1、Designation: D7111 14D7111 15Standard Test Method forDetermination of Trace Elements in Middle Distillate Fuelsby Inductively Coupled Plasma Atomic EmissionSpectrometry (ICP-AES)1This standard is issued under the fixed designation D7111; the number immediately following the designation indicates the
2、 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 test method covers the determination of selec
3、ted elements in middle distillate fuels by inductively coupled plasmaatomic emission spectrometry (ICP-AES). The specific elements are listed in Table 1. The concentration range of this test methodis approximately 0.10.1 mgkg to 2.0 mg/kg. The test method may be used for concentrations outside of th
4、is range; however, theprecision statements may not be applicable. Middle distillate fuels covered in this test method have all distillation fractionscontained within the boiling range of 150150 C to 390C.390 C. This includes, but is not limited to, diesel fuels and aviationturbine fuels.1.2 This tes
5、t method is not intended to analyze insoluble particulates. However, very small particulate matter (smaller than amicrometre) will be carried into the plasma and be included in the quantitative analysis.1.3 This test method may give a result that is higher than the true value if an analyte is presen
6、t in the sample in a form whichis sufficiently volatile. For example, hexamethyldisiloxane will generate a biased high result for silicon.1.4 The values stated in SI units are to be regarded as standard.1 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid F
7、uels, and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved May 1, 2014April 1, 2015. Published July 2014May 2015. Originally approved in 2005. Last previous edition approved in 20112014 asD7111 11.D7111 14. DOI: 10.1520/D7111-14.10.1520
8、/D7111-15.TABLE 1 Elements and Recommended WavelengthsElement Wavelengths, nmAluminum 308.215, 396.153Barium 455.403, 493.408Calcium 393.366Chromium 267.716, 283.563Cobalt 228.615, 236.375, 238.892Copper 324.752Iron 259.939Lithium 670.784Lead 220.353, 224.688, 283.306Magnesium 279.553Manganese 257.6
9、10Molybdenum 202.030, 204.597, 281.616Nickel 221.648, 341.476Phosphorus 177.495, 178.287,185.944, 214.914, 213.618Palladium 340.458, 342.124Platinum 214.423Potassium 766.490Sodium 588.995Silicon 251.611Silver 328.068Strontium 407.771Tin 283.999, 189.991Titanium 334.940Vanadium 310.230Zinc 213.857Thi
10、s document is not an ASTM standard and 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 editio
11、ns as appropriate. In all cases only 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.
12、United States11.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2.
13、Referenced Documents2.1 ASTM Standards:2D2880 Specification for Gas Turbine Fuel OilsD3605 Test Method for Trace Metals in Gas Turbine Fuels by Atomic Absorption and Flame Emission SpectroscopyD4057 Practice for Manual Sampling of Petroleum and Petroleum ProductsD4306 Practice for Aviation Fuel Samp
14、le Containers for Tests Affected by Trace ContaminationD5185 Test Method for Multielement Determination of Used and Unused Lubricating Oils and Base Oils by InductivelyCoupled Plasma Atomic Emission Spectrometry (ICP-AES)D6299 Practice for Applying Statistical Quality Assurance and Control Charting
15、Techniques to Evaluate Analytical Measure-ment System PerformanceD6792 Practice for Quality System in Petroleum Products and Lubricants Testing LaboratoriesD7260 Practice for Optimization, Calibration, and Validation of Inductively Coupled Plasma-Atomic Emission Spectrometry(ICP-AES) for Elemental A
16、nalysis of Petroleum Products and Lubricants2.2 Military Standard:MIL-F-16884MMIL-DTL-16884 Military Specification, Fuel, Naval Distillate33. Terminology3.1 Definitions:3.1.1 calibration, nthe determination of the values of the significant parameters by comparison with values indicated by a setof re
17、ference standards.3.1.2 calibration curve, nthe graphical or mathematical representation of a relationship between the assigned (known) valuesof standards and the measured responses from the measurement system.3.1.3 calibration standard, na standard having an accepted value (reference value) for use
18、 in calibrating a measurementinstrument or system.3.1.4 detection limit, na stated limiting value that designates the lowest concentration that can be determined with confidenceand that is specific to the analytical procedure used.3.1.5 emission spectroscopy, nmeasurement of the energy spectrum emit
