ASTM D5059-21

Standard Test Methods for Lead and Manganese in Gasoline by X-Ray Fluorescence Spectroscopy

SIGNIFICANCE AND USE
4.1 These test methods determine the concentration of lead (from alkyl addition) in gasoline. These alkyl additives improve the antiknock properties.  
4.2 Test Method C is used to ensure compliance of trace lead as required by federal regulations for lead-free gasoline (40 CFR Part 80).  
4.3 Test Method D is used to determine the concentration of manganese in aviation gasoline.
SCOPE
1.1 These test methods cover the determination of lead and manganese gasoline additives content by X-Ray Fluorescence Spectroscopy (XRF). These test methods cover the determination of the total lead content of a gasoline within the following concentration ranges:    
0.010 g Pb/US gal to 5.0 g Pb/US gal  
0.012 g Pb/UK gal to 6.0 g Pb/UK gal  
0.0026 g Pb/L to 1.32 g Pb/L and total manganese content of aviation gasoline within the concentration range of 25 mg Mn/L to 250 mg Mn/L.  
1.1.1 Test Methods A and B cover the range of 0.10 g Pb/US gal to 5.0 g Pb/US gal. Test Method C covers the range of 0.010 g Pb/US gal to 0.50 g Pb/US gal.  
1.1.2 These Methods A, B, and C are applicable to gasoline containing lead additives. These test methods compensate for normal variation in gasoline composition and are independent of lead alkyl type.  
1.1.3 Test Method D is applicable to aviation gasoline containing manganese additives.  
1.2 Test Method A (formerly in withdrawn Test Method D2599)—Sections 5 – 10.
Test Method B (formerly in withdrawn Test Method D2599)—Sections 11 – 16.
Test Method C (formerly in withdrawn Test Method D3229)—Sections 17 – 23.
Test Method D—Sections 24 – 29.  
1.3 The values stated in SI are to be regarded as the standard. For reporting purposes the values stated in grams per U.S. gallon are the preferred units in the United States. Note that in other countries, other units can be preferred.  
1.4 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Sections 5, 6, 11, and 18.  
1.5 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.

General Information

• Status: Published
• Publication Date: 31-Mar-2021
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• Refers: ASTM D6299-23a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Dec-2023
• Refers: ASTM D6792-23c - Standard Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
• Effective Date: 01-Nov-2023
• Refers: ASTM D6792-23b - Standard Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
• Effective Date: 01-Oct-2023
• Refers: ASTM D6299-17b - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Dec-2017
• Refers: ASTM D6299-17a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Nov-2017
• Refers: ASTM D6299-17 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Jan-2017
• Refers: ASTM D6299-13e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Oct-2013
• Refers: ASTM D4057-06(2011) - Standard Practice for Manual Sampling of Petroleum and Petroleum Products
• Effective Date: 01-Jun-2011
• Refers: ASTM D3341-05(2011) - Standard Test Method for Lead in Gasoline<char: emdash>Iodine Monochloride Method
• Effective Date: 01-May-2011
• Refers: ASTM D6299-10 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-10e2 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-09 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2009
• Refers: ASTM D6299-08 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Oct-2008
• Refers: ASTM D6299-07e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2007
• Refers: ASTM D6299-07 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2007

Overview

ASTM D5059-21 establishes standard test methods for determining the concentration of lead and manganese in gasoline using X-Ray Fluorescence Spectroscopy (XRF). These methods address the content of lead, present as alkyl additives improving antiknock properties, and manganese, chiefly present in aviation gasoline. The standard provides analytical procedures suitable for a wide range of concentrations, supporting compliance with regulatory requirements for fuels, including those mandated by the U.S. Environmental Protection Agency (EPA) for "lead-free" gasoline.

The test methods in ASTM D5059-21 support laboratories, fuel producers, and regulatory agencies by offering reliable and repeatable approaches to quantify these metals in different fuel matrices, ensuring quality assurance, regulatory compliance, and the protection of public health and the environment.

