An American National Standard

Designation: D 3414 – 98 (Reapproved 2004)

Standard Test Method for

1. Scope 3. Terminology
1.1 This test method provides a means for the identification 3.1 Definitions:
of waterborne oil samples by the comparison of their infrared 3.1.1 For definitions of terms used in this test method refer
spectra with those of potential source oils. to Terminology E 131 and Terminology D 1129.
1.2 This test method is applicable to weathered or unweath- 3.2 Definitions of Terms Specific to This Standard:
ered samples, as well as to samples subjected to simulated 3.2.1 weathering of waterborne oil—the combined effects
weathering. of evaporation, solution, emulsification, oxidation, biological
1.3 This test method is written primarily for petroleum oils. decomposition, etc.
1.4 This test method is written for linear transmission, but
could be readily adapted for linear absorbance outputs. 4. Summary of Test Method
1.5 This standard does not purport to address all of the 4.1 The spill sample and potential source oil(s) are treated
safety concerns, if any, associated with its use. It is the identically to put them in an appropriate form for analysis by
responsibility of the user of this standard to establish appro- infrared spectrophotometry. The oils are transferred to suitable
priate safety and health practices and determine the applica- infrared cells and the spectra are recorded from 4000 to 600
bility of regulatory limitations prior to use. Specific precau- cm −1 for KBr cells, and to 650 cm-1 for HATR cells with ZnSe
tionary statements are given in Section 8. crystals. All analyses are performed on the same instrument
using the same sample cell, which is cleaned between samples.
2. Referenced Documents The spectra of the sample and the potential source oil(s) are
2.1 ASTM Standards: 2 then compared by superimposing one upon the other, looking
D 1129 Terminology Relating to Water at particular portions of the spectra. A high degree of coinci-
D 1193 Specification for Reagent Water dence between the spectra of the sample and a potential source
D 3325 Practice for Preservation of Waterborne Oil oil indicates a common origin. This test method is recom-
Samples mended for use by spectroscopists experienced in infrared oil
D 3326 Practice for Preparation of Samples for Identifica- identification or under close supervision of such qualified
tion of Waterborne Oils persons.
D 3415 Practice for Identification of Waterborne Oils
E 131 Terminology Relating to Molecular Spectroscopy 5. Significance and Use
E 168 Practices for General Techniques of Infrared Quan- 5.1 This test method provides a means for the comparison of
titative Analysis waterborne oil samples with potential sources. The waterborne
E 275 Practice for Describing and Measuring Performance samples may be emulsified in water or obtained from beaches,
of Ultraviolet, Visible, and Near Infrared Spectrophotom- boats, oil-soaked debris, and so forth.
eters 5.2 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 relation-
1
This test method is under the jurisdiction of ASTM Committee D19 on Water ship to the unknown oil.
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water. 5.3 The analysis is capable of comparing most oils. Diffi-
Current edition approved June 1, 2004. Published June 2004. Originally culties may be encountered if a spill occurs in an already
approved in 1975. Last previous edition approved in 1998 as D 3414–98.
2
polluted area, that is, the spilled-oil mixes with another oil.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
5.4 In certain cases, there may be interfering substances
Standards volume information, refer to the standard’s Document Summary page on which require modification of the infrared test method or the
the ASTM website. use of other test methods (see Practice D 3326, Method D.)

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 3414 – 98 (2004)
TABLE 1 Specifications for Infrared Spectrophotometers 6.4.2 Disposable Pasteur Pipets and Hypodermic Syringes.
Abscissa accuracy Better than 6 5 cm−1 from 4000 to 2000 6.4.3 Window-Polishing Kit.
cm−1 range; better than 6 3 cm−1 6.4.4 Centrifuge.
from 2000 to 600 cm−1(or below).
Abscissa repeatability 2.5 cm−1 from 4000 to 2000 cm −1; 1.5 6.4.5 Vortex Mixer.
cm−1 from 2000 to 600 cm−1(or below). 6.4.6 Hot Plate.
Ordinate accuracy 6 1 % of full scale. 6.4.7 Light-Box, for viewing spectra.
Ordinate repeatability within 1 % of full scale.

