NOTICE: This standard has either been superseded and replaced by a new version or

withdrawn.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: D 3921 – 96
AMERICAN SOCIETY FOR TESTING AND MATERIALS
100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Method for

Oil and Grease and Petroleum Hydrocarbons in Water 1
This standard is issued under the fixed designation D 3921; 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.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope dures and a Discussion on Reporting Low-Level Data2

1.1 This test method covers the determination of D 5789 Practice for Writing Quality Control Specifications
fluorocarbon-extractable substances as an estimation of the for Standard Test Methods for Organic Constituents3
combined oil and grease and the petroleum hydrocarbon E 168 Practices for General Techniques of Infrared Quan-
contents of a sample of water or waste water in the range from titative Analysis4
0.5 to 100 mg/L. It is the user’s responsibility to assume the 3. Terminology
validity of the standard for untested types of water.
3.1 Definitions—For definitions of terms used in this test
1.2 This test method defines oil and grease in water and
method, refer to Terminology D 1129 and Practices E 168.
waste water as that matter which is extractable in the test
3.2 Definitions of Terms Specific to This Standard:
method and measured by infrared absorption. Similarly, this
3.2.1 oil and grease—the organic matter extracted from
test method defines petroleum hydrocarbons in water and waste
water or waste water and measured by this test method.
water as that oil and grease which is not adsorbed by silica gel
3.2.2 petroleum hydrocarbons—the oil and grease remain-
in the test method and that is measured by infrared absorption.
ing in solution after contact with silica gel and measured by
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1.3 Low-boiling organic materials are lost by evaporation
during the manipulative transfers. However, these evaporative
this test method.
4. Summary of Test Method
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losses are generally much lower than those experienced with
gravimetric procedures that require solvent evaporation before 4.1 The acidified sample of water or waste water is ex-
the residue is weighed. tracted serially with three 30-mL volumes of 1, 1, 2-trichloro-1,
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1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
2, 2-trifluoroethane (referred to in this test method as sol-
vent). 5 The extract is diluted to 100 mL and a portion is
responsibility of the user of this standard to establish appro- examined by infrared spectroscopy 6 to measure the amount of
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
ASTM D3921-96
oil and grease removed from the original sample. A major
portion of the remaining extract is contacted with silica gel to
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remove polar substances, thereby providing a solution of
2. Referenced Documents
petroleum hydrocarbons. This treated extract is then similarly
2.1 ASTM Standards: examined by infrared spectroscopy.
D 1129 Terminology Relating to Water2
D 1193 Specification for Reagent Water2 5. Significance and Use
D 2777 Practice for Determination of Precision and Bias of 5.1 The presence of oil and grease in domestic and indus-
Applicable Methods of Committee D-19 on Water2 trial waste water is of concern to the public because of its
D 3325 Practice for Preservation of Waterborne Oil deleterious aesthetic effect and its impact on aquatic life.
Samples3 Regulations and standards have been established that require
D 3370 Practices for Sampling Water from Closed Con- monitoring of oil and grease in water and waste water. This test
duits2 method provides an analytical procedure to measure oil and
D 3856 Guide for Good Laboratory Practices in Laborato- grease in water and waste water.
ries Engaged in Sampling and Analysis of Water2
6. Interferences
D 4210 Practice for Interlaboratory Quality Control Proce-
6.1 Since the constituents oil and grease and petroleum
1
This test method is under the jurisdiction of ASTM Committee D-19 on Water
4
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Annual Book of ASTM Standards, Vol 03.06.
5
Organic Substances in Water. Gruenfeld, M., “Extraction of Dispersed Oils from Water for Quantitative
Current edition approved Feb. 10, 1996. Published April 1996. Originally Analysis by Infrared Spectrophotometry,” Environmental Science and Technology,
published as D 3921 – 80. Last previous edition D 3921 – 85 (90). Vol 7, 1973, pp. 636–639.
2 6
Annual Book of ASTM Standards, Vol 11.01. Consult the manufacturer’s operation manual for the specific instructions
3
Annual Book of ASTM Standards, Vol 11.02. related to the infrared spectrometer or analyzer to be used.