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Key Topics

• Scope and Range
  • Determines total lead content from 0.010 g Pb/US gal to 5.0 g Pb/US gal; corresponding ranges in UK gallons and liters are also covered.
  • Measures total manganese in aviation gasoline from 25 mg Mn/L to 250 mg Mn/L.
  • Test Methods A, B, and C apply to gasoline with lead additives regardless of alkyl lead type; Test Method D applies to manganese in aviation gasoline.
• Test Methodology
  • Multiple XRF-based procedures (A, B, C for lead; D for manganese) provide flexibility based on analyte concentration.
  • Procedures account for variations in sample matrix and incorporate quality control measures.
• Regulatory Alignment
  • Ensures compliance with federal standards (e.g., 40 CFR Part 80) for gasoline additives.
• Units and Reporting
  • Preferred reporting in the United States is grams per U.S. gallon; other regional units (UK gallons, liters) are also addressed.
  • Emphasizes proper unit conversion and clear reporting for international applicability.
• Safety and Quality
  • Highlights necessary precautions due to toxicity and flammability of sample materials and solvents.
  • Mandates daily instrument calibration and routine analysis of quality control (QC) samples.

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Applications

The ASTM D5059-21 standard is vital in several areas of fuel quality assurance and regulatory compliance:

• Fuel Refining and Blending
  • Essential for gasoline producers to monitor additive levels and meet product specifications.
• Regulatory Compliance
  • Used by regulatory agencies and testing laboratories to verify trace lead in unleaded gasoline and manganese in aviation fuels.
  • Supports adherence to legal limits outlined by the EPA and international standards bodies.
• Aviation Fuel Testing
  • Provides a specific method (Test Method D) for measuring manganese in aviation gasoline, critical for safe operation and compliance.
• Analytical Laboratories
  • Laboratories rely on these procedures for robust, repeatable, and internationally recognized methods of analysis.
• Environmental Monitoring
  • Accurate quantification of lead and manganese aids in evaluating the environmental impact of fuel use and supports initiatives to reduce toxic emissions.

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Related Standards

ASTM D5059-21 references and aligns with several related standards and practices to ensure comprehensive coverage and integration within the petroleum quality framework:

• ASTM D3341 - Test Method for Lead in Gasoline by Iodine Monochloride Method.
• ASTM D4057 - Practice for Manual Sampling of Petroleum and Petroleum Products.
• ASTM D4177 - Practice for Automatic Sampling of Petroleum and Petroleum Products.
• ASTM D6299 - Practice for Applying Statistical Quality Assurance and Control Charting Techniques.
• ASTM D6792 - Practice for Quality Management Systems in Petroleum Testing Laboratories.
• 40 CFR Part 80 - U.S. federal regulation governing fuel and fuel additive controls.
• International standardization guidelines, including those from the WTO’s Technical Barriers to Trade (TBT) Committee.

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Keywords: ASTM D5059-21, lead in gasoline, manganese in aviation gasoline, X-ray fluorescence spectroscopy, XRF, fuel additives, fuel quality, regulatory compliance, petroleum testing, aviation fuel, ASTM standards.

Standards Content (Sample)

