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2、 93 (Reapproved 1999)An American National StandardStandard Test Method forComparison of Waterborne Petroleum Oils ByFluorescence Analysis1This standard is issued under the fixed designation D 3650; the number immediately following the designation indicates the year oforiginal adoption or, in the cas
3、e of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the comparison of waterborne petroleum oils with oils from possib
4、le sources by means of fluorescence spectroscopy (1).2 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,
5、 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 signature
6、s 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 hea
7、vy residual oils, oil weathered under Arctic conditions, or oil that has been protected from weathering by collecting in a thick layer.1.3 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to e
8、stablish appro- priate safety and health practices and determine the applica- bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:D 1129 Terminology Relating to Water3D 1193 Specification for Reagent Water3D 1796 Test Method for Water and Sediment in Fuel Oils by
9、the Centrifuge Method (Laboratory Procedure)41 This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Organic Substances in Water.Current edition approved May 15, 1993. Published July 1993. Origina
10、lly published as D3650 78. Last previous edition D3650 90.D 3325 Practice for Preservation of Waterborne OilSamples5D 3326 Practices for Preparation of Samples for Identifica- tion of Waterborne Oils5D 3328 Test Methods for Comparison of Waterborne Petro- leum Oils by Gas Chromatography5D 3414 Test
11、Method for Comparison of Waterborne Petro- leum Oils by Infrared Spectroscopy5D 3415 Practice for Identification of Waterborne Oils5D 4489 Practices for Sampling of Waterborne Oils5E 131 Terminology Relating to Molecular Spectroscopy6E 275 Practice for Describing and Measuring Performance of Ultravi
12、olet, Visible, and Near Infrared Spectrophotom- eters6E 520 Practice for Describing Detectors in Emission andAbsorption Spectroscopy73. Terminology3.1 DefinitionsFor definitions of terms used in this test method refer to Terminology D 1129, Practice D 3415, and Terminology E 131.4. Summary of Test M
13、ethod4.1 This test method consists of fluorescence analyses of dilute solutions of oil in spectroquality cyclohexane. In most cases the emission spectra, with excitation at 254 nm, over the spectral range from 280 to 500 nm, are adequate for matching.4.2 Identification of the sample is made by direc
14、t visual comparison of the samples spectrum with the spectra from possible source samples.NOTE 1When weathering has occurred, it may be necessary to consider known weathering trends when matching spectra (Fig. 1 and Fig.2).5. Significance and Use5.1 This test method is useful for rapid identificatio
15、n of waterborne petroleum oil samples as well as oil samples2 The boldface numbers in parentheses refer to the references at the end of this test method.3 Annual Book of ASTM Standards, Vol 11.01.4 Annual Book of ASTM Standards, Vol 05.01.5 Annual Book of ASTM Standards, Vol 11.02.6 Annual Book of A
16、STM Standards, Vol 14.01.7 Annual Book of ASTM Standards, Vol 03.06.*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.1D 3650 93 (1999)6.3 Possible interferences from Ram
17、an or RayleighTyndallscattering are not observed in the emission scan ranges selected.FIG. 1 Fluorescence Spectra for a Typical No. 2 Fuel Oil(Unweathered and Weathered One Day)FIG. 2 Fluorescence Spectra for a Typical No. 6 Fuel Oil(Unweathered and Weathered One Day)obtained from fuel or storage ta
18、nks, or from sand, vegetation, or other substrates. This test method is applicable to weathered and unweathered neat oil samples.5.2 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 in
19、strument) of possible source samples. A match of the entire spectrum between the unknown and possible source sample indicates a common source.6. Interferences7. Apparatus7.1 FluorescenceSpectrophotometer(orSpectro-fluorometer)An instrument recording in the spectral range of220 nm to at least 600 nm
20、for both excitation and emission responses and capable of meeting the specifications stated in Table 1.7.2 Excitation SourceA high-pressure xenon lamp (a150-W xenon lamp has proven acceptable). Other continuum sources, such as deuterium or high-pressure xenon-mercury, which have sufficient intensity
21、 in the ultraviolet region, could be used as excitation sources.NOTE 4Line 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
22、Fluorescence CellsStandard cells, made from fluorescence-free fused silica with a pathlength of 10 mm anda height of 45 mm.7.4 Recorder or ComputerStrip 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 da
23、ta point per nanometre.7.5 Cell-Filling DeviceDisposable Pasteur capillary pi- pet.7.6 Volumetric FlasksLow-actinic glass, ground-glass stoppered volumetric flasks (100-mL).7.7 Micropipet, 10 to 50-L capacity.7.8 Analytical Balance, with a precision of at least 60.1 mg.7.9 Weighing Pans, 5 to 7-mm d
24、iameter, 18 mm deep, made of aluminum or equivalent.7.10 Test Tubes, disposable 15-mL glass test tubes.TABLE 1 Specifications for Fluorescence SpectrophotometersWavelength ReproducibilityExcitation monochromatorbetter than6 2 nm Emission monochromatorbetter than 62 nm Gratings (Typical Values)Excita
25、tion monochromatorminimum of 600 lines/mm blazed atA6.1 The fluorescence spectrum will be distorted if an oilsample has been contaminated by an appreciable amount, for example, 1 % of common chemical impurities such as other300 nmEmission monochromatorminimum of 600 lines/mm blazed at300 nm or 500 n
26、m ABoils that are fluorescent on excitation at 254 nm.Photomultiplier TubeNOTE 2Storage of samples in improper containers (for example,Either S-20Cor S-5DResponseEplastics) may result in contamination. This interference can be eliminatedby observing proper procedures for collection and preservation
