1、Designation: D7845 13D7845 16Standard Test Method forDetermination of Chemical Species in Marine Fuel Oil byMultidimensional Gas Chromatography MassChromatography/Mass Spectrometry1This standard is issued under the fixed designation D7845; the number immediately following the designation indicates t
2、he year oforiginal adoption or, in the case of revision, 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. Scope Scope*1.1 This test method covers the quantitative d
3、etermination of a variety of chemical species in marine fuel oil (bunker fuel oil)by gas chromatography mass chromatography/mass spectrometry. By using the same conditions and by selecting required massspectral selected ions, the test method may be used for the determination of other species than th
4、ose for which precision statementsand limits of detection have been established.1.2 An example list of chemical species for which a limit of quantification has been determined by means of this test methodis given in Table 1.1.3 Other refinery hydrocarbon fractions and their mixtures may be tested us
5、ing the same test method conditions. However, theprecision of this test method reflects the compounds in Table 1.1 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.04.0M on Mass Spe
6、ctroscopy.Current edition approved April 1, 2013April 1, 2016. Published May 2013April 2016. Originally approved in 2013. Last previous edition approved in 2013 as D7845 13.DOI: 10.1520/D7845-13.10.1520/D7845-16.TABLE 1 Component TableLimit of Quantitationmg/kgn-butyl alcohol 10Cyclohexanol 10n-buty
7、l ether 10n-butyl acylate 10n-butyl acrylate 10Styrene 10alpha-pinene 10Phenol 20alpha-methyl styrene 10beta-pinene 104-methyl styrene 10trans-B-methyl styrene 103-methyl styrene 102-methyl styrene 10Dicyclopentadiene 10Limonene 10Indene 201-phenyl ethanol 20para, alpha-Dimethyl styrene 202,5 dimeth
8、yl styrene 202,4 dimethyl styrene 202-phenyl ethanol (phenylethanol) 202-Ethyl Phenol 502,4 Dimethyl Phenol 204-Ethyl Phenol (co elutes with 3-ethylphenol) 202-Phenoxy-1-propanol 502-Phenoxy ethanol 504-isopropylphenol 501-Phenoxy-2-Propanol 20Styrene Glycol 50This document is not an ASTM standard a
9、nd is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only
10、 the current versionof the standard as published by ASTM is to be considered the official document.*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 States11.4 Results are report
11、ed to the nearest 1.0 1.0 mgmg/kg.kg.1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the
12、 user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards2 For referencedASTM standards,
13、visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.D7845 162D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techn
14、iques to Evaluate Analytical Measure-ment System Performance2.2 Other Standards:ISO 8217:2010 Petroleum ProductsFuels (Class F)Specifications of Marine Fuels33. Terminology3.1 Definitions:3.1.1 direct or open split interface, nany GC/MS interface used to maintain atmospheric pressure at capillary co
15、lumn outlet.3.1.2 reconstructed ion chromatogram (RIC), na limited mass chromatogram representing the intensities of ion massspectrometric currents for only those ions having particular mass to charge ratios used in this test method to selectively extract andidentify components in the presence of a
16、complex hydrocarbon matrix.3.1.3 total ion chromatogram (TIC), nmass spectrometer computer output representing either the summed intensities of allscanned ion currents or a sample of the current in the ion beam for each spectrum scan plotted against the corresponding spectrumnumber.3.1.4 wall coated
17、 open tubular (WCOT), na type of capillary column prepared by coating or bonding the inside wall of thecapillary with a thin film of stationary phase.4. Summary of Test Method4.1 A suitable internal standard, ethylbenzene d-10 is added to the sample, which is then introduced into a gas chromatograph
18、equipped with two columns configured with a Deans switching system between the two columns. The sample first passes throughthe polydimethylsiloxane (WCOT) pre-column which then performs a separation of the light hydrocarbon fraction and eliminatesthe high boiling hydrocarbon fraction to vent.The com
19、pounds of interest and internal standard are transferred to the high resolutionpolydimethylsiloxane (WCOT) analytical column for chromatographic separation. An auxiliary carrier gas is used to elute higherboiling hydrocarbons from the pre-column in back flush mode in order to prepare for the next an
