Standard Practice for Optimization, Sample Handling, Calibration, and Validation of X-ray Fluorescence Spectrometry Methods for Elemental Analysis of Petroleum Products and Lubricants

SIGNIFICANCE AND USE
3.1 Accurate elemental analyses of samples of petroleum and petroleum products are required for the determination of chemical properties, which are in turn used to establish compliance with commercial and regulatory specifications.
SCOPE
1.1 This practice covers information relating to sampling, calibration and validation of X-ray fluorescence instruments for elemental analysis, including all kinds of wavelength dispersive (WDXRF) and energy dispersive (EDXRF) techniques. This practice includes sampling issues such as the selection of storage vessels, transportation, and sub-sampling. Treatment, assembly, and handling of technique-specific sample holders and cups are also included. Technique-specific requirements during analytical measurement and validation of measurement for the determination of trace elements in samples of petroleum and petroleum products are described. For sample mixing, refer to Practice D5854. Petroleum products covered in this practice are considered to be a single phase and exhibit Newtonian characteristics at the point of sampling.  
1.2 Applicable Test Methods—This practice is applicable to the XRF methods under the jurisdiction of ASTM Subcommittee D02.03 on Elemental Analysis, and those under the jurisdiction of the Energy Institute’s Test Method Standardization Committee (Table 1). Some of these methods are technically equivalent though they may differ in details (Table 2).
TABLE 1 XRF Standard Test Methods for Analysis of Petroleum Products and Lubricants    
Technique  
Analysis  
ASTM  
EI  
WD-XRF  
Sulfur in Petroleum Products  
D2622  
Additive Elements in Lubricating Oils and Additives  
D4927  
IP 407  
Lead in Gasoline  
D5059  
IP 228  
Lead in Gasoline  
IP 489  
Sulfur in Gasoline  
D6334  
Additive Elements in Lube Oils and Additives  
D6443  
Vanadium and Nickel  
IP 433  
Sulfur  
IP 447  
Sulfur in Automotive Fuels  
IP 497  
Chlorine and Bromine  
IP 503  
Sulfur in Ethanol as Blending Agent  
IP 553  
Si, Cr, Ni, Fe, and Cu in Used Greases  
IP 560  
Several Metals in Burner Fuels Derived from Waste Mineral Oils  
IP 593  
MWD-XRF  
Sulfur in Gasoline and Diesel  
D7039  
Silicon in Gasoline and Naphtha  
D7757  
ED-XRF  
Sulfur in Petroleum Products  
D4294  
IP 336  
Sulfur in Gasoline  
D6445  
Additive Elements in Lubricating Oils  
D6481  
Sulfur in Automotive Fuels  
D7212  
IP 531  
Sulfur in Automotive Fuels  
D7220  
IP 532  
Additive Elements in Lubricating Oils  
D7751  
Lead in Gasoline  
IP 352  
Sulfur in Automotive Fuels  
IP 496  
Low Sulfur in Automotive Fuels  
IP 600
TABLE 2 Technically Equivalent XRF Test Methods for Petroleum Products and LubricantsA    
Analysis  
ASTM  
EI  
Other  
Sulfur by WD-XRF  
D2622  
DIN 51400T6;
JIS K3541  
Additive Elements by WE-XRF  
D4927  
IP 407  
DIN 51391T2  
Lead in Gasoline  
D5059  
IP 228  
Sulfur by ED-XRF  
D4294  
IP 336  
ISO 8754  
Sulfur in Automotive Fuels  
D7212  
IP 531  
Sulfur in Automotive Fuels  
D7220  
IP 532  
(A) Nadkarni, R. A., Guide to ASTM Test Methods for the Analysis of Petroleum Products and Lubricants, 2nd edition, ASTM International, West Conshohocken, PA, 2007.  
1.3 Applicable Fluids—This practice is applicable to petroleum and petroleum products with vapor pressures at sampling and storage temperatures less than or equal to 101 kPa (14.7 psi). Use Practice D4057 or IP 475 to sample these materials. Refer to Practice D5842 when sampling materials that also require Reid vapor pressure (RVP) determination.  
1.4 Non-applicable Fluids—Petroleum products whose vapor pressure at sampling and sample storage conditions are abov...

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7343 − 12 (Reapproved 2017)
Designation: 558/07
Standard Practice for
Optimization, Sample Handling, Calibration, and Validation
of X-ray Fluorescence Spectrometry Methods for Elemental
Analysis of Petroleum Products and Lubricants
This standard is issued under the fixed designation D7343; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope tion Committee (Table 1). Some of these methods are techni-
cally equivalent though they may differ in details (Table 2).
