ASTM D7066-04(2017)

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: D7066 −04 (Reapproved 2017)
Standard Test Method for
dimer/trimer of chlorotrifluoroethylene (S-316) Recoverable
Oil and Grease and Nonpolar Material by Infrared
Determination
This standard is issued under the fixed designation D7066; 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 1.7 This international standard was developed in accor-
dance with internationally recognized principles on standard-
1.1 This test method covers the determination of oil and
ization established in the Decision on Principles for the
grease and nonpolar material in water and wastewater by an
Development of International Standards, Guides and Recom-
infrared (IR) determination of dimer/trimer of chlorotrifluoro-
2 mendations issued by the World Trade Organization Technical
ethylene (S-316) extractable substances from an acidified
Barriers to Trade (TBT) Committee.
sample. Included in this estimation of oil and grease are any
other compounds soluble in the solvent.
2. Referenced Documents
1.2 This test method is applicable to measurement of the
2.1 ASTM Standards:
light fuel although loss of some light ends during extraction
D1129 Terminology Relating to Water
can be expected.
D1193 Specification for Reagent Water
1.3 This test method defines oil and grease in water and
D3370 Practices for Sampling Water from Closed Conduits
wastewater as that which is extractable in the test method and
D3856 Guide for Management Systems in Laboratories
-1
measured by IR absorption at 2930 cm or 3.4 microns.
Engaged in Analysis of Water
Similarly, this test method defines nonpolar material in water
D2777 Practice for Determination of Precision and Bias of
and wastewater as that oil and grease which is not adsorbed by
Applicable Test Methods of Committee D19 on Water
silica gel in the test method and measured by IR absorption at
D5847 Practice for Writing Quality Control Specifications
-1
2930 cm .
for Standard Test Methods for Water Analysis
1.4 This test method covers the range of 5 to 100 mg/L and E168 Practices for General Techniques of Infrared Quanti-
may be extended to a lower or higher level by extraction of a
tative Analysis
larger or smaller sample volume collected separately. E178 Practice for Dealing With Outlying Observations
1.5 The values stated in SI units are to be regarded as
3. Terminology
standard. No other units of measurement are included in this
standard.
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to
1.6 This standard does not purport to address all of the
Terminology D1129 and Practices E168.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.2 Definitions of Terms Specific to This Standard:
priate safety, health, and environmental practices and deter-
3.2.1 nonpolar material, n—the oil and grease remaining in
mine (Guide D3856) the applicability of regulatory limitations
solution after contact with silica gel and measured by this test
prior to use.
method.
3.2.2 oil and grease, n—the organic matter extracted from
1 water or wastewater and measured by this test method.
This test method is under the jurisdiction of ASTM Committee D19 on Water
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
3.2.3 solvent, n—dimer/trimerofchlorotrifluoroethylene(S-
Organic Substances in Water.
316).
Current edition approved Sept. 1, 2017. Published September 2017. Originally
approved in 2004. Last previous edition approved in 2011 as D7066 – 04 (2011).
DOI: 10.1520/D7066-04R17.
The sole source of supply of the material S-316 known to the committee at this
time is Horiba Instruments, Irvine, CA. If you are aware of alternative suppliers, For referenced ASTM standards, visit the ASTM website, www.astm.org, or
please provide this information to ASTM International Headquarters. Your com- contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ments will receive careful consideration at a meeting of the responsible technical Standards volume information, refer to the standard’s Document Summary page on
committee, which you may attend. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7066 − 04 (2017)
4. Summary of Test Method 7.10 Volumetric flasks, glass, various (10, 25, 50, 100, and
200-mL).
4.1 An acidified 250-mL sample of water or wastewater is
extracted serially with three 15-mLvolumes of dimer/trimer of 7.11 TFE-fluorocarbon spritz bottle, one-piece wash bottle
chlorotrifluoroethylene(S-316).Theextractisdilutedto50mL for rinsing.
and a portion is examined by infrared spectroscopy (IR) for an
7.12 Repeating pipetter, glass, 15-mL, (optional).
oil and grease measurement. A portion of the extract is
7.13 Volumetric pipettes, glass, various (0.50, 1.00, 5.00,
contacted with silica gel to remove polar substances, thereby
10.0 and 25.0-mL, including a 1.00 serological pipet graduated
producing a solution containing nonpolar material. The non-
in 0.01-mL increments and a 5.00-mL serological pipet gradu-
polar material is measured by infrared spectroscopy.
ated in 0.1-mL increments, or equivalent).
