1、Designation: D7343 12Designation: 558/07Standard Practice forOptimization, Sample Handling, Calibration, and Validationof X-ray Fluorescence Spectrometry Methods for ElementalAnalysis of Petroleum Products and Lubricants1This standard is issued under the fixed designation D7343; the number immediate
2、ly following the designation indicates the 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*1.1 This pra
3、ctice covers information relating to sampling,calibration and validation of X-ray fluorescence instrumentsfor elemental analysis, including all kinds of wavelengthdispersive (WDXRF) and energy dispersive (EDXRF) tech-niques. This practice includes sampling issues such as theselection of storage vess
4、els, transportation, and sub-sampling.Treatment, assembly, and handling of technique-specificsample holders and cups are also included. Technique-specificrequirements during analytical measurement and validation ofmeasurement for the determination of trace elements insamples of petroleum and petrole
5、um products are described.For sample mixing, refer to Practice D5854. Petroleum prod-ucts covered in this practice are considered to be a single phaseand exhibit Newtonian characteristics at the point of sampling.1.2 Applicable Test MethodsThis practice is applicable tothe XRF methods under the juri
6、sdiction of ASTM Subcommit-tee D02.03 on Elemental Analysis, and those under thejurisdiction of the Energy Institutes Test Method Standardiza-tion Committee (Table 1). Some of these methods are techni-cally equivalent though they may differ in details (Table 2).1.3 Applicable FluidsThis practice is
7、applicable to petro-leum and petroleum products with vapor pressures at samplingand storage temperatures less than or equal to 101 kPa (14.7psi). Use Practice D4057 or IP 475 to sample these materials.Refer to Practice D5842 when sampling materials that alsorequire Reid vapor pressure (RVP) determin
8、ation.1.4 Non-applicable FluidsPetroleum products whose va-por pressure at sampling and sample storage conditions areabove 101 kPa (14.7 psi) and liquefied gases (that is, LNG,LPG, etc.) are not covered by this practice.1.5 Sampling MethodsThe physical sampling and meth-ods of sampling from a primar
9、y source are not covered by thisguide. It is assumed that samples covered by this practice area representative sample of the primary source liquid. Refer toPractice D4057 or IP 475 for detailed sampling procedures.1.6 The values stated in SI units are to be regarded as thestandard. The values given
10、in parentheses are for informationonly.1.7 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 regulatory l
11、imitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D2622 Test Method for Sulfur in Petroleum Products byWavelength Dispersive X-ray Fluorescence SpectrometryD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4294 Test Method for Sulfur in Petroleum and PetroleumPro
12、ducts by Energy Dispersive X-ray Fluorescence Spec-trometryD4927 Test Methods for Elemental Analysis of Lubricantand Additive ComponentsBarium, Calcium,Phosphorus, Sulfur, and Zinc by Wavelength-DispersiveX-Ray Fluorescence SpectroscopyD5059 Test Methods for Lead in Gasoline by X-Ray Spec-troscopyD5
13、842 Practice for Sampling and Handling of Fuels forVolatility Measurement1This practice is under the jurisdiction of ASTM Committee D02 on PetroleumProducts and Lubricants and is the direct responsibility of Subcommittee D02.03 onElemental Analysis.Current edition approved Dec. 1, 2012. Published De
14、cember 2012. Originallyapproved in 2007. Last previous edition approved in 2007 as D734307. DOI:10.1520/D7343-07.This practice was jointly prepared by ASTM International and the EnergyInstitute.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at s
15、erviceastm.org. For Annual Book 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. Un
16、ited States1D5854 Practice for Mixing and Handling of Liquid Samplesof Petroleum and Petroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6334 Test Method for Sulfur in Gasoline by WavelengthDi
17、spersive X-Ray FluorescenceD6443 Test Method for Determination of Calcium, Chlorine,Copper, Magnesium, Phosphorus, Sulfur, and Zinc inUnused Lubricating Oils and Additives by WavelengthDispersive X-ray Fluorescence Spectrometry (Mathemati-cal Correction Procedure)D6445 Test Method for Sulfur in Gaso
18、line by Energy-Dispersive X-ray Fluorescence Spectrometry (Withdrawn2009)3D6481 Test Method for Determination of Phosphorus,Sulfur, Calcium, and Zinc in Lubrication Oils by EnergyDispersive X-ray Fluorescence SpectroscopyD7039 Test Method for Sulfur in Gasoline and Diesel Fuelby Monochromatic Wavele
