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
Spectroscopy1
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-

1.1 These test methods cover the determination of lead and priate safety, health, and environmental practices and deter-
manganese gasoline additives content by X-Ray Fluorescence mine the applicability of regulatory limitations prior to use.
Spectroscopy (XRF). These test methods cover the determina- For specific hazard statements, see Sections 5, 6, 11, and 18.
tion of the total lead content of a gasoline within the following 1.5 This international standard was developed in accor-
concentration ranges: dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
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 Development of International Standards, Guides and Recom-
0.0026 g Pb ⁄L to 1.32 g Pb ⁄L mendations issued by the World Trade Organization Technical
and total manganese content of aviation gasoline within the Barriers to Trade (TBT) Committee.
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
0.10 g Pb ⁄US gal to 5.0 g Pb ⁄US gal. Test Method C covers the 2.1 ASTM Standards:2
range of 0.010 g Pb ⁄US gal to 0.50 g Pb ⁄US gal. D3341 Test Method for Lead in Gasoline—Iodine Mono-
1.1.2 These Methods A, B, and C are applicable to gasoline chloride Method
containing lead additives. These test methods compensate for D4057 Practice for Manual Sampling of Petroleum and
normal variation in gasoline composition and are independent Petroleum Products
of lead alkyl type. D4177 Practice for Automatic Sampling of Petroleum and
1.1.3 Test Method D is applicable to aviation gasoline Petroleum Products
containing manganese additives. D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
1.2 Test Method A (formerly in withdrawn Test Method Measurement System Performance
D2599)—Sections 5 – 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)—Sections 11 – 16. Laboratories
Test Method C (formerly in withdrawn Test Method 2.2 Federal Standards:3
D3229)—Sections 17 – 23. 40 CFR Part 80 Regulation of Fuels and Fuel Additives
Test Method D—Sections 24 – 29.
3. Summary of Test Method
1.3 The values stated in SI are to be regarded as the
standard. For reporting purposes the values stated in grams per 3.1 There are three alternative test methods for lead in
U.S. gallon are the preferred units in the United States. Note gasoline and one method for manganese in aviation gasoline,
that in other countries, other units can be preferred. as follows.
1.4 This standard does not purport to address all of the 3.1.1 Test Method A (Bismuth Internal Standard Method
safety concerns, if any, associated with its use. It is the High Concentration)—One volume of sample is mixed thor-
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, [Link], or
Products, Liquid Fuels, and Lubricants and are the direct responsibility of contact ASTM Customer Service at service@[Link]. 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.
3
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. [Link].

*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
intensities of the lead L-α1 radiation at 1.175 Å and the bismuth 6.1 Purity of Reagents—Reagent grade chemicals shall be
L-α1 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.4 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-α1 the determinations.
radiation to the net intensity of the incoherently scattered
tungsten L-α1 radiation is obtained on a portion of the sample. 6.2 Hydrocarbon-Soluble Bismuth.
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
known concentration. used when they are certified to conform to 6.1.
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-α1 radiation at following:
1.175 Å, the bismuth L-α1 radiation at 1.144 Å, and a back- 3.00 g Bi ⁄US gal at 15.5 °C (60 °F) or
ground at 1.194 Å are determined. A blank, made with iso- 3.60 g Bi ⁄UK gal at 15.5 °C (60 °F) or
0.793 g Bi ⁄L at 15 °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-
the ratio of the net counting rate at 1.175 Å to the gross muth 2-ethylhexoate internal standard solution. If the standard is blended
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
the same ratios. stabilize solution.
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. Concentrated TEL is not
Tube Voltage 50 kV used to make up standard solutions. The concentrated solution is too
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)
4
Detector Proportional or Scintillation ACS Reagent Chemicals, Specifications and Procedures for Reagents and
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 the American 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.