5. Significance and Use
7.14 Benchtop shaker, (optional).
5.1 The presence and concentration of oil and grease in
7.15 Glass stirring rod, (optional).
domestic and industrial wastewater is of concern to the public
7.16 Analytical balance.
because of its deleterious aesthetic effect and its impact on
7.17 Syringes, 50 and 500 mL.
aquatic life.
5.2 Regulations and standards have been established that
8. Reagents
require monitoring of oil and grease in water and wastewater.
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
6. Interferences
allreagentsshallconformtothespecificationoftheCommittee
6.1 Soaps, detergents, surfactants, and other materials may
on Analytical Reagents of the American Chemical Society,
form emulsions that may reduce the amount of oil and grease
where such specifications are available. Other grades may be
extracted from a sample. This test method contains procedures
used, provided it is first ascertained that the reagent is of
that can assist the analyst in breaking such emulsions.
sufficiently high purity to permit its use without lessening the
6.2 Organic compounds and other materials not considered accuracy of the determination.
as oil and grease on the basis of chemical structure may be
8.2 Purity of Water—Unless otherwise indicated, references
extracted and measured as oil and grease. Of those measured,
to laboratory or reagent water shall be understood to mean
certain ones may be adsorbed by silica gel while others may
reagent water conforming to Specification D1193, Type II.
not. Those not adsorbed are measured as nonpolar material.
8.3 Isooctane (2,2,4-trimethylpentane) 98 % minimum
purity, for use in calibration.
7. Apparatus
8.4 Octanoic Acid 98 % minimum purity, for use in calibra-
7.1 All glassware that will come in contact with the sample
tion.
must be rinsed with dimer/trimer of chlorotrifluoroethylene
(S-316) prior to beginning this procedure.
8.5 Silica Gel, Anhydrous, 75–150 micrometres, Davisil
Grade 923 (Supelco 21447-7A, or equivalent). Dry at
7.2 Cell(s), quartz, 10-mm path length (lower concentra-
200–250°C for 24 hour minimum and store in a desiccator or
tions may require a longer pathlength), two required for
tightly sealed container. Determine the dimer/trimer of chloro-
double-beam operation, one required for single-beam
trifluoroethylene (S-316) soluble material content of the silica
operation, or built-in or drop-in cell for infrared filtometer
gel by extracting 10 g of silica gel with 25 mLof dimer/trimer
analyzer operation.
of chlorotrifluoroethylene (S-316) and collect the elute in a
7.3 Filter paper, ashless, quantitative, general-purpose, 11-
flask. Filter and fill a quartz cell for analysis by IR. The
cm, Whatman #40 or equivalent.
dimer/trimer of chlorotrifluoroethylene (S-316) soluble mate-
7.4 Glass funnel.
rial must be less than 5 mg/L.
7.5 Glass wide mouth sample bottle, minimum 250-mL,
8.6 Sodium Sulfate (Na SO ), ACS, granular anhydrous.
2 4
with screw cap having a fluoropolymer liner.
Dry at 200–250°C for 24 hours minimum and store in a tightly
sealed container until use.
7.6 Glass graduated cylinder, 100-mL
NOTE 1—Powdered sodium sulfate should not be used because water
7.7 Infrared spectrometer, double-beam dispersive, single-
may cause it to solidify.
beam dispersive, Fourier transform, filtometers or other ca-
-1
pable of making measurements at 2930 cm . 8.7 Solvent—dimer/trimer of chlorotrifluoroethylene,IR
spectroscopy grade.
7.8 Magnetic stirrer, with small TFE-fluorocarbon stirring
bar. 8.8 Sulfuric Acid (1 + 1)—Slowly and carefully add 1
volume of sulfuric acid (H SO , sp gr 1.84) to 1 volume of
2 4
7.9 Glass separatory-funnel, 500mL, with fluoropolymer
water, stirring and cooling the solution during the addition
stopcock and stopper.
(optional HCl replacement).
