Designation: D 3921 – 96 (Reapproved 2003)e1

Standard Test Method for

Oil and Grease and Petroleum Hydrocarbons in Water1
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.

e1 NOTE—Editorial changes were made throughout in January 2003.

1. Scope D 3856 Guide for Good Laboratory Practices in Laborato-

1.1 This test method covers the determination of ries Engaged in Sampling and Analysis of Water2
fluorocarbon-extractable substances as an estimation of the D 5847 Practice for Writing Quality Control Specifications
for Standard Test Methods for Water Analysis3
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combined oil and grease and the petroleum hydrocarbon

contents of a sample of water or waste water in the range from E 168 Practices for General Techniques of Infrared Quan-
0.5 to 100 mg/L. It is the user’s responsibility to assume the titative Analysis4
validity of the standard for untested types of water. 3. Terminology
1.2 This test method defines oil and grease in water and
waste water as that matter which is extractable in the test 3.1 Definitions—For definitions of terms used in this test
method and measured by infrared absorption. Similarly, this method, refer to Terminology D 1129 and Practices E 168.
test method defines petroleum hydrocarbons in water and waste 3.2 Definitions of Terms Specific to This Standard:
water as that oil and grease which is not adsorbed by silica gel 3.2.1 oil and grease—the organic matter extracted from
in the test method and that is measured by infrared absorption. water or waste water and measured by this test method.
1.3 Low-boiling organic materials are lost by evaporation 3.2.2 petroleum hydrocarbons—the oil and grease remain-
during the manipulative transfers. However, these evaporative ing in solution after contact with silica gel and measured by
losses are generally much lower than those experienced with this test method.
gravimetric procedures that require solvent evaporation before 4. Summary of Test Method
the residue is weighed.
1.4 This standard does not purport to address all of the 4.1 The acidified sample of water or waste water is ex-
safety concerns, if any, associated with its use. It is the tracted serially with three 30-mL volumes of 1, 1, 2-trichloro-1,
responsibility of the user of this standard to establish appro- 2, 2-trifluoroethane (referred to in this test method as sol-
priate safety and health practices and determine the applica- vent). 5 The extract is diluted to 100 mL and a portion is
bility of regulatory limitations prior to use. examined by infrared spectroscopy 6 to measure the amount of
oil and grease removed from the original sample. A major
2. Referenced Documents portion of the remaining extract is contacted with silica gel to
2.1 ASTM Standards: remove polar substances, thereby providing a solution of
D 1129 Terminology Relating to Water2 petroleum hydrocarbons. This treated extract is then similarly
D 1193 Specification for Reagent Water2 examined by infrared spectroscopy.
D 2777 Practice for Determination of Precision and Bias of 5. Significance and Use
Applicable Methods of Committee D19 on Water2
D 3325 Practice for Preservation of Waterborne Oil 5.1 The presence of oil and grease in domestic and indus-
Samples3 trial waste water is of concern to the public because of its
D 3370 Practices for Sampling Water from Closed Con- deleterious aesthetic effect and its impact on aquatic life.
duits2 Regulations and standards have been established that require
monitoring of oil and grease in water and waste water. This test

1
This test method is under the jurisdiction of ASTM Committee D19 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 Jan. 10, 2003. Published January 2003. Originally Analysis by Infrared Spectrophotometry,” Environmental Science and Technology,
approved in 1980. Last previous edition approved in 1996 as D 3921 – 96. 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.

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 D 3921 – 96 (2003)e1
method provides an analytical procedure to measure oil and 8.3 Calibration Oil and Grease, similar in composition to
grease in water and waste water. oil and grease determined by this test method for possible use
as calibration material.
6. Interferences 8.4 Cetane (n-Hexadecane), 99 % minimum purity, for
6.1 Since the constituents oil and grease and petroleum possible use in calibration mixture.
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
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. pH of 2 or lower. The amount of reagent required will be
7.7 Separatory Funnel, 2000-mL, with TFE-fluorocarbon dependent upon the pH of the sample at the time of collection
stopcock (one for each sample analyzed during any one period and upon its buffer capacity.
of time).
7.8 Volumetric Flask, 100-mL (minimum of six required for 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). The preferred material is a sample of the same oil and grease that is known
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.
Obtain its exact weight by difference. Fill to the mark with