2
 D5059 − 21
NOTE 5—When this lead standard solution is prepared with TEL, the samples can be carried out using control chart techniques.5
lead concentration can be determined with Test Method D3341. When the QC sample result causes the laboratory to be in an
6.8 Toluene. (Warning—Flammable. Vapor harmful.) out-of-control situation, such as exceeding the laboratory’s
control limits, instrument re-calibration may be required. An
7. Calibration ample supply of QC sample material shall be available for the
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
7.2 Allow the lead standards and bismuth internal standard 9.1 Obtain sample in accordance with Practices D4057 or
solutions to come to room temperature. D4177.
7.3 Pipet accurately 10 mL of each standard into separate 9.2 Prepare the samples to be analyzed as described in 7.3
glass-stoppered bottles or flasks and add an equal, accurately and 7.4 for the standard lead solutions and determine the ratio,
measured volume of the bismuth internal standard solution to R, as described in 7.5.
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
appropriate), and determine the counting rate at the lead L-α1 10.1 Report the lead content obtained as g Pb/US gal at
line (1.175 Å) and at the bismuth L-α1 line (1.144 Å). 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
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
this many counts, the technique that allows the greatest statistical NOTE 8—To convert grams per US gallon at 15.5 °C (60 °F) to: (a)
precision in the time allotted for each analysis should be used. Sample grams per UK gallon at 15.5 °C (60 °F) multiply by 1.200 and (b) grams
stability should also be considered in determining counting rate. Variation per litre at 15.5 °C, multiply by 0.2642.
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 TEST METHOD B (SCATTERED TUNGSTEN
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
A = counting rate at 1.175 Å, and instrumental conditions or others giving equivalent results:
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
per gallon. Analyzing Crystal Lithium Fluoride (LiF)
Optical Path Air, Helium
NOTE 7—Many modern X-ray spectrometer instruments will plot and (Warning—Compressed gas under pressure)
Collimation Fine
store the calibration curve, slope, and related information in the instrument 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.
8. Quality Control Checks Detector Proportional or Scintillation
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 5
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.

3
 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. 14.1 Follow the requirements specified in 8.1 for samples
NOTE 9—The X-ray spectrometer and manner of use should comply analyzed by Test Method B.
with the regulations governing the use of ionizing radiation or recommen-
dations of the International Commission of Radiological Protection, or 15. Procedure
both.
15.1 Obtain sample in accordance with Practices D4057 or
D4177.
12. Reagents and Materials
15.2 Remove the standard lead solution and the gasoline
12.1 Iso-octane. (Warning—Extremely flammable.) samples from the refrigerator and bring them to room tempera-
12.2 Lead (Pb) Standard Solution—Dissolve tetraethyllead ture.
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen- 15.3 Establish the calibration factor, F, as described in 13.4.
ate (see Note 4), or other suitable lead containing compound in This must be done each day the method is in use.
iso-octane (Warning—Extremely flammable), toluene, or a
mixture of these two solvents. When TEL is used, refer to Note 15.4 Determine the ratio, R', for the samples as shown in
5. This standard solution shall contain an accurately known 13.1, 13.2, and 13.3 and obtain the lead content of the samples
lead concentration of approximately the following magnitude: by multiplying R' by the calibration factor, F.
5 g Pb ⁄US gal at 15.5 °C (60 °F) 16. Report
6 g Pb ⁄UK gal at 15.5 °C (60 °F)
1.3 g Pb ⁄L at 15.5 °C 16.1 Report the lead content obtained as g Pb/UK gal at
12.2.1 Keep the standard solution refrigerated when not in 15.5 °C (60 °F), g Pb/US gal at 15.5 °C (60 °F) to the nearest
use. 0.01 g, or g Pb/L at 15.5 °C to the nearest 0.003 g, as
appropriate and reference this test method.
13. Calibration
13.1 Place the standard lead solution in the sample cell TEST METHOD C (LOW-LEAD METHOD)
using techniques consistent with good operating practice for
the spectrometer employed. Insert the cell in the X-ray beam 17. Apparatus
using the instrumental conditions described in Section 10 and 17.1 X-ray Spectrometer, as described in 5.1. See Note 9.
allow the spectrometer atmosphere to reach equilibrium (when
appropriate). Take one intensity reading at each of the follow- 18. Reagents and Materials
ing wavelength settings, then replace the standard solution with 18.1 Reagents are described in Section 6.
a fresh portion and repeat the readings. Repeat this procedure
18.2 Lead (Pb) Solution, Standard (0.500 g Pb ⁄gal)—Dilute
with iso-octane.
an aliquot of the standard prepared in 6.6 appropriately so that
Analytical line, lead L-α1 λ = 1.175 Å
WL-α1 (incoherent) λ = 1.500 Å, calculated for 90° instrument
it contains 0.500 g Pb ⁄US gal at 60 °F (15.6 °C). Keep refrig-
geometry (Note 7) erated when not in use. (Warning—TEL is toxic by ingestion.)
Background position λ = 1.211 Å
19. Calibration
NOTE 10—Calculated for the case where the angle between the incident
radiation and take-off collimator is 90°, using the equation for: 19.1 Make exact dilutions of the 0.500 g Pb ⁄gal standards to
Compton scatter λ'2λ 5 0.024 ~ 1 2 cos φ ! (2)
give 0.30 g Pb ⁄US gal, 0.10 g Pb ⁄US gal, 0.050 g Pb ⁄US gal,
0.010 g Pb ⁄US gal, 0.005 g Pb ⁄US gal and 0.001 g Pb ⁄US gal
where: at 60 °F in toluene, iso-octane, or a mixture of these two
λ' = wavelength of incoherent scattered radiation, solvents. Retain a 0.000 g Pb ⁄gal standard as a blank.
λ = wavelength of incident radiation (WL-α1 ), and
φ = angle between incident and scattered radiation. 19.2 Allow all solutions to come to room temperature.
13.2 Determine the corrected background by multiplying 19.3 Pipet accurately 20.0 mL of each standard (including
the intensity of the background at λ = 1.211 Å by the following the 0.500 g Pb ⁄gal standard) and the blank into separate
ratio obtained on the iso-octane blank: glass-stoppered bottles or flasks and add accurately 2.0 mL of
the bismuth internal standard to each one. Mix thoroughly.
Background at A 5 1.175 Å
(3) 19.4 Place one of these solutions in the sample cell using
Background at A 5 1.211Å techniques consistent with good operating practice for the
13.3 Take the mean of the two intensity readings at each spectrometer employed. Place the cell in the instrument, allow
wavelength setting and calculate the ratio, R', as follows: the atmosphere to reach equilibrium (if appropriate), and
determine counting rates at the Pb L-α1 line (1.175 Å), the Bi
R' 5 ~ Lead L 2 α 1 2 corrected background! / (4)
L-α1 line (1.144 Å), and the background (1.194 Å).
~ Incoherent WL 2 α 1 2 background! 19.5 Determine the ratio, R, for each standard and the blank
13.4 Divide the lead concentration of the standard solution as follows:
by R' to obtain the calibration factor, F. R 5 ~ A 2 C ! /B (5)