4 5
Consult the manufacturer’s operation manual for the specific instructions The material S-316, available from Horiba Instruments, Irvine, CA, or
related to the infrared spectrometer or analyzer to be used. equivalent, has been found suitable for use.
D7066 − 04 (2017)
8.9 Hydrochloric acid,ACS,1+1.Mix equal volumes of 10. Preparation of Calibration and Spiking Solutions
NOTE 2—The calibration standard specified in this procedure reflects
concentrated HCl and water
the objective of the test to detect recoverable oil and grease and nonpolar
8.10 Sodium Chloride (NaCl), crystalline, ACS, or use in
material in wastewater with an unknown composition of oil and grease. In
breaking emulsions, if needed. Wet thoroughly with solvent
a few cases, the composition of the oil and grease in a sample will be
known.However,inordertoobtainconsistentresultsbetweensamplesets
before using.
and between laboratories with different wastewater matrices, calibration
with the known oil and grease in a sample should not be used in this test
9. Sampling
method.
9.1 Collect the sample in accordance with the principles
10.1 Calibration and Solvent Mixtures:
described in Practices D3370, using a glass bottle equipped
NOTE 3—The calibration procedure below calls for transferring, by
with a screw cap having a fluoropolymer liner. Prerinse the
pipette or syringe, a volume of standard into a volumetric flask to obtain
sample bottle and cap with the solvent prior to sample
a desired concentration. Transfer volumes have been rounded for ease of
collection. Do not rinse the sample bottle with the sample to be
measurement and calculation. It is highly recommended that calibration
analyzed. Fill bottle with minimal headspace to prevent loss of
standards be prepared on a weight basis (that is, pipette a volume into a
tared flask and weigh the amount pipetted), then converted to mg/mL by
volatile constituants. Do not allow the sample to overflow the
using the densities of octanoic acid (0.9100 g/mL) and isooctane (0.6920
bottle during collection. Preventing overflow may not be
g/mL). A solution containing equal volumes of isooctane and octanoic
possible in all sampling situations, however, measures should
acid will have a density of 0.801 g/mL.To assure the most accurate
be taken to minimize overflow at all times.
concentrations, use the smallest serological pipet or syringe for
9.2 A sample of about 250 mL is required for this test. Use
measurements. The volume should always be greater than ⁄2
the entire sample because removing a portion would not
the volume of the pipet or syringe.
apportion the oil and grease that adheres to the bottle surfaces.
Ideally,alinearcalibrationcurvewillbeobtainedfromthese
The high probability that extractable matter may adhere to
standards. As discussed in Section 11, the concentrations of
samplingequipmentandresultinmeasurementsthatarebiased
these standards can be adjusted to stay within the linear range
low precludes the collection of composite samples for deter-
of the IR instrument.
mination of oil and grease. Therefore, samples must be
10.1.1 Calibration Stock Solution—Place 0.55 mL of oc-
collected as grab samples. If a composite measurement is
tanoic acid and 0.72 mL of isooctane in a 10-mL volumetric
required, individual grab samples collected at prescribed time
flask and fill to the mark with solvent. Mix well. The resulting
intervals may be analyzed separately and the concentrations
concentration is 50 mg/mL each octanoic acid and isooctane
averaged. Alternatively, samples can be collected in the field
(100 mg/mLtotal oil and grease). This solution will be termed
and composited in the laboratory. For example, collect four
“Stock Solution”.
individual 63-mL samples over the course of a day. In the
10.1.2 Diluted Stock Solution—Place 2.5 mL of the Stock
laboratory, pour each 63-mLsample into the separatory funnel,
Solution to a 50-mL volumetric flask and fill to mark with
rinse each of the four bottles (and caps) sequentially with 10
solvent. Diluted Stock Solution = 5.0 mg/mL (5000 µg/mL).
mL of solvent, and use the solvent for the extraction (12.2.2).