7. Reagents
5.5 It is desirable, whenever possible, to apply other inde- 7.1 Purity of Reagents—Reagent grade chemicals shall be
pendent analytical test methods to reinforce the findings of the used in all tests unless otherwise indicated. It is intended that
infrared test method (see Practice D 3415). all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society,
6. Apparatus where such specifications are available.6 For sample treatment
6.1 Infrared Spectrophotometer—An instrument3 capable and for cleaning cells, special spectroquality reagents are
of recording in the spectral range from 4000 to 600 cm−1 and required. Other grades may be used, provided it is first
meeting the specifications is shown in Table 1. Refer also to established that the reagent is of sufficiently high purity to
Practice E 275. Fourier transform infrared spectrophotometers permit its use without decreasing the accuracy of the determi-
meet these specifications. nation.
7.2 Purity of Water— Unless otherwise indicated references
NOTE 1—Although this test method is written for the use of dispersive to water shall be understood to mean reagent water conforming
infrared spectroscopy, Fourier transform infrared spectroscopy can also be to Specification D 1193, Type II.
used for oil comparison.
7.3 Magnesium Sulfate—anhydrous, reagent grade, for dry-
6.2 Sample Cells: ing samples.
6.2.1 Demountable Cells—The cell generally used is a 7.4 Solvents—Spectroquality solvents for sample treatment
demountable liquid cell using a 0.05-mm spacer. This cell is and cleaning cells include cyclohexane, pentane, hexane,
usable for all oil types, the heavy oils being analyzed as methylene chloride, and methanol.
smears. For light oils, a sealed cell can be used, provided that
the sample is known to be dry. Another type used is a 8. Precautions
low-capacity demountable cell using a silver halide window 8.1 Take normal safety precautions when handling organic
with a 0.025-mm depression.4 Satisfactory oil spectra can be solvents. Take precautions to ensure that wet oil samples do not
obtained with this cell with as little as 10 µL of oil, compared come in contact with water-soluble cell window materials.
to the nearly 100 µL required for the standard cells. This cell Most spectrophotometers require humidity control (to about
can also be used to screen for the presence of water in oil 45 %), particularly if they have humidity-sensitive detectors
samples. such as those with cesium iodide optics. The primary precau-
6.2.2 Horizontal Attentuated Reflectance Apparatus tion which must be taken to provide the best possible results is
(HATR), may be used instead of demountable cells. If so, all that all samples analyzed should be treated in an identical
analyses must be performed with the same HATR apparatus. 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
first samples must be repeated to ensure that the spectra are not
bromide.
significantly different.
NOTE 2—Sodium chloride should not be used; results obtained using
this window material, although consistent with each other, are not directly 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 5 to give results significantly different from oil is collected in a glass jar (precleaned with cyclohexane and
those obtained with potassium bromide or silver chloride, based on
quantitative comparisons.
dried) having a TFE-fluorocarbon-lined cap. In the same time
frame, samples are collected of potential source samples that
6.3.2 Zinc selenide is the material of choice for the HATR are to be compared to the waterborne sample.
apparatus. 9.2 Laboratory—See Annex A1.
6.4 Accessories:
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 D 3325.

3
Consult the manufacturer’s operating manual for specific instructions on using
6
this apparatus. “Reagent Chemicals, American Chemical Society Specifications,” American
4
The Mini-cell made by Wilks Scientific Corp., S. Norwalk, CT, has been found 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
5
Brown, C. W., Lynch, P. F., and Ahmadjian, 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”.

