1、Designation: D 3326 07Standard Practice forPreparation of Samples for Identification of WaterborneOils1This standard is issued under the fixed designation D 3326; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last rev
2、ision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice covers the preparation for analysis ofwaterborne oils recovered from water. The identification isbased upon the
3、 comparison of physical and chemical charac-teristics of the waterborne oils with oils from suspect sources.These oils may be of petroleum or vegetable/animal origin, orboth. Seven procedures are given as follows:SectionsProcedure A (for samples of more than 50-mL volumecontaining significant quanti
4、ties of hydrocarbonswith boiling points above 280C) 8 to 12Procedure B (for samples containing significant quantities ofhydrocarbons with boiling points above 280C) 13 to 17Procedure C (for waterborne oils containing significantamounts of components boiling below 280C andto mixtures of these and hig
5、her boiling components) 18 to 22Procedure D (for samples containing both petroleum andvegetable/animal derived oils) 23 to 27Procedure E (for samples of light crudes and medium distillatefuels) 28 to 34Procedure F (for thin films of oil-on-water) 35 to 39Procedure G (for oil-soaked samples) 40 to 44
6、1.2 Procedures for the analytical examination of the water-borne oil samples are described in Practice D 3415, D 3328,D 3414, and D 3650. Refer to the individual oil identificationtest methods for the sample preparation method of choice. Thedeasphalting effects of the sample preparation method shoul
7、dbe considered in selecting the best methods.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regula
8、tory limitations prior to use. Specific cautionstatements are given in Sections 6 and 32.2. Referenced Documents2.1 ASTM Standards:2D95 Test Method for Water in Petroleum Products andBituminous Materials by DistillationD 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 3325
9、Practice for Preservation of Waterborne OilSamplesD 3328 Test Methods for Comparison of Waterborne Petro-leum Oils by Gas ChromatographyD 3414 Test Method for Comparison of Waterborne Petro-leum Oils by Infrared SpectroscopyD 3415 Practice for Identification of Waterborne OilsD 3650 Test Method for
10、Comparison of Waterborne Petro-leum Oils By Fluorescence AnalysisD 4489 Practices for Sampling of Waterborne OilsE1 Specification for ASTM Liquid-in-Glass ThermometersE 133 Specification for Distillation Equipment3. Terminology3.1 DefinitionsFor definitions of terms used in this prac-tice, refer to
11、Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 animal/vegetable-derived oilsa mixture made ofmono-, di-, and triglyceride esters of fatty acids and othersubstances of animal or vegetable origin, or both.3.2.2 Simulated weathering of waterborne oils by distilla-tion consi
12、ders only the effect of evaporation, which likely isthe most significant short-term weathering effect in the envi-ronment.3.2.3 Simulated weathering of waterborne oils by evapora-tion under ultraviolet light simulates the loss of light compo-nents on weathering, as well as some oxidative weathering.
13、1This practice is under the jurisdiction of ASTM Committee D19 on Water andis the direct responsibility of Subcommittee D19.06 on Methods for Analysis forOrganic Substances in Water.Current edition approved Aug. 1, 2007. Published August 2007. Originallyapproved in 1974. Last previous edition approv
14、ed in 2002 as D 3326 90 (2002).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International,
15、 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4. Significance and Use4.1 Identification of a recovered oil is determined by com-parison with known oils selected because of their possiblerelationship to the particular recovered oil, for example,suspected or ques
16、tioned sources. Thus, samples of such knownoils must be collected and submitted along with the unknownfor analysis. It is unlikely that identification of the sources ofan unknown oil by itself can be made without direct matching,that is, solely with a library of analyses.5. Reagents and Materials5.1
17、 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee onAnalytical Reagents of theAmerican Chemical Society.3Special ancillary procedures such as fluorescence may require
18、higher purity grades of solvents. Other grades may be usedprovided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.5.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean
