1、Designation: D7343 12 (Reapproved 2017)Designation: 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; th
2、e number immediately 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.
3、Scope1.1 This practice 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 theselectio
4、n of storage vessels, 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 petr
5、oleum and petroleum 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 metho
6、ds under the jurisdiction 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 Fluids
7、This practice is applicable to petro-leum and petroleum products with vapor pressures at samplingand storage temperatures less than or equal to 101 kPa(14.7 psi). Use Practice D4057 or IP 475 to sample thesematerials. Refer to Practice D5842 when sampling materialsthat also require Reid vapor pressu
8、re (RVP) determination.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 sampl
9、ing from a primary 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.1
10、.6.1 ExceptionThe values given in parentheses are forinformation only.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
11、 applica-bility of regulatory limitations prior to use.1This practice is under the jurisdiction of ASTM Committee D02 on PetroleumProducts, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-mittee D02.03 on Elemental Analysis.Current edition approved June 1, 2017. Published Jul
12、y 2017. Originally approvedin 2007. Last previous edition approved in 2012 as D7343 12. DOI: 10.1520/D7343-12R17.This practice was jointly prepared by ASTM International and the EnergyInstitute.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United
13、 StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers t
14、o Trade (TBT) Committee.11.8 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organiza
15、tion TechnicalBarriers to Trade (TBT) Committee.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 Pe
16、troleum and PetroleumProducts 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
17、by X-Ray Spec-troscopyD5842 Practice for Sampling and Handling of Fuels forVolatility MeasurementD5854 Practice for Mixing and Handling of Liquid Samplesof Petroleum and Petroleum ProductsD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalM
18、easurement System PerformanceD6334 Test Method for Sulfur in Gasoline by WavelengthDispersive 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
19、Spectrometry (Mathemati-cal Correction Procedure)D6445 Test Method for Sulfur in Gasoline 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 Spectr
20、oscopyD7039 Test Method for Sulfur in Gasoline, Diesel Fuel, JetFuel, Kerosine, Biodiesel, Biodiesel Blends, andGasoline-Ethanol Blends by Monochromatic WavelengthDispersive X-ray Fluorescence SpectrometryD7212 Test Method for Low Sulfur in Automotive Fuels byEnergy-Dispersive X-ray Fluorescence Spe
21、ctrometry Us-ing a Low-Background Proportional CounterD7220 Test Method for Sulfur in Automotive, Heating, andJet Fuels by Monochromatic Energy Dispersive X-rayFluorescence SpectrometryD7751 Test Method for Determination of Additive Elementsin Lubricating Oils by EDXRF AnalysisD7757 Test Method for
22、Silicon in Gasoline and RelatedProducts by Monochromatic Wavelength DispersiveX-ray Fluorescence Spectrometry2.2 Energy Institute Standards:4IP 228 Determination of lead content of gasoline X-rayspectrometric methodIP 336 Determination of sulfur content Energy-dispersiveX-ray fluorescence methodIP 3
23、52 Determination of lead content of automotive gasoline Energy-dispersive X-ray fluorescence spectrometrymethod2For 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 s
24、tandards Document Summary page onthe ASTM website.3The 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 PetroleumP
25、roducts and LubricantsTechnique Analysis 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 43
26、3Sulfur IP 447Sulfur in Automotive Fuels 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 D
27、7757ED-XRF Sulfur in Petroleum Products 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 Sulf
28、ur in Automotive Fuels IP 600TABLE 2 Technically 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 8754Su
29、lfur in Automotive Fuels D7212 IP 531Sulfur 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 12 (2017)2IP407 Determination of barium, calcium, phosphoru
30、s, 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 Wavelengthdispersive X-ray fluorescence spectrometryIP 475 Methods of test for petr
31、oleum 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 fuels Wav
32、elength 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 spectrometry
33、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 WDXRF MethodIP
34、 593 Determination of Pb, Ni, Cr, Cu, Zn, As, Cd, Tl, Sb,Co, Mn, and V in Burner Fuels derived 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 pe
35、troleumand petroleum products are required for the determination ofchemical properties, which 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
36、analysissamples. Good laboratory practices in this area include:4.1.1 Samples received by the 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
37、contami-nate those requiring trace element analysis.4.1.2 All laboratory equipment used specifically 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 re
38、commended.4.1.4 Sample preparation should be carried out in a cleanarea. This area should use 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 tha
39、t the gloves do not contain interferingelements or elements of interest, since they may cause 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
40、sample inplace during analysis. The choice of the sample cell or cup, thematerial in which it 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 samp
41、le types to be measured either in a liquid orpowder form. It is important to check that the cup 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 thefil
42、m is taut with no wrinkles.5.1.1.1 Within XRF spectrometers heat is produced, bothfrom the spectrometer 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 samp
43、le cups specificallydesigned for volatile samples (see 8.3).5.1.1.2 The cup size may be important. 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 smal
44、lestdiameter sample cups should be used. Cups with diameterswell in excess of the area detected 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; ex
45、amples include fuel oils and wax products.The sample cup should be able to withstand the temperatureused in this process. In general, most plastic sample cellsshould withstand temperatures up to 70 C.5.1.2 Sample Cell HolderMany manufacturers recom-mend metal holders to hold sample cups while they a
46、retransferred into the XRF instrument. These holders can bemade from aluminum, stainless steel, 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
47、if thematerial from the holder causes an interference with theanalyte. Generally, this is not a 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
48、XRF instrument manufacturers and accessorysuppliers. It is important to examine the film types 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 p
49、hysical resistance of film to the liquidintend for analysis, andD7343 12 (2017)3(4) Element contaminants contained 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 precision of analysis can beaffected more if thinner films are used. One way to avoid thisis to recalibrate or adjust calibrations using mon