1
 NOTICE:¬This¬standard¬has¬either¬been¬superseded¬and¬replaced¬by¬a¬new¬version¬or
discontinued.¬Contact¬ASTM¬International¬(www.astm.org)¬for¬the¬latest¬information.¬
D 3921
hydrocarbons are defined as the results of the test procedure, 8.5 Isooctane (2,2,4-Trimethylpentane), 99 % minimum pu-
interferences are precluded by definition. Interpretation of test rity, for possible use in calibration mixture.
results on the basis of chemical structure, pollution potential, or 8.6 Silica Gel 8, 100 to 200 mesh, which has been deacti-
treatability should be approached with caution, however, be- vated with 2 % water.
cause of the diversity of substances measured by this proce- 8.7 Sodium Bisulfate (NaHSO4), monohydrate.
dure. 8.8 Sodium Sulfate (Na2SO4), anhydrous, granular.
6.2 Organic solvents and certain other organic compounds 8.9 Solvent —1, 1, 2-trichloro-1, 2, 2- trifluoroethane. 9
not considered as oil and grease on the basis of chemical
NOTE 1—Frequently, this solvent will extract plasticizer from the liner
structure may be extracted and measured as oil and grease. Of of its shipping container. Check for such contamination by evaporating
those measured, certain ones may be adsorbed by silica gel 100 mL of solvent in a steam bath and weighing its residue. If this value
while others may not. Those which are not adsorbed are exceeds 0.1 mg, purify the solvent by distillation and check the overhead
measured as petroleum hydrocarbons. material for residue. Store the purified solvent in clean, glass bottles
having TFE-Fluorocarbon cap liners. Purification of this solvent as a
7. Apparatus matter of course is highly desirable.
7.1 Cell(s), quartz, 10-mm path length, two required for 8.10 Sulfuric Acid (1 + 1)—Slowly and carefully add 1
double-beam operation, one required for single-beam opera- volume of sulfuric acid (H 2SO4, sp gr 1.84) to 1 volume of
tion, or built-in cell for nondispersive infrared analyzer opera- water, stirring and cooling the solution during the addition.
tion.
7.2 Filter Paper, ashless, quantitative, general-purpose, 9. Sampling
11-cm or equivalent. 9.1 Collect the sample in accordance with the principles
7.3 Glass Bottle, approximately 1000-mL, with screw cap described in Practices D 3370, using a glass bottle equipped
having a TFE-fluorocarbon liner. with a screw cap having a TFE-fluorocarbon liner.
7.4 Graduated Cylinder, 1000-mL. 9.2 A sample of about 750 mL is required for this test. Use
7.5 Infrared Spectrometer, double-beam dispersive, single- the entire sample since no portion should be removed for other

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beam dispersive, Fourier transform, or nondispersive infrared tests.
analyzer. 9.3 Preserve the sample with a sufficient quantity of either
7.6 Magnetic Stirrer, with small TFE-fluorocarbon stirring sulfuric acid (see 8.10) or sodium bisulfate (see 8.7) to attain a
bar.
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7.7 Separatory Funnel, 2000-mL, with TFE-fluorocarbon
pH of 2 or lower. The amount of reagent required will be
dependent upon the pH of the sample at the time of collection

of time). Document Preview

stopcock (one for each sample analyzed during any one period

7.8 Volumetric Flask, 100-mL (minimum of six required for

and upon its buffer capacity.