19、 reagent water that meetsthe purity specifications of Type I or Type II water, as specifiedin Specification D 1193.6. Caution6.1 Solvents used in this practice are volatile, flammable, ormay cause the harm to the health of the user. Specifically,benzene is a known carcinogen, while chloroform and ca
20、rbontetrachloride are suspected carcinogens. Consequently, it isimportant that extractions and separations utilizing these sub-stances must be carried out in a laboratory hood with aminimum linear face velocity of 38 to 45 m/min (125 to 150ft/min) located in a regulated area posted with signs bearin
21、g thelegends: NO SMOKING or (if appropriate) DANGER-CHEMICAL CARCINOGEN-AUTHORIZED PERSONNELONLY, or both.7. Sampling7.1 Collect representative samples in accordance with Prac-tices D 4489.7.2 Preserve the waterborne oil samples in accordance withPractice D 3325.7.3 The portion of the sample used mu
22、st be representative ofthe total sample. If the material is liquid, thoroughly stir thesample as received, warming if necessary to ensure uniformity.PROCEDURE ALARGE SAMPLES8. Scope8.1 This procedure covers the preparation for analysis ofsamples in which the volumes of waterborne oil in theenvironme
23、ntal and suspect source samples equal or exceed 50mLand in which the oil portion contains significant amounts ofhydrocarbons with boiling points above 280C.NOTE 1The boiling point may be ascertained by injecting the neatsamples into the gas chromatograph and checking the elution times abovethat of p
24、entadecane on a nonpolar column.8.2 The preparation of samples containing mostly hydrocar-bons of boiling points below 280C, such as petroleumdistillate fuels, is beyond the scope of this procedure (seeProcedure C or E).9. Summary of Procedure9.1 A neat portion of the waterborne oil is retained. If
25、notpossible to obtain a neat portion, then retain a portion of thewaterborne oil as received. This is to be used in those analysesperformed on samples containing significant quantities ofhydrocarbons with boiling points below 280C. Preparation ofthese samples is beyond the scope of this procedure, b
26、ut arecovered in Procedure C.NOTE 2Waterborne oil samples containing significant quantities ofhydrocarbons with boiling points below 280C (see Note 1), such asgasoline and kerosene, can usually be obtained as neat samples withoutany sample preparation.9.2 The waterborne oil sample is dissolved in an
27、 equalvolume of chloroform or dichloromethane and centrifuged toremove the free water, solids, and debris. The water layer, ifpresent, is separated from the organic layer. Other debris, ifpresent, is removed by filtration through glass wool.NOTE 3The use of spectrograde cyclohexane is required for t
28、heextraction of samples to be analyzed by fluorescence spectrometry by TestMethod D 3650. Separation of water may be accomplished by centrifu-gation or dying, or both, with anhydrous sodium sulfate.9.3 When centrifugation will not separate the water from thechloroform solution of the sample, it is r
29、efluxed with anaromatic or petroleum distillate solvent in accordance withTestMethod D95.NOTE 4Pressure filtration has also been found useful for breakingemulsions.9.4 Aportion of the solvent/sample solution is retained. Thesolvent may be removed by evaporation. This portion of thesample may be used
30、 in the preliminary gas chromatographicanalysis, Test Methods D 3328 (Test Method A), and otheranalyses in which the results are unaffected by weathering.9.5 The remainder of the solvent/sample solution is distilledusing nitrogen purge to a liquid temperature of 280C toremove the solvent and simulat
31、e weathering conditions asnearly as possible. The distillate may be discarded or saved forcharacterization by gas chromatography (Test MethodsD 3328). This simulated weathering treatment is necessary tobring the unweathered suspect samples and the waterborne oilsample to as nearly comparable physica
32、l condition for subse-quent analysis as possible. Analyses requiring the use of thistreated residue include elemental analysis; gas chromato-graphic analysis (Test Methods D 3328, Test Methods A andB); an infrared procedure (Test Method D 3414); a fluores-cence test method (Test Method D 3650); and
33、any applicabletest method or practice described in Practice D 3415.3Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemic
34、als, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D 3326 072NOTE 5The distillate might yield useful information but is discardedin this practice.10. Apparatus10.1 Centrifuge, capable of whirling two
35、or more filled100-mL centrifuge tubes at a speed that is controlled to give arelative centrifugal force (rcf) between 500 and 800 at the tipof the tubes.10.2 Centrifuge Tubes, cone shaped, 100 mL.10.3 Distillation Apparatus for Water Determination,asspecified in Test Method D95.10.4 Distillation App
