ASTM D8193-18

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: D8193 − 18
Standard Test Method for
Total Oil and Grease (TOG) and Total Petroleum
Hydrocarbon (TPH) in Water and Wastewater with Solvent
Extraction Using Non-Dispersive Mid-IR Transmission
Spectroscopy
This standard is issued under the fixed designation D8193; 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 lower concentrations by adjusting the water or solvent volume
used in the liquid-liquid extraction.
1.1 This test method covers the determination of total oil
1.5 The values stated in SI units are to be regarded as
and grease (TOG) that can be extracted from water or waste-
standard. No other units of measurement are included in this
watersamplesbycyclohexaneandmeasuredbynon-dispersive
-1
standard.
IR spectroscopy from 1370–1380 cm . Treating the extract
with Florisil to remove polar substances prior to the IR
1.6 This standard does not purport to address all of the
measurement enables determination of the total petroleum
safety concerns, if any, associated with its use. It is the
(TPH).
responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
1.2 This method also considers the volatile fraction of
mine the applicability of regulatory limitations prior to use.
petroleum hydrocarbons which is lost by gravimetric methods
1.7 This international standard was developed in accor-
that require solvent evaporation prior to weighing, as well as
dance with internationally recognized principles on standard-
by solventless IR methods that require drying of the employed
ization established in the Decision on Principles for the
solid phase material prior to measurement. Similarly, a more
Development of International Standards, Guides and Recom-
complete fraction of extracted petroleum hydrocarbon is ac-
mendations issued by the World Trade Organization Technical
cessible by this method as compared to GC methods that use a
Barriers to Trade (TBT) Committee.
time window for quantification, as petroleum hydrocarbons
eluting outside these windows are also quantified.
2. Referenced Documents
1.3 This method defines total oil and grease in water as
2.1 ASTM Standards:
material that can be extracted with cyclohexane and measured
D1129 Terminology Relating to Water
-1
by IR absorption in the region of 1370–1380 cm (7.25–7.3
D1141 Practice for the Preparation of Substitute Ocean
µm). Similarly, total petroleum hydrocarbon in water is defined
Water
as material that can be extracted with cyclohexane, remains in
D1193 Specification for Reagent Water
the extract after filtration over Florisil and is measured by IR
D2777 Practice for Determination of Precision and Bias of
-1
absorptionintheregionof1370–1380cm (7.25–7.3µm).The
Applicable Test Methods of Committee D19 on Water
concentration of total grease is defined as the difference
D3370 Practices for Sampling Water from Closed Conduits
between the total oil and grease and total petroleum hydrocar-
D5847 Practice for Writing Quality Control Specifications
bon concentrations.
for Standard Test Methods for Water Analysis
1.4 This method covers the range of 0.5 to 1000 mg/L for D7678 Test Method for Total Oil and Grease (TOG) and
total oil and grease as well as for total petroleum hydrocarbons TotalPetroleumHydrocarbons(TPH)inWaterandWaste-
and has a method detection limit (MDL) of 0.5 mg/L. The water with Solvent Extraction using Mid-IR Laser Spec-
range and method detection limit may be extended to higher or troscopy
E168 Practices for General Techniques of Infrared Quanti-
tative Analysis
This test method is under the jurisdiction of ASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 15, 2018. Published January 2019. DOI: 10.1520/ contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
D8193-18. Standards volume information, refer to the standard’s Document Summary page on
Florisil is a trademark by U.S. Silica Company, Frederick, MD. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8193 − 18
2.2 ISO Standards: This test method contains procedures that can assist the analyst
ISO 9377-2 Determination of Hydrocarbon Oil Index in breaking such emulsions.
2.3 Code of Federal Regulations (CFR) Publications:
6.2 Organic compounds and other materials not considered
40 CFR Part 136 Guidelines Establishing Test Procedures
as oil and grease or petroleum hydrocarbons based on their
for the Analysis of Pollutants
chemical structure (for example, halogenated or cyclic hydro-
49 CFR Part 172 Hazardous Materials Table, Special
carbons) may be extracted and measured by the method.
