1、Designation: D8110 17Standard Test Method forElemental Analysis of Distillate Products by InductivelyCoupled Plasma Mass Spectrometry (ICP-MS)1This standard is issued under the fixed designation D8110; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、 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.INTRODUCTIONCertain elements present in distillate petroleum can either adversely or constructively
3、 affect theperformance of the product and thus impacts its utility and market value.The industry has traditionallyrelied on inductively coupled plasma atomic emission spectrometry (ICP-AES) or atomic absorptionspectrometry (AAS) to determine the concentration of these elements present in the product
4、. Asspecifications have become more stringent, a need to extend these measurements to lowerconcentrations by employing more sensitive measurement technologies has arisen. Inductivelycoupled plasma mass spectrometry is ideal for this application for most distillate petroleum products.By applying ICP-
5、MS for elemental analysis of these products, the concentration range of detectableelements can be extended from low to sub ng/g (ppb mass) to 1000 ng/g (ppb mass) for someelements.1. Scope1.1 This test method describes the procedure for the deter-mination of trace elements in light and middle distil
6、latepetroleum products using inductively coupled plasma massspectrometry (ICP-MS).1.2 This test method should be used by analysts experiencedin the use of inductively coupled plasma mass spectrometry(ICP-MS) with knowledge of interpretation of spectral,isobaric, polyatomic, and matrix interferences,
7、 as well asprocedures for their correction or reduction.1.3 The table in 6.1 lists elements for which the test methodapplies along with recommended isotope. Actual workingdetection limits are sample dependent and, as the samplematrix varies, these detection limits may also vary.1.4 The concentration
8、 range of this test method is typicallyfrom low to sub ng/g (ppb mass) to 1000 ng/g (ppb mass),however the precision and bias statement is specified for asmaller concentration range based on test samples analyzed inthe ILS, see the table in Section 18. The test method may beused for concentrations o
9、utside of this range; however, theprecision statements may not be applicable.1.4.1 This test method shall be further developed to extendthat table to include additional elements.1.5 This test method uses metallo-organic standards (orga-nometallic or organosoluble metal complex) for calibration anddo
10、es not purport to quantitatively determine insoluble particu-lates. Analytical results are particle size dependent, and lowresults are obtained for particles larger than a few micrometersas these particles may settle out in the sample container and arenot effectively transported through the sample i
11、ntroductionsystem.1.6 Elements present at concentrations above the upper limitof the calibration curves can be determined with additional,appropriate dilutions and with no degradation of precision.1.7 The values stated in SI units are to be regarded asstandard. No other units of measurement are incl
12、uded in thisstandard.1.8 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 limitations prior t
13、o use. Specific warningstatements are given in 8.2, 8.7, and Section 9.1.9 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
14、-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edit
15、ion approved May 1, 2017. Published May 2017. DOI: 10.1520/D8110-17.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization e
16、stablished in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.12. Referenced Documents2.1 ASTM Standards:2D3605 Test Method for Trace Metals in Gas Turbine Fuelsby
17、Atomic Absorption and Flame Emission SpectroscopyD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4175 Terminology Relating to Petroleum Products, LiquidFuels, and LubricantsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD4306 Practice for Aviation Fuel
18、Sample Containers forTests Affected by Trace ContaminationD4307 Practice for Preparation of Liquid Blends for Use asAnalytical StandardsD4628 Test Method for Analysis of Barium, Calcium,Magnesium, and Zinc in Unused Lubricating Oils byAtomic Absorption SpectrometryD4927 Test Methods for Elemental An
19、alysis of Lubricantand Additive ComponentsBarium, Calcium,Phosphorus, Sulfur, and Zinc by Wavelength-DispersiveX-Ray Fluorescence SpectroscopyD4951 Test Method for Determination ofAdditive Elementsin Lubricating Oils by Inductively Coupled PlasmaAtomic Emission SpectrometryD5185 Test Method for Mult
20、ielement Determination ofUsed and Unused Lubricating Oils and Base Oils byInductively Coupled Plasma Atomic Emission Spectrom-etry (ICP-AES)D6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6300 Practice for
