ASTM D3414-98(2011)e1
(Test Method)Standard Test Method for Comparison of Waterborne Petroleum Oils by Infrared Spectroscopy (Withdrawn 2018)
Standard Test Method for Comparison of Waterborne Petroleum Oils by Infrared Spectroscopy (Withdrawn 2018)
SIGNIFICANCE AND USE
This test method provides a means for the comparison of waterborne oil samples with potential sources. The waterborne samples may be emulsified in water or obtained from beaches, boats, oil-soaked debris, and so forth.
The unknown oil is identified by the similarity of its infrared spectrum with that of a potential source oil obtained from a known source, selected because of its possible relationship to the unknown oil.
The analysis is capable of comparing most oils. Difficulties may be encountered if a spill occurs in an already polluted area, that is, the spilled-oil mixes with another oil.
In certain cases, there may be interfering substances which require modification of the infrared test method or the use of other test methods (see Practice D3326, Method D.)
It is desirable, whenever possible, to apply other independent analytical test methods to reinforce the findings of the infrared test method (see Practice D3415).
SCOPE
1.1 This test method provides a means for the identification of waterborne oil samples by the comparison of their infrared spectra with those of potential source oils.
1.2 This test method is applicable to weathered or unweathered samples, as well as to samples subjected to simulated weathering.
1.3 This test method is written primarily for petroleum oils.
1.4 This test method is written for linear transmission, but could be readily adapted for linear absorbance outputs.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Specific precautionary statements are given in Section 8.
WITHDRAWN RATIONALE
This test method provides a means for the identification of waterborne oil samples by the comparison of their infrared spectra with those of potential source oils.
Formerly under the jurisdiction of Committee D19 on Water, this test method was withdrawn in November 2018. This standard was withdrawn without replacement due to its limited use by the industry.
General Information
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Standards Content (Sample)
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
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Designation:D3414 −98 (Reapproved 2011)
Standard Test Method for
Comparison of Waterborne Petroleum Oils by Infrared
Spectroscopy
This standard is issued under the fixed designation D3414; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—This test method received editorial corrections in June 2011.
1. Scope 3. Terminology
1.1 This test method provides a means for the identification 3.1 Definitions—For definitions of terms used in this test
method refer to Terminology E131 and Terminology D1129.
of waterborne oil samples by the comparison of their infrared
spectra with those of potential source oils.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 weatheringofwaterborneoil—thecombinedeffectsof
1.2 This test method is applicable to weathered or unweath-
ered samples, as well as to samples subjected to simulated evaporation, solution, emulsification, oxidation, biological
decomposition, etc.
weathering.
1.3 This test method is written primarily for petroleum oils.
4. Summary of Test Method
1.4 This test method is written for linear transmission, but
4.1 The spill sample and potential source oil(s) are treated
could be readily adapted for linear absorbance outputs.
identically to put them in an appropriate form for analysis by
infrared spectrophotometry.The oils are transferred to suitable
1.5 This standard does not purport to address all of the
infraredcellsandthespectraarerecordedfrom4000to600cm
safety concerns, if any, associated with its use. It is the
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for KBr cells, and to 650 cm for HATR cells with ZnSe
responsibility of the user of this standard to establish appro-
crystals. All analyses are performed on the same instrument
priate safety and health practices and determine the applica-
usingthesamesamplecell,whichiscleanedbetweensamples.
bility of regulatory limitations prior to use. Specific precau-
The spectra of the sample and the potential source oil(s) are
tionary statements are given in Section 8.
then compared by superimposing one upon the other, looking
2. Referenced Documents
at particular portions of the spectra. A high degree of coinci-
dencebetweenthespectraofthesampleandapotentialsource
2.1 ASTM Standards:
oil indicates a common origin. This test method is recom-
D1129Terminology Relating to Water
mended for use by spectroscopists experienced in infrared oil
D1193Specification for Reagent Water
identification or under close supervision of such qualified
D3325Practice for Preservation of Waterborne Oil Samples
persons.
D3326PracticeforPreparationofSamplesforIdentification
of Waterborne Oils
5. Significance and Use
D3415Practice for Identification of Waterborne Oils
5.1 Thistestmethodprovidesameansforthecomparisonof
E131Terminology Relating to Molecular Spectroscopy
waterborne oil samples with potential sources.The waterborne
E168Practices for General Techniques of Infrared Quanti-
samples may be emulsified in water or obtained from beaches,
tative Analysis
boats, oil-soaked debris, and so forth.
E275PracticeforDescribingandMeasuringPerformanceof
5.2 The unknown oil is identified by the similarity of its
Ultraviolet and Visible Spectrophotometers
infrared spectrum with that of a potential source oil obtained
from a known source, selected because of its possible relation-
This test method is under the jurisdiction ofASTM Committee D19 on Water
ship to the unknown oil.
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water.
5.3 The analysis is capable of comparing most oils. Diffi-
Current edition approved June 15, 2011. Published July 2011. Originally
culties may be encountered if a spill occurs in an already
approved in 1975. Last previous edition approved in 2004 as D3414 – 98 (2004).
polluted area, that is, the spilled-oil mixes with another oil.