Provisions, Hazardous Materials Communications, Emer-
gency Response Information, Training Requirements, and
7. Apparatus
Security Plans
7.1 All glassware that will come in contact with the sample
shall be thoroughly cleaned, rinsed with distilled water, and
3. Terminology
dried at 130°C.
3.1 Definitions:
7.2 Temperature controlled absorption spectrometer with an
3.1.1 For definitions of terms used in this test method, refer
automaticfillingsystemandatransmissioncell.Thespectrom-
to Terminology D1129 and Practices E168.
eter should use a light source and an optical interference filter
3.1.2 total oil and grease (TOG), n—material that can be
-1
transmitting in the range from 1370–1380 cm . The path
extracted from water or wastewater by this test method and
length of the transmission cell shall be between 1–1.5 mm. In
which can be measured by infrared absorption in the region
-1 -1 order for the spectrometer to qualify, the standard deviation of
from 1370 cm to 1380 cm .
10 blank measurements should be less than 0.06 mAU.
3.1.3 total petroleum hydrocarbon (TPH), n—non-polar or-
7.3 Glass wide mouth sample bottle, suggested 1 L, either
ganic material that can be extracted from water or wastewater,
with screw cap having a fluoropolymer liner or a wide-necked
andwhichcanbemeasuredbyinfraredabsorptionintheregion
-1 -1 glass flask with a ground neck with either glass or fluoropo-
from 1370 cm to 1380 cm .
lymerstopper.Thesamplingbottleshallallowdirectextraction
3.2 Definitions of Terms Specific to This Standard:
from the bottle.
3.2.1 grease, n—the difference between TOG and TPH of a
7.4 Micro-separator, for example see figure in AnnexA2 or
sample.
other suitable device for phase separation (optional).
4. Summary of Test Method
7.5 Solid phase extraction cartridges containing Florisil
with PTFE or stainless steel frits (for TPH).
4.1 An acidified 900-mL sample of water or wastewater is
extracted with 50 mL of cyclohexane. A part of the extract is
7.6 Beakers 50–100 mL.
measured with infrared spectroscopy to quantify the total oil
7.7 Magnetic stirrer, with PTFE-fluorocarbon stirring bar
and grease (TOG) concentration. The remaining part of the
(optional).
extract is treated by Florisil to remove polar substances. The
7.8 Volumetric flasks, glass, various (50, 100, and 200 mL).
treated extract is measured with infrared spectroscopy to
quantify the total petroleum hydrocarbon concentration (TPH).
7.9 Teflon spritz bottle, one-piece wash bottle for rinsing.
The difference between TOG and TPH provides the amount of
7.10 Volumetricpipettes,glass,various(10,20,and40mL).
grease extracted from the sample.
7.11 Analytical balance.
5. Significance and Use
7.12 Graduated glass syringes, 250 µL (optional).
5.1 The presence and concentration of total petroleum
7.13 Benchtop shaker, (optional).
hydrocarbons, as well as total oil and grease, in domestic and
7.14 Glass stirring rod, (optional).
industrial wastewater is of concern to the public because of its
deleterious aesthetic effect and its impact on aquatic life.
8. Reagents and Materials
5.2 Regulations and standards have been established that
8.1 Purity of Reagents—Reagent grade chemicals shall be
require monitoring of total petroleum hydrocarbons as well as
used in all tests. Unless otherwise indicated, it is intended that
total oil and grease in water and wastewater.
all reagents shall conform to the specification of the committee
on analytical reagents of the American Chemical Society,
6. Interferences
where such specifications are available. Other grades may be
6.1 Soaps, detergents, surfactants, and other materials may
used, provided it is first ascertained that the reagent is of
form emulsions that could reduce the amount of oil and grease
sufficiently high purity to permit its use without lessening the
as well as petroleum hydrocarbons extracted from a sample.
accuracy of the determination.