10.1.3 Calibration Solution A—Place 1.0 mL of Diluted
Do not exceed 50 mLof total solvent during the extraction and
Stock Solution in a 10-mLvolumetric flask and fill to the mark
rinse procedure.
withsolvent.CalibrationSolutionA=0.5mg/mL(500µg/mL),
9.3 Preserve the sample with a sufficient quantity of either
equivalent to 100 mg/L oil and grease in a 250-mL water
sulfuric (see 8.8) or hydrochloric acid (see 8.9)toapHof2or
sample extracted into a 50-mL volume of solvent.
lower and refrigerate at 0–4°C from the time of collection until
10.1.4 Calibration Solution B—Place 0.50 mL of Diluted
extraction. The amount of acid required will be dependent
Stock Solution in a 10-mLvolumetric flask and fill to the mark
upon the pH and buffer capacity of the sample at the time of
with solvent. Calibration Solution B = 0.25 mg/mL (250
collection. If the amount of acid required is not known, make
µg/mL), equivalent to 50 mg/L oil and grease in a 250-mL
the pH measurement on a separate sample that will not be
water sample extracted into a 50-mL volume of solvent.
analyzed. Introduction of pH paper to an actual sample or
10.1.5 Calibration Solution C—Place 0.20 mL of Diluted
sample cap may remove some oil from the sample. To more
Stock Solution in a 10-mLvolumetric flask and fill to the mark
accurately calculate the final oil concentration of the extract,
with solvent. Calibration Solution C = 0.1 mg/mL (100
the volume of acid added to each sample can be recorded, then
µg/mL), equivalent to 20 mg/L of oil and grease in a 250-mL
subtracted from the final measured sample volume.
water sample extracted into a 50-mL solvent volume.
If the sample is to be shipped by commercial carrier, U.S.
10.1.6 Calibration Solution D—Place 0.10 mL of Diluted
Department of Transportation regulations limit the pH to a
Stock Solution in a 10-mLvolumetric flask and fill to the mark
minimum (see 40 CFR, Part 136, Table II, Footnote 3) of 1.96
with solvent. Calibration Solution D = 0.050 mg/mL (50
if HCl is used and 1.15 if H SO is used (see 49 CFR, Part
2 4
µg/mL), equivalent to 10 mg/L of oil and grease in a 250-mL
172).Collectanadditional1or2samplealiquotsforthematrix
water sample extracted into a 50-mL solvent volume.
spike and matrix spike duplicate (14.1.5) and preserve with
10.1.7 Calibration Solution E—Place 0.05 mL of Diluted
acid.
Stock Solution in a 10-mLvolumetric flask and fill to the mark
9.4 Refrigerate the sample at <4°C from the time of with solvent. Calibration Solution E = 0.025 mg/mL (25
collection until extraction. Freezing the sample may break the µg/mL), equivalent to 5 mg/L of oil and grease in a 250-mL
bottle. water sample extracted into a 50-mL solvent volume.
D7066 − 04 (2017)
10.2 Spiking Solution: If a sample is encountered that exceeds the calibration range,
10.2.1 Transfer equal volumes of octanoic acid and isooc- dilute the sample extract to bring the concentration into the
tane in a volumetric flask, beaker, or jar. Mix well. calibration range.
10.2.2 Pour 220 to 250 mL of water into a sample bottle.
11.2 The calibration contains a minimum of 5 nonzero
Record the volume.
points and a solvent blank (Section 11.3).
10.2.3 Using a syringe, dispense 15 µL of the octanoic
11.3 For double-beam operation, fill the reference cell and
acid/isooctane solution under the surface of the water. Cap the
-1
the sample cell with solvent and scan from 3200 cm (3.13
bottle and shake well.
-1
microns) to 2700 cm (3.70 microns). A nearly horizontal,
10.2.4 Calculate the total oil and grease concentration by
straight line should be obtained. If not, check cells for
dividing 12.0 mg (mass of 15 µL for solution density of 0.801
cleanliness, matching, etc. Drain and clean the sample cell. For
g/mLassuming no loss of volume due to mixing) by the water
single-beam and infrared filtometer analyzers, obtain spectral
volume in liters (0.220 to 0.250 L).
data for the solvent at this time.After running, drain, and clean
10.2.5 Calculate the isooctane concentration by dividing
the sample cell.
5.80 mg (mass of 7.5 µL of isooctane) by the water volume in
liters.
11.4 Fill the sample cell with Calibration Solution E. Scan
10.2.6 Calculatetheoctanoicacidconcentrationbydividing
as in 11.3; drain, and clean the sample cell.