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.
Designation: D5059 − 21
Standard Test Methods for
Lead and Manganese in Gasoline by X-Ray Fluorescence
Spectroscopy
This standard is issued under the fixed designation D5059; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope* responsibility of the user of this standard to establish appro-
priate safety, health, and environmental practices and deter-
1.1 These test methods cover the determination of lead and
mine the applicability of regulatory limitations prior to use.
manganese gasoline additives content by X-Ray Fluorescence
For specific hazard statements, see Sections 5, 6, 11, and 18.
Spectroscopy (XRF). These test methods cover the determina-
1.5 This international standard was developed in accor-
tion of the total lead content of a gasoline within the following
dance with internationally recognized principles on standard-
concentration ranges:
ization established in the Decision on Principles for the
0.010 g Pb ⁄US gal to 5.0 g Pb ⁄US gal
Development of International Standards, Guides and Recom-
0.012 g Pb ⁄UK gal to 6.0 g Pb ⁄UK gal
0.0026gPb⁄Lto1.32gPb⁄L mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
and total manganese content of aviation gasoline within the
concentration range of 25 mg Mn/L to 250 mg Mn/L.
2. Referenced Documents
1.1.1 Test Methods A and B cover the range of
2.1 ASTM Standards:
0.10 g Pb⁄US galto5.0 g Pb⁄US gal.TestMethodCcoversthe
D3341 Test Method for Lead in Gasoline—Iodine Mono-
range of 0.010 g Pb⁄US gal to 0.50 g Pb⁄US gal.
chloride Method
1.1.2 These MethodsA, B, and C are applicable to gasoline
D4057 Practice for Manual Sampling of Petroleum and
containing lead additives. These test methods compensate for
Petroleum Products
normal variation in gasoline composition and are independent
D4177 Practice for Automatic Sampling of Petroleum and
of lead alkyl type.
Petroleum Products
1.1.3 Test Method D is applicable to aviation gasoline
D6299 Practice for Applying Statistical Quality Assurance
containing manganese additives.
and Control Charting Techniques to Evaluate Analytical
1.2 Test Method A (formerly in withdrawn Test Method
Measurement System Performance
D2599)—Sections5–10.
D6792 Practice for Quality Management Systems in Petro-
Test Method B (formerly in withdrawn Test Method
leum Products, Liquid Fuels, and Lubricants Testing
D2599)—Sections11–16.
Laboratories
Test Method C (formerly in withdrawn Test Method
2.2 Federal Standards:
D3229)—Sections17–23.
40 CFR Part 80 Regulation of Fuels and Fuel Additives
Test Method D—Sections24–29.
3. Summary of Test Method
1.3 The values stated in SI are to be regarded as the
3.1 There are three alternative test methods for lead in
standard. For reporting purposes the values stated in grams per
gasoline and one method for manganese in aviation gasoline,
U.S. gallon are the preferred units in the United States. Note
as follows.
that in other countries, other units can be preferred.
3.1.1 Test Method A (Bismuth Internal Standard Method
1.4 This standard does not purport to address all of the
High Concentration)—One volume of sample is mixed thor-
safety concerns, if any, associated with its use. It is the
oughly with an equal volume of bismuth internal standard
1 2
These test methods are under the jurisdiction of Committee D02 on Petroleum For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Products, Liquid Fuels, and Lubricants and are the direct responsibility of contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Subcommittee D02.03 on Elemental Analysis. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved April 1, 2021. Published April 2021. Originally the ASTM website.
approved in 1990. Last previous edition approved in 2020 as D5059 – 20. DOI: Available from U.S. Government Printing Office, Superintendent of
10.1520/D5059-21. Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http://
Initially published as D2599 – 67T and D3229 – 73, now withdrawn. www.access.gpo.gov.
*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
D5059 − 21
solution. The mixture is placed in the X-ray beam and the 6. Reagents and Materials
intensitiesofthelead L-α radiationat1.175 Åandthebismuth
6.1 Purity of Reagents—Reagent grade chemicals shall be
L-α radiation at 1.144 Å are determined. The lead concentra-
used in all tests. Unless otherwise indicated, it is intended that
tion of the sample is measured by comparing the ratio of gross
all reagents conform to the specifications of the Committee on
counting rate at 1.175 Å with the gross counting rate at 1.144 Å
Analytical Reagents of the American Chemical Society where
to a previous prepared calibration curve of concentration
such specifications are available. Other grades may be used,
versus the same ratios.
provided it is first ascertained that the reagent is of sufficiently
3.1.2 Test Method B (Scattered Tungsten Radiation
high purity to permit its use without lessening the accuracy of
Method)—The ratio of the net X-ray intensity of the lead L-α
the determinations.
