ASTM D3650-93(2011)
(Test Method)Standard Test Method for Comparison of Waterborne Petroleum Oils By Fluorescence Analysis (Withdrawn 2018)
Standard Test Method for Comparison of Waterborne Petroleum Oils By Fluorescence Analysis (Withdrawn 2018)
SIGNIFICANCE AND USE
This test method is useful for rapid identification of waterborne petroleum oil samples as well as oil samples obtained from fuel or storage tanks, or from sand, vegetation, or other substrates. This test method is applicable to weathered and unweathered neat oil samples.
The unknown oil is identified through the comparison of the fluorescence spectrum of the oil with the spectra (obtained at similar instrumental settings on the same instrument) of possible source samples. A match of the entire spectrum between the unknown and possible source sample indicates a common source.
SCOPE
1.1 This test method covers the comparison of waterborne petroleum oils with oils from possible sources by means of fluorescence spectroscopy (1). Useful references for this test method include: (2) and (3) for fluorescence analysis in general and (4), (5), and (6) for oil spill identification including fluorescence.
1.2 This test method is applicable to crude or refined petroleum products, for any sample of neat oil, waterborne oil, or sample of oil-soaked material. Unless the samples are collected soon after the spill occurs, it is not recommended that volatile fuels such as gasoline, kerosine, and No. 1 fuel oils be analyzed by this test method, because their fluorescence signatures change rapidly with weathering. Some No. 2 fuel oils and light crude oils may only be identifiable up to 2 days weathering, or less, depending on the severity of weathering. In general, samples weathered up to 1 week may be identified, although longer periods of weathering may be tolerated for heavy residual oils, oil weathered under Arctic conditions, or oil that has been protected from weathering by collecting in a thick layer.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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.
WITHDRAWN RATIONALE
This test method covers the comparison of waterborne petroleum oils with oils from possible sources by means of fluorescence spectroscopy.
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
Designation:D3650 −93 (Reapproved 2011)
Standard Test Method for
Comparison of Waterborne Petroleum Oils By
Fluorescence Analysis
This standard is issued under the fixed designation D3650; 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* 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the comparison of waterborne
D1129 Terminology Relating to Water
petroleum oils with oils from possible sources by means of
D1193 Specification for Reagent Water
fluorescence spectroscopy (1). Useful references for this test
D3325 Practice for Preservation of Waterborne Oil Samples
methodinclude: (2)and (3)forfluorescenceanalysisingeneral
D3326 Practice for Preparation of Samples for Identification
and (4), (5), and (6) for oil spill identification including
of Waterborne Oils
fluorescence.
D3415 Practice for Identification of Waterborne Oils
1.2 This test method is applicable to crude or refined
D4489 Practices for Sampling of Waterborne Oils
petroleum products, for any sample of neat oil, waterborne oil,
E131 Terminology Relating to Molecular Spectroscopy
or sample of oil-soaked material. Unless the samples are
E275 Practice for Describing and Measuring Performance of
collectedsoonafterthespilloccurs,itisnotrecommendedthat
Ultraviolet and Visible Spectrophotometers
volatile fuels such as gasoline, kerosine, and No. 1 fuel oils be
E520 Practice for Describing Photomultiplier Detectors in
analyzed by this test method, because their fluorescence
Emission and Absorption Spectrometry
signatures change rapidly with weathering. Some No. 2 fuel
oils and light crude oils may only be identifiable up to 2 days
3. Terminology
weathering,orless,dependingontheseverityofweathering.In
3.1 Definitions—For definitions of terms used in this test
general, samples weathered up to 1 week may be identified,
method refer to Terminology D1129, Practice D3415, and
although longer periods of weathering may be tolerated for
Terminology E131.
heavy residual oils, oil weathered under Arctic conditions, or
4. Summary of Test Method
oil that has been protected from weathering by collecting in a
thick layer.