20、alysis cycle. The resultingchromatogram is then processed by mass spectral analysis based on selected or extracted ion monitoring.5. Significance and Use5.1 The test method allows the quantitation of chemical species at low levels in marine fuel oils and cutter stocks.Agreat manytypes and concentrat
21、ions of chemical species are found in marine fuel oils.Aroot cause relationship between the presence of suchspecies or their concentration in fuels and any failure modes allegedly induced by the use of these fuels has not been established.This test method is necessary to establish test conditions re
22、quired for future ISO 8217:2010 Petroleum products- Fuels (classF)-Specifications of marine fuel oils as defined in section 5.5 and Annex B item (d). Additional compounds may be determinedby using the same conditions and by selecting required mass spectral selected ions, accordingly.6. Apparatus6.1
23、Gas Chromatography:6.1.1 Gas ChromatographAny gas chromatograph equipped with a flame ionization detector (FID) and having sensitivity of0.010.01 mg mg/kg. kg. The gas chromatograph must be capable of linear temperature control from 5050 C to 320C320 C forthe capillary column oven. The gas chromatog
24、raph must be capable of controlling multiple valve events. Carrier gas flowcontrollers and or electronic pressure control modules shall be capable of precise control where the required flow rates are low.Pressure control devices and gauges shall be capable of precise control for the typical pressure
25、s required. The temperature programrate must repeat to within 0.1C0.1 C and provide retention time repeatability of 0.05 min 0.05 min throughout the temperatureprogram.6.1.2 Pre-Column ColumnWCOT Column, 25 m 25 m long by 0.53-mm0.53 mm inside diameter fused silica WCOT columnwith a 1.0-micron1.0 mi
26、cron film thickness of polydimethyl siloxane or any column with suitable chromatographic resolution.6.1.3 Analytical ColumnWCOT Column, 100 m 100 m by 0.25-mm0.25 mm inside diameter fused silica WCOT column witha 0.5-micron0.5 micron film thickness of polydimethyl siloxane or any column with suitabl
27、e chromatographic resolution.6.1.4 Purged Packed InjectorAn injection port that allows controlled injection of the sample at a temperature sufficient to passthe high boiling point fraction to the pre-column or any gas chromatographic injector system to perform the same function.6.1.4.1 The injection
28、 port liner shall be replaced to remove non-volatile materials.6.1.5 Electronic Pressure ControlElectronic pneumatic control of carrier gas flows. It can be flow or pressure programmedto speed up elution of components.6.1.6 Low-Volume Connector and TeesA special union or tee for connecting two lengt
29、hs of tubing 1.6-mm1.6 mm insidediameter and smaller; sometimes referred to as a zero dead-volume union, tee, or an active splitting device.3 Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http:/www.ansi.org.D7845 1636.1.7 Pre-ColumnA poly
30、dimethylsiloxane WCOT column used to isolate the light hydrocarbons to include methane ton-hexadecane from the higher boiling portion of the sample for transfer to the analytical column for further separation andquantification.6.1.8 Deans Switching Backflush Configuration4 (Fig. 1)A column backflush
31、 configuration utilizing dynamic pressuredifferential which provides suitable means to remove the heavier hydrocarbon fraction from the pre-column or any similarconfiguration that allows for controlled chromatographic separation of components of interest and heavier hydrocarbon fraction.An alternati
32、ve Deans switching backflush configuration is shown on Fig. 2.6.2 Mass Spectrometry:6.2.1 Mass Spectrometer, capable of producing electron ionization spectra at 70 electron volts or higher, and capable of scanningthe range of the specified quantitation masses or (m/e). The mass scan range shall cove
33、r the masses of interest for quantitation andshould yield at least 5 scans across the peak width at half peak width for a 11 mgkg to 3 mg/kg ethylbenzene d10 peak and coverthe masses of interest for quantitation. A scan range set for specific ions is defined in Table 2.6.2.1.1 The mass spectrometer
34、shall be capable of being interfaced to a gas chromatograph and WCOT columns. The interfaceshall be at a high enough temperature to prevent condensation of components boiling up to 350C.350 C. Usually, 20C20 Cabove the final column temperature is adequate. Direct column interface to the mass spectro