2
 D 3414 – 98 (2004)

FIG. 1 Complete Spectrum of a No. 2 Fuel Oil, Analyzed in Triplicate

11. Analytical Procedures other must be also (see Practices D 3326 for the deasphalting procedure.
It should be noted that 15 parts of solvent (versus 40) is all that is
11.1 Recording Spectra for Dispersive Instruments: necessary for quantitative precipitation of the asphaltene fraction.)
11.1.1 Operate the instrument in accordance with the manu-
facturer’s instructions. Refer to Practices E 168 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
peak comparison of the spill spectrum with those of the various
polystyrene film in accordance with Practice E 275. Observe
potential sources. A light-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
before every oil spill set and the spectrum retained with spectra
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
the same day.
polystyrene spectrum at 2850.7 and 1583.1 cm−1 which should
12.2 Sample Spectra
be distinct and well defined.7 This is also true for the sideband
at 3100 cm−1 which should have a clear inflection with a 12.2.1 Fig. 1 shows the infrared spectrum of a No. 2 fuel oil
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
absorbance to read 0.02 A (95 % T) at 1975 6 20 cm−1. 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 techniques are used. The “oil fingerprint” region between 900
spectra can be compared from a common baseline. to 700 cm−1 can be seen to have a large amount of fine detail
11.1.5 Scan the spectrum from 4000 to 600 cm−1 using characteristic of a light oil.
normal operating conditions and slit settings. 12.2.2 Figs. 2-5 show spectra from 2000 to 600 cm−1 for
11.2 FTIR Instruments: four oils weathered over 4 days. They show the general effects
11.2.1 Collect data from a background scan (air only) under of weathering on baselines between 1300 and 900 cm−1 and
conditions identical to those under which the sample will be relative changes of individual peaks in the“ 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. 12.2.3 Fig. 6 and Fig. 7 show details of weathering of
11.2.3 Collect data from 650 cm-1 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 Annex A1 and Prac- 12.3.1 The overlay method consists of a visual comparison
tice D 3326 for sample preparation. of the spectrum of a spill with that of a potential source in the
NOTE 5—The primary objective in sample preparation is the removal of 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 accomplished using a light-box or even recording two spectra
at all possible, the use of solvent should be avoided. It is sometimes on the same chart.
necessary to use solvent in order to break refractory emulsions or to 12.3.1.1 First ensure that the spectra have comparable
extract the oil from solid substrates. It must be remembered that for valid baselines at 1975 cm−1, that is, that they were set at an
comparisons of spectra, both oils being compared must have been
absorbance of 0.02 (95 % T).
prepared the same way, that is, if one is deasphalted with pentane, the
12.3.1.2 Next, examine the absorbance at 1377 cm−1 to
obtain qualitative assurance that the samples were analyzed at
7
the same thickness, that is, same cell path length (see 12.3.2).
Tables of Wavenumbers For The Calibration of Infrared Spectrometers,
IUPAC, Commission on Molecular Structure and Spectroscopy, Butterworth and 12.3.1.3 Then examine the curve for overall similarities in
Co., Toronto, Canada, 1961. shape from 4000 to 600 cm−1. For petroleum oils, the baseline

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 D 3414 – 98 (2004)

FIG. 2 No. 2 Fuel Oil Progressive Weathering Effects, 0 to 4 Days

FIG. 3 No. 4 Fuel Oil Progressive Weathering Effects, 0 to 4 Days

will tend to move downward with weathering (to higher and 920 cm−1. There also would be a corresponding increase in
absorbance between 1350 to 900 cm−1) but with little relative the peak at 722 cm−1.
change of the peaks in that range. 12.3.1.6 Finally, scrutinize the “oil fingerprint” region (900
12.3.1.4 Examine the 1770 to 1685 cm−1 region to deter- to 700 cm −1) for similarities. If slight variations do occur in
mine the extent of weathering—particularly in the 1708 cm −1 this region, the peaks are examined for possible changes
region where carbonyls from oxidative weathering first appear. induced by weathering. The sequential steps are outlined in
12.3.1.5 Before making a detailed comparison, make sure 12.3.2 through 12.3.7.
there are no interferences from residual foreign materials:
(a) (a) For water in the spill sample, check in the 3400 NOTE 6—Animal or vegetable oils would have a pronounced ester
cm−1 region for a broad peak. (If water is suspected to be carbonyl at 1730 to 1740 cm −1. In that case, the spectra are compared
directly in order to identity without consideration of weathering changes
present, check first in a low-capacity silver halide cell). If an
described as follows for petroleum oils.
appreciable amount of water is present, redry the sample.
(b) (b) For residual MgSO4 from the drying procedure, 12.3.2 Examine the intensity of the 1377 cm −1 peak since it
check the 610 cm−1 region for a small, sharp peak, and look for is a good indicator of the sample thickness. An absorbance
peak increases at 1075 and 1175 cm−1. value between 0.85 and 1.00 at 1377 cm −1 gives the optimum
(c) (c) For residual pentane, if the sample has been spectrum. The matching of oil spectra from a common source
deasphalted, look for the presence of small twin peaks at 910 is considerably easier when samples are of the same thickness.