4.1 This test method consists of fluorescence analyses of
dilute solutions of oil in spectroquality cyclohexane. In most
1.3 The values stated in SI units are to be regarded as
cases the emission spectra, with excitation at 254 nm, over the
standard. No other units of measurement are included in this
spectral range from 280 to 500 nm, are adequate for matching.
standard.
4.2 Identification of the sample is made by direct visual
1.4 This standard does not purport to address all of the
comparison of the sample’s spectrum with the spectra from
safety concerns, if any, associated with its use. It is the
possible source samples.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
NOTE 1—When weathering has occurred, it may be necessary to
bility of regulatory limitations prior to use. consider known weathering trends when matching spectra (Fig. 1 and Fig.
2).
5. Significance and Use
This test method is under the jurisdiction of ASTM Committee D19 on Water
5.1 This test method is useful for rapid identification of
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
waterborne petroleum oil samples as well as oil samples
Organic Substances in Water.
Current edition approved May 1, 2011. Published June 2011. Originally
approved in 1978. Last previous edition approved in 2006 as D3650 – 93 (2006). For referenced ASTM standards, visit the ASTM website, www.astm.org, or
DOI: 10.1520/D3650-93R11. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
The boldface numbers in parentheses refer to the references at the end of this Standards volume information, refer to the standard’s Document Summary page on
test method. the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3650−93 (2011)
6.3 Possible interferences from Raman or RayleighTyndall
scattering are not observed in the emission scan ranges
selected.
7. Apparatus
7.1 Fluorescence Spectrophotometer (or Spectro-
fluorometer)—An instrument recording in the spectral range of
220 nm to at least 600 nm for both excitation and emission
responses and capable of meeting the specifications stated in
Table 1.
7.2 Excitation Source—A high-pressure xenon lamp (a
150-W xenon lamp has proven acceptable). Other continuum
sources, such as deuterium or high-pressure xenon-mercury,
FIG. 1 Fluorescence Spectra for a Typical No. 2 Fuel Oil (Un-
which have sufficient intensity in the ultraviolet region, could
weathered and Weathered One Day)
be used as excitation sources.
NOTE 4—Line sources such as a low-pressure mercury lamp may also
be used for excitation at 254 nm, if the flexibility of using arbitrary
excitation wavelengths or excitation spectra is not desired and if source
intensity is adequate.
7.3 Fluorescence Cells—Standard cells, made from
fluorescence-free fused silica with a pathlength of 10 mm and
a height of 45 mm.
7.4 Recorder or Computer—Strip chart or X-Y recorder,
with a response time less than 1 s for full-scale deflection, or a
computer capable of digitizing the data at a rate of 1 data point
per nanometre.
7.5 Cell-Filling Device—Disposable Pasteur capillary pipet.
7.6 Volumetric Flasks—Low-actinic glass, ground-glass
FIG. 2 Fluorescence Spectra for a Typical No. 6 Fuel Oil (Un-
stoppered volumetric flasks (100-mL).
weathered and Weathered One Day)
7.7 Micropipet, 10 to 50-µL capacity.
obtained from fuel or storage tanks, or from sand, vegetation,
7.8 AnalyticalBalance,withaprecisionofatleast 60.1mg.
or other substrates.This test method is applicable to weathered
7.9 Weighing Pans, 5 to 7-mm diameter, 18 mm deep, made
and unweathered neat oil samples.
of aluminum or equivalent.
5.2 Theunknownoilisidentifiedthroughthecomparisonof
the fluorescence spectrum of the oil with the spectra (obtained
TABLE 1 Specifications for Fluorescence Spectrophotometers
at similar instrumental settings on the same instrument) of
Wavelength Reproducibility
possible source samples. A match of the entire spectrum
Excitation monochromator better than± 2 nm
between the unknown and possible source sample indicates a
Emission monochromator better than ±2 nm
Gratings (Typical Values)
common source.
