1、Designation: D 3328 06Standard Test Methods forComparison of Waterborne Petroleum Oils by GasChromatography1This standard is issued under the fixed designation D 3328; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of las
2、t 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. Scope1.1 This test method covers the comparison of petroleumoils recovered from water or beaches with oils from suspectsources by
3、 means of gas chromatography (1, 2, 3).2Such oilsinclude distillate fuel, lubricating oil, and crude oil. The testmethod described is for capillary column analyses using eithersingle detection (flame ionization) or dual detection (flameionization and flame photometric) for sulfur containing spe-cies
4、.1.2 This test method provides high resolution for criticalexamination of fine structure that is resistant to weathering.The flame-photometric detection for sulfur components is anadjunct, not a substitute, for flame-ionization detection in theidentification of waterborne petroleum oils (4-12). For
5、thisreason, flame photometric detection is optional.1.3 This standard does not purport to address the safetyconcerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety andhealth practices and determine the applicability of regulator
6、ylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D 1129 Terminology Relating to WaterD 1193 Specification for Reagent WaterD 2549 Test Method for Separation of Representative Aro-matics and Nonaromatics Fractions of High-Boiling Oilsby Elution ChromatographyD 3325 Practice for Pr
7、eservation of Waterborne OilSamplesD 3326 Practice for Preparation of Samples for Identifica-tion of Waterborne OilsD 3415 Practice for Identification of Waterborne OilsD 4489 Practices for Sampling of Waterborne OilsD 5739 Practice for Oil Spill Source Identification by GasChromatography and Positi
8、ve Ion Electron Impact LowResolution Mass SpectrometryE 355 Practice for Gas Chromatography Terms and Rela-tionships3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Practice D 3415, Terminology D 1129, andPractice E 355.4. Significance and Use4.1 Identification
9、 of a recovered oil is determined by com-parison with known oils, selected because of their possiblerelationship to the particular recovered oil. The known oils arecollected from suspected sources. Samples of such known oilsmust be collected and submitted along with the unknown foranalysis.At presen
10、t, identification of the source of an unknownoil by itself cannot be made (for example, from a library ofknown oils).4.2 The use of a flame-photometric detector in addition tothe flame-ionization detector provides a second, independentprofile of the same oil, that is, significantly more information
11、isavailable from a single analysis with dual detection.4.3 Many close similarities (within uncertainties of sam-pling and analysis) will be needed to establish identity beyonda reasonable doubt. The analyses described will distinguishmany, but not all samples. For cases in which this method doesnot
12、clearly identify a pair of samples, and for important caseswhere additional comparisons are needed to strengthen con-clusions, other analyses will be required (refer to PracticeD 3415). In particular, Practice D 5739 is useful for such cases.5. Interferences5.1 Compounds that have the same retention
13、 time as petro-leum hydrocarbons will interfere in the comparison of theunknown with known oils. This is particularly true if animal fat1These test methods are under the jurisdiction of ASTM Committee D19 onWater and are the direct responsibility of Subcommittee D19.06 on Methods forAnalysis for Org
14、anic Substances in Water.Current edition approved Aug. 15, 2006. Published August 2006. Originallyapproved in 1974. Last previous edition approved in 2000 as D 3328 00.2The boldface numbers in parentheses refer to the references at the end of thesetest methods.3For referenced ASTM standards, visit t
15、he 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, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
16、 United States.or vegetable oil, naturally occurring hydrocarbons, or spill-treatment chemicals are present in relatively large amounts.Independent analysis, for example, infrared spectroscopy, willestablish the presence of these contaminants if their presence issuspected.Animal or vegetable oils ca
17、n be removed effectivelyby Test Method D 2549 or by Practices D 3326 (Method D).NOTE 1Test Method D 2549 will also remove the aromatic fraction.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated it is intended thatall reagents
18、 shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Soci-ety.46.2 Unless otherwise indicated references to water shall beunderstood to mean reagent water that meets the purityspecifications of Type I or Type II water presented in Specifi-cation D 11