10. Calibration
calibration plus one for each sample analyzed during any one NOTE 2—A choice of two calibration species is available to the analyst.
period of time). ASTM D3921-96
The preferred material is a sample of the same oil and grease that is known
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to be present in the sample of water or waste water awaiting analysis. The
8. Reagents other material is a mixture of isooctane and cetane. This latter blend is to
be used when the same (as described) material is not available.
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 10.1 If the blend of isooctane and cetane is to be used for
all reagents shall conform to the specification of the Committee calibration, prepare a calibration mixture by pipetting 15 mL of
on Analytical Reagents of the American Chemical Society, 7 isooctane and 15 mL of cetane into a glass-stoppered bottle.
where such specifications are available. Other grades may be Mix the contents well and maintain the integrity of the mixture
used, provided it is first ascertained that the reagent is of by keeping the container tightly sealed except when a portion
sufficiently high purity to permit its use without lessening the is withdrawn for blending.
accuracy of the determination. 10.2 Calibration Solution Blend A—Place about 20 mL of
8.2 Purity of Water— Unless otherwise indicated, refer- solvent into a 100-mL volumetric flask, stopper, and weigh. To
ences to water (not sample water) shall be understood to mean this flask quickly add about 1 mL of either the calibration oil
reagent water conforming to Specification D 1193, Type II. and grease or the calibration mixture of isooctane and cetane.
8.3 Calibration Oil and Grease, similar in composition to Obtain its exact weight by difference. Fill to the mark with
oil and grease determined by this test method for possible use solvent and mix the liquid well by shaking the flask. Calculate
as calibration material. the exact concentration of the calibrating material in solution in
8.4 Cetane (n-Hexadecane), 99 % minimum purity, for terms of mg/100 mL. If the calibration oil and grease is used,
possible use in calibration mixture. proceed to 10.3. If the calibration mixture is used, multiply this
calculated concentration (about 730 mg/100 mL) by 1.4 (refer
7
Reagent Chemicals, American Chemical Society Specifications, American
8
Chemical Society, Washington, DC. For suggestions on the testing of reagents not Silica Gel, Davison Chemical Grade 923 has been found to be satisfactory for
listed by the American Chemical Society, see Analar Standards for Laboratory this purpose. Other available types from the same or different suppliers may be
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia suitable.
9
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, This solvent is available also as Freon 113, Freon TF, Freon PCA, Genetron
MD. 113, Genesolve D, and as other names.

2
 NOTICE:¬This¬standard¬has¬either¬been¬superseded¬and¬replaced¬by¬a¬new¬version¬or
discontinued.¬Contact¬ASTM¬International¬(www.astm.org)¬for¬the¬latest¬information.¬
D 3921
to Note 3). This new concentration value (about 1022 mg/100 10.9 Fill the sample cell with Blend B. Scan as in 10.8;
mL) is to be used for Blend A throughout the remainder of this drain, and clean the sample cell.
test method. 10.10 Fill the sample cell with Blend C. Scan as in 10.8;
drain, and clean the sample cell.
NOTE 3—Dating back to at least 1951,10 for many years a mixture of
isooctane, cetane, and benzene was accepted as a standard for calibration. 10.11 Fill the sample cell with Blend D. Scan as in 10.8;
Concern regarding the hazards of exposure to benzene, which acts here drain, and clean the sample cell.
only as a diluent having no contribution at 2930 cm−1 (3.41 µm), has 10.12 Fill the sample cell with Blend E. Scan as in 10.8;
prompted elimination of this chemical as a component for calibration. To drain, and clean the sample cell.
maintain relevance between current and future analytical data with those 10.13 Fill the sample cell with Blend F. Scan as in 10.8;
of the past, it is necessary to compensate for differences in concentration drain, and clean the sample cell.
and in density between the former and the present calibration standards.
The factor of 1.4 accomplishes this because the weight ratio of combined
10.14 For each double-beam spectrum obtained in 10.9
isooctane plus cetane in the new two-way mixture to that in the older through 10.13, draw a baseline similar to that found in Fig. 1.
three-way mixture is 1.000 to 0.714, or 1.40. Henceforth, all concentra- Obtain the net absorbance for the peak that occurs near 2930
tions involving the calibration mixture will be based upon the converted cm−1 (3.41 µm). Obtain net values for single-beam and
value obtained in 10.2. nondispersive infrared runs as recommended.
10.3 Calibration Solution Blend B—Dilute 4 mL of Blend A NOTE 5—For infrared instruments having computer capability, data
with solvent in a 100-mL volumetric flask (about 41 mg/100 may be obtained automatically or as described in 10.14. However, all data
mL). must be obtained consistently by one means or the other, not a combina-
10.4 Calibration Solution Blend C—Dilute 3 mL of Blend A tion of the two.
with solvent in a 100-mL volumetric flask (about 31 mg/100 10.15 On linear graph paper, plot the new absorbance
mL). values, found in 10.14 or as permitted in Note 5, versus the
10.5 Calibration Solution Blend D—Dilute 50 mL of Blend respective mg/100 mL values for each of the blends examined.
B with solvent in a 100-mL volumetric flask (about 20 mg/100 The points should lie very nearly in a straight line. Draw the
mL). best-fitting straight line through the points and keep this