21、Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD6443 Test Method for Determination of Calcium, Chlorine,Copper, Magnesium, Phosphorus, Sulfur, and Zinc inUnused Lubricating Oils and Additives by WavelengthDispersive X-ray Fluorescence Spectrometry
22、 (Mathemati-cal Correction Procedure)D6732 Test Method for Determination of Copper in JetFuels by Graphite Furnace Atomic Absorption Spectrom-etryD6792 Practice for Quality System in Petroleum Productsand Lubricants Testing LaboratoriesD7111 Test Method for Determination of Trace Elements inMiddle D
23、istillate Fuels by Inductively Coupled PlasmaAtomic Emission Spectrometry (ICP-AES)D7220 Test Method for Sulfur in Automotive, Heating, andJet Fuels by Monochromatic Energy Dispersive X-rayFluorescence SpectrometryD7343 Practice for Optimization, Sample Handling,Calibration, and Validation of X-ray
24、Fluorescence Spec-trometry Methods for Elemental Analysis of PetroleumProducts and LubricantsD7778 Guide for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Terminology3.1 DefinitionsFor definitions of other terms used in thistest method, refer to Terminology D4175.3
25、.2 Definitions of Terms Specific to This Standard:3.2.1 analyte, nan element whose concentration is beingdetermined. D51853.2.2 calibration, nthe determination of the values of thesignificant parameters by comparison with values indicated bya set of reference standards. D71113.2.3 calibration curve,
26、 nthe graphical or mathematicalrepresentation of a relationship between the assigned (known)values of standards and the measured responses from themeasurement system. D71113.2.4 calibration blank, na volume of solvent containingthe same matrix as the calibration standards (see Section 12).3.2.5 cali
27、bration standard, na standard having an ac-cepted value (reference value) for use in calibrating a measure-ment instrument or system (see Section 12). D71113.2.6 calibration stock solution, na solution preparedfrom the stock standard(s) or solution(s) to verify the instru-ment response with respect
28、to analyte concentration.3.2.7 concentric nebulizer, na device that generates anaerosol by flowing a liquid through a central capillary con-tained within a concentric tube through which gas flows at ahigh velocity.3.2.8 inductively-coupled plasma (ICP), na high-temperature discharge generated by flo
29、wing an ionizable gasthrough a magnetic field induced by a radio frequency coilsurrounding the tubes that carry the gas. D71113.2.9 inductively coupled plasma mass spectrometry (ICP-MS), nan analytical technique that that utilizes ICP togenerate elemental ions that are then separated and quantitated
30、by mass spectrometry.3.2.10 internal standard, nchemical standard having anaccepted value (and added to the fuel test specimen andcalibration standard) to determine the emission intensity ratioof an element to the internal standard. D71113.2.10.1 DiscussionThis is used to measure the relativeinstrum
31、ent response to the other analytes that are componentsof the same solution. The internal standards must be analytesthat are not a sample component.3.2.11 linear response range, nthe elemental concentra-tion range over which the calibration curve is a straight line,within the precision of the test me
32、thod. D51853.2.12 mass spectrometry, nthe analytical process of sepa-rating and determining ions according to their mass-to-chargeratio.3.2.13 method detection limit (MDL), nthe minimumconcentration of an analyte that can be identified, measuredand reported with 99 % confidence that the analyte conc
33、entra-tion is greater than background noise.2For 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 standards Document Summary page onthe ASTM website.D8110 1723.2.13.1
34、 DiscussionThis confidence level is determinedfrom analysis of a sample in a given matrix containing theanalyte(s).3.2.14 method of standard additions, na techniquewhereby a known amount of the analyte is added to a portionof the sample and measured along with the sample as received;extrapolation of
35、 the measurements allows the concentration ofthe analyte in the original sample to be calculated.3.2.15 m/z, nmass to charge ratio, the measured signal foran ion determined by mass spectrometry; the charge is typi-cally 1, so that the m/z = the mass.3.2.16 quality control reference solution (QCS), n
36、a solu-tion with the certified concentration(s) of the analytes (areference source that is a secondary source to the calibrationstandards is preferred) and used for a verification of theinstruments calibration.3.2.17 radio frequency (RF), nthe range of frequenciesbetween 3 kHz and 300 GHz. D71113.2.