Available from International Organization for Standardization (ISO), ISO
Central Secretariat, BIBC II, Chemin de Blandonnet 8, CP 401, 1214 Vernier, Reagent Chemicals, American Chemical Society Specifications, American
Geneva, Switzerland, http://www.iso.org. Chemical Society, Washington, DC, www.chemistry.org. For suggestions on the
Available from U.S. Government Printing Office, Superintendent of testing of reagents not listed by the American Chemical Society, see the United
Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http:// States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention,
www.access.gpo.gov. Inc. (USPC), Rockville, MD, http://www.usp.org.
D8193 − 18
8.2 Cyclohexane, minimum purity 99.5 %, used for extrac- volume. Use the entire sample because removing a portion
tion. would not apportion the hydrocarbons that adhere to the bottle
surfaces. The high probability that extractable matter may
8.3 Purity of Water—Unless otherwise indicated, references
adhere to sampling equipment and result in measurements that
to laboratory or reagent water shall be understood to mean
have a low bias precludes the collection of composite samples
reagent water conforming to Specification D1193, Type II.
for determination of total oil and grease and total petroleum
8.4 n-Octane, 99.0 % minimum purity, for use in calibra-
hydrocarbon. Therefore, samples must be collected as grab
tion.
samples. If a composite measurement is required, individual
grab samples collected at prescribed time intervals may be
8.5 2,2,4 Trimethylpentane, 99.0 % minimum purity, for use
in calibration. analyzed separately and the concentrations averaged.
Alternatively, samples can be collected in the field and com-
8.6 1:1 (w/w) Mixture of Mineral Oil Type A (Diesel Oil
posited in the laboratory. For example, collect three individual
Without Additives) and Mineral Oil Type B (Lubricating Oil
300-mL samples over the course of a day. In the laboratory,
WithoutAdditives), for use as laboratory control sample (LCS).
extract each 300-mL sample with 15 mL and combine the
Areadily prepared 1:1 (w:w) mixture of these oils may be used
7 extracts in a 50-mL volumetric flask and fill up to mark with
(for example, BAM K010 ).
solvent prior to measurement (12.2 and 12.3).
8.7 Florisil, grain size 75 µm to 150 µm (100 mesh to 200
10.5 Preserve the sample with a sufficient quantity of
mesh), heated to 140°C for 16 h and stored in a desiccator.
sulfuric acid (see 8.9) or hydrochloric acid (see 8.10)toapH
Florisil is a trade name for a prepared diatomaceous substance,
of 2 or lower and refrigerate at 1–6°C from the time of
mainly consisting of anhydrous magnesium silicate.
collection until extraction.The amount of acid required will be
8.8 Sodium Sulfate (Na SO ), anhydrous, granular.
2 4
dependent upon the pH and buffer capacity of the sample at the
8.9 Sulfuric Acid (1+1)—Slowly and carefully add 1 vol- time of collection. If the amount of acid required is not known,
ume of sulfuric acid (H SO , sp gr 1.84) to 1 volume of water, makethepHmeasurementonaseparatesamplethatwillnotbe
2 4
stirring and cooling the solution during addition. analyzed. Introduction of pH paper to an actual sample or
sample cap may remove some oil from the sample. In case the
8.10 Hydrochloric acid, ACS, (1 + 1)—Mix equal volumes
bottlecontainingthesamplecannotbeweighedbeforeaddition
of concentrated HCl and water.
of the acid, the volume of acid added to each sample can be
8.11 Stearyl stearate (C H O ), minimum purity 98.0 %,
36 72 2
recorded and then subtracted from the final measured sample
for qualification of Florisil used for TPH measurements.
amount. If the sample is to be shipped by commercial carrier,
U.S. Department of Transportation regulations limit the pH to
9. Hazards
a minimum of 1.15 if H SO is used and 1.96 if HCl is used
2 4
9.1 Normal laboratory safety applies to this method. Ana-
(see 40 CFR Part 136, Table II Footnote 3 and 49 CFR Part
lysts should wear safety glasses, gloves and lab coats.Analysts
172).
should review the Safety Data Sheets (SDS) for all reagents
10.6 All samples must be refrigerated at 1–6 °C from the
used in this method. Additional hazards may be presented by
time of collection until extraction. All samples must be
theparticularsamplebeingtestedsopropercaremustbetaken.
analyzed within 28 days of the date and time of collection (40
CFR 136, Table II). Extracted samples can be stored up to two
10. Sampling
weeks between 7°C and 10°C.