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10.6 Calibration Solution Blend E—Dilute 30 mL of Blend calibration graph for use with the test samples. Alternatively,
C with solvent in a 100-mL volumetric flask (about 9 mg/100 determine the equation of the best-fitting straight line calcu-
mL). lated by a linear regression technique. Record this equation for
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10.7 Calibration Solution Blend F—Dilute 10 mL of Blend
E with solvent in a 100-mL volumetric flask (about 0.9 mg/100
use with the test samples.

mL).
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11. Procedure
NOTE 4—During the calibration events which follow, the cell used for NOTE 6—This procedure applies to all samples regardless of the type of
the blends must be thoroughly cleaned with fresh solvent and then dried infrared instrumentation used for measurement. Thus, to comply with this
prior to the addition of a new blend. Take care to avoid insertion of the cell test method, no extraction is to be attempted in a nondispersive infrared
ASTM D3921-96
stopper so tightly that the cell could burst from expansion of its contents analyzer or any other instrument capable of automatic or semiautomatic
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as it resides in the light beam. It is desirable to flush the cell compartment extraction.
of the spectrometer with nitrogen or dry air to prevent chemical reaction 11.1 Extraction:
of solvent fumes with components of the instrument. For double-beam
operation, either block the light beam from the reference cell containing
11.1.1 Mix the sample by shaking the original sample bottle.
solvent or remove the reference cell from the instrument during the Check the pH of the liquid by touching pH-sensitive paper to
intervals between scans in order to protect the solvent from unnecessary the cap. If necessary, add sufficient sulfuric acid or sodium
warming. However, place the reference cell in the reference beam during bisulfate to attain a pH of 2 or less.
all scans. For single-beam operation, use the same cell throughout the 11.1.2 Add 30 mL of solvent to the sample in the original
calibration procedure. Rely upon sole recommendations of the manufac- sample bottle. Recap immediately and shake the bottle vigor-
turer for single-beam and nondispersive infrared analyzers since variations
ously for 2 min. Allow the bottle to stand until the contents
in design make it impractical to offer instructions for their use with this
method. Also, in relation to nondispersive infrared operation, reference to settle and bubbles disappear. Remove the cap carefully to
scanning or running, or both, should be interpreted to mean obtaining a release any pressure build-up and immediately transfer the
reading or a plot of the 2930-cm −1
(3.41-µm) band. contents of the bottle to a clean separatory funnel. Wash down
10.8 Fill the reference cell (for double-beam operation) and the transfer funnel with clean solvent, stopper the separatory
the sample cell with solvent and scan from 3200 cm −1 (3.13 funnel, and recap the bottle. Allow the contents of the
µm) to 2700 cm −1 (3.70 µm). A nearly horizontal, straight line separatory funnel to settle. Transfer the bottom layer into a
should be obtained. If it is not, check cells for cleanliness, clean 100-mL volumetric flask through filter paper and about 1
matching, etc. Drain and clean the sample cell. Obtain spectral g of sodium sulfate that have been prewetted with solvent to
data for the solvent at this time for single-beam and nondis- remove any organic material which could contaminate the
persive infrared instruments, also. After running, drain, and sample.
clean the sample cell. NOTE 7—Use of the sodium sulfate is absolutely necessary to protect
the activity level of the silica gel that will be used later.

10 11.1.3 Add another 30 mL of solvent to the original sample

Simard, R. G., Hasegawa, I., Bandaruk, W., and Headington, C. E., “Infrared
Spectrophotometric Determination of Oil and Phenols in Water”, Analytical bottle, recap, and shake the container to obtain good contact
Chemistry, Vol 23, 1951, pp. 1384–1387. between the liquid and all inner surfaces. Transfer this new
3