19、ted by or from an object under some form of energeticstimulation; for example, light or electrical discharge.3.1.6 inductively coupled plasma, na high temperature discharge generated by passing an ionizable gas through a magneticfield induced by a radio frequency coil surrounding the tubes that carr
20、y the gas.3.1.7 radio frequency, nthe range of frequencies between 3 kHz and 300 GHz.3.1.8 standard, na physical or chemical reference used as a basis for comparison or calibration.3.2 Definitions of Terms Specific to This Standard:3.2.1 detection limit, nthe lowest concentration value for an elemen
21、t that can be determined by ICP analysis and that iscalculated by multiplying three times the standard deviation of ten repetitive element analyses of the blank solution.3.2.2 internal standard, na chemical standard having an accepted value (and added to the fuel test specimen and calibrationstandar
22、d) to determine the emission intensity ratio of an element to the internal standard.4. Summary of Test Method4.1 Calibration standards are prepared by mixing organometallic standard materials in kerosine. An internal standard materialis added to the calibration standards and fuel samples. The calibr
23、ation standards and the fuel samples are aspirated into theICP-AES instrument. The concentrations of the elements in the fuel are calculated by comparing emission intensity ratios of thefuel and calibration standards to the internal standard.4.2 Consult Practice D7260 regrading the optimum operation
24、 of any ICP-AES system.5. Significance and Use5.1 Trace elemental analysis is used to indicate the level of contamination of middle distillate fuels. Trace metals in turbine fuelscan cause corrosion and deposition on turbine components at elevated temperatures. Some diesel fuels have specification l
25、imit2 For referencedASTM standards, 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.3 Naval Sea Systems Command (NAVSEA), SEA03R42, 1333 Isaa
26、c Hull Ave., SE, Washington, DC 20376.Available online at http:/quicksearch.dla.mil orhttp:/D7111 152requirements for trace metals to guard against engine deposits. Trace level copper in middle distillate aviation turbine fuel cansignificantly accelerate thermal instability of the fuel leading to ox
27、idation and production of detrimental insoluble deposits in theengine.5.2 Gas turbine fuel oil Specification D2880 provides recommended upper limits for five trace metals (calcium, lead, sodium,potassium, and vanadium). Military specification MIL-F-16884MMIL-DTL-16884 for naval distillate fuel sets
28、requirements formaximum concentrations of the same five metals. Both specifications designate Test Method D3605, an atomic absorption/flameemission method, for the quantitative analysis of four of the metals.Test Method D3605 does not cover potassium.This test methodprovides an alternative to Test M
29、ethod D3605, covers potassium and a number of additional elements.5.3 There are several sources of multi-element contamination of naval distillate fuel. Sea water is pumped into the diesel fueltanks (as ballast) to trim ships.Also, some of the oilers (fuel supply ships) have dirty tanks. Corrosion p
30、roducts come from unlinedtanks, piping, pumps, and heat exchangers.6. Interferences6.1 Elemental wavelengths listed in Tables 1 and 2 have been found to be free of spectral interferences with all other elementslisted in Tables 1 and 2 in the concentration range of this test method.6.2 If a spectral
31、interference does exist, then selecting an analytical wavelength other than those listed in Table 1 or Table 2 maybe used as long as the new wavelength possesses appropriate sensitivity for the scope of the method.6.3 Alternatively, the ICP spectrometer manufacturers software may be used to provide
32、corrections to interferences that cannotbe avoided by wavelength selection and background correction.6.4 An empirical method for correcting for spectral interferences is detailed in Test Method D5185, Section 6.1 (Spectral).7. Apparatus7.1 Inductively-Coupled Plasma Atomic Emission SpectrometerAny c
33、ommercial sequential or simultaneous ICP-AESinstrument capable of measuring emission intensities of the elements of interest (and listed in Table 1). A vacuum or inert gasoptical path is required for analysis of any element at wavelengths below 190 nm.7.2 NebulizerA Babington-type high solids nebuli
34、zer is recommended to reduce the possibility of clogging from particulate.For samples without particulates, a concentric nebulizer is recommended to provide higher sensitivity for low concentrations andfor low sensitivity elements. For unknown samples, a Babington-type high solids nebulizer is recom