10.1 Weigh the dried bottle before sample collection. Pre-
rinse the sample bottle and cap with the solvent (8.2) and dry
11. Quality Control
it prior to sample collection. Do not rinse the sample bottle
with the sample to be analyzed.
11.1 To ensure analytical values obtained using this test
method are valid and accurate within the confidence limits of
10.2 Collect the sample in accordance with the principles
the test, the instrument manufacturer’s instructions and the
described in Practices D3370, using a glass bottle as specified
following procedures must be followed when performing the
in 7.3.
testmethod.Calibrationsmadebytheinstrumentmanufacturer
10.3 Fill the bottle to approximately 80 %. Filling the bottle
may be used for analysis.
above 80 % of total volume or allowing the bottle to overflow
11.2 Instrument Calibration:
will make extraction more difficult and lead to erroneous
11.2.1 Bring all solutions to 22 6 3°C.
results.
11.2.2 Calibration Solution S:
10.4 Asamplevolumeofabout900mLisrecommendedfor
11.2.2.1 Prepare a stock solution by weighing in 9.00 g
this test. Weigh the bottle containing the sample to determine
n-octane and 1.00 g 2,2,4 Trimethylpentane.
the actual sampled amount. Alternatively, record the sampled
NOTE 1—A 10 % solution of 2,2,4 Trimethylpentane in n-Octane was
7 foundtoproviderepresentativevaluesforTOGandTPHforabroadrange
The sole source of supply of BAM K010 known to the committee at this time
of samples, ranging from heavy crude oil to lighter condensates including
is German Federal Institute for Materials Research and Testing, Berlin. If you are
fuels and lubricants.
aware of alternative suppliers, please provide this information to ASTM Interna-
tional Headquarters.Your comments will receive careful consideration at a meeting NOTE 2—The calibration standard specified in this procedure reflects
of the responsible technical committee, which you may attend. the objective of the test to detect recoverable oil and grease and petroleum
D8193 − 18
hydrocarbon material in water and wastewater with an unknown compo-
11.2.11.4 Determine the constants of a second order poly-
sition of oil and grease. In a few cases, the composition of the oil and
nomial which, in a least squares sense, represents the best fit to
grease in a sample will be known. In such cases, it is possible to develop
the absorbance measured and the concentration of the calibra-
acalibrationwiththeknowntargetoil.Aslongasallotherstepsinthistest
tion solutions.
method are followed, such calibrations may be used for internal monitor-
ing or internal reporting. However, for such calibrations it is not possible
NOTE 3—Even though solvent of high purity is used for analysis, it can
to develop reproducibility statements and the repeatability statement of
contain small amounts of non-cyclic hydrocarbons and even polar
this test method will not be valid. In order to obtain consistent results
components.Furthermore,therewillbeavariationinthiscontentbetween
between laboratories, it is required to use the standard calibration outlined
production batches (lot numbers), even from the same producer. To avoid
in Section 11 when reporting TOG or TPH values citing the ASTM
that variation in product quality affects the results of this test method,
designated number.
solvent of the same lot number must be used for reference and sample
11.2.3 Calibration Solution A: measurement.
11.2.3.1 Weigh 1.8 g of Calibration Solution S in a 100 mL
11.3 Calibration Verification:
volumetric flask and fill to the mark with cyclohexane.