19、ngth Dispersive X-ray Fluores-cence SpectrometryD7212 Test Method for Low Sulfur in Automotive Fuels byEnergy-Dispersive X-ray Fluorescence Spectrometry Us-ing a Low-Background Proportional CounterD7220 Test Method for Sulfur in Automotive, Heating, andJet Fuels by Monochromatic Energy Dispersive X-
20、rayFluorescence SpectrometryD7751 Test Method for Determination of Additive Elementsin Lubricating Oils by EDXRF AnalysisD7757 Test Method for Silicon in Gasoline and RelatedProducts by Monochromatic Wavelength DispersiveX-ray Fluorescence Spectrometry2.2 Energy Institute Standards:4IP 228 Determina
21、tion of lead content of gasoline X-rayspectrometric methodIP 336 Determination of sulfur content Energy-dispersiveX-ray fluorescence methodIP 352 Determination of lead content of automotivegasoline- Energy-dispersive X-ray fluorescence spectrom-etry methodIP407 Determination of barium, calcium, phos
22、phorus, sulfurand zinc by wavelength dispersive X-ray fluorescencespectrometryIP 433 Determination of vanadium and nickel content Wavelength dispersive X-ray fluorescence spectrometryIP 447 Determination of sulfur content - Wavelength dis-persive X-ray fluorescence spectrometryIP 475 Methods of test
23、 for petroleum and its productsIP 489 Determination of low lead contents in gasolines -Wavelength dispersive X-ray fluorescence spectrometryIP 496 Determination of sulfur content of automotive fuels Energy-dispersive X-ray fluorescence spectrometryIP 497 Determination of sulfur content of automotive
24、 fuels -Wavelength dispersive X-ray fluorescence spectrometryIP 503 Determination of chlorine and bromine content -Wavelength dispersive X-ray fluorescence spectrometryIP 531 Determination of sulfur content of automotive fuels Low-background proportional counter energy-dispersiveX-ray fluorescence s
25、pectrometry methodIP 532 Determination of the sulfur content of automotivefuels Polarized X-ray fluorescence spectrometryIP 553 Ethanol as a Blending Component for Petrol Determination of Sulfur Content WDXRF MethodIP 560 Determination of Silicon, Chromium, nickel, Iron,and Copper in Used Greases WD
26、XRF Method3The last approved version of this historical standard is referenced onwww.astm.org.4Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,U.K., http:/www.energyinst.org.uk.TABLE 1 XRF Standard Test Methods for Analysis of PetroleumProducts and LubricantsTechnique Analysis
27、 ASTM EIWD-XRF Sulfur in Petroleum Products D2622Additive Elements in LubricatingOils and AdditivesD4927 IP 407Lead in Gasoline D5059 IP 228Lead in Gasoline IP 489Sulfur in Gasoline D6334Additive Elements in Lube Oils andAdditivesD6443Vanadium and Nickel IP 433Sulfur IP 447Sulfur in Automotive Fuels
28、 IP 497Chlorine and Bromine IP 503Sulfur in Ethanol as BlendingAgentIP 553Si, Cr, Ni, Fe, and Cu in UsedGreasesIP 560Several Metals in Burner FuelsDerived from Waste Mineral OilsIP 593MWD-XRF Sulfur in Gasoline and Diesel D7039Silicon in Gasoline and Naphtha D7757ED-XRF Sulfur in Petroleum Products
29、D4294 IP 336Sulfur in Gasoline D6445Additive Elements in LubricatingOilsD6481Sulfur in Automotive Fuels D7212 IP 531Sulfur in Automotive Fuels D7220 IP 532Additive Elements in LubricatingOilsD7751Lead in Gasoline IP 352Sulfur in Automotive Fuels IP 496Low Sulfur in Automotive Fuels IP 600TABLE 2 Tec
30、hnically Equivalent XRF Test Methods for PetroleumProducts and LubricantsAAnalysis ASTM EI OtherSulfur by WD-XRF D2622 DIN 51400T6;JIS K3541Additive Elements by WE-XRFD4927 IP 407 DIN 51391T2Lead in Gasoline D5059 IP 228Sulfur by ED-XRF D4294 IP 336 ISO 8754Sulfur in Automotive Fuels D7212 IP 531Sul
31、fur in Automotive Fuels D7220 IP 532ANadkarni, R. A., Guide to ASTM Test Methods for the Analysis of PetroleumProducts and Lubricants, 2nd edition, ASTM International, West Conshohocken,PA, 2007.D7343 122IP 593 Determination of Pb, Ni, Cr, Cu, Zn, As, Cd, Tl, Sb,Co, Mn, and V in Burner Fuels derived
32、 from WasteMineral Oils WDXRF MethodIP 600 Petroleum Products Determination of Low SulfurContent of Automotive Fuels EDXRF Spectrometry3. Significance and Use3.1 Accurate elemental analyses of samples of petroleumand petroleum products are required for the determination ofchemical properties, which
33、are in turn used to establishcompliance with commercial and regulatory specifications.4. Sample Handling4.1 It is necessary to use precautions to minimize thepossibility of contamination of trace elemental analysissamples. Good laboratory practices in this area include:4.1.1 Samples received by the
34、laboratory and required fortrace element analysis should be stored in a designated specificlocation for storage while awaiting analysis. This area, when-ever possible, should not contain samples that could contami-nate those requiring trace element analysis.4.1.2 All laboratory equipment used specif