DOI: 10.1520/D3414-11E01.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
5.4 In certain cases, there may be interfering substances
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
which require modification of the infrared test method or the
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. use of other test methods (see Practice D3326, Method D.)
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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D3414−98 (2011)
TABLE 1 Specifications for Infrared Spectrophotometers
6.4.2 Disposable Pasteur Pipets and Hypodermic Syringes.
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Abscissa accuracy Better than ± 5 cm from 4000 to 2000 6.4.3 Window-Polishing Kit.
−1 −1
cm range; better than ± 3 cm
6.4.4 Centrifuge.
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from 2000 to 600 cm (or below).
−1 −1 6.4.5 Vortex Mixer.
Abscissa repeatability 2.5 cm from 4000 to 2000 cm ;1.5
−1 −1
cm from 2000 to 600 cm (or below). 6.4.6 Hot Plate.
Ordinate accuracy ± 1 % of full scale.
6.4.7 Light-Box, for viewing spectra.
Ordinate repeatability within 1 % of full scale.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be
5.5 It is desirable, whenever possible, to apply other inde-
used in all tests unless otherwise indicated. It is intended that
pendent analytical test methods to reinforce the findings of the
all reagents shall conform to the specifications of the Commit-
infrared test method (see Practice D3415).
tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. For sample treatment
6. Apparatus
and for cleaning cells, special spectroquality reagents are
6.1 Infrared Spectrophotometer—Aninstrument capableof
required. Other grades may be used, provided it is first
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recording in the spectral range from 4000 to 600 cm and
established that the reagent is of sufficiently high purity to
meeting the specifications is shown in Table 1. Refer also to
permit its use without decreasing the accuracy of the determi-
Practice E275. Fourier transform infrared spectrophotometers
nation.
meet these specifications.
7.2 Purity of Water—Unless otherwise indicated references
NOTE 1—Although this test method is written for the use of dispersive
towatershallbeunderstoodtomeanreagentwaterconforming
infraredspectroscopy,Fouriertransforminfraredspectroscopycanalsobe
to Specification D1193, Type II.
used for oil comparison.
7.3 Magnesium Sulfate—Anhydrous,reagentgrade,fordry-
6.2 Sample Cells:
ing samples.
6.2.1 Demountable Cells—The cell generally used is a
demountable liquid cell using a 0.05-mm spacer. This cell is
7.4 Solvents—Spectroquality solvents for sample treatment
usable for all oil types, the heavy oils being analyzed as
and cleaning cells include cyclohexane, pentane, hexane,
smears. For light oils, a sealed cell can be used, provided that
methylene chloride, and methanol.
the sample is known to be dry. Another type used is a
8. Precautions
low-capacity demountable cell using a silver halide window
with a 0.025-mm depression. Satisfactory oil spectra can be
8.1 Take normal safety precautions when handling organic
obtained with this cell with as little as 10 µL of oil, compared
solvents.Takeprecautionstoensurethatwetoilsamplesdonot
to the nearly 100 µL required for the standard cells. This cell
come in contact with water-soluble cell window materials.
can also be used to screen for the presence of water in oil
Most spectrophotometers require humidity control (to about
samples.
45%), particularly if they have humidity-sensitive detectors
6.2.2 Horizontal Attentuated Reflectance Apparatus
such as those with cesium iodide optics. The primary precau-
(HATR), may be used instead of demountable cells. If so, all
tion which must be taken to provide the best possible results is
analyses must be performed with the same HATR apparatus.
that all samples analyzed should be treated in an identical
fashion, run in the same cell, on the same instrument and
6.3 Cell Windows:
preferably on the same day by the same operator.
6.3.1 Potassium or silver bromide should be used for
demountable cells. Silver chloride may be substituted for the
NOTE 3—If the samples cannot be analyzed the same day, one of the
bromide. first samples must be repeated to ensure that the spectra are not
significantly different.
NOTE 2—Sodium chloride should not be used; results obtained using
thiswindowmaterial,althoughconsistentwitheachother,arenotdirectly
9. Sampling
comparable to those from the other window materials. Sodium chloride
9.1 On-Scene—A representative sample of the waterborne
was shown by Brown, et al to give results significantly different from
those obtained with potassium bromide or silver chloride, based on
oil is collected in a glass jar (precleaned with cyclohexane and
quantitative comparisons.
dried) having a TFE-fluorocarbon-lined cap. In the same time
6.3.2 Zinc selenide is the material of choice for the HATR frame, samples are collected of potential source samples that
are to be compared to the waterborne sample.
apparatus.
6.4 Accessories: 9.2 Laboratory—See Annex A1.
6.4.1 Reference Beam Attenuator, for setting baseline with
10. Preservation of Sample
the low-capacity silver halide cell.
10.1 Refer to Practice D3325.
Consult the manufacturer’s operating manual for specific instructions on using
this apparatus. “Reagent Chemicals, American Chemical Society Specifications,” American
TheMini-cellmadebyWilksScientificCorp.,S.Norwalk,CT,hasbeenfound Chemical Society, Washington, DC. For suggestions on the testing of reagents not
to be satisfactory for this purpose. listed by the American Chemical Society, see Rosin, J.,“ Reagent Chemicals and
Brown, C.W., Lynch, P. F., andAhmadjian, M. “Identification of Oil Slicks by Standards,” D. Van Nostrand Co., New York, NY, and the “United States
Infrared Spectroscopy,” NTIS Accession No. ADA 040975, 1976. Pharmacopeia”.