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.
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 D 3921 – 96 (2003)e1
solvent and mix the liquid well by shaking the flask. Calculate µm) to 2700 cm −1 (3.70 µm). A nearly horizontal, straight line
the exact concentration of the calibrating material in solution in should be obtained. If it is not, check cells for cleanliness,
terms of mg/100 mL. If the calibration oil and grease is used, matching, etc. Drain and clean the sample cell. Obtain spectral
proceed to 10.3. If the calibration mixture is used, multiply this data for the solvent at this time for single-beam and nondis-
calculated concentration (about 730 mg/100 mL) by 1.4 (refer persive infrared instruments, also. After running, drain, and
to Note 3). This new concentration value (about 1022 mg/100 clean the sample cell.
mL) is to be used for Blend A throughout the remainder of this 10.9 Fill the sample cell with Blend B. Scan as in 10.8;
test method. drain, and clean the sample cell.
NOTE 3—Dating back to at least 1951,10 for many years a mixture of
10.10 Fill the sample cell with Blend C. Scan as in 10.8;
isooctane, cetane, and benzene was accepted as a standard for calibration. drain, and clean the sample cell.
Concern regarding the hazards of exposure to benzene, which acts here 10.11 Fill the sample cell with Blend D. Scan as in 10.8;
only as a diluent having no contribution at 2930 cm−1 (3.41 µm), has drain, and clean the sample cell.
prompted elimination of this chemical as a component for calibration. To 10.12 Fill the sample cell with Blend E. Scan as in 10.8;
maintain relevance between current and future analytical data with those drain, and clean the sample cell.
of the past, it is necessary to compensate for differences in concentration 10.13 Fill the sample cell with Blend F. Scan as in 10.8;
and in density between the former and the present calibration standards.
The factor of 1.4 accomplishes this because the weight ratio of combined
drain, and clean the sample cell.
isooctane plus cetane in the new two-way mixture to that in the older 10.14 For each double-beam spectrum obtained in 10.9
three-way mixture is 1.000 to 0.714, or 1.40. Henceforth, all concentra- through 10.13, draw a baseline similar to that found in Fig. 1.
tions involving the calibration mixture will be based upon the converted Obtain the net absorbance for the peak that occurs near 2930
cm−1 (3.41 µm). Obtain net values for single-beam and
--`-`-`,,`,,`,`,,`---

value obtained in 10.2.

10.3 Calibration Solution Blend B—Dilute 4 mL of Blend A nondispersive infrared runs as recommended.
with solvent in a 100-mL volumetric flask (about 41 mg/100 NOTE 5—For infrared instruments having computer capability, data
mL). may be obtained automatically or as described in 10.14. However, all data
10.4 Calibration Solution Blend C—Dilute 3 mL of Blend A must be obtained consistently by one means or the other, not a combina-
with solvent in a 100-mL volumetric flask (about 31 mg/100 tion of the two.
mL). 10.15 On linear graph paper, plot the new absorbance
10.5 Calibration Solution Blend D—Dilute 50 mL of Blend values, found in 10.14 or as permitted in Note 5, versus the
B with solvent in a 100-mL volumetric flask (about 20 mg/100 respective mg/100 mL values for each of the blends examined.
mL). The points should lie very nearly in a straight line. Draw the
10.6 Calibration Solution Blend E—Dilute 30 mL of Blend best-fitting straight line through the points and keep this
C with solvent in a 100-mL volumetric flask (about 9 mg/100 calibration graph for use with the test samples. Alternatively,
mL). determine the equation of the best-fitting straight line calcu-
10.7 Calibration Solution Blend F—Dilute 10 mL of Blend lated by a linear regression technique. Record this equation for
E with solvent in a 100-mL volumetric flask (about 0.9 mg/100 use with the test samples.
mL).
11. Procedure
NOTE 4—During the calibration events which follow, the cell used for
the blends must be thoroughly cleaned with fresh solvent and then dried NOTE 6—This procedure applies to all samples regardless of the type of
prior to the addition of a new blend. Take care to avoid insertion of the cell infrared instrumentation used for measurement. Thus, to comply with this
stopper so tightly that the cell could burst from expansion of its contents test method, no extraction is to be attempted in a nondispersive infrared
as it resides in the light beam. It is desirable to flush the cell compartment analyzer or any other instrument capable of automatic or semiautomatic
of the spectrometer with nitrogen or dry air to prevent chemical reaction extraction.
of solvent fumes with components of the instrument. For double-beam 11.1 Extraction:
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
all scans. For single-beam operation, use the same cell throughout the bisulfate to attain a pH of 2 or less.
calibration procedure. Rely upon sole recommendations of the manufac- 11.1.2 Add 30 mL of solvent to the sample in the original
turer for single-beam and nondispersive infrared analyzers since variations sample bottle. Recap immediately and shake the bottle vigor-
in design make it impractical to offer instructions for their use with this ously for 2 min. Allow the bottle to stand until the contents
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
separatory funnel to settle. Transfer the bottom layer into a
clean 100-mL volumetric flask through filter paper and about 1
10
Simard, R. G., Hasegawa, I., Bandaruk, W., and Headington, C. E., “Infrared
g of sodium sulfate that have been prewetted with solvent to
Spectrophotometric Determination of Oil and Phenols in Water”, Analytical remove any organic material which could contaminate the
Chemistry, Vol 23, 1951, pp. 1384–1387. sample.