27、of samples. Refer to Practice D 3325.NOTE 3“Spectroquality” cyclohexane may not have a low enough fluorescence solvent blank. Lots vary in the content of fluorescent impurities, which may increase with storage time even if the bottle is unopened.6.2 Oil residues may build up in fluorescence cells pa
28、rticu- larly after prolonged usage with heavy oils. In such a case, follow the procedure using nitric acid for cleaning glassware(10.1.3).ResolutionExcitation monochromatorbetter than 2 nmEmission monchromatorbetter than 2 nmTime Constantnot to exceed one secondA Or designed to have a good efficienc
29、y in this spectral region.B See Practice E 520.C Photomultiplier tubes such as Hamamatsu R-446-UR.D Photomultiplier tubes such as RCA 1P28 or Hamamatsu R-106.E Or equivalent having a good spectral response in the spectral region from 280to 600 nm.2D 3650 93 (1999)7.11 Micropipet, or microsyringe, 9-
30、L capacity; with anaccuracy of 1 % and reproducibility of 0.1 % of pipet capacity.7.12 Micropipet, 200-L capacity with disposable tips; with an accuracy of 1 % and reproducibility of 0.1 % of pipettor capacity.7.13 Solvent Dispenser, adjustable to deliver 10 mL.7.14 Vortex Mixer.8. Reagents and Mate
31、rials8.1 Purity of ReagentsSpectroquality grade reagents should be used in all instances unless otherwise stated. It is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemi- cal Society, where such specifications are available.8
32、8.2 Purity of Water References to water shall be under- stood to mean Type IV reagent water conforming to Specifi- cation D 1193. However, since fluorescent organic impurities in the water may constitute an interference, the purity of the water should be checked by running a water blank using the sa
33、me instrument conditions as for the solvent blank.8.3 Acetone (CH 3COCH3).8.4 Nitric Acid (sp gr 1.42)Concentrated nitric acid(HNO3).8.5 Cyclohexane, spectroquality grade,9 with a fluorescencesolvent blank less than 2 % of the intensity of the major peak of the sample fluorescence generated with the
34、 same instrumen- tal settings over the emission range used. Cyclohexane is dispensed throughout the procedure from a 500-mL TFE- fluorocarbon wash bottle. For prolonged storage, cyclohexane should be stored only in glass. Check the suitability of the solvent by running a solvent blank. The solvent b
35、lank can also be used to check for scatter.NOTE 5Cyclohexane can be reused, if necessary, after one or more distillations in an all-glass still. The distilled cyclohexane must have no detectable fluorescence (2 %) in the 280 to 500-nm region of the spectrum when excited at 254 nm.NOTE 6Methylcyclohe
36、xane can also be used as a solvent, instead of cyclohexane. This is useful, particularly if the solution is needed for low-temperature luminescence measurements as well.8.6 Aluminum Foil.9. Sampling and Sample Preparation9.1 Collect a representative sample as directed in PracticeD 4489.9.2 Preserve
37、samples in containers as specified in Practice D 3325. However, to avoid dewaxing, do not cool samples below 5C.9.3 Preparation of Oil Samples, as described in Practices D 3326. Avoid the use of deasphalting procedures, if possible. Spectroquality cyclohexane is the preferred solvent for sample prep
38、aration for fluorescence.8 “Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi- cal Soc., Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see “Analar Standards for Laboratory Chemicals,” BDH Ltd., Poole, Dorset, U.K., and t
39、he “United States Pharmacopeia.”9 Matheson Coleman/Bell (MC/B Cx2285) cyclohexane has given acceptablesolvent blanks or an equivalent solvent may be used.9.4 Preparation of Solutions for Fluorescence AnalysisEither of the following techniques for diluting the prepared oil sample with cyclohexane may
40、 be used:9.4.1 Weighing TechniqueTo prepare oil solutions at a concentration of approximately 20 g/mL, weigh out 0.0016 60.0001 g of oil (equivalent weight for each sample) onto a clean aluminum weighing pan using a micropipet. Transfer weighed oil sample into a clean 100 mL, low-actinic glass volum
41、etric flask by creasing the aluminum pan and washing the oil directly into the volumetric flask using spectroquality cyclohexane dispensed from a TFE-fluorocarbon wash bottle. Dilute the solution up to volume (100 mL) and shake vigor- ously several times and allow the prepared solution to stand for3
42、0 min and shake again prior to performing the analysis to ensure that all oil dissolves. Occasionally, depending on fluorescence yield of the oil tested and instrumentation used, it may be necessary to use 100 ppm concentration to get adequate fluorescence intensity. In these cases, weigh out 0.0078
43、 60.0001 g of oil and proceed as above.NOTE 7It is preferable that the prepared solution be used the same day. Do not use solutions that have been standing for periods in excess of6 h unless they have been refrigerated. In no case use solutions more than2 days old.9.4.2 Volume TechniqueAllow the pre
44、pared oil sample to come to room temperature and shake until they are homoge- neous. Transfer 9 L of the oil to a 15-mL disposable glass test tube with a micropipet or microsyringe and add 10 mL of spectroquality cyclohexane with a solvent dispenser. Place a cap of aluminum foil over the top of the
45、test tube and vortex for approximately 30 s. With a micropipet, transfer 200 L of this solution to a second 15-mL test tube and then add 10 mL of cyclohexane. Place a cap of aluminum foil over the top of the second test tube and vortex for approximately 30 s. Prepare all samples in this manner.NOTE
46、8If a micropipet with disposable plunger and tips is used, potential cross contamination is avoided. Otherwise, careful cleaning following the procedures specified in 10.1 is required.10. Preparation of Apparatus10.1 Cleaning Glassware:10.1.1 Clean all glassware used in this procedure in the following manner: first rinse vol