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 D 3414 – 98 (2004)

FIG. 4 No. 6 Fuel Oil Progressive Weathering Effects, 0 to 4 Days

FIG. 5 Crude Oil Progressive Weathering Effects, 0 to 4 Days

12.3.3 If the spectra are of the same sample thickness, NOTE 8—If neither the spill nor suspect show signs of oxidative
compare overall shapes over the entire curves. If obvious major weathering, then any differences in the spectra are real and the oils do not
differences (peaks or peak ratios) appear in the region between match (NM).
2000 to 600 cm −1, then the spectrum of the suspect oil is 12.3.5 Next, examine the region from 1350 to 900 cm−1,
designated a nonmatch (NM). If peak-for-peak similarities do with special emphasis on the peaks at 1304, 1165, and 1032
exist in the overall shape of the entire curves, proceed to the cm−1. These peaks generally remain constant in shape and
next step. relative to each other in size with weathering except for a
NOTE 7—There are exceptions, namely in those cases when a contami- general shift of the baseline (between 1300 and 900 cm−1) to
nant is obviously present, for example, ester carbonyl com-pound. In some higher absorbances (see Figs. 2-5). As the baseline shifts to
instances, the contaminant can be removed selectively by saponification. higher absorbances the peak shapes tend to broaden, particu-
When it cannot, it may be indeterminate (I) whether or not the two oils larly with light oils—especially in the 1165 cm−1 region. The
being compared have a common origin. 1165 unit also broadens with the presence of carbonyl impu-
12.3.4 Examine 1685, 1708, and 1770 cm −1 for indications rities (likely ester C-O-C asymmetrical stretch). Taking these
of weathering. Here, many weathered oils display well-defined factors into account, if the curves are unlike, the oils do not
carbonyl peaks, particularly at 1708 to 1710 cm −1. Even if the match (NM).
peaks are present in the carbonyl region in the spilled oil but 12.3.6 The next area scrutinized is the critical “oil finger-
not in the suspect oil, continue to the next step. print” region which uniquely characterizes an oil (900 to 700

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 D 3414 – 98 (2004)

FIG. 6 Weathering Changes of Light and Heavy Oils

FIG. 7 Weathering of a Typical Lubricating Oil

cm−1). When the spilled oil is the same as the suspect oil, the NOTE 9—The 875 cm−1 point was selected to give good overlays of the
peak shapes, amplitudes, and locations correspond, point for 900 to 700 cm−1 region.
point, to each other. This spectral overlay is designated as a 12.3.7 If an oil has been altered by weathering, the analyst
“match.” For detailed examination of this region, lay one curve must take such effects into consideration. If the effects are
over the other in such a way that the curve traces coincide at moderate, the analyst can account for them as outlined below.
875 cm−1 prior to a peak-by-peak comparison. If the effects are severe, the best procedure is to weather