4
 D5059 − 21
where: 24.2 Film – X-ray Transparent Film—Any film that resists
A = counting rate at 1.175 Å, attack by the sample and is sufficiently X-ray transparent may
B = counting rate at 1.144 Å, and be used.
C = counting rate at 1.194 Å.
25. Reagents and Materials
19.6 Determine the corrected ratio, Rc, as follows:
25.1 Purity of Reagents—Reagent grade chemicals shall be
Rc 5 R 2 Rb (6) used in all tests. Unless otherwise indicated, it is intended that
where: Rb = ratio for blank. all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
19.7 Plot a calibration curve (see Note 7) relating Rc to the
such specifications are available.4 Other grades may be used,
grams of lead per gallon. Determine the slope, S, of the
provided it is first ascertained that the reagent is of sufficiently
resulting line if it is straight as follows:
high purity to permit its use without lessening the accuracy of
S 5 ~ g Pb/US gal! /R c (7) the determinations.
25.2 Iso-octane. (Warning—Extremely flammable.)
20. Quality Control Checks
25.3 Toluene. (Warning—Flammable. Vapor harmful.)
20.1 Follow the requirements specified in 8.1 for samples
analyzed by Test Method C. 25.4 Manganese (Mn) Standard Solution—Hydrocarbon-
soluble manganese with a certifiable manganese concentration
21. Procedure is dissolved with a suitable solvent. Commercially prepared
certified standards may also be used.
21.1 Obtain sample in accordance with Practices D4057 or
D4177. 25.5 Solvent—Appropriate mixture of iso-octane and tolu-
ene used to prepare the manganese standard solution. A ratio of
21.2 Prepare the samples to be analyzed and a blank as 75/25 iso-octane to toluene has been found to be suitable.
described in 19.3 and 19.4 for the standard lead solutions and
determine the ratio, Rc, as described in 19.5 and 19.6 using the 26. Calibration
blank determined at the time of analysis.
26.1 Make exact dilutions of the mg Mn/L standards to
cover the concentration range, for example, 10 mg Mn/L,
22. Calibration 25 mg Mn/L, 50 mg Mn/L, 100 mg Mn/L, 150 mg Mn ⁄L,
22.1 Calculate the lead content of the samples by relating Rc 200 mg Mn/L, and 300 mg Mn/L in toluene, iso-octane, or a
to the previously determined calibration curve. If S was mixture of these two solvents. Retain a 0.000 mg Mn/L
calculated in 19.7 determine lead content as follows: standard as a blank. Commercially prepared standards can be
Pb, g Pb/US gal 5 R c 3 S (8) used.
26.2 Place one of these solutions in the sample cell using
23. Report techniques consistent with good operating practice for the
23.1 Report the lead content obtained in 22.1 as spectrometer employed. Place the cell in the instrument, and
g Pb ⁄US gal at 60 °F (15.6 °C) to the nearest 0.005 g and determine counting rates at the Mn kα1 line (2.104 Å or
reference this test method. 5.898 keV), and for the corresponding background region.
26.3 Determine the net intensity, IMn, for each standard and
TEST METHOD D (MANGANESE MEASUREMENT) the blank sample as follows (see Note 7):
I Mn 5 ~ A 2 B ! (9)
24. Apparatus
24.1 X-ray Fluorescence Spectrometer (XRF), capable of where:
measuring manganese and of being operated under the follow- A = counting rate of Mn line or region of interest, and
ing instrumental conditions or other conditions giving equiva- B = counting rate of background.
lent results. 26.4 Plot a calibration curve (see Note 7) relating IMn to the
24.1.1 XRF instrumentation can be Energy Dispersive milligrams of manganese per liter.
(EDXRF) or Wavelength dispersive (WDXRF).
Tube Voltage 20 kV to 60 kV
27. Quality Control Checks
Tube Current $20 mA (WDXRF), 27.1 Confirm the calibration of the instrument each day it is
$0.1 mA (EDXRF)
Analyzing Crystal Lithium Fluoride (LiF) in use by analyzing a quality control (QC) sample containing a
for WDXRF quantifiable concentration of manganese, that is, independent
Optical Path Air or Helium (Warning—Compressed gas under pressure)) of the calibration curve. It is advisable to analyze additional
Detector Proportional or Scintillation (WDXRF), Solid state or SDD
detector (EDXRF) 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
NOTE 11—The X-ray spectrometer and manner of use should comply
with the regulations governing the use of ionizing radiation or recommen- the quality of the results. Analysis of result(s) from these QC
dations of the International Commission of Radiological Protection, or samples can be carried out using control chart techniques.5
both. When the QC sample result causes the laboratory to be in an