Excitation monochromator minimum of 600 lines/mm blazed at
A
300 nm
6. Interferences
Emission monochromator minimum of 600 lines/mm blazed at
A
6.1 The fluorescence spectrum will be distorted if an oil 300 nm or 500 nm
sample has been contaminated by an appreciable amount, for
B
Photomultiplier Tube
example, 1 % of common chemical impurities such as other
C D E
Either S-20 or S-5 Response
oils that are fluorescent on excitation at 254 nm.
NOTE 2—Storage of samples in improper containers (for example, Resolution
Excitation monochromator better than 2 nm
plastics) may result in contamination. This interference can be eliminated
Emission monchromator better than 2 nm
by observing proper procedures for collection and preservation of
samples. Refer to Practice D3325.
Time Constant
NOTE 3—“Spectroquality” cyclohexane may not have a low enough
fluorescence solvent blank. Lots vary in the content of fluorescent
not to exceed one second
impurities, which may increase with storage time even if the bottle is
A
Or designed to have a good efficiency in this spectral region.
unopened.
B
See Practice E520.
C
6.2 Oil residues may build up in fluorescence cells particu- Photomultiplier tubes such as Hamamatsu R-446-UR.
D
Photomultiplier tubes such as RCA 1P28 or Hamamatsu R-106.
larly after prolonged usage with heavy oils. In such a case,
E
Or equivalent having a good spectral response in the spectral region from 280 to
follow the procedure using nitric acid for cleaning glassware
600 nm.
(10.1.3).
D3650−93 (2011)
7.10 Test Tubes, disposable 15-mL glass test tubes. Spectroquality cyclohexane is the preferred solvent for sample
preparation for fluorescence.
7.11 Micropipet, or microsyringe, 9-µL capacity; with an
accuracy of 1 % and reproducibility of 0.1 % of pipet capacity. 9.4 Preparation of Solutions for Fluorescence Analysis—
Either of the following techniques for diluting the prepared oil
7.12 Micropipet, 200-µLcapacity with disposable tips; with
sample with cyclohexane may be used:
an accuracy of 1 % and reproducibility of 0.1 % of pipettor
9.4.1 Weighing Technique—To prepare oil solutions at a
capacity.
concentrationofapproximately20µg/mL,weighout0.0016 6
7.13 Solvent Dispenser, adjustable to deliver 10 mL.
0.0001 g of oil (equivalent weight for each sample) onto a
clean aluminum weighing pan using a micropipet. Transfer
7.14 Vortex Mixer.
weighed oil sample into a clean 100 mL, low-actinic glass
8. Reagents and Materials
volumetric flask by creasing the aluminum pan and washing
the oil directly into the volumetric flask using spectroquality
8.1 Purity of Reagents—Spectroquality grade reagents
cyclohexane dispensed from a TFE-fluorocarbon wash bottle.
should be used in all instances unless otherwise stated. It is
Dilute the solution up to volume (100 mL) and shake vigor-
intended that all reagents shall conform to the specifications of
ouslyseveraltimesandallowthepreparedsolutiontostandfor
theCommitteeonAnalyticalReagentsoftheAmericanChemi-
30 min and shake again prior to performing the analysis to
cal Society, where such specifications are available.
ensure that all oil dissolves. Occasionally, depending on
8.2 Purity of Water—References to water shall be under-
fluorescence yield of the oil tested and instrumentation used, it
stood to mean Type IV reagent water conforming to Specifi-
maybenecessarytouse100ppmconcentrationtogetadequate
cationD1193. However,sincefluorescentorganicimpurities in
fluorescence intensity. In these cases, weigh out 0.0078 6
thewatermayconstituteaninterference,thepurityofthewater
0.0001 g of oil and proceed as above.
should be checked by running a water blank using the same
NOTE 7—It is preferable that the prepared solution be used the same
instrument conditions as for the solvent blank.
day. Do not use solutions that have been standing for periods in excess of
8.3 Acetone (CH COCH ).
6 h unless they have been refrigerated. In no case use solutions more than
3 3
2 days old.