19、93.6.3 AirFor use with the flame-ionization and flame-photometric detectors; may be obtained using a laboratory pureair generator, or from a zero grade tank supply.6.4 Carrier Gas High-purity grade helium is used ascarrier gas.6.5 Cyclohexane High-purity (HPLC-grade). For samplepreparation and for u
20、se in reference standards.6.6 HydrogenFor use with the flame-ionization andflame-photometric detectors; may be obtained using a hydro-gen generator, or from a prepurified grade tank supply.6.7 Methylene ChlorideFor use in reference standards andglassware cleaning.6.8 Normal Alkane StandardsNormal al
21、kanes, decanethrough hexatriacontane, for use as reference compounds.6.9 ThiopheneFor use in optimization of flame-photometric detector.7. Reference Standards7.1 Normal Paraffnic HydrocarbonsPrepared mixtures ofapproximately decane to hexatriacontane, or selected indi-vidual normal paraffins, are ru
22、n under normal analysis condi-tions to determine retention times of compounds.7.2 Resolution MixtureEqual mixtures of n-heptadecane,n-octadecane, pristane and phytane in solution. See Annex A1for details (A1.2.1).8. Sampling8.1 Collect a representative sample in accordance withPractice D 4489.8.2 If
23、 the sample is not to be analyzed within 1 week, itshould be preserved in accordance with Practice D 3325because of the possibility of bacterial decomposition of normalparaffins in the sample.8.3 The sample should be prepared for analysis in accor-dance with Practices D 3326, because of the great va
24、riety ofmaterials and circumstances associated with collecting petro-leum oils from the environment. For heavier oils, a procedureto deasphalt the oil may be necessary.9. Summary of Test Method9.1 This test method uses a gas chromatographic capillarycolumn system for the separation of petroleum hydr
25、ocarbons.The effluent of the column may be detected with a flame-ionization detector, or it may be split (1 + 2) between a flameionization and a flame-photometric detector. The flame photo-metric detector is equipped with a narrow bandpass interfer-ence filter for spectral isolation of the sulfur em
26、ission at 394nm. The relative peak size of each component (as indicated byretention time) of recovered oil is compared visually with therelative peak size of each component (of like retention time) ofthe suspected source.NOTE 2This duel detector method is based on the early work done byKahn (13), Ga
27、rza (4), and Adlard (7).9.2 In this test method, elution of characteristic hydrocar-bons occurs generally in order of increasing boiling point.10. Apparatus10.1 Chromatographic ColumnFused silica capillary col-umn with bonded phase SE-30 or equivalent, 30 m by 0.32 mminside diameter (0.1 m film thic
28、kness).NOTE 3Other columns, providing equivalent or better resolution maybe substituted (seeAnnexA1), but the analysis time will be increased withlonger columns.10.2 Gas ChromatographA commercial or custom de-signed gas chromatograph with heated injection and detectorzones and a column oven capable
29、of being programmed from75C to at least 325C for heavier oils (higher boiling thangasolines, jet fuels, etc.).10.2.1 For light distillate fuels, the chromatograph must becapable of programming from 50C and also be capable ofmaintaining isothermal control at 50C.10.2.2 Carrier Gas Pressure Regulator
30、is substituted pres-sure regulator for the mass flow controllers to give moreprecise rates in the low flow ranges (1 to 5 mL/mm).10.2.3 Injection Port The use of glass injector inserts thatcan be replaced or cleaned frequently, or both, will prolong theuseful life of the column (3).10.2.4 DetectorsA
31、 hydrogen-flame ionization detector isalways used for analyses. A flame-photometric detector with a394 nm bandpass filter is used for dual detection (9, 10, 11, 12).10.2.5 Carrier Gas Makeup is required at the effluent of thecolumn with a temperature independent mass flow controller.10.2.6 Effluent
32、SplitterAn effluent splitter with a splitratio of 1 + 2 (FID/FPD) is required for dual detection.10.2.7 Bleeder for Reference CompoundA device forin-line bleed of a reference compound (thiophene and cyclo-hexane) into the carrier flow for detector optimization isrequired, when using a flame-photomet
33、ric detector.10.2.8 Recorder, or an integrator or computer data handlingsystem capable of acquiring data at a rate compatible with thehigh resolution of the capillary column. Alternatively, a strip-chart recorder is required to measure detector response at4“Reagent Chemicals, American Chemical Socie
34、ty Specifications,” Am. Chemi-cal Soc., Washington, DC. For suggestions on the testing of reagents not listed bytheAmerican Chemical Society, see “Reagent Chemicals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc., New York, NY, and the “United StatesPharmacopeia.”D 3328 062full-scale range