radiation to the net intensity of the incoherently scattered
6.2 Hydrocarbon-Soluble Bismuth.
tungsten L-α radiation is obtained on a portion of the sample.
The lead content is determined by multiplying this ratio by a
NOTE 2—Bismuth 2-Ethylhexoate has been found suitable to use. Other
calibration factor obtained with a standard lead solution of bismuth containing materials that are hydrocarbon-soluble may also be
used when they are certified to conform to 6.1.
known concentration.
3.1.3 Test Method C (Bismuth Internal Standard Method, 6.3 Bismuth Internal Standard Solution—Dilute the
Low Concentration)—Twenty millilitres of sample is mixed hydrocarbon-soluble bismuth with a suitable solvent. If bis-
thoroughly with two millilitres of bismuth internal standard muth 2-ethylhexoate is used, add 2-ethylhexanoic acid as a
solution. The mixture is placed in the X-ray beam of a stabilizer (see Note 3) to obtain a solution containing the
spectrometer and the intensities of the lead L-α radiation at following:
1.175 Å, the bismuth L-α radiation at 1.144 Å, and a back-
1 3.00 g Bi ⁄US gal at 15.5 °C (60 °F) or
3.60 g Bi ⁄UK gal at 15.5 °C (60 °F) or
ground at 1.194 Å are determined. A blank, made with iso-
0.793gBi⁄Lat15°C
octane and bismuth internal standard, is run using the same
procedure. The lead concentration is measured by determining NOTE 3—Some stability difficulties have been experienced with bis-
muth 2-ethylhexoate internal standard solution. If the standard is blended
the ratio of the net counting rate at 1.175 Å to the gross
to contain 5 % 2-ethylhexanoic acid, the standard has been found to last
counting rate at 1.144 Å for the sample, subtracting the
almost indefinitely. The 2-ethylhexanoic acid stabilizes iso-octane,
comparable ratio found for the blank, and comparing to a
toluene, and benzene solutions of the bismuth 2-ethylhexoate which are
previously prepared calibration curve of concentration versus
otherwise stable for only a day or two. Normal octanoic acid does not
stabilize solution.
the same ratios.
3.1.4 Test Method D (Manganese, Neat Measurement
6.4 Iso-octane. (Warning—Extremely flammable.)
Method for Aviation Gasoline).
6.5 Solvent, capable of dissolving the bismuth internal
standard. Mixed xylenes and dodecane have been found
4. Significance and Use
suitable to use.
4.1 These test methods determine the concentration of lead
6.6 Hydrocarbon-Soluble Lead—Either tetraethyllead
(from alkyl addition) in gasoline. These alkyl additives im-
(TEL) or a lead-containing compound (for example, lead
prove the antiknock properties.
naphthenate) with a certifiable lead concentration.
4.2 Test Method C is used to ensure compliance of trace
6.7 Lead (Pb) Standard Solution—Dissolve tetraethyllead
lead as required by federal regulations for lead-free gasoline
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen-
(40 CFR Part 80).
ate (see Note 4), or other suitable lead containing compound in
4.3 Test Method D is used to determine the concentration of
iso-octane (Warning—Extremely flammable), toluene, or a
manganese in aviation gasoline.
mixture of these two solvents. This standard solution shall
contain an accurately known lead concentration of approxi-
mately the following magnitude:
TEST METHOD A (BISMUTH INTERNAL
5 g Pb ⁄US gal at 15.5 °C (60 °F) or
STANDARD)
6 g Pb ⁄UK gal at 15.5 °C (60 °F) or
1.3 g Pb ⁄L at 15.5 °C
5. Apparatus
6.7.1 Keep the standard solution refrigerated when not in
5.1 X-ray Spectrometer, capable of measuring radiations use.
mentioned in 3.1.1 and of being operated under the following
NOTE 4—A lead naphthenate solution of same lead concentration has
instrumental conditions or other giving equivalent results:
also proven satisfactory as a calibration material. ConcentratedTELis not
used to make up standard solutions. The concentrated solution is too
Tube Voltage 50 kV
Tube Current 20 mA to 45 mA acutely toxic to be handled safely under normal laboratory conditions.
Analyzing Crystal Lithium Fluoride (LiF)
Optical Path Air, Helium
(Warning—Compressed gas under pressure)
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Detector Proportional or Scintillation
Standard-Grade Reference Materials, American Chemical Society, Washington,
NOTE 1—The X-ray spectrometer and manner of use should comply
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical
with the regulations governing the use of ionizing radiation or recommen-
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
dations of the International Commission of Radiological Protection, or U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
both. copeial Convention, Inc. (USPC), Rockville, MD.
D5059 − 21
NOTE 5—When this lead standard solution is prepared with TEL, the
samples can be carried out using control chart techniques.
lead concentration can be determined with Test Method D3341.
When the QC sample result causes the laboratory to be in an
out-of-control situation, such as exceeding the laboratory’s
6.8 Toluene. (Warning—Flammable. Vapor harmful.)