11.3.1 Use the calibration constants obtained in 11.2.11.4
11.2.3.2 Calibration Solution A = 18000 mg/L (1000 mg/L
and the absorbance values measured in 11.2.11.3 to calculate
oil in water).
the predicted concentrations for all calibration samples. The
11.2.4 Calibration Solution B:
calibration is verified if the difference between the actual and
11.2.4.1 Place 40.0 mL of Calibration Solution A in a
predicted concentration is smaller than 61.5 % of the mea-
100-mL volumetric flask and fill to mark with solvent.
sured value or 613 mg/L oil in solvent concentration (60.7
11.2.4.2 Calibration Solution B = 7200 mg/L (400 mg/L oil
mg/L oil in water), whichever is greater.
in water).
11.3.2 If calibration cannot be verified, recalibrate the
11.2.5 Calibration Solution C:
instrument.
11.2.5.1 Place 20.0 mL of Calibration Solution B in a
NOTE4—Periodiccalibrationverificationiscarriedoutbymeasurement
100-mL volumetric flask and fill to mark with solvent.
of the 50 mg/L LCS. If the LCS fails, a measurement of one of the
11.2.5.2 CalibrationSolutionC=1440mg/L(80mg/Loilin
calibration standards can be used to verify the calibration. In this case the
water).
result shall fall within the limits defined in 11.3.1.
11.2.6 Calibration Solution D:
11.4 Standardization of Sample Cleanup:
11.2.6.1 Place 10.0 mL of Calibration Solution C in a
11.4.1 The sample cleanup procedure required for the mea-
100-mL volumetric flask and fill to mark with solvent.
surement of total petroleum hydrocarbons uses Florisil solid
11.2.6.2 Calibration Solution D = 144 mg/L(8.0 mg/Loil in
phase extraction cartridges. Such cartridges can be bought
water).
ready-made or can be prepared in the lab. Each time a new
11.2.7 Calibration Solution E:
batch of Florisil cartridges is used, the suitability shall be
11.2.7.1 Weigh1.35gofCalibrationSolutionSina100mL
tested. Cartridges may be qualified by the manufacturer and
volumetric flask and fill to the mark with cyclohexane.
used as delivered.
11.2.7.2 CalibrationSolutionE=13500mg/L(750mg/Loil
11.4.2 If solid phase extraction cartridges with plastic hous-
in water).
ing are used, ensure that the cartridges do not affect the results.
11.2.8 Calibration Solution F:
Measure a blank using only cyclohexane. The instrument
11.2.8.1 Place 20.0 mL of Calibration Solution E in a
reading must be ≤0.5 mg/L and ≥-0.5 mg/L.
100-mL volumetric flask and fill to mark with solvent.
11.4.3 Prepare 1800 mg of Mineral Oil Type A and Type B
11.2.8.2 Calibration Solution F = 2700 mg/L (150 mg/L oil
(1:1 (w/w)) (8.6) in a 100 mLvolumetric flask. Fill to the mark
in water).
with cyclohexane.
11.2.9 Calibration Solution G:
11.4.4 Measure the solution without any cleanup and note
11.2.9.1 Place 20.0 mL of Calibration Solution F in a
the result on the flask.
100-mL volumetric flask and fill to mark with solvent.
11.4.5 Draw the solution through the Florisil cartridge and
11.2.9.2 Calibration Solution G = 540 mg/L(30 mg/Loil in
perform a measurement of the treated extract. The instrument
water).
reading shall be at least 95 % of the untreated value obtained
11.2.10 Calibration Solution H:
in 11.4.4.
11.2.10.1 Place 10.0 mL of Calibration Solution G in a
11.4.6 Prepare 65 mg stearyl stearate (8.11) in a 100 mL
100-mL volumetric flask and fill to mark with solvent.
volumetric flask. Fill to the mark with cyclohexane.
11.2.10.2 Calibration SolutionH=54 mg/L (3 mg/L oil in
11.4.7 Measure the solution without any cleanup and note
water).
the result on the flask.
11.2.11 Measu
...