6
 D 3414 – 98 (2004)

FIG. 8 Flow Chart for Infrared Spectral Comparisons of Oil

artificially a sample of the suspect to about the same degree as present, remains stable even with weathering and is an excel-
the spill (see Practices D 3326)8. For the shorter time frame, lent indicator of a lubricating oil. The 1010 and 675 cm−1
under 1 week, the weathering changes are qualitatively well bands lose structure on weathering (see Fig. 7). The 722 cm−1
known. The lighter oils weather faster during this period; the band is very strong in paraffin-based lubricating oils and
heavier oils progressively more slowly. The following de- diminishes slightly with weathering. It is another excellent clue
scribes the significant weathering effects for different oil for the classification of lubricating oils. Some No. 2 or diesel
classes: oils weather to leave a residue with a large 722 cm−1 band and
12.3.7.1 Light distillate fuel oils and diesels display losses strongly resemble lubricating oils.
in band structure at 849, 810, 790, 782, 766, and 700 wave
numbers (cm−1). There are apparent increases at 871, 832, and 13. Report
722 cm−1 due in part to a downward shift of baseline (see Fig. 13.1 Based upon the visual comparison of the spectra and
2 and Fig. 6). after considering 12.2, report the sample of unknown origin as
12.3.7.2 No. 4 fuel oils show a decrease in the ratio of belonging to one of the categories below (see Table 2 for a
744/722 cm−1 peaks. There is an apparent increase at 722 cm−1 summary of degrees of match):
with concomitant decreases at 700, 744, 766, 782, 790, and 810 13.1.1 Match (M)—Like one or more of the samples sub-
cm−1(see Fig. 3). mitted for comparison. The spectra must be a virtual overlay
12.3.7.3 No. 5 and No. 6 fuel oils show minimal weathering with only minor differences permissible in the 900 to 700 cm −1
effects, with slow development of the carbonyl peak at 1708 region (on the order of 0 to 2 mm (to 1.5 % transmittance)
cm−1 and an apparent increase in absorbance at 722 cm−1 (see maximum for a spectrum approximately 15 cm from top to
Fig. 4). bottom).
12.3.7.4 Crude oils weather differently depending on the 13.1.2 Probable Match (PM)—Like one or more of the
nature of the crude oil. Light crude oils will weather like light samples submitted for comparison except: differences attribut-
fuel oils; heavy crude oils like heavy fuel oils (see Figs. 4-6.) able to specific contamination, differences in sample thickness,
12.3.7.5 Lubricating oils may have additives with bands at or changes that could be attributed to weathering (for example,
675, 1010, and 1235 cm−1. The 1235 cm−1 additive peak, if carbonyl formation; baseline lowering from 1375 to 900 cm−1
with no marked peak ratio changes, that is, same general shape;
8 moderate changes in the fingerprint, 900 to 700 cm−1
Anderson, C. P., Killeen, T. J., Taft, J. B., and Bentz, A. P., “Artificial Oil
Weathering Techniques,” Paper 527, 1979 Pittsburgh Conference on Analytical region—on the order of 2 to 7 mm (1.5–5 % T) displacement
Chemistry and Applied Spectroscopy. on peaks known to change).

7
 D 3414 – 98 (2004)
TABLE 2 Degree of Match
Designation Symbol Characteristics
Match M Virtual overlay. Only minor differences in 900 to 700 cm−1 region (0 to 2 mm to 1.5 % T).
Probable match PM Differences can all be attributed to weathering (carbonyl formation; baseline lowering from 1375 to 900 cm−1 with
no peak ratio changes; moderate differences in 900 to 700 cm−1 region (2 to 7 mm; 1.5 to 5 % T) or
differences due to specific contaminations.
Indeterminate A I Strong indications of a common origin, but weathering, contamination or thickness differences are greater than PM.
Nonmatch NM Spectra different; different peaks or peak ratios.
A
Indeterminate spectra are similar. However, the differences are of such a nature that the analyst cannot say categorically (in a forensic sense) that the oils have different
origins.

13.1.3 Indeterminate (I)—Like one or more of the samples 14. Precision and Bias
submitted for comparison except for certain differences as
14.1 No statement is made about either the precision or bias
described in 13.1.2. Such differences would be of increased
of this test method for measuring waterborne oils, since the
magnitude over those for PM, but the overall similarity of the
result merely states whether there is conformance to the criteria
two oils suggests a common origin. Gross weathering, con-
tamination or cell thickness differences may make it impossible for success specified in the procedure.
to ascertain whether the unknown is the same oil or a totally
different oil.
13.1.4 Nonmatch (NM)—Unlike the samples submitted for
comparison. This includes presence or absence of peaks in one
of the spectra, peak reversals, etc.

ANNEXES

(Mandatory Information)

A1. LABORATORY SAMPLING

A1.1 Field samples are subsampled in the laboratory, taking A1.1.2 Oil on Sand or Debris—For oil samples on sand or
approximately 1 g of oil, if available. The oil is withdrawn as debris, the oil is floated off with water, if possible; otherwise,
free of water and debris as possible. it is extracted with pentane or hexane and dried (see Practices
A1.1.1 Thin Films— For oil samples present as thin films D 3326, Method B).
on water, extract the film from the surface by placing a layer of A1.1.3 Emulsified Oil— Oil emulsions can be broken by
spectroquality hexane (4 to 5 mm on the surface); stir and adding pentane or hexane and centrifuging. Sodium chloride
withdraw with a Pasteur pipet. Repeat, if necessary, to remove will assist in breaking fresh-water emulsions. Separate layers
all the oil. Then evaporate the solvent under dry nitrogen. and work up as in Practice D 3326, Method B.