control limits, instrument re-calibration may be required. An
ample supply of QC sample material shall be available for the
7. Calibration
intended period of use, and shall be homogeneous and stable
7.1 Make dilutions of the lead (Pb) standard solution to give
under the anticipated storage conditions. If possible, the QC
0.10 g Pb⁄US gal, 1.00 g Pb⁄US gal, 2.00 g Pb⁄US gal,
sample shall be representative of samples typically analyzed
3.00 g Pb⁄US gal, 4.00 g Pb⁄US gal and 5.00 g Pb⁄US gal at
and the average and control limits of the QC sample shall be
15.5 °C (60 °F) or 0.10 g Pb⁄UK gal, 1.00 g Pb⁄UK gal,
determined prior to monitoring the measurement process. The
2.50 g Pb⁄UK gal, 3.50 g Pb⁄UK gal, 5.00 g Pb⁄UK gal, and
QC sample precision shall be checked against the ASTM
6.00 g Pb⁄UK gal at 15.5 °C (60 °F) or 0.025 g Pb⁄L,
method precision to ensure data quality. Further guidance on
0.264 g Pb⁄L, 0.529 g Pb⁄L, 0.793 g Pb⁄L, 1.057 g Pb⁄L,
quality control can be found in Practices D6299 and D6792.
1.322 g Pb⁄L at 15 °C in toluene, iso-octane, or a mixture of
these solvents.
9. Procedure
9.1 Obtain sample in accordance with Practices D4057 or
7.2 Allow the lead standards and bismuth internal standard
D4177.
solutions to come to room temperature.
9.2 Prepare the samples to be analyzed as described in 7.3
7.3 Pipet accurately 10 mL of each standard into separate
and 7.4 for the standard lead solutions and determine the ratio,
glass-stoppered bottles or flasks and add an equal, accurately
R, as described in 7.5.
measured volume of the bismuth internal standard solution to
each one. Mix thoroughly. 9.3 Determine the lead content of the samples by relating
the R values obtained to the previously determined calibration
7.4 Place one of these solutions in the sample cell using
curve.
techniques consistent with good operating practice for the
spectrometer employed. Place the cell in the instrument, allow
10. Report
the spectrometer atmosphere to reach equilibrium (if
10.1 Report the lead content obtained as g Pb/US gal at
appropriate), and determine the counting rate at the lead L-α
15.5 °C(60 °F)orgPb/UKgalat15.5 °C(60 °F)tothenearest
line (1.175 Å) and at the bismuth L-α line (1.144 Å).
0.01 g, or g Pb/L at 15.5 °C to the nearest 0.003 g, as
NOTE 6—When possible, collect at least 100 000 counts at each line.
appropriate and reference this test method.
When sensitivity or concentration, or both, makes it impractical to collect
NOTE 8—To convert grams per US gallon at 15.5 °C (60 °F) to: (a)
this many counts, the technique that allows the greatest statistical
grams per UK gallon at 15.5 °C (60 °F) multiply by 1.200 and (b) grams
precision in the time allotted for each analysis should be used. Sample
per litre at 15.5 °C, multiply by 0.2642.
stability should also be considered in determining counting rate. Variation
in counting rates should be observed and if the counting rate tends to go
in one direction only, the sample is probably decomposing. If this occurs,
TEST METHOD B (SCATTERED TUNGSTEN
shortercountingtimesshouldbeusedconsistentwithacceptablestatistical
precision. RADIATION)
7.5 Determine the ratio, R, for each standard as follows:
11. Apparatus
R 5 A/B (1)
11.1 X-ray Spectrometer, capable of measuring radiations
where:
mentioned in 3.1.2 and of being operated under the following
instrumental conditions or others giving equivalent results:
A = counting rate at 1.175 Å, and
B = counting rate at 1.144 Å.
Tube Voltage 50 kV
Tube Current 20 mA to 45 mA
7.6 Plot a calibration curve relating R to the grams of lead
Tube Target Tungsten
Analyzing Crystal Lithium Fluoride (LiF)
per gallon.
Optical Path Air, Helium
(Warning—Compressed gas under pressure)
NOTE 7—Many modern X-ray spectrometer instruments will plot and
Collimation Fine
storethecalibrationcurve,slope,andrelatedinformationintheinstrument
Pulse Height Analyzer Threshold discrimination set as low as pos-
computer system, as an alternative to hand-plotting this information.
sible consistent with the removal of noise with
respect to the detector employed.
Detector Proportional or Scintillation
8. Quality Control Checks
Counting Technique Fixed Time
8.1 Confirm the calibration of the instrument each day it is
11.1.1 Two restrictions are imposed upon the period of the
in use by analyzing a quality control (QC) sample containing a
fixed time: namely, that it is 30 s or greater, and that it is such
quantifiable concentration of lead, that is, independent of the
calibration curve. It is advisable to analyze additional QC
samples as appropriate, such as at the beginning and end of a
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis,
batch of samples or after a fixed number of samples, to ensure
“Section 3, Control Charts for Individuals,” 6th ed., ASTM International, W. Con-
the quality of the results. Analysis of result(s) from these QC shohocken, PA.
D5059 − 21
that the count on the position of minimum intensity (back- 14. Quality Control Checks
ground at A = 1.211 Å) should exceed 200 000.
...