6.83 mg (mass of 7.5 µLof octanoic acid) by the water volume
11.5 Fill the sample cell with Calibration Solution D. Scan
in liters.
as in 11.3; drain, and clean the sample cell.
10.2.7 If necessary, this solution can be made more or less
concentrated to suit the concentration needed for the matrix 11.6 Fill the sample cell with Calibration Solution C. Scan
as in 11.3; drain, and clean the sample cell.
spike. A fresh spiking solution should be prepared weekly or
bi-weekly.
11.7 Fill the sample cell with Calibration Solution B. Scan
as in 11.3; drain, and clean the sample cell.
11. Calibration
NOTE 4—The cell(s) used for calibration must be initially thoroughly 11.8 Fill the sample cell with Calibration Solution A. Scan
cleaned with solvent and dried prior to beginning the calibration proce-
as in 11.3; drain, and clean the sample cell.
dure. To reduce the solvent expense, it may be prudent to use methylene
11.9 For each double-beam spectrum obtained in 11.4 –
chloride or a solvent other than the solvent used for extraction. However,
all traces of methylene chloride or other solvent must be removed so that
11.8, draw a baseline. Obtain the net absorbance for the peak
-1
they do not compromise the measurement. Baking the cell at an elevated
that occurs near 2930 cm (3.41 microns). Obtain net values
temperature to remove all traces of solvent is recommended. Cool cell to
for single-beam and infrared filtometer analyzer runs as rec-
room temperature before use.
ommended by IR manufacturer.
11.1 Thesamecellormatchedcellsshouldbeusedthrough-
NOTE5—Forinfraredinstrumentshavingcomputercapability,datamay
out the calibration. Take care to avoid insertion of the cell
beobtainedautomaticallyorasdescribedin11.10.However,alldatamust
stoppersotightlythatthecellcouldburstfromexpansionofits
be obtained consistently by one means or the other, not a combination of
contents as it resides in the light beam. It is desirable to flush
the two.
the cell compartment of the spectrometer with nitrogen or dry
11.10 For each point, subtract the response of the reference
air to prevent chemical reaction of solvent fumes with compo-
blank (Section 11.3) from the response for the standard.
nents of the instrument. For double-beam operation, either
Calculate the calibration factor (CF ) in each of the five
x
block the light beam from the reference cell containing solvent
standards using the reference-blank-subtracted response and
or remove the reference cell from the instrument during the
the following equation:
intervals between scans in order to protect the solvent from
CF 5 H 2 H /C (1)
~ !
unnecessary warming. However, place the reference cell in the
x x RB x
reference beam during all scans. Rely upon recommendations
where:
of the manufacturer for single-beam and infrared filtometer
CF = calibration factor,
x
analyzers because variations in design make it impractical to
H = response of standard,
x
offer instructions for their use with this test method. Also, in
H = response of reference blank, and
RB
relation to infrared filtometer operation, reference to scanning
C = concentration of standard.
x
or running, or both, should be interpreted to mean obtaining a
-1
11.11 Calculate the mean calibration factor (CF ), the
reading or a plot at 2930-cm or 3.4 microns. m
standard deviation of the calibration factor (SD), and the
In the procedure below, the IR instrument is calibrated from
relative standard deviation (RSD) of the calibration factor,
0.025 to 0.5 mg/mL (25 to 500 µg/mL), equivalent to 5 to 100
mg/L of oil and grease in water, assuming a 250-mL sample RSD 5 100 3SD/CF (2)
m
extracted into 50 mLof solvent. If the IR instrument cannot be
where:
calibrated to 0.5 mg/mL (500 µg/mL), calibrate to a lesser
RSD = relative standard deviation of calibration factor,
range, but always use 5 calibration points if the IR instrument
SD = standard deviation of calibration factor, and
allows it. Ideally, the calibration curve obtained will be linear
CF = average of calibration factors (CF ).
m x
(refer to 11.12). If linearity cannot be achieved past a certain
concentration, consider that concentration the upper bounds of 11.12 If RSD ≤ 15 %, linearity through the origin can be
thecalibrationandadjustthecalibrationstandardsaccordingly. assumed and CF may be used for calculations. If RSD >
m
...