on Water and 4
Annual Book of ASTM Standards, Vol 06.03.
is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for 5
Annual Book of ASTM Standards, Vol 11.02.
Organic Substances in Water. 6
Discontinued; see 1993 Annual Book of ASTM Standards, Vol 11.02.
Current edition approved May 25, 1990. Published October 1990. Originally 7
Annual Book of ASTM Standards, Vol 14.03.
published as D3326 – 74 T. Last previous edition D 3326 – 84. 8
Annual Book of ASTM Standards, Vol 14.02.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
D 3326
the most significant short-term weathering effect in the envi- PROCEDURE A—LARGE SAMPLES
ronment.
8. Scope
3.2.3 Simulated weathering of waterborne oils by evapora-
8.1 This procedure covers the preparation for analysis of
tion under ultraviolet light simulates the loss of light compo-
samples in which the volumes of waterborne oil in the
nents on weathering, as well as some oxidative weathering.
environmental and suspect source samples equal or exceed 50
mL and in which the oil portion contains significant amounts of
4. Significance and Use
hydrocarbons with boiling points above 280°C.
4.1 Identification of a recovered oil is determined by com-
NOTE 1—The boiling point may be ascertained by injecting the neat
parison with known oils selected because of their possible
samples into the gas chromatograph and checking the elution times above
relationship to the particular recovered oil, for example,
that of pentadecane on a nonpolar column.
suspected or questioned sources. Thus, samples of such known
8.2 The preparation of samples containing mostly hydrocar-
oils must be collected and submitted along with the unknown
bons of boiling points below 280°C, such as petroleum
for analysis. It is unlikely that identification of the sources of
distillate fuels, is beyond the scope of this procedure (see
an unknown oil by itself can be made without direct matching,
Procedure C or E).
that is, solely with a library of analyses.
9. Summary of Procedure
5. Reagents and Materials
9.1 A neat portion of the waterborne oil is retained. If not
5.1 Purity of Reagents—Reagent grade chemicals shall be
possible to obtain a neat portion, then retain a portion of the
used in all tests. Unless otherwise indicated, it is intended that
waterborne oil as received. This is to be used in those analyses
all reagents shall conform to the specifications of the Commit-
performed on samples containing significant quantities of
tee on Analytical Reagents of the American Chemical Society.
hydrocarbons with boiling points below 280°C. Preparation of
Special ancillary procedures such as fluorescence may require
these samples is beyond the scope of this procedure, but are
higher purity grades of solvents. Other grades may be used
covered in Procedure C.
provided it is first ascertained that the reagent is of sufficiently
NOTE 2—Waterborne oil samples containing significant quantities of
high purity to permit its use without lessening the accuracy of
hydrocarbons with boiling points below 280°C (see Note 1), such as
the determination.
gasoline and kerosene, can usually be obtained as neat samples without
5.2 Purity of Water— Unless otherwise indicated, refer-
any sample preparation.
ences to water shall be understood to mean reagent Type II
9.2 The waterborne oil sample is dissolved in an equal
water conforming to Specification D 1193.
volume of chloroform or dichloromethane and centrifuged to
remove the free water, solids, and debris in accordance with
6. Caution
Test Method D 96. The water layer, if present, is separated
6.1 Solvents used in this practice are volatile, flammable, or
from the organic layer. Other debris, if present, is removed by
may cause the harm to the health of the user. Specifically,
filtration through glass wool.
benzene is a known carcinogen, while chloroform and carbon
tetrachloride are suspected carcinogens. Consequently, it is NOTE 3—The use of spectrograde cyclohexane is required for the
extraction of samples to be analyzed by fluorescence spectrometry by Test
important that extractions and separations utilizing these sub-
Method D 3650. Separation of water may be accomplished by centrifu-
stances must be carried out in a laboratory hood with a
gation 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 D 95.
ONLY, or both.
NOTE 4—Pressure filtration has also been found useful for breaking
7. Sampling
emulsions.
7.1 Collect representative samples in accordance with Prac-
9.4 A portion of the solvent/sample solution is retained. The
tices D 4489.
solvent may be removed by evaporation. This portion of the
7.2 Preserve the waterborne oil samples in accordance with
sample may be used in the preliminary gas chromatographic
Practice D 3325.
analysis, Test Methods D 3328 (Test Method A), and other
7.3 The portion of the sample used must be representative of
analyses in which the results are unaffected by weathering.
the total sample. If the material is liquid, thoroughly stir the
9.5 The remainder of the solvent/sample solution is distilled
sample as received, warming if necessary to ensure uniformity.
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
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
D 3328). 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
D 3326
treated residue include elemental analysis (Test Methods 11. Reagents and Materials
D 3327); gas chromatographic analysis (Test Methods D 3328,
11.1 Filter Paper, medium retention, medium fast speed,
Test Methods A and B); an infrared procedure (Test Method
prewashed with solvent used.
D 3414); a fluorescence test method (Test Method D 3650);
11.2 Glass Wool, prewashed with solvent used.
and any applicable test method or practice described in Practice
11.3 Solvent—Chloroform (stabilized with ethanol) or
D 3415.
dichloromethane is used for dissolution of the waterborne oil
samples. If water is to be removed by distillation, an aromatic,
NOTE 5—The distillate might yield useful information but is discarded
in this practice. petroleum distillate, or volatile spirits solvent is required as
specified in Test Method D 95. The safety precautions associ-
10. Apparatus
ated with the use of the solvent selected should be considered
10.1 Centrifuge, capable of whirling two or more filled
before it is used (see Note 3).
100-mL centrifuge tubes at a speed that is controlled to give a
relative centrifugal force (rcf) between 500 and 800 at the tip
12. Procedure
of the tubes, as specified in Test Method D 96.
12.1 Retention of Neat Samples:
10.2 Centrifuge Tubes, cone shaped, 100 mL, as specified in
12.1.1 Decant or siphon off a portion of the neat waterborne
Test Method D 96.
oil if possible.
10.3 Distillation Apparatus for Water Determination,as
12.1.2 If not possible to obtain a neat sample, retain a
specified in Test Method D 95.
portion of the original oil.
10.4 Distillation Apparatus for Simulated Weathering,as
12.2 Removal of Water, Sediment, and Debris:
described in Specification E 133 except fitted with nitrogen-
12.2.1 Transfer about 50 mL of original waterborne oil to a
stripping tubulation as illustrated in Fig. 1.
100-mL centrifuge tube. Add about 50 mL of chloroform or
10.5 Distillation Flask, 200 mL, as described in Specifica-
dichloromethane to the tube and mix thoroughly. For waxy
tion E 133.
samples, use chloroform. Warm solutions to 50°C to prevent
10.6 Thermometer, ASTM high distillation, having a range
precipitation (see Note 3).
from − 2 to + 400°C and conforming to the requirements for
12.2.1.1 Centrifuge the mixture at 500 to 800 rcf (relative
thermometer 8C as prescribed in Specification E 1.
centrifugal force) for 10 min to separate free water and solids
10.7 Flowmeter, to regulate flow of nitrogen to distillation
as specified in Test Method D 96. For waxy samples, use
flask. It should be calibrated and graduated for the range 10 to
chloroform. Warm solutions to 50°C to prevent precipitation
15 mL/min.
(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 D 95 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
mL/min. Terminate distillation at a liquid temperature of
280°C. Shut off the nitrogen flow when the temperature of the
liquid in the distillation flask cools belo
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