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 D 3921 – 96 (2003)e1

FIG. 1 Absorbance Values

NOTE 7—Use of the sodium sulfate is absolutely necessary to protect sample. Do not attempt to proceed since accurate, quantitative results for
the activity level of the silica gel that will be used later. the test are not obtainable.
11.1.3 Add another 30 mL of solvent to the original sample 11.1.5 Wash down the filter assembly with fresh solvent and

--`-`-`,,`,,`,`,,`---
bottle, recap, and shake the container to obtain good contact bring the level of the liquid to the mark in the flask. Shake the
between the liquid and all inner surfaces. Transfer this new flask to completely mix the extract. Carefully release any
wash to the separatory funnel, replace the stopper, and shake pressure build-up.
the mixture vigorously for 2 min. After allowing the contents to 11.1.6 Drain the remaining contents of the separatory funnel
settle, partially remove the glass stopper to release any pres- into a 1000-mL graduated cylinder and record the volume for
sure. Transfer the bottom layer through the same filter assem- later calculations in 12.3 and 12.4.
bly into the same 100-mL volumetric flask as in 11.1.2. 11.2 First Infrared Absorbance Measurement—Measure the
infrared absorbance of the extract in a manner identical to that
NOTE 8—If sodium sulfate cakes when contacted with the extract, flush
with a few millilitres of solvent which is then added to the 100-mL used for the calibration blends in Note 4, 10.8, 10.9, 10.14 and
volumetric flask, remove the solid with a clean spatula, and add about 1 Note 5 by substituting the extract for the blend in 10.9. If the
g of fresh sodium sulfate to the filter. Wash the fresh salt with solvent and gross absorbance exceeds 0.8 (16 % transmittance), dilute one
discard this liquid before resuming regular filtration. part of the extract to ten parts total with solvent and scan the
11.1.4 Repeat 11.1.3 with a final 30 mL of solvent. Break diluted extract. Keep a record of each dilution for use in 12.3.
any emulsions in the separatory funnel as much as possible 11.3 Silica Gel Treatment:
before draining the extract. Do not allow any emulsion to enter 11.3.1 Remove sufficient extract from the 100-mL volumet-
the 100-mL volumetric flask. ric flask to lower the level of the liquid to about 20 mm below
the base of the neck of the flask. Add about 3 g of silica gel to
NOTE 9—Certain types of samples, such as those containing a large the liquid; finally, insert a magnetic stirring bar.
amount of detergent, form a thick emulsion resembling mayonnaise
during the extraction process. If such an emulsion cannot be broken by NOTE 10—Silica gel, as obtained from the supplier, may exist in any
any attempted means, the test method is not applicable to the problem degree of activation. This test method requires the use of 2 % deactivated