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: D5059 − 20 D5059 − 21
Standard Test Methods for
Lead and Manganese in Gasoline by X-Ray Fluorescence
Spectroscopy
This standard is issued under the fixed designation D5059; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope*
1.1 These test methods cover the determination of lead and manganese gasoline additives content by X-Ray Fluorescence
Spectroscopy (XRF). These test methods cover the determination of the total lead content of a gasoline within the following
concentration ranges:
0.010 g Pb ⁄US gal to 5.0 g Pb ⁄US gal
0.012 g Pb ⁄UK gal to 6.0 g Pb ⁄UK gal
0.0026 g Pb ⁄L to 1.32 g Pb ⁄L
and total manganese content of aviation gasoline within the concentration range of 25 mg Mn/L to 250 mg Mn/L.
1.1.1 Test Methods A and B cover the range of 0.10 g Pb ⁄US gal to 5.0 g Pb ⁄US gal. Test Method C covers the range of
0.010 g Pb ⁄US gal to 0.50 g Pb ⁄US gal.
1.1.2 These Methods A, B, and C are applicable to gasoline containing lead additives. These test methods compensate for normal
variation in gasoline composition and are independent of lead alkyl type.
1.1.3 Test Method D is applicable to aviation gasoline containing manganese additives.
1.2 Test Method A (formerly in withdrawn Test Method D2599)—Sections 5 – 10.
Test Method B (formerly in withdrawn Test Method D2599)—Sections 11 – 16.
Test Method C (formerly in withdrawn Test Method D3229)—Sections 17 – 23.
Test Method D—Sections 24 – 29.
1.3 The values stated in SI are to be regarded as the standard. For reporting purposes the values stated in grams per U.S. gallon
are the preferred units in the United States. Note that in other countries, other units can be preferred.
1.4 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, health, and environmental practices and determine the applicability of
regulatory limitations prior to use. For specific hazard statements, see Sections 5, 6, 11, and 18.
These test methods are under the jurisdiction of Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and are the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved May 1, 2020April 1, 2021. Published June 2020April 2021. Originally approved in 1990. Last previous edition approved in 20192020 as
D5059 – 14 (2019).D5059 – 20. DOI: 10.1520/D5059-20.10.1520/D5059-21.
Initially published as D2599 – 67T and D3229 – 73, now withdrawn.
*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
D5059 − 21
1.5 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:
D3341 Test Method for Lead in Gasoline—Iodine Monochloride Method
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6792 Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
2.2 Federal Standards:
40 CFR Part 80 Regulation of Fuels and Fuel Additives
3. Summary of Test Method
3.1 There are three alternative test methods for lead in gasoline and one method for manganese in aviation gasoline, as follows.
3.1.1 Test Method A (Bismuth Internal Standard Method High Concentration)—One volume of sample is mixed thoroughly with
an equal volume of bismuth internal standard solution. The mixture is placed in the X-ray beam and the intensities of the lead L-α
radiation at 1.175 Å and the bismuth L-α radiation at 1.144 Å are determined. The lead concentration of the sample is measured
by comparing the ratio of gross counting rate at 1.175 Å with the gross counting rate at 1.144 Å to a previous prepared calibration
curve of concentration versus the same ratios.
3.1.2 Test Method B (Scattered Tungsten Radiation Method)—The ratio of the net X-ray intensity of the lead L-α radiation to the
net intensity of the incoherently scattered tungsten L-α radiation is obtained on a portion of the sample. The lead content is
determined by multiplying this ratio by a calibration factor obtained with a standard lead solution of known concentration.
3.1.3 Test Method C (Bismuth Internal Standard Method, Low Concentration)—Twenty millilitres of sample is mixed thoroughly
with two millilitres of bismuth internal standard solution. The mixture is placed in the X-ray beam of a spectrometer and the
intensities of the lead L-α radiation at 1.175 Å, the bismuth L-α radiation at 1.144 Å, and a background at 1.194 Å are determined.
1 1
A blank, made with iso-octane and bismuth internal standard, is run using the same procedure. The lead concentration is measured
by determining the ratio of the net counting rate at 1.175 Å to the gross counting rate at 1.144 Å for the sample, subtracting the
comparable ratio found for the blank, and comparing to a previously prepared calibration curve of concentration versus the same
ratios.