8.4 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
9.4.2 Volume Technique—Allow the prepared oil sample to
(HNO ).
come to room temperature and shake until they are homoge-
8.5 Cyclohexane, spectroquality grade, with a fluorescence
neous.Transfer 9 µLof the oil to a 15-mLdisposable glass test
solvent blank less than 2 % of the intensity of the major peak
tube with a micropipet or microsyringe and add 10 mL of
of the sample fluorescence generated with the same instrumen-
spectroquality cyclohexane with a solvent dispenser. Place a
tal settings over the emission range used. Cyclohexane is
capofaluminumfoiloverthetopofthetesttubeandvortexfor
dispensed throughout the procedure from a 500-mL TFE-
approximately 30 s. With a micropipet, transfer 200 µL of this
fluorocarbon wash bottle. For prolonged storage, cyclohexane
solution to a second 15-mL test tube and then add 10 mL of
should be stored only in glass. Check the suitability of the
cyclohexane. Place a cap of aluminum foil over the top of the
solvent by running a solvent blank. The solvent blank can also
second test tube and vortex for approximately 30 s. Prepare all
be used to check for scatter.
samples in this manner.
NOTE 5—Cyclohexane can be reused, if necessary, after one or more
NOTE 8—If a micropipet with disposable plunger and tips is used,
distillations in an all-glass still. The distilled cyclohexane must have no
potential cross contamination is avoided. Otherwise, careful cleaning
detectable fluorescence (<2 %) in the 280 to 500-nm region of the
following the procedures specified in 10.1 is required.
spectrum when excited at 254 nm.
NOTE 6—Methylcyclohexane can also be used as a solvent, instead of
10. Preparation of Apparatus
cyclohexane. This is useful, particularly if the solution is needed for
low-temperature luminescence measurements as well.
10.1 Cleaning Glassware:
8.6 Aluminum Foil.
10.1.1 Clean all glassware used in this procedure in the
following manner: first rinse volumetric flasks and cells three
9. Sampling and Sample Preparation
times with spectroquality cyclohexane. Prior to the use of
glassware and cells throughout this procedure, rinse again with
9.1 Collect a representative sample as directed in Practice
D4489. spectroquality cyclohexane.
10.1.2 If there is water present, rinse the glassware three
9.2 Preserve samples in containers as specified in Practice
times with spectroquality acetone, and then three times with
D3325. However, to avoid dewaxing, do not cool samples
cyclohexaneasin10.1.1.Usedetergentsonlyiftheyhavebeen
below 5°C.
checked for low fluorescence. If laboratory detergent solutions
9.3 Preparation of Oil Samples, as described in Practices
are used, repeated rinsing with Type IVreagent (see 8.3) water
D3326. Avoid the use of deasphalting procedures, if possible.
will be required.
10.1.3 When working with heavy oils, a cleaning procedure
using organic solvents may not be sufficient. Heavy oils build
“Reagent Chemicals,American Chemical Society Specifications,”Am. Chemi-
up a residue on cells that solvent cleaning will not remove. If
cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by
the solvent blank shows significant impurities, a residual film
theAmerican Chemical Society, see “Analar Standards for Laboratory Chemicals,”
BDH Ltd., Poole, Dorset, U.K., and the “United States Pharmacopeia.” on the cell, rather than an impure solvent, may be the cause.
D3650−93 (2011)
Soak the cells in undiluted nitric acid for 1 h. Observe proper 12. Interpretation of Spectra
safety precautions by using adequate eye and hand protection.
12.1 Overlay the spectrum of the unknown sample with the
RinsethecellsrepeatedlywithTypeIVreagentwater,andthen
spectra of the suspect samples. Note five features when
proceed as in 10.1.2.
comparing the oil spectra: (1) general shape, (2) number of
10.2 Calibration of Spectrophotometer:
peaks,(3)wavelengthscorrespondingtothepeaks,(4)ratiosof
10.2.1 Adjust and calibrate the spectroph
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