37、18 reagent blank, na volume of solvent containing thesame matrix as the samples.4. Summary of Test Method4.1 This test method describes the multi-element determi-nation of trace elements by inductively coupled plasma massspectrometry (ICP-MS). Sample material in solution is intro-duced by pneumatic
38、nebulization into a radio frequency plasmawhere energy transfer processes cause desolvation,atomization, and ionization. The ions are extracted from theplasma through a differentially pumped vacuum interface andseparated on the basis of their mass-to-charge ratio (m/z) by amass spectrometer. The ion
39、s transmitted through the massselector are detected by a dynode electron multiplier assemblyand the ion information processed by a data handling system.Interferences relating to the technique must be recognized anda correction factor applied or the interferences must be reducedthrough the use of col
40、lision/reaction cell technology or alter-natively through mass spectrometers utilizing high resolutionor MS/MS modes of operation (see Section 6 on interferences).Such corrections must include compensation for isobaricelemental interferences and interferences from polyatomic ionsderived from the pla
41、sma gas, reagents, sample matrix, peristal-tic pump tubing, sample introduction system, cones, etc.Internal standardization or the method of standard additionsmust be used to correct for instrumental drift as well assuppressions or enhancements of instrument response causedby the sample matrix.4.2 A
42、 weighed portion (approximately 1 g is typical) of athoroughly homogenized light or middle distillate petroleumsample is diluted, by mass with o-xylene, or other suitablesolvent (10 to 100 is typical) to bring the sample analyteswithin the measurement range or when necessary or desired.Standards are
43、 prepared in the same manner. Internal Standardssuch as those listed in 8.6 may be added to the solutions and themethod of standard addition may be used to compensate forvariations in test specimen introduction efficiency and elementionization efficiency in the plasma. In choosing an internalstandar
44、d, one should consider purity (freedom from analyte),sensitivity/isotope abundance, interferences (polyatomic andisobaric), quadrupole mass bias, ionization energies (that is,internal standard versus analyte), soluble/compatible with thesample matrix and coexistent species, and so forth. Thesolution
45、s are introduced to the ICP-MS instrument using aperistaltic pump equipped with appropriate solvent resistanttubing, syringe pump, or alternatively by self-aspiration. Bycomparing measured m/z peak intensities of elements in thetest specimen with m/z peak intensities measured with thestandards, the
46、concentrations of elements in the test specimencan be calculated.5. Significance and Use5.1 Petroleum products may contain elements either in traceconcentrations (for example, ng/g (ppb mass) or in minor tomajor levels (ppm to mass %). These elements might becharacteristic of the crude petroleum or
47、might originate fromspecific inclusions of additives for beneficial effect in therefined product. Often, such additives have product specifica-tions which control the quality of a product in commerce.Hence, it is important to determine these elements as accu-rately as possible. Other elements presen
48、t at trace levels maybe harmful to combustion engines causing wear or reducedperformance, may cause poisoning of catalysts, or may be ofenvironmental concern as combustion emissions. ICP-MSinstrumentation is well-suited for determining these elementsand is particularly useful for the determination o
49、f the tracelevel elements that may not be readily achieved by othertechniques.5.2 Various elemental analytical techniques such as atomicabsorption spectrometry (AAS), for example, Test MethodD3605 and D4628; inductively coupled plasma atomic emis-sion spectrometry (ICP-AES), for example, Test MethodsD7111, D4951, and D5185; X-ray fluorescence (XRF), forexample, Practice D7343, Test Method D7220, Test MethodsD4927, and Test Method D6443; or graphite furnace atomicabsorption spectrometry (GFAAS), for example, Test MethodD6732 are used for this purpose. This tes
