1、Designation: D3328 06 (Reapproved 2013)Standard Test Methods forComparison of Waterborne Petroleum Oils by GasChromatography1This standard is issued under the fixed designation D3328; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision,
2、 the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () 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 su
3、spectsources by 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 cont
4、aining spe-cies.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 oi
5、ls (4-12). For 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 applicabili
6、ty of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2549 Test Method for Separation of Representative Aro-matics and Nonaromatics Fractions of High-Boiling Oilsby Elution ChromatographyD3325 Prac
7、tice for Preservation of Waterborne Oil SamplesD3326 Practice for Preparation of Samples for Identificationof Waterborne OilsD3415 Practice for Identification of Waterborne OilsD4489 Practices for Sampling of Waterborne OilsD5739 Practice for Oil Spill Source Identification by GasChromatography and
8、Positive Ion Electron Impact LowResolution Mass SpectrometryE355 Practice for Gas Chromatography Terms and Relation-ships3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Practice D3415, Terminology D1129, andPractice E355.4. Significance and Use4.1 Identificati
9、on 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 pres
10、ent, 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 informatio
11、n 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 doesno
12、t clearly identify a pair of samples, and for important caseswhere additional comparisons are needed to strengthenconclusions, other analyses will be required (refer to PracticeD3415). In particular, Practice D5739 is useful for such cases.5. Interferences5.1 Compounds that have the same retention t
13、ime as petro-leum hydrocarbons will interfere in the comparison of theunknown with known oils. This is particularly true if animal fator vegetable oil, naturally occurring hydrocarbons, or spill-treatment chemicals are present in relatively large amounts.Independent analysis, for example, infrared s
14、pectroscopy, will1These test methods are under the jurisdiction of ASTM Committee D19 onWaterand are the direct responsibility of Subcommittee D19.06 on Methods forAnalysis for Organic Substances in Water.Current edition approved Feb. 15, 2013. Published March 2013. Originallyapproved in 1974. Last
15、previous edition approved in 2006 as D3328 06. DOI:10.1520/D3328-06R13.2The boldface numbers in parentheses refer to the references at the end of thesetest methods.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Boo
16、k of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1establish the pres
17、ence of these contaminants if their presence issuspected.Animal or vegetable oils can be removed effectivelyby Test Method D2549 or by Practices D3326 (Method D).NOTE 1Test Method D2549 will also remove the aromatic fraction.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shal
18、l beused in all tests. Unless otherwise indicated it is intended thatall reagents 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
19、 purityspecifications of Type I or Type II water presented in Specifi-cation D1193.6.3 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 GasHigh-purity grade helium is used ascarrie
20、r gas.6.5 CyclohexaneHigh-purity (HPLC-grade). For samplepreparation and for use in reference standards.6.6 HydrogenFor use with the flame-ionization and flame-photometric detectors; may be obtained using a hydrogengenerator, or from a prepurified grade tank supply.6.7 Methylene ChlorideFor use in r
21、eference standards andglassware cleaning.6.8 Normal Alkane StandardsNormal alkanes, 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 ofapproximatel
22、y decane to hexatriacontane, or selected indi-vidual normal paraffins, are run 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. Samplin
23、g8.1 Collect a representative sample in accordance withPractice D4489.8.2 If the sample is not to be analyzed within 1 week, itshould be preserved in accordance with Practice D3325 be-cause of the possibility of bacterial decomposition of normalparaffins in the sample.8.3 The sample should be prepar
24、ed for analysis in accor-dance with Practices D3326, because of the great variety 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
25、 chromatographic capillarycolumn system for the separation of petroleum hydrocarbons.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
26、narrow bandpass interfer-ence filter for spectral isolation of the sulfur emission 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.NOT
27、E 2This duel detector method is based on the early work done byKahn (13), Garza (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 bonde
28、d phase SE-30 or equivalent, 30 m by 0.32 mminside diameter (0.1 m film thickness).NOTE 3Other columns, providing equivalent or better resolution maybe substituted (see AnnexA1), but the analysis time will be increased withlonger columns.10.2 Gas ChromatographA commercial or custom de-signed gas chr
29、omatograph with heated injection and detectorzones and a column oven capable 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 o
30、fmaintaining isothermal control at 50C.10.2.2 Carrier Gas Pressure Regulator 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 PortThe use of glass injector inserts thatcan be replaced or cleaned frequent
31、ly, or both, will prolong theuseful life of the column (3).10.2.4 DetectorsA 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 th
32、ecolumn with a temperature independent mass flow controller.10.2.6 Effluent SplitterAn effluent splitter with a split ratioof 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 ca
33、rrier flow for detector optimization isrequired, when using a flame-photometric detector.10.2.8 Recorder, or an integrator or computer data handlingsystem capable of acquiring data at a rate compatible with the4“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-cal Soc., Washin
34、gton, 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.”D3328 06 (2013)2high resolution of the capillary column. Alternatively,
35、a strip-chart recorder is required to measure detector response atfull-scale range 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 filter
36、traps to be placed in line to remove trace hydrocarbon andwater impurities from the helium, hydrogen, nitrogen, and airgas supplies.10.5 FPD LinearizerOptional accessory to facilitate com-parison of FPD chromatograms.10.6 Glass Insert, packed with glass wool (optional).NOTE 4For instruments that can
37、 use this instrument, splitless injectionof an oil in cyclohexane solution simplifies the analysis by eliminating theneed 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 downst
38、ream end of the system andpressurize the carrier gas supply to a gage pressure 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 aqueou
39、s soap solution to locate minor leaks.Do not use the soap solution near the ionization 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 o
40、n the detector(s).11.3.2 For new columns, follow the manufacturers instruc-tions 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.
41、Ignite the flame(s) (see 11.4 foroptimization).11.3.5 Adjust the carrier gas flow 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 ba
42、seline shift at high temperatures, then thecolumn is ready for use; otherwise, 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 nece
43、ssary to cyclethrough the temperature program to remove any accumulatedvolatiles.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
44、the FDPoptimization.12. Operating Conditions for Analysis (Notes 6-8)NOTE 6One 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 sam
45、e time that it permits the use of smallsamples. For those who may encounter this 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 foun
46、d satisfactory for combustion for the FPD, that is, oxygen isnot necessary.NOTE 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.TABLE 1 Operating
47、 Conditions for Chromatographic Columns (11, 12, 13)Column 30mby0.32mmIDby0.1mfilmthickness,fused capillaryPacking bonded phase SE-30, or equivalentCarrier gas:Flow, mL/min:heliumColumnMakeup gas1to240Temperature, C:Injection portColumn:250Heavier oils:Initial 60 hold 4 minFinal 280 (FID) 250 (FID/F
48、PD) 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/min) 2.5 (10)Sensitivity, mV 1Sample size, LA1.0 (cyclohexane solution)Effluent split ration (FPD procedures) 1 + 2 (FID/FPD)AThe precise rate is dict
49、ated by the design of the gas chromatograph.D3328 06 (2013)312.1 Operating conditions are summarized in Table 1;apparatus operated under these conditions should achievepartial resolution of two pairs of normal and isoprenoidhydrocarbons found in many, but not all, crude oils and certainpetroleum 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 eq