35、mended to reduce thepossibility of clogging from particulate.7.3 Spray Chamber, suitable for organic materials.7.4 Peristaltic PumpA peristaltic pump is required to provide a constant flow of liquid to the ICP. Viton pump tubing isrecommended for use with fuels and kerosine.7.5 Membrane Filter, 47 m
36、m diameter, 0.8 m or 1.0 m pore size.7.6 Membrane Filter Holder Assembly, for 47 mm diameter filters, with filtration flask.7.7 Pipette, 1000 L.7.8 Volumetric Flasks, 25 mL and 50 mL, glass.7.9 Glass or High Density Polyethylene (HDPE) Bottles, 125 mL, round.7.10 Analytical Balance, measuring to 0.0
37、001 g.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where suchTABLE 2 Internal Stand
38、ards, Recommended Wavelengths, andApproximate Use ConcentrationsInternalStandardWavelength,nmConcentration,mg/kgScandium 361.383 1-2Yttrium 371.029 1-5D7111 153specifications are available.4 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purityto
39、permit its use without lessening the accuracy of the determination.8.2 Organometallic Standards, single element and multielement organometallic standards, nominal 100 mg/kg of each elementof interest.8.3 Internal Standard, fuel soluble yttrium, cobalt, scandium or other single element organometallic
40、 standard, not a componentof the fuel test specimen or calibration standard, nominal 5000 mg/kg.8.4 Kerosine, with analyte concentrations below the detection limits of the instrument. The kerosine can be screened for thepresence of analytes as detailed in 12.1 by performing a wavelength scan for ana
41、lyte wavelengths.8.5 Argon Gas, 99.995 % minimum purity. (WarningArgon may be a compressed gas under high pressure.)8.6 Nitrogen Gas, 99.999 % minimum purity. (WarningNitrogen may be a compressed gas under high pressure.)8.7 Nitric Acid, 10 % aqueous solution. (WarningNitric acid may cause severe bu
42、rns.)8.8 Quality Control (QC) Samples, preferably are portions of one or more fuel or kerosine materials that are stable andrepresentative of the samples of interest. These QC samples can be used to check the validity of the testing process as describedin Section 18. If a suitable QC fuel is not ava
43、ilable, obtain a stable QC concentrate, and dilute it with kerosine on the day of theQC check to the trace level required as described in 12.3. Use HDPE plastic bottles to contain concentrated organometallicsolutions and for sodium analysis.9. Hazards9.1 Gases under high pressure and corrosive acid
44、are used in this method. Wear appropriate personal protective equipment whenworking with nitric acid. Use only apparatus rated for handling the high gas pressures that occur in this test method.10. Sampling and Test Specimens10.1 Samples shall be taken in accordance with procedures described in Prac
45、tice D4057. Suitable sample containers for aviationfuels are described in Practice D4306. Use HDPE plastic containers for sodium analysis.10.2 Samples shall be thoroughly mixed in their containers immediately prior to testing.10.3 If particulate matter is observed in the sample, filter it through a
46、0.8 m or 1.0 m (nylon, TFE-fluorocarbon, celluloseacetate/cellulose nitrate, or other compatible material) membrane filter into an acid-cleaned flask and retain the filtrate for analysis.Follow the same filtration procedure for the kerosine blank material used for the analysis of these samples.11. P
47、reparation of Apparatus11.1 SpectrometerPrepare the ICP spectrometer according to the manufacturers instructions and parameter settings fororganic materials and the elements of interest. At least three integrations should be made for all samples (standards, blank, fuels)run. Table 1 provides recomme
48、nded element wavelengths for fuels; however, other wavelengths may be used due to possibleinstrument variations or spectral interferences. The optical path can be purged with argon or another high purity gas (for example,nitrogen) recommended by the manufacturer. Before igniting the plasma, inspect
49、the quartz torch to make sure that it is clean. Ifcarbon build-up is observed, replace the torch and make the manufacturers recommended adjustments for this problem. Warm upthe instrument while purging the optics for the time period recommended by the ICP manufacturer. If necessary, replace theperistaltic pump tubing and adjust the solution uptake to the desired rate. Ignite the torch, then begin aspirating kerosine throughthe nebulizer and into the spray chamber. Continue plasma warm-up/stabilization for the duration specified by