1.1 This practice covers information relating to sampling,
calibration and validation of X-ray fluorescence instruments 1.3 Applicable Fluids—This practice is applicable to petro-
for elemental analysis, including all kinds of wavelength leum and petroleum products with vapor pressures at sampling
dispersive (WDXRF) and energy dispersive (EDXRF) tech- and storage temperatures less than or equal to 101 kPa
niques. This practice includes sampling issues such as the (14.7 psi). Use Practice D4057 or IP 475 to sample these
selection of storage vessels, transportation, and sub-sampling. materials. Refer to Practice D5842 when sampling materials
Treatment, assembly, and handling of technique-specific that also require Reid vapor pressure (RVP) determination.
sample holders and cups are also included. Technique-specific
1.4 Non-applicable Fluids—Petroleum products whose va-
requirements during analytical measurement and validation of
por pressure at sampling and sample storage conditions are
measurement for the determination of trace elements in
above 101 kPa (14.7 psi) and liquefied gases (that is, LNG,
samples of petroleum and petroleum products are described.
LPG, etc.) are not covered by this practice.
For sample mixing, refer to Practice D5854. Petroleum prod-
1.5 Sampling Methods—The physical sampling and meth-
ucts covered in this practice are considered to be a single phase
ods of sampling from a primary source are not covered by this
and exhibit Newtonian characteristics at the point of sampling.
guide. It is assumed that samples covered by this practice are
1.2 Applicable Test Methods—This practice is applicable to
a representative sample of the primary source liquid. Refer to
the XRF methods under the jurisdiction ofASTM Subcommit-
Practice D4057 or IP 475 for detailed sampling procedures.
tee D02.03 on Elemental Analysis, and those under the
1.6 The values stated in SI units are to be regarded as the
jurisdiction of the Energy Institute’s Test Method Standardiza-
standard.
1.6.1 Exception—The values given in parentheses are for
This practice is under the jurisdiction ofASTM Committee D02 on Petroleum
information only.
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-
1.7 This standard does not purport to address all of the
mittee D02.03 on Elemental Analysis.
CurrenteditionapprovedJune1,2017.PublishedJuly2017.Originallyapproved
safety concerns, if any, associated with its use. It is the
in 2007. Last previous edition approved in 2012 as D7343 – 12. DOI: 10.1520/
responsibility of the user of this standard to establish appro-
D7343-12R17.
priate safety and health practices and determine the applica-
This practice was jointly prepared by ASTM International and the Energy
Institute. bility of regulatory limitations prior to use.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7343 − 12 (Reapproved 2017)
D7343 − 12 (2017)
TABLE 1 XRF Standard Test Methods for Analysis of Petroleum
D4057 Practice for Manual Sampling of Petroleum and
Products and Lubricants
Petroleum Products
Technique Analysis ASTM EI
D4294 Test Method for Sulfur in Petroleum and Petroleum
WD-XRF Sulfur in Petroleum Products D2622
Products by Energy Dispersive X-ray Fluorescence Spec-
Additive Elements in Lubricating D4927 IP 407
trometry
Oils and Additives
Lead in Gasoline D5059 IP 228
D4927 Test Methods for Elemental Analysis of Lubricant
Lead in Gasoline IP 489
and Additive Components—Barium, Calcium,
Sulfur in Gasoline D6334
Additive Elements in Lube Oils and D6443 Phosphorus, Sulfur, and Zinc by Wavelength-Dispersive
Additives
X-Ray Fluorescence Spectroscopy
Vanadium and Nickel IP 433
D5059 Test Methods for Lead in Gasoline by X-Ray Spec-
Sulfur IP 447
Sulfur in Automotive Fuels IP 497 troscopy
Chlorine and Bromine IP 503
D5842 Practice for Sampling and Handling of Fuels for