3.1.4 Test Method D (Manganese, Neat Measurement Method for Aviation Gasoline).
4. Significance and Use
4.1 These test methods determine the concentration of lead (from alkyl addition) in gasoline. These alkyl additives improve the
antiknock properties.
4.2 Test Method C is used to ensure compliance of trace lead as required by federal regulations for lead-free gasoline (40 CFR
Part 80).
4.3 Test Method D is used to determine the concentration of manganese in aviation gasoline.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from U.S. Government Printing Office, Superintendent of Documents, 732 N. Capitol St., NW, Washington, DC 20401-0001, http://www.access.gpo.gov.
D5059 − 21
TEST METHOD A (BISMUTH INTERNAL STANDARD)
5. Apparatus
5.1 X-ray Spectrometer, capable of measuring radiations mentioned in 3.1.1 and of being operated under the following
instrumental conditions or other giving equivalent results:
Tube Voltage 50 kV
Tube Current 20 mA to 45 mA
Analyzing Crystal Lithium Fluoride (LiF)
Optical Path Air, Helium
(Warning—Compressed gas under pressure)
Detector Proportional or Scintillation
NOTE 1—The X-ray spectrometer and manner of use should comply with the regulations governing the use of ionizing radiation or recommendations of
the International Commission of Radiological Protection, or both.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determinations.
6.2 Hydrocarbon-Soluble Bismuth.
NOTE 2—Bismuth 2-Ethylhexoate has been found suitable to use. Other bismuth containing materials that are hydrocarbon-soluble may also be used when
they are certified to conform to 6.1.
6.3 Bismuth Internal Standard Solution—Dilute the hydrocarbon-soluble bismuth with a suitable solvent. If bismuth
2-ethylhexoate is used, add 2-ethylhexanoic acid as a stabilizer (see Note 3) to obtain a solution containing the following:
3.00 g Bi ⁄US gal at 15.5 °C (60 °F) or
3.60 g Bi ⁄UK gal at 15.5 °C (60 °F) or
0.793 g Bi ⁄L at 15 °C
NOTE 3—Some stability difficulties have been experienced with bismuth 2-ethylhexoate internal standard solution. If the standard is blended to contain
5 % 2-ethylhexanoic acid, the standard has been found to last almost indefinitely. The 2-ethylhexanoic acid stabilizes iso-octane, toluene, and benzene
solutions of the bismuth 2-ethylhexoate which are otherwise stable for only a day or two. Normal octanoic acid does not stabilize solution.
6.4 Iso-octane. (Warning—Extremely flammable.)
6.5 Solvent, capable of dissolving the bismuth internal standard. Mixed xylenes and dodecane have been found suitable to use.
6.6 Hydrocarbon-Soluble Lead—Either tetraethyllead (TEL) or a lead-containing compound (for example, lead naphthenate) with
a certifiable lead concentration.
6.7 Lead (Pb) Standard Solution—Dissolve tetraethyllead (TEL) (Warning—TEL is toxic by ingestion), lead naphthenate (see
Note 4), or other suitable lead containing compound in iso-octane (Warning—Extremely flammable), toluene, or a mixture of
these two solvents. This standard solution shall contain an accurately known lead concentration of approximately the following
magnitude:
ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference Materials, American Chemical Society, Washington, DC. For
suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and
the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
D5059 − 21
5 g Pb ⁄US gal at 15.5 °C (60 °F) or
6 g Pb ⁄UK gal at 15.5 °C (60 °F) or
1.3 g Pb ⁄L at 15.5 °C
6.7.1 Keep the standard solution refrigerated when not in use.
NOTE 4—A lead naphthenate solution of same lead concentration has also proven satisfactory as a calibration material. Concentrated TEL is not used to
make up standard solutions. The concentrated solution is too acutely toxic to be handled safely under normal laboratory conditions.
NOTE 5—When this lead standard solution is prepared with TEL, the lead concentration can be determined with Test Method D3341.
6.8 Toluene. (Warning—Flammable. Vapor harmful.)
7. Calibration
7.1 Make dilutions of the lead (Pb) standard solution to give 0.10 g Pb ⁄US gal, 1.00 g Pb ⁄US gal, 2.00 g Pb ⁄US gal,
3.00 g Pb ⁄US gal, 4.00 g Pb ⁄US gal and 5.00 g Pb ⁄US gal at 15.5 °C (60 °F) or 0.10 g Pb ⁄UK gal, 1.00 g Pb ⁄UK gal,
2.50 g Pb ⁄UK gal, 3.50 g Pb ⁄UK gal, 5.00 g Pb ⁄UK gal, and 6.00 g Pb ⁄UK gal at 15.5 °C (60 °F) or 0.025 g Pb ⁄L, 0.264 g Pb ⁄L,
0.529 g Pb ⁄L, 0.793 g Pb ⁄L, 1.057 g Pb ⁄L, 1.322 g Pb ⁄L at 15 °C in toluene, iso-octane, or a mixture of these solvents.
7.2 Allow the lead standards and bismuth internal standard solutions to come to room temperature.
7.3 Pipet accurately 10 mL of each standard into separate glass-stoppered bottles or flasks and add an equal, accurately measured