A2. CELL LOADING PROCEDURE (LIQUID CELLS) (REFER TO PRACTICES E 168)

A2.1 Liquid cells (sealed or sealed-demountable cells) are NOTE A2.3—Use care to avoid forming bubbles.
generally used with potassium bromide (KBr) windows and a A2.3 Stopper the cell with TFE-fluorocarbon plugs, taking
0.05-mm TFE-fluorocarbon or lead spacer. care to avoid creating air bubbles or applying undue pressure.
NOTE A2.1—If the sample is suspected of being wet, use AgBr Insert the bottom plug first using a twisting motion. Gently
windows which will resist reaction with water. insert the top plug.
NOTE A2.2—For light oils (low viscosity) such as No. 2 fuel oil, the
sealed cell should be used. It reduces evaporation losses and eliminates NOTE A2.4—If an oil is too viscous to flow in a liquid cell, a
pathlength as a variable. DO NOT use a sealed cell if there is ANY chance transmission spectrum still can be obtained. A large drop of the oil is
that the sample is wet! placed on the center of a KBr window. Another KBr window is placed
over this with a 0.05-mm TFE-fluorocarbon or lead spacer forming a
A2.2 Incline the cell with one port at top and the other uniform oil smear. Always use the same spacer for obtaining spectra to be
below. Fill the cell from the bottom port using a Pasteur pipet. compared.

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 D 3414 – 98 (2004)

A3. CELL LOADING PROCEDURE (LOW-CAPACITY SILVER HALIDE CELL)

A3.1 The low-capacity cell consists of two silver bromide A3.1.2 Place the flat side of the second window over the
(AgBr) or silver chloride (AgCl) windows with a 0.025-mm sample and carefully press together to obtain a 0.025-mm
cavity pressed into the silver halide. The advantage of using pathlength.
this cell lies in the small amount of sample required for an A3.1.3 Slide the windows around on each other, with one
analysis and the ease of cleaning the cell. edge up, to work out all air bubbles.
A3.1.1 Place a drop of oil sample into the cavity of one A3.1.4 Gently lay the windows in the TFE-fluorocarbon
AgBr or AgCl window. holder and screw in the retaining ring.

A4. CELL AND CRYSTAL CLEANING PROCEDURES

A4.1 Thoroughly clean cell windows and crystals. Monitor A4.1.2 Store cells and window components in a desiccator.
the complete removal of residual hydrocarbon materials by
examining the infrared absorption in the 3000 to 2900 cm −1 A4.2 HATR With ZnSe Plate:
region. A clean cell will show no absorption in this region.
A4.2.1 Clean the ZnSe plate thoroughly with cyclohexane.
A4.1.1 For sealed demountable cells: dismantle cells com- Soap and water may be used on this cell. It is critical that the
pletely and thoroughly rinse each component. Rinse the win- crystal not be scratched. The window may be repolished by a
dows with a solvent such as cyclohexane; the rest of the cell commercial service which specializes in this process.
(spacers, end plates, parts, and plugs) rinse with another
suitable solvent such as methylene chloride.

A5. CARE OF CELL WINDOWS

A5.1 Potassium Bromide (KBr)—Keep potassium bromide A5.2 Silver Bromide (AgBr)—Handle AgBr windows care-
windows in a desiccator when not in use, since moisture will fully to avoid scratching since they are very soft. These
fog them. If they become scratched, grind them on fine emery windows may react with their aluminum containers; therefore,
paper (600 grit). For deep scratches, first use a coarser grade prevent their contact with the metal. Also, protect them from
emery paper (220 grit), then polish the windows on an optical light as much as possible, since they darken on exposure to
lap using polishing rouge. (Detailed instructions are given by ultraviolet light. These limitations require occasional replace-
the manufacturers of the commercially available window- ment of these windows. The replacement frequency is gov-
polishing kits.)9 erned by the spectral baseline changes due to these factors. A
new window will register about 43 % transmission at 4000
9
Application Notes: How to Polish Crystals, Barnes Engineering Co. cm−1, when it drops to 33 %, it should be discarded.

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