Sulfur in Ethanol as Blending IP 553
Volatility Measurement
Agent
Si, Cr, Ni, Fe, and Cu in Used IP 560
D5854 Practice for Mixing and Handling of Liquid Samples
Greases
of Petroleum and Petroleum Products
Several Metals in Burner Fuels IP 593
D6299 Practice for Applying Statistical Quality Assurance
Derived from Waste Mineral Oils
MWD-XRF Sulfur in Gasoline and Diesel D7039 and Control Charting Techniques to Evaluate Analytical
Silicon in Gasoline and Naphtha D7757
Measurement System Performance
ED-XRF Sulfur in Petroleum Products D4294 IP 336
D6334 Test Method for Sulfur in Gasoline by Wavelength
Sulfur in Gasoline D6445
Additive Elements in Lubricating D6481 Dispersive X-Ray Fluorescence
Oils
D6443 TestMethodforDeterminationofCalcium,Chlorine,
Sulfur in Automotive Fuels D7212 IP 531
Copper, Magnesium, Phosphorus, Sulfur, and Zinc in
Sulfur in Automotive Fuels D7220 IP 532
Additive Elements in Lubricating D7751
Unused Lubricating Oils and Additives by Wavelength
Oils
Dispersive X-ray Fluorescence Spectrometry (Mathemati-
Lead in Gasoline IP 352
cal Correction Procedure)
Sulfur in Automotive Fuels IP 496
Low Sulfur in Automotive Fuels IP 600
D6445 Test Method for Sulfur in Gasoline by Energy-
Dispersive X-ray Fluorescence Spectrometry (Withdrawn
2009)
TABLE 2 Technically Equivalent XRF Test Methods for Petroleum
D6481 Test Method for Determination of Phosphorus,
A
Products and Lubricants
Sulfur, Calcium, and Zinc in Lubrication Oils by Energy
Analysis ASTM EI Other
Dispersive X-ray Fluorescence Spectroscopy
Sulfur by WD-XRF D2622 DIN 51400T6;
JIS K3541 D7039 Test Method for Sulfur in Gasoline, Diesel Fuel, Jet
Additive Elements by WE- D4927 IP 407 DIN 51391T2
Fuel, Kerosine, Biodiesel, Biodiesel Blends, and
XRF
Gasoline-Ethanol Blends by Monochromatic Wavelength
Lead in Gasoline D5059 IP 228
Sulfur by ED-XRF D4294 IP 336 ISO 8754 Dispersive X-ray Fluorescence Spectrometry
Sulfur in Automotive Fuels D7212 IP 531
D7212 Test Method for Low Sulfur inAutomotive Fuels by
Sulfur in Automotive Fuels D7220 IP 532
Energy-Dispersive X-ray Fluorescence Spectrometry Us-
A
Nadkarni, R. A., Guide to ASTM Test Methods for the Analysis of Petroleum
ing a Low-Background Proportional Counter
Products and Lubricants, 2nd edition, ASTM International, West Conshohocken,
D7220 Test Method for Sulfur in Automotive, Heating, and
PA, 2007.
Jet Fuels by Monochromatic Energy Dispersive X-ray
Fluorescence Spectrometry
D7751 Test Method for Determination ofAdditive Elements
in Lubricating Oils by EDXRF Analysis
1.8 This international standard was developed in accor-
D7757 Test Method for Silicon in Gasoline and Related
dance with internationally recognized principles on standard-
Products by Monochromatic Wavelength Dispersive
ization established in the Decision on Principles for the
X-ray Fluorescence Spectrometry
Development of International Standards, Guides and Recom- 4
2.2 Energy Institute Standards:
mendations issued by the World Trade Organization Technical
IP 228 Determination of lead content of gasoline – X-ray
Barriers to Trade (TBT) Committee.
spectrometric method
IP 336 Determination of sulfur content – Energy-dispersive
2. Referenced Documents
X-ray fluorescence method
2.1 ASTM Standards:
IP352 Determination of lead content of automotive gasoline
D2622 Test Method for Sulfur in Petroleum Products by
– Energy-dispersive X-ray fluorescence spectrometry
Wavelength Dispersive X-ray Fluorescence Spectrometry
method
2 3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or The last approved version of this historical standard is referenced on
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM www.astm.org.
Standards volume information, refer to the standard’s Document Summary page on Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,
the ASTM website. U.K., http://www.energyinst.org.uk.