volume of the bismuth internal standard solution to each one. Mix thoroughly.
7.4 Place one of these solutions in the sample cell using techniques consistent with good operating practice for the spectrometer
employed. Place the cell in the instrument, allow the spectrometer atmosphere to reach equilibrium (if appropriate), and determine
the counting rate at the lead L-α line (1.175 Å) and at the bismuth L-α line (1.144 Å).
1 1
NOTE 6—When possible, collect at least 100 000 counts at each line. When sensitivity or concentration, or both, makes it impractical to collect this many
counts, the technique that allows the greatest statistical precision in the time allotted for each analysis should be used. Sample stability should also be
considered in determining counting rate. Variation in counting rates should be observed and if the counting rate tends to go in one direction only, the
sample is probably decomposing. If this occurs, shorter counting times should be used consistent with acceptable statistical precision.
7.5 Determine the ratio, R, for each standard as follows:
R 5 A/B (1)
where:
A = counting rate at 1.175 Å, and
B = counting rate at 1.144 Å.
7.6 Plot a calibration curve relating R to the grams of lead per gallon.
NOTE 7—Many modern X-ray spectrometer instruments will plot and store the calibration curve, slope, and related information in the instrument computer
system, as an alternative to hand-plotting this information.
8. Quality Control Checks
8.1 Confirm the calibration of the instrument each day it is in use by analyzing a quality control (QC) sample containing a
quantifiable concentration of lead, that is, independent of the calibration curve. It is advisable to analyze additional QC samples
as appropriate, such as at the beginning and end of a batch of samples or after a fixed number of samples, to ensure the quality
of the results. Analysis of result(s) from these QC samples can be carried out using control chart techniques. When the QC sample
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, “Section 3, Control Charts for Individuals,” 6th ed., ASTM International, W. Conshohocken,
PA.
D5059 − 21
result causes the laboratory to be in an out-of-control situation, such as exceeding the laboratory’s control limits, instrument
re-calibration may be required. An ample supply of QC sample material shall be available for the intended period of use, and shall
be homogeneous and stable under the anticipated storage conditions. If possible, the QC sample shall be representative of samples
typically analyzed and the average and control limits of the QC sample shall be determined prior to monitoring the measurement
process. The QC sample precision shall be checked against the ASTM method precision to ensure data quality. Further guidance
on quality control can be found in Practices D6299 and D6792.
9. Procedure
9.1 Obtain sample in accordance with PracticePractices D4057 or D4177.
9.2 Prepare the samples to be analyzed as described in 7.3 and 7.4 for the standard lead solutions and determine the ratio, R, as
described in 7.5.
9.3 Determine the lead content of the samples by relating the R values obtained to the previously determined calibration curve.
10. Report
10.1 Report the lead content obtained as g Pb/US gal at 15.5 °C (60 °F) or g Pb/UK gal at 15.5 °C (60 °F) to the nearest 0.01 g,
or g Pb/L at 15.5 °C to the nearest 0.003 g, as appropriate.appropriate and reference this test method.
NOTE 8—To convert grams per US gallon at 15.5 °C (60 °F) to: (a) grams per UK gallon at 15.5 °C (60 °F) multiply by 1.200 and (b) grams per litre
at 15.5 °C, multiply by 0.2642.
TEST METHOD B (SCATTERED TUNGSTEN RADIATION)
11. Apparatus
11.1 X-ray Spectrometer, capable of measuring radiations mentioned in 3.1.2 and of being operated under the following
instrumental conditions or others giving equivalent results:
Tube Voltage 50 kV
Tube Current 20 mA to 45 mA
Tube Target Tungsten
Analyzing Crystal Lithium Fluoride (LiF)
Optical Path Air, Helium
(Warning—Compressed gas under pressure)
Collimation Fine
Pulse Height Analyzer Threshold discrimination set as low as pos-
sible consistent with the removal of noise with
respect to the detector employed.
Detector Proportional or Scintillation
Counting Technique Fixed Time
11.1.1 Two restrictions are imposed upon the period of the fixed time: namely, that it is 30 s or greater, and that it is such that the
count on the position of minimum intensity (background at A = 1.211 Å) should exceed 200 000.
NOTE 9—The X-ray spectrometer and ma
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