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D3414−98 (2011)
FIG. 1 Complete Spectrum of a No. 2 Fuel Oil, Analyzed in Triplicate
othermustbealso(seePracticesD3326forthedeasphaltingprocedure.It
11. Analytical Procedures
should be noted that 15 parts of solvent (versus 40) is all that is necessary
11.1 Recording Spectra for Dispersive Instruments:
for quantitative precipitation of the asphaltene fraction.)
11.1.1 Operatetheinstrumentinaccordancewiththemanu-
facturer’s instructions. Refer to Practices E168 for more
12. Interpretation of Spectra
information on handling cells.
12.1 Ultimately, oil identification is based on a peak-by-
11.1.2 Check the calibration daily by scanning a 0.05-mm
peakcomparisonofthespillspectrumwiththoseofthevarious
polystyrene film in accordance with Practice E275. Observe
potential sources.Alight-box is convenient for superimposing
whether the test spectra are within the limits of the instrument
these spectra. When the results are to be used for forensic
specifications. This calibration check should be performed
purposes, comparisons must be made on spectra obtained by
beforeeveryoilspillsetandthespectrumretainedwithspectra
using the same sample preparation, sample cell, and the same
from the spill and suspects as part of the case record.
instrumental conditions, preferably with the same operator on
11.1.3 Test the resolution by observing the sidebands in the
−1
the same day.
polystyrenespectrumat2850.7and1583.1cm whichshould
be distinct and well defined. This is also true for the sideband
12.2 Sample Spectra:
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at 3100 cm which should have a clear inflection with a
12.2.1 Fig.1showstheinfraredspectrumofaNo.2fueloil
displacement of at least 1 to 3% T where T=transmittance.
to illustrate the general spectral characteristics of an oil
11.1.4 Place the sample in a liquid cell (see Annex A2 or
analyzed by infrared transmission through KBr windows. This
Annex A3) and insert cell into the infrared beam. Set the
particular illustration is actually a superposition of three
−1
absorbance to read 0.02 A (95% T) at 1975 620 cm .
independent spectra which graphically show how reproducible
the triplicates are, even with a demountable cell, if proper
NOTE 4—The absorbance is set at a fixed value so that the resultant
spectra can be compared from a common baseline.
techniques are used. The “oil fingerprint” region between 900
−1
−1
to 700 cm can be seen to have a large amount of fine detail
11.1.5 Scan the spectrum from 4000 to 600 cm using
characteristic of a light oil.
normal operating conditions and slit settings.
−1
12.2.2 Figs. 2-5 show spectra from 2000 to 600 cm for
11.2 FTIR Instruments:
four oils weathered over 4 days.They show the general effects
11.2.1 Collectdatafromabackgroundscan(aironly)under
−1
of weathering on baselines between 1300 and 900 cm and
conditions identical to those under which the sample will be
relativechangesofindividualpeaksinthe“fingerprint”region.
run, that is, with the cell in the instrument and all instrument
The figures are, respectively: No. 2, No. 4, No. 6 fuel oils, and
parameters the same.
a Louisiana crude with curves at 0, 1, 2, 3, and 4 days outdoor
11.2.2 Normalize the absorbance before comparing the
weathering.
spectra.
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12.2.3 Fig. 6 and Fig. 7 show details of weathering of
11.2.3 Collect data from 650 cm for HATR cells with
various oil types as described in 12.3.7.
ZnSe, due to the sprectral absorbance cutoff for ZnSe.
12.3 Overlay Method:
11.3 Preparation of Sample—Refer to AnnexA1 and Prac-
tice D3326 for sample preparation.
12.3.1 The overlay method consists of a visual comparison
of the spectrum of a spill with that of a potential source in the
NOTE5—Theprimaryobjectiveinsamplepreparationistheremovalof
sequence as follows and outlined in Fig. 8. This may be
water to protect the sample cells and get a “clean” spectrum of the oil. If
at all possible, the use of solvent should be avoided. It is sometimes accomplished using a light-box or even recording two spectra
necessary to use solvent in order to break refractory emulsions or to
on the same chart.
extract the oil from solid substrates. It must be remembered that for valid
12.3.1.1 First ensure that the spectra have comparable
comparisons of spectra, both oils being compared must have been
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baselines at 1975 cm , that is, that they were set at an
prepared the same way, that is, if one is deasphalted with pentane, the
absorbance of 0.02 (95% T).
−1
12.3.1.2 Next, examine the absorbance at 1377 cm to
TablesofWavenumbersForTheCalibrationofInfraredSpectrometers,IUPAC,
obtain qualitative assurance that the samples were analyzed at
Commission on Molecular Structure and Spectroscopy, Butterworth and Co.,
Toronto, Canada, 1961. the same thickness, that is, same cell path le
...
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