35、 of 1 mV with a response time of 1 s (or less).A second recorder, or dual-pen recorder, is required for dualdetection10.3 SyringeA microsyringe of 0.5 to 1 L capacity.10.4 Gas TrapsAny commerically available gas filtertraps to be placed in line to remove trace hydrocarbon andwater impurities from th
36、e helium, hydrogen, nitrogen, and airgas supplies.10.5 FPD Linearizer Optional accessory to facilitatecomparison of FPD chromatograms.10.6 Glass Insert, packed with glass wool (optional).NOTE 4For instruments that can use this instrument, splitless injec-tion of an oil in cyclohexane solution simpli
37、fies the analysis by eliminat-ing the need to deasphalt most oil samples.11. Preparation of Chromatograph11.1 Install the column in the chromatograph, as describedin the manufacturers instructions.11.2 Shut off the downstream end of the system andpressurize the carrier gas supply to a gage pressure
38、of approxi-mately 15 psi (103 kPa) above the operating pressure. Shut offthe cylinder valve and observe the pressure gage. Consider thesystem tight if no pressure drop is noted in 10 to 15 min. Usea small amount of aqueous soap solution to locate minor leaks.Do not use the soap solution near the ion
39、ization detector.11.3 Column Conditioning for New Columns:NOTE 5For previously conditioned columns, proceed to 11.3.4.11.3.1 During conditioning, disconnect the column at thedetector end to avoid deposition of volatiles on the detector(s).11.3.2 For new columns, follow the manufacturers instruc-tion
40、s for column conditioning.11.3.3 Adjust the carrier gas flow as indicated in Table 1.11.3.4 Adjust the hydrogen and air flow, and the air/hydrogen flow ratio to the detector(s), as specified for theinstrument being used. Ignite the flame(s) (see 11.4 foroptimization).11.3.5 Adjust the carrier gas fl
41、ow as indicated in Table 1.11.3.6 Program the column temperature as indicated inTable 1, and hold at the maximum temperature while monitor-ing the effluent. If there are no peaks in the chromatogram andthere is minimal baseline shift at high temperatures, then thecolumn is ready for use; otherwise,
42、recondition it.11.3.7 Return the oven temperature to 75C.11.3.8 If the column is to be moved or stored, disconnectand seal the ends of the column. When the column is to bereused, even after conditioning, it is always necessary to cyclethrough the temperature program to remove any accumulatedvolatile
43、s.11.4 Optimization of DetectorsAdjust hydrogen and airflows to give optimal detector responses for a given signalprovided by the reference compound bleeder (10.2.7). Usecyclohexane for FID optimization and thiophene for the FDPoptimization.12. Operating Conditions for Analysis (Notes 6-8)NOTE 6One
44、of the problems frequently encountered with the flamephotometric detector is “flameout” when large amounts of solvent areinjected with the sample. The recommended sample preparation procedureavoids this problem at the same time that it permits the use of smallsamples. For those who may encounter thi
45、s problem, a simple modifica-tion has been suggested (8) which consists of reversing the hydrogen gasand air/oxygen gas inlets to the detector.NOTE 7For oil identification under the recommended procedure, airhas been found satisfactory for combustion for the FPD, that is, oxygen isnot necessary.NOTE
46、 8See the manufacturers manual for maintenance informationfor the FPD. Present flame photometric units should not be heated above250C, unless the photometer is removed from the heated zone by fiberoptics.12.1 Operating conditions are summarized in Table 1;apparatus operated under these conditions sh
47、ould achievepartial resolution of two pairs of normal and isoprenoidhydrocarbons found in many, but not all, crude oils and certainTABLE 1 Operating Conditions for Chromatographic Columns (11, 12, 13)Column 30mby0.32mmIDby0.1mfilmthickness,fused capillaryPacking bonded phase SE-30, or equivalentCarr
48、ier gas:Flow, mL/min:heliumColumnMakeup gas1to240Temperature, C:Injection portColumn:250Heavier oils:Initial 60 hold 4 minFinal 280 (FID) 250 (FID/FPD) hold 30 minLighter oils:Initial 40 hold 10 minFinal 280 hold 10 minDetector 300 (FID) 250 (FID/FPD)Program Rate, C/minA38AChart speed, in/min (mm/mi
49、n) 2.5 (10)Sensitivity, mV 1Sample size, LA1.0 (cyclohexane solution)Effluent split ration (FPD procedures) 1 + 2 (FID/FPD)AThe precise rate is dictated by the design of the gas chromatograph.D 3328 063petroleum products. In order of emergence from the column,these are heptadecane and pristane, and octadecane and phy-tane.12.1.1 Periodically analyze the resolution mixture to test thecolumn performance, monitor the instrument performance andthermally equilibrate the system (see Annex A1 for details).After system maintenance, new column i
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