36、aratus for Simulated Weathering,asdescribed in Specification E 133 except fitted with nitrogen-stripping tubulation as illustrated in Fig. 1.10.5 Distillation Flask, 200 mL, as described in Specifica-tion E 133.10.6 Thermometer, ASTM high distillation, having a rangefrom 2 to + 400C and conforming t
37、o the requirements forthermometer 8C as prescribed in Specification E1.10.7 Flowmeter, to regulate flow of nitrogen to distillationflask. It should be calibrated and graduated for the range 10 to15 mL/min.11. Reagents and Materials11.1 Filter Paper, medium retention, medium fast speed,prewashed with
38、 solvent used.11.2 Glass Wool, prewashed with solvent used.11.3 SolventChloroform (stabilized with ethanol) ordichloromethane is used for dissolution of the waterborne oilsamples. If water is to be removed by distillation, an aromatic,petroleum distillate, or volatile spirits solvent is required ass
39、pecified in Test Method D95. The safety precautions associ-ated with the use of the solvent selected should be consideredbefore it is used (see Note 3).12. Procedure12.1 Retention of Neat Samples:12.1.1 Decant or siphon off a portion of the neat waterborneoil if possible.12.1.2 If not possible to ob
40、tain a neat sample, retain aportion of the original oil.12.2 Removal of Water, Sediment, and Debris:12.2.1 Transfer about 50 mL of original waterborne oil to a100-mL centrifuge tube. Add about 50 mL of chloroform ordichloromethane to the tube and mix thoroughly. For waxysamples, use chloroform. Warm
41、 solutions to 50C to preventprecipitation (see Note 3).12.2.1.1 Centrifuge the mixture at 500 to 800 rcf (relativecentrifugal force) for 10 min to separate free water and solids.For waxy samples, use chloroform. Warm solutions to 50C toprevent precipitation (see Note 3).12.2.1.2 Withdraw the water l
42、ayer if present. Decant thechloroform or dichloromethane solution to a sample bottle.Filter through a glass wool plug, if necessary, to afford a cleanseparation.12.2.2 Process those samples from which water cannot beseparated by centrifugation by Test Method D95distillationprocedure. Filter the dry
43、solution through medium retentionfilter paper. Rinse filter paper with solvent to remove oil. Forwaxy samples, use chloroform and keep filter funnel andcontents at 50C during filtration (see Note 3).12.2.3 Starting at 12.1, treat all reference or suspect samplesin an identical fashion. If it is appa
44、rent that the reference orsuspect samples contain less than 1 % water and sediment,centrifugation may be eliminated and the reference or suspectsamples should be diluted with an equal volume of chloroformor dichloromethane before proceeding.12.3 Removal of Solvent and Simulated Weathering:12.3.1 Tra
45、nsfer approximately 100 mL of the solution to achemically clean 200-mL flask. Assemble apparatus so theASTM high distillation thermometer (8C) and nitrogen strip-ping tubulation are about 6 mm from the bottom of the flask.Direct flow away from thermometer bulb to prevent localcooling of thermometer
46、(see Fig. 1).12.3.2 Perform distillation using a nitrogen flow of 10 to 15mL/min. Terminate distillation at a liquid temperature of280C. Shut off the nitrogen flow when the temperature of theliquid in the distillation flask cools below 175C. Pour the hotresidue into a suitable container.12.3.3 Treat
47、 all reference and suspect oils in the samemanner as the waterborne oil samples. Repeat 12.2.1-12.3.2.PROCEDURE BLIMITED SAMPLE VOLUMES OFHEAVY OILS13. Scope13.1 This procedure covers the preparation for analysis ofwaterborne oil samples of petroleum derived origin in whichFIG. 1 Adaptation of ASTM
48、Distillation Flask for ToppingChloroform Solutions of Oil to Simulate WeatheringD 3326 073the volumes equal or are less than 1 mL. An aliquot of largeroil samples may also be used.13.2 The procedure is applicable to oils containing signifi-cant amounts of hydrocarbons boiling above 280C.13.3 The pre
49、paration of samples containing lower boilinghydrocarbon is beyond the scope of this procedure, but iscovered by Procedures C and E.14. Summary of Procedure14.1 The sample is dissolved in pentane or hexane, and thewater and insolubles are removed by centrifugation. Theorganic solvent phase is dried with anhydrous magnesiumsulfate, filtered, and the volatile components and solvents areremoved by evaporation under a nitrogen stream (see Note 3).15. Apparatus15.1 Centrifuge, see 10.1.15.2 Centrifuge Tubes, see 10.2.15.3 Flow Control on Nitrogen Cylinder, to