5
 D5059 − 21
out-of-control situation, such as exceeding the laboratory’s Test Method A Test Method B Test Method C
control limits, instrument re-calibration may be required. An (Bismuth Internal (Scattered Tungsten (Low Lead
Standard) Radiation) Method)
ample supply of QC sample material shall be available for the Units of X
intended period of use and shall be homogeneous and stable 0.103 + 0.030X 0.037 + 0.039X 0.018 + 0.15X g Pb ⁄US gal at
under the anticipated storage conditions. If possible, the QC 15.5 °C (60 °F)
0.124 + 0.030X 0.044 + 0.039X ... g Pb ⁄UK gal at
sample shall be representative of samples typically analyzed 15.5 °C (60 °F)
and the average and control limits of the QC sample shall be 0.027 + 0.030X 0.010 + 0.039X ... g Pb ⁄L at 15 °C
determined prior to monitoring the measurement process. The
NOTE 12—The precision of the analyses are based on the use of
QC sample precision shall be checked against the ASTM tetraethyl lead standards only, and users of the test method are cautioned
method precision to ensure data quality. Further guidance on that the precision of the analyses using other lead containing standards
quality control can be found in Practices D6299 and D6792. may not apply.

28. Procedure 30.2 Bias—A result from these test methods does not differ
from the actual value by more than the reproducibility of the
28.1 Obtain sample in accordance with Practices D4057 or
test methods.
D4177.
28.2 Prepare the samples to be analyzed as described in 26.2 NOTE 13—The bias was determined from analysis of NIST reference
for the standard manganese solutions and determine the net materials by four laboratories.
intensity, IMn, as described in 26.3. 30.3 The precision of Test Method D as obtained by
28.3 Calculate the manganese content of the samples by statistical examination of interlaboratory test results is as
relating IMn to the previously determined calibration curve. follows. In this study, nineteen laboratories analyzed twelve
samples of aviation gasoline in duplicate.
29. Report 30.3.1 Repeatability—The difference between successive
29.1 Report the manganese content obtained in 28.3 as mg test results, obtained by the same operator with the same
Mn/L to the nearest 1 mg Mn ⁄L and reference this test method. apparatus under constant operating conditions on identical test
material, would in the long run, in the normal and correct
30. Precision and Bias6 operation of the test method, exceed the following values only
30.1 The precision of Test Methods A, B, and C as obtained in