D7343 − 12 (2017)
IP407 Determinationofbarium,calcium,phosphorus,sulfur tamination. The development of clean area sample handling
and zinc by wavelength dispersive X-ray fluorescence protocols is encouraged.
spectrometry
IP 433 Determination of vanadium and nickel content – 5. Sample Preparation
Wavelength dispersive X-ray fluorescence spectrometry
5.1 Choice of Sample Carrier—XRF testing requires a
IP 447 Determination of sulfur content – Wavelength
sample cell and a support film to hold the liquid sample in
dispersive X-ray fluorescence spectrometry
place during analysis.The choice of the sample cell or cup, the
IP 475 Methods of test for petroleum and its products
material in which it is held, and the type of support film used
IP 489 Determination of low lead contents in gasolines –
can all influence the result.
Wavelength dispersive X-ray fluorescence spectrometry
5.1.1 Sample Cell—The most common cell is a plastic cup,
IP 496 Determination of sulfur content of automotive fuels
ofwhichvariousdesignsareavailable.Thesedesignsallowfor
– Energy-dispersive X-ray fluorescence spectrometry
a variety of sample types to be measured either in a liquid or
IP497 Determination of sulfur content of automotive fuels –
powder form. It is important to check that the cup type used is
Wavelength dispersive X-ray fluorescence spectrometry
best suited for the compositions of samples to be analyzed.
IP 503 Determination of chlorine and bromine content –
Liquid sample cups usually have a seal that ensures the film is
Wavelength dispersive X-ray fluorescence spectrometry
sealed to a level above that of the liquid in the cell and that the
IP 531 Determination of sulfur content of automotive fuels
film is taut with no wrinkles.
–Low-backgroundproportionalcounterenergy-dispersive
5.1.1.1 Within XRF spectrometers heat is produced, both
X-ray fluorescence spectrometry method
from the spectrometer components themselves and from the
IP 532 Determination of the sulfur content of automotive
interaction of X-rays with the sample. Petroleum products that
fuels – Polarized X-ray fluorescence spectrometry
are not stable due to volatility should only be placed into
IP 553 Ethanol as a Blending Component for Petrol –
vented sample cups or special sealed sample cups specifically
Determination of Sulfur Content – WDXRF Method
designed for volatile samples (see 8.3).
IP 560 Determination of Silicon, Chromium, nickel, Iron,
5.1.1.2 The cup size may be important. Depending on the
and Copper in Used Greases – WDXRF Method
film type used to support the liquid, different films will sag due
IP 593 Determination of Pb, Ni, Cr, Cu, Zn,As, Cd, Tl, Sb,
to the weight of sample and relax due to chemical interaction,
Co, Mn, and V in Burner Fuels derived from Waste
or heat, or both. To reduce this sagging effect, the smallest
Mineral Oils – WDXRF Method
diameter sample cups should be used. Cups with diameters
IP 600 Petroleum Products – Determination of Low Sulfur
well in excess of the area detected by the spectrometer are
Content of Automotive Fuels – EDXRF Spectrometry
likely to increase errors due to sagging.
5.1.1.3 A number of petroleum products require heating to
3. Significance and Use
ensurehomogenizationpriortoanalysisortoenabletransferto
3.1 Accurate elemental analyses of samples of petroleum
the sample cell; examples include fuel oils and wax products.
and petroleum products are required for the determination of
The sample cup should be able to withstand the temperature
chemical properties, which are in turn used to establish
used in this process. In general, most plastic sample cells
compliance with commercial and regulatory specifications.
should withstand temperatures up to 70 °C.
5.1.2 Sample Cell Holder—Many manufacturers recom-
4. Sample Handling
mend metal holders to hold sample cups while they are
transferred into the XRF instrument. These holders can be
4.1 It is necessary to use precautions to minimize the
possibility of contamination of trace elemental analysis made from aluminum, stainless steel, or other materials. It is
samples. Good laboratory practices in this area include: important to recognize that these represent a potential spectral
4.1.1 Samples received by the laboratory and required for contamination to the analysis either if the spectrometer is to
determine an analyte that the holder is made from or if the
trace element analysis should be stored in a designated specific
location for storage while awaiting analysis. This area, when- material from the holder causes an interference with the
ever possible, should not contain samples that could contami- analyte. Generally, this is not a problem for elements with
nate those requiring trace element analysis. atomic number <30. For elements with atomic number >30 it
is advisable to check the potential contamination from the
4.1.2 All laboratory equipment used specifically for trace
element analysis should be free of any source of contamina- sample cup holder using a blank.