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 D 3921 – 96 (2003)e1
material. To prepare fresh silica gel for use, first weigh a quantity of the V = volume of extracted water found in 11.1.6, L.
material in a clean, tared container having a screw cap lined with either
aluminum or TFE-fluorocarbon. Add solvent to make a slurry and mix
well. After the gel has settled, remove as much of the liquid as practical. 13. Precision and Bias 11
Place the container in a clean oven at 100°C or less to remove the 13.1 To permit acquisition of precision data for this test
remainder of the solvent. Following this, raise the temperature to 150°C method, a group of 18 samples representing 6 concentration
and heat the gel for at least 2 h. Remove the container from the oven, levels of oil and grease in triplicate was analyzed by a single
immediately seal with the screw cap, and store in a dry atmosphere for
several hours as it cools slowly. Later, add water equal to 2 % of the
operator in each of 18 different laboratories. One sample of the
weight of the gel and, again, immediately seal with the screw cap. Shake highest concentration level was considered suspect due to a
the container to increase contact between the water and the gel. Allow the handling difficulty and, therefore, not included in the statistical
container to stand for several hours to reach equilibrium. Do not expose data. A total of 244 data points was accepted for oil and grease
the gel to the atmosphere any more than necessary when removing and 233 for petroleum hydrocarbons. All statistical data
portions for use. regarding this test were obtained in accordance to Practice
11.3.2 Place the flask on a magnetic stirrer and stir the D 2777.
extract for 10 min at a rate sufficient to cause continuous 13.2 The precision obtained in the analytical results for this
convection of the silica gel but not so great as to cause test method reflects several factors, including the accuracy with
splashing or a vortex down to the stirring bar. which samples can be prepared, the handling of samples, the
11.3.3 Allow the silica gel to settle completely. extraction step, the operator technique, the level of material,
the instrumental error, as well as unknown effects. Along with
NOTE 11—It is important that no silica gel enter the sample cell. This is
particularly true when a nondispersive infrared analyzer is used.
the 18 unknown samples that originated in a petroleum refinery
discharge water air-flotation unit, a control sample of known
11.4 Second Infrared Absorbance Measurement—Measure oil and grease content at the 16.4-mg/L level was analyzed by
the infrared absorbance of the treated extract in a manner 16 laboratories. The overall precision, St, found by analysis of
identical to that used in 11.2. Keep a record of each dilution for this known control sample is 1.5 mg/L; bias is + 2.4 %. These
use in 12.4. values reflect only the errors inherent in sample preparation,
sample handling, and infrared instrumental portions of the
12. Calculation method.
12.1 Determine the amount of oil and grease in the un- 13.3 The overall precision for the oil and grease section of
treated extract by entering either the calibration graph or the the test method in the concentration range of 0.6 to 66 mg/L
straight-line equation of 10.15 with the absorbance found in may be expressed by the equation:
11.2. St 5 0.167 x 1 0.333
12.2 Determine the amount of petroleum hydrocarbons in
the treated extract by entering either the calibration graph or
the straight-line equation of 10.15 with the absorbance found in where:
11.4. St = overall precision, and
12.3 To the nearest 0.1 mg/L, calculate the concentration of x = concentration of oil and grease determined, mg/L.
oil and grease in the original water or waste water sample as The single-operator precision of this section may be ex-
follows: pressed by the equation:
R3D So 5 0.122 x 1 0.148
oil and grease, mg/L 5 V
where:
where: So = single-operator precision, and
R = amount of oil and grease in 100 mL of untreated x = concentration of oil and grease determined, mg/L.
extract, as found in 12.1, mg, 13.4 The overall precision for the petroleum hydrocarbons
D = dilution factor, if any, as utilized in 11.2, where section of the test method in the concentration range of 0.3 to
D = volume of diluted extract⁄volume of undiluted extract; and 51 mg/L may be expressed by the equation:
V = volume of extracted water found in 11.1.6, L. St 5 0.160 x 1 0.329
12.4 To the nearest 0.1 mg/L, calculate the concentration of
petroleum hydrocarbons in the original water or waste water
sample as follows: where:
St = overall precision, and
R3D x = concentration of petroleum hydrocarbons determined,
Petroleum hydrocarbons, mg/L 5 V
mg/L.
The single-operator precision of this section may be ex-
where: pressed by the equation:
R = amount of petroleum hydrocarbons in 100 mL of
treated extract, as found in 12.2, mg,
D = dilution factor, if any, as utilized in 11.4,
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11
Supporting data for the precision and bias statements are available from ASTM
D = volume of diluted extract⁄volume of undiluted extract;and
Headquarters. Request RR: D19-1066.