35、meter may be used. An open splitinterface with computer controlled programmable flow controller(s) may also be used, to maintain all components within thelinearity of the mass spectrometer and at the same time maintain detectability of lower concentration chemical components.6.2.1.2 Acquistion mode
36、selected ion monitoring (SIM) extracted ion mode or full scan mode using the quantitative andqualitative ions referenced in Table 2. Additional compounds may be added by selecting and collecting data in full scan mode.6.2.1.3 Tuning shall be performed for low mass resolution using perfluorotributyla
37、mine mass fragment ions at m/z 69, 131, and219 amu. The mass spectrometer is tuned either automatically or manually for optimum performance.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemicals should be used in all tests. Unless otherwise indicated, it is intended that allreagents
38、conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where suchspecifications are available.5 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purityto permit its use without lessening the accuracy o
39、f the determination.7.2 Carrier GasHelium and hydrogen have been used successfully. The recommended minimum purity of the carrier gas usedis 99.999 mol %. Additional purification using commercially available scrubbing reagents may be necessary to remove traceoxygen, which may deteriorate the perform
40、ance of the GC WCOT.7.3 Calibration StandardThis standard shall be prepared by adding the chemicals to include those in Table 1 prepared fromhigh (99+ %) purity reagent grade materials.7.4 Standards for Calibration and IdentificationChemical compounds used to prepare standards should be 99 % or grea
41、terpurity (see Table 1). If reagents of high purity are not available, an accurate assay of the reagent shall be performed using a properlycalibrated GC or other techniques. The concentration of the impurities that overlap the other calibration components shall beknown and used to correct the concen
42、tration of the calibration components. The use of only high purity reagents is strongly4 Deans, DavidD. R., Chromatographia, Vol 1, 18-22, 1968.5 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not lis
43、ted bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.FIG. 1 Deans Switching Backflush, Configuration AD7845 164recommended
44、 because of the error that may be introduced from impurity corrections. Standards are used for calibration as wellas for establishing the identification by retention time in conjunction with mass spectral match.7.5 n-hexadecane99+ % purity or better.7.6 Dilution SolventsReagent grade toluene, 99.9 %
45、 (or suitable dilution solvent).7.7 Internal StandardsDeuterated analog of ethylbenzene, as specified, shall be used as internal standard because of thesimilar chromatographic characteristics as the components analyzed.8. Preparation of Apparatus8.1 AssemblyConfigure the GC system in a multidimensio
46、nal configuration as described in Table 3 and Table 4. Connect theWCOT columns to the chromatographic system, including the multidimensional switching device, using low volume connectorsFIG. 2 Deans Switching Backflush, Configuration BTABLE 2 Mass Spectrometer Compound Quantitation Ions (Retention T
47、ime Data Based on Configuration A)RetentionTimeCompound CAS # Quantifying Qualifier 1 Qualifier 2 Qualifier 321.55 Ethylbenzene-d10 25837-05-2 116 11513.55 n-butyl alcohol 71-36-3 56 7422.58 Cyclohexanol 108-93-0 82 100 4422.61 n-butyl ether 142-96-1 87 101 13022.78 n-butyl acylate 141-32-2 55 128 7
48、322.78 n-butyl acrylate 141-32-2 55 128 7323.23 Styrene 100-42-5 10426.03 alpha-pinene 80-56-8 93 136 12126.66 Phenol 108-95-2 94 6627.79 alpha-methyl styrene 98-83-9 118 10328.21 beta-pinene 19902-08-0 93 136 12128.46 4-methyl styrene 622-97-9 117 118 116 10328.57 trans-B-methyl styrene 873-66-5 11
49、7 118 103 7728.66 3-methyl styrene 100-80-1 117 118 116 10329.95 2-methyl styrene 611-15-4 117 118 103 7730.11 Dicyclopentadiene 77-73-6 66 13230.43 Limonene 5989-27-5 68 93 136 12131.11 Indene 95-13-6 116 115 63 8931.16 1-phenyl ethanol 98-85-1 107 122 7932.93 para, alpha-Dimethyl styrene 1195-32-0 132 117 10233.29 2,5 dimethyl styrene 2039-89-6 132 117 7733.47 2,4 dimethyl styrene 2234-20-0 132 117 7733.57 2-phenyl ethanol (phenylethanol) 60-12-8 122 103 7734.05 2-Ethyl Phenol 90-00-6 107 122 7734.55 2,4 Dimethyl Phenol 105-67-9 122 107
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