tion.This may require that specific equipment be used only for
5.1.3 Sample Support Films—Many support films are avail-
trace element analysis. able from both XRF instrument manufacturers and accessory
4.1.3 Analyses of blank samples are highly recommended. suppliers. It is important to examine the film types specified in
4.1.4 Sample preparation should be carried out in a clean any method being used. There are four criteria that should be
area. This area should use surfaces that can be decontaminated considered when selecting a X-ray transmission sample sup-
easily if a spillage occurs. port film:
4.1.5 Operators should wear clean, fresh, protective gloves (1) Thickness of film,
for sample preparation for trace element analysis. Tests should (2) Composition of film,
be run to confirm that the gloves do not contain interfering (3) Chemical and physical resistance of film to the liquid
elements or elements of interest, since they may cause con- intend for analysis, and
D7343 − 12 (2017)
(4) Element contaminants contained within the film. they should be inspect
...


This 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. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D7343 − 12 D7343 − 12 (Reapproved 2017)
Designation: 558/07
Standard Practice for
Optimization, Sample Handling, Calibration, and Validation
of X-ray Fluorescence Spectrometry Methods for Elemental
Analysis of Petroleum Products and Lubricants
This standard is issued under the fixed designation D7343; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope*Scope
1.1 This practice covers information relating to sampling, calibration and validation of X-ray fluorescence instruments for
elemental analysis, including all kinds of wavelength dispersive (WDXRF) and energy dispersive (EDXRF) techniques. This
practice includes sampling issues such as the selection of storage vessels, transportation, and sub-sampling. Treatment, assembly,
and handling of technique-specific sample holders and cups are also included. Technique-specific requirements during analytical
measurement and validation of measurement for the determination of trace elements in samples of petroleum and petroleum
products are described. For sample mixing, refer to Practice D5854. Petroleum products covered in this practice are considered
to be a single phase and exhibit Newtonian characteristics at the point of sampling.
1.2 Applicable Test Methods—This practice is applicable to the XRF methods under the jurisdiction of ASTM Subcommittee
D02.03 on Elemental Analysis, and those under the jurisdiction of the Energy Institute’s Test Method Standardization Committee
(Table 1). Some of these methods are technically equivalent though they may differ in details (Table 2).
1.3 Applicable Fluids—This practice is applicable to petroleum and petroleum products with vapor pressures at sampling and
storage temperatures less than or equal to 101 kPa (14.7 psi). 101 kPa (14.7 psi). Use Practice D4057 or IP 475 to sample these
materials. Refer to Practice D5842 when sampling materials that also require Reid vapor pressure (RVP) determination.
1.4 Non-applicable Fluids—Petroleum products whose vapor pressure at sampling and sample storage conditions are above 101
kPa (14.7 psi) 101 kPa (14.7 psi) and liquefied gases (that is, LNG, LPG, etc.) are not covered by this practice.
1.5 Sampling Methods—The physical sampling and methods of sampling from a primary source are not covered by this guide.
It is assumed that samples covered by this practice are a representative sample of the primary source liquid. Refer to Practice
D4057 or IP 475 for detailed sampling procedures.
1.6 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.6.1 Exception—The values given in parentheses are for information only.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory
limitations prior to use.
This practice is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved Dec. 1, 2012June 1, 2017. Published December 2012July 2017. Originally approved in 2007. Last previous edition approved in 20072012 as
D7343D7343 – 12.–07. DOI: 10.1520/D7343-07.10.1520/D7343-12R17.