35、ically for traceelement analysis should be free of any source of contamina-tion. This may require that specific equipment be used only fortrace element analysis.4.1.3 Analyses of blank samples are highly recommended.4.1.4 Sample preparation should be carried out in a cleanarea. This area should use
36、surfaces that can be decontaminatedeasily if a spillage occurs.4.1.5 Operators should wear clean, fresh, protective glovesfor sample preparation for trace element analysis. Tests shouldbe run to confirm that the gloves do not contain interferingelements or elements of interest, since they may cause
37、con-tamination. The development of clean area sample handlingprotocols is encouraged.5. Sample Preparation5.1 Choice of Sample CarrierXRF testing requires asample cell and a support film to hold the liquid sample inplace during analysis. The choice of the sample cell or cup, thematerial in which it
38、is held, and the type of support film usedcan all influence the result.5.1.1 Sample CellThe most common cell is a plastic cup,of which various designs are available. These designs allow fora variety of sample types to be measured either in a liquid orpowder form. It is important to check that the cu
39、p type used isbest suited for the compositions of samples to be analyzed.Liquid sample cups usually have a seal that ensures the film issealed to a level above that of the liquid in the cell and that thefilm is taut with no wrinkles.5.1.1.1 Within XRF spectrometers heat is produced, bothfrom the spe
40、ctrometer components themselves and from theinteraction of X-rays with the sample. Petroleum products thatare not stable due to volatility should only be placed intovented sample cups or special sealed sample cups specificallydesigned for volatile samples (see 8.3).5.1.1.2 The cup size may be import
41、ant. Depending on thefilm type used to support the liquid, different films will sag dueto the weight of sample and relax due to chemical interaction,or heat, or both. To reduce this sagging effect, the smallestdiameter sample cups should be used. Cups with diameterswell in excess of the area detecte
42、d by the spectrometer arelikely to increase errors due to sagging.5.1.1.3 A number of petroleum products require heating toensure homogenization prior to analysis or to enable transfer tothe sample cell; examples include fuel oils and wax products.The sample cup should be able to withstand the tempe
43、ratureused in this process. In general, most plastic sample cellsshould withstand temperatures up to 70C.5.1.2 Sample Cell HolderMany manufacturers recom-mend metal holders to hold sample cups while they aretransferred into the XRF instrument. These holders can bemade from aluminum, stainless steel,
44、 or other materials. It isimportant to recognize that these represent a potential spectralcontamination to the analysis either if the spectrometer is todetermine an analyte that the holder is made from or if thematerial from the holder causes an interference with theanalyte. Generally, this is not a
45、 problem for elements withatomic number 30 itis advisable to check the potential contamination from thesample cup holder using a blank.5.1.3 Sample Support FilmsMany support films are avail-able from both XRF instrument manufacturers and accessorysuppliers. It is important to examine the film types
46、specified inany method being used. There are four criteria that should beconsidered when selecting a X-ray transmission sample sup-port film:(1) Thickness of film,(2) Composition of film,(3) Chemical and physical resistance of film to the liquidintend for analysis, and(4) Element contaminants contai
47、ned within the film.5.1.3.1 Film thickness typically ranges from 2 to6formost applications. Consideration should be given to the varia-tions in thickness from batch to batch of films. For thinnerfilms, the relative variance in film thickness is often higher thanthat of the thicker films, thus precis
48、ion of analysis can beaffected more if thinner films are used. One way to avoid thisis to recalibrate or adjust calibrations using monitors each timea new batch of film is used.5.1.3.2 Film types are composed of different polymer ma-terials. Those containing oxygen or nitrogen will absorb lighterele
49、ments more than those that do not. Examples of oxygen andnitrogen containing polymers are polyester and polyamide. Forthe determination of elements lighter than sulfur, these filmsshould be avoided in favor of polymers containing only carbonand hydrogen, provided that the film is not attacked by thesample.5.1.3.3 Chemical resistance is often a compromise with filmtype. Often, the best resistance is offered by polymers contain-ing oxygen or nitrogen. Physical aspects such as temperaturewill also be an issue especially if hot liquids are to bemeasured.