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 D 3921 – 96 (2003)e1
So 5 0.141 x 1 0.048 TABLE 1 Acceptable Range of Precision and Bias
Proficiency QC Check
Spike
Maximum Acceptance Acceptance
Concentration
where: mg/L
Acceptable Range for Range for
So = single-operator precision, and Standard Deviation Mean Recovery QC Check
20 (O and G) 4.78 mg/L 6.9–33.1 mg/L 9–31 mg/L
x = concentration of petroleum hydrocarbons deter- 20 (Pet HC) 5.29 mg/L 7.5–32.5 9.4–30.6
mined, mg/L.
13.5 The data presented in 13.3 and 13.4 may not apply to
other types of water. 14.3.2 This study should be repeated until the single-
13.6 The unknown samples were not assayed independently operator precision and the mean value are within acceptable
since to do so would require use of the same technique as that limits. Refer to Practice D 5847 to develop limits for spikes at
used in this study. Thus, the bias introduced by the test method other concentrations.
is indeterminable. 14.3.3 The analyst is permitted to modify the procedure, use
alternate solvents, or use alternate extraction procedures, such
14. Quality Assurance/Quality Control as solid phase extraction, or both, to improve the procedure or
14.1 Minimum quality control requirements are an initial lower analytical costs. Tetrachlorethene (perchloroethylene)
demonstration of proficiency, plus analysis of method blanks has been recommended as an alternative solvent. Any time
and quality control samples. Recovery spikes and duplicates such modifications are made, the initial demonstration of
may be required for specific programs. For a general discussion proficiency must be successfully repeated.
of quality control and good laboratory practices, see Practice 14.4 Ongoing Quality Control Sample—To ensure that the
D 5847 and Guide D 3856. test method is in control, analyze a single quality control
14.2 Method Blank— Before processing any samples, the sample (prepared as in 14.3.1) containing 20 mg/L of oil and
analyst shall demonstrate that all glassware and reagent inter- grease daily or with each batch of up to 20 samples. The value
ferences are under control. Each time a set of samples is obtained should be within the range listed in Table 1 if the test
extracted or reagents are changed, analyze a method blank. The is in control.
blank result shall be low enough that it will not unduly 14.5 Duplicates and Matrix Spikes—Due to the inherent
influence the data (that is, <5 mg/L). variability of oil and grease sampling and samples, results from
14.3 Initial Demonstration of Proficiency: duplicates and matrix spikes may be inconsistent or inconclu-
14.3.1 Select a representative spike concentration; 20 mg/L sive. However, some programs may require analysis of these
is recommended. Use a material as described in Section 10. QC samples. Collect additional 1-L sample bottles for each
The spike material should be from a different source than the duplicate and matrix spike sample to be analyzed should they
material used for calibration. Add spike concentrate to at least be desired. Refer to Practice D 5847 for guidelines on reporting
seven 1-L aliquots of water, and analyze each aliquot according and evaluating these results.
to the procedures in Sections 10 and 11. Calculate the mean
and standard deviation of these values and compare to the 15. Keywords
acceptable range of precision and bias found in Table 1. 15.1 oil and grease; petroleum hydrocarbons

APPENDIX

(Nonmandatory Information)

X1. EXAMPLE CALCULATIONS FOR QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) STATISTICS

X1.1 This example12shows the calculation of control limits X1.2 Calculation of Precision and Bias Criteria for the
for oil and grease. The limits for petroleum hydrocarbons were Initial Demonstration of Proficiency
calculated in the same manner. Eighteen operators analyzed X1.2.1 Precision—The value of F for 6 3 36 dof = 3.40.
five concentration levels in triplicate. The degrees of freedom The maximum acceptable standard deviation is:
(dof) for the study was 36:
2.59 mg/L 3 =3.40 5 4.78
~operators 3 replicates! 2 ~operators! 5 ~18 3 3! 2 18 5 36
At 20 mg/L, the single operator precision SO is 2.59 mg/L, X1.2.2 Bias—The Student’s t for 6 dof is 3.71. The accep-
and the overall precision ST is 3.67 mg/L (using the formulas tance limits for a 20 mg/L test concentration is:
for precision and bias in Section 13).
--`-`-`,,`,,`,`,,`---

20 6 @3.71 mg/L 3 =~S t!2 2 ~~So!2/7!# 5 20 6 13.1 mg/L

12
Reference statistics are from the Interlaboratory Method Study and calcula-
tions are based on Practice D 5847 and Practice D 2777. or 6.9 to 33.1 mg/L.

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X1.3 Calculation of Bias Criteria for Quality Control 20 6 3~3.67! mg/L 5 20 6 11 mg/L
Samples
X1.3.1 The acceptance criteria for the verification of control This yields an acceptable range of 9 to 31 mg/L.
at the representative concentration is calculated as:
X 6 3St

or

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