This practice was jointly prepared by ASTM International and the Energy Institute.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7343 − 12 (2017)
TABLE 1 XRF Standard Test Methods for Analysis of Petroleum
Products and Lubricants
Technique Analysis ASTM EI
WD-XRF Sulfur in Petroleum Products D2622
Additive Elements in Lubricating D4927 IP 407
Oils and Additives
Lead in Gasoline D5059 IP 228
Lead in Gasoline IP 489
Sulfur in Gasoline D6334
Additive Elements in Lube Oils and D6443
Additives
Vanadium and Nickel IP 433
Sulfur IP 447
Sulfur in Automotive Fuels IP 497
Chlorine and Bromine IP 503
Sulfur in Ethanol as Blending IP 553
Agent
Si, Cr, Ni, Fe, and Cu in Used IP 560
Greases
Several Metals in Burner Fuels IP 593
Derived from Waste Mineral Oils
MWD-XRF Sulfur in Gasoline and Diesel D7039
Silicon in Gasoline and Naphtha D7757
ED-XRF Sulfur in Petroleum Products D4294 IP 336
Sulfur in Gasoline D6445
Additive Elements in Lubricating D6481
Oils
Sulfur in Automotive Fuels D7212 IP 531
Sulfur in Automotive Fuels D7220 IP 532
Additive Elements in Lubricating D7751
Oils
Lead in Gasoline IP 352
Sulfur in Automotive Fuels IP 496
Low Sulfur in Automotive Fuels IP 600
TABLE 2 Technically Equivalent XRF Test Methods for Petroleum
A
Products and Lubricants
Analysis ASTM EI Other
Sulfur by WD-XRF D2622 DIN 51400T6;
JIS K3541
Additive Elements by WE- D4927 IP 407 DIN 51391T2
XRF
Lead in Gasoline D5059 IP 228
Sulfur by ED-XRF D4294 IP 336 ISO 8754
Sulfur in Automotive Fuels D7212 IP 531
Sulfur in Automotive Fuels D7220 IP 532
A
Nadkarni, R. A., Guide to ASTM Test Methods for the Analysis of Petroleum
Products and Lubricants, 2nd edition, ASTM International, West Conshohocken,
PA, 2007.
1.8 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D2622 Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-ray Fluorescence Spectrometry
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4294 Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry
D4927 Test Methods for Elemental Analysis of Lubricant and Additive Components—Barium, Calcium, Phosphorus, Sulfur,
and Zinc by Wavelength-Dispersive X-Ray Fluorescence Spectroscopy
D5059 Test Methods for Lead in Gasoline by X-Ray Spectroscopy
D5842 Practice for Sampling and Handling of Fuels for Volatility Measurement
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
D7343 − 12 (2017)
D5854 Practice for Mixing and Handling of Liquid Samples of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6334 Test Method for Sulfur in Gasoline by Wavelength Dispersive X-Ray Fluorescence
D6443 Test Method for Determination of Calcium, Chlorine, Copper, Magnesium, Phosphorus, Sulfur, and Zinc in Unused
Lubricating Oils and Additives by Wavelength Dispersive X-ray Fluorescence Spectrometry (Mathematical Correction
Procedure)
D6445 Test Method for Sulfur in Gasoline by Energy-Dispersive X-ray Fluorescence Spectrometry (Withdrawn 2009)
D6481 Test Method for Determination of Phosphorus, Sulfur, Calcium, and Zinc in Lubrication Oils by Energy Dispersive X-ray
Fluorescence Spectroscopy
D7039 Test Method for Sulfur in Gasoline, Diesel Fuel, Jet Fuel, Kerosine, Biodiesel, Biodiesel Blends, and Gasoline-Ethanol
Blends by Monochromatic Wavelength Dispersive X-ray Fluorescence Spectrometry
D7212 Test Method for Low Sulfur in Automotive Fuels by Energy-Dispersive X-ray Fluorescence Spectrometry Using a
Low-Background Proportional Counter
D7220 Test Method for Sulfur in Automotive, Heating, and Jet Fuels by Monochromatic Energy Dispersive X-ray Fluorescence
Spectrometry
D7751 Test Method for Determination of Additive Elements in Lubricating Oils by EDXRF Analysis
D7757 Test Method for Silicon in Gasoline and Related Products by Monochromatic Wavelength Dispersive X-ray Fluorescence
Spectrometry
2.2 Energy Institute Standards:
IP 228 Determination of lead content of gasoline – X-ray spectrometric method
IP 336 Determination of sulfur content – Energy-dispersive X-ray fluorescence method
IP 352 Determination of lead content of automotive gasoline- gasoline – Energy-dispersive X-ray fluorescence spectrometry
method
IP 407 Determination of barium, calcium, phosphorus, sulfur and zinc by wavelength dispersive X-ray fluorescence
spectrometry
IP 433 Determination of vanadium and nickel content – Wavelength dispersive X-ray fluorescence spectrometry
IP 447 Determination of sulfur content -– Wavelength dispersive X-ray fluorescence spectrometry
IP 475 Methods of test for petroleum and its products
IP 489 Determination of low lead contents in gasolines -– Wavelength dispersive X-ray fluorescence spectrometry
IP 496 Determination of sulfur content of automotive fuels – Energy-dispersive X-ray fluorescence spectrometry
IP 497 Determination of sulfur content of automotive fuels -– Wavelength dispersive X-ray fluorescence spectrometry
IP 503 Determination of chlorine and bromine content -– Wavelength dispersive X-ray fluorescence spectrometry
IP 531 Determination of sulfur content of automotive fuels – Low-background proportional counter energy-dispersive X-ray
fluorescence spectrometry method
IP 532 Determination of the sulfur content of automotive fuels – Polarized X-ray fluorescence spectrometry
IP 553 Ethanol as a Blending Component for Petrol —– Determination of Sulfur Content —– WDXRF Method
IP 560 Determination of Silicon, Chromium, nickel, Iron, and Copper in Used Greases —– WDXRF Method
IP 593 Determination of Pb, Ni, Cr, Cu, Zn, As, Cd, Tl, Sb, Co, Mn, and V in Burner Fuels derived from Waste Mineral Oils
—– WDXRF Method
IP 600 Petroleum Products —– Determination of Low Sulfur Content of Automotive Fuels —– EDXRF Spectrometry
3. Significance and Use
3.1 Accurate elemental analyses of samples of petroleum and petroleum products are required for the determination of chemical
properties, which are in turn used to establish compliance with commercial and regulatory specifications.
4. Sample Handling
4.1 It is necessary to use precautions to minimize the possibility of contamination of trace elemental analysis samples. Good
laboratory practices in this area include:
4.1.1 Samples received by the laboratory and required for trace element analysis should be stored in a designated specific
location for storage while awaiting analysis. This area, whenever possible, should not contain samples that could contaminate those
requiring trace element analysis.
4.1.2 All laboratory equipment used specifically for trace element analysis should be free of any source of contamination. This
may require that specific equipment be used only for trace element analysis.
4.1.3 Analyses of blank samples are highly recommended.
The last approved version of this historical standard is referenced on www.astm.org.
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR, U.K., http://www.energyinst.org.uk.
D7343 − 12 (2017)
4.1.4 Sample preparation should be carried out in a clean area. This area should use surfaces that can be decontaminated easily
if a spillage occurs.
4.1.5 Operators should wear clean, fresh, protective gloves for sample preparation for trace element analysis. Tests should be
run to confirm that the gloves do not contain interfering elements or elements of interest, since they may cause contamination. The
development of clean area sample handling protocols is encouraged.
5. Sample Preparation
5.1 Choice of Sample Carrier—XRF testing requires a sample cell and a support film to hold the liquid sample in place during
analysis. The choice of the sample cell or cup, the material in which it is held, and the type of support film used can all influence
the result.
5.1.1 Sample Cell—The most common cell is a plastic cup, of which various designs are available. These designs allow for a
variety of sample types to be measured either in a liquid or powder form. It is important to check that the cup type used is best
suited for the compositions of samples to be analyzed. Liquid sample cups usually have a seal that ensures the film is sealed to
a level above that of the liquid in the cell and that the film is taut with no wrinkles.
5.1.1.1 Within XRF spectrometers heat is produced, both from the spectrometer components themselves and from the
interaction of X-rays with the sample. Petroleum products that are not stable due to volatility should only be placed into vented
sample cups or special sealed sample cups specifically designed for volatile samples (see 8.3).
5.1.1.2 The cup size may be important. Depending on the film type used to support the liquid, different films will sag due to
the weight of sample and relax due to chemical interaction, or heat, or both. To reduce this sagging effect, the smallest diameter
sample cups should be used. Cups with diameters well in excess of the area detected by the spectrometer are likely to increase
errors due to sagging.
5.1.1.3 A number of petroleum products require heating to ensure homogenization prior to analysis or to enable transfer to the
sample cell; examples include fuel oils and wax products. The sample cup should be able to withstand the temperature used in this
process. In general, most plastic sample cells should withstand temperatures up to 70°C.70 °C.
5.1.2 Sample Cell Holder—Many manufacturers recommend metal holders to hold sample cups while they are transferred into
the XRF instrument. These holders can be made from aluminum, stainless steel, or other materials. It is important to recognize that
these represent a potential spectral contamination to the analysis either if the spectrometer is to determine an analyte that the holder
is made from or if the material from the holder causes an interference with the analyte. Generally, this is not a problem for elements
with atomic number <30. For elements with atomic number >30 it is advisable to check the potential contamination from the
sample cup holder using a blank.
5.1.3 Sample Support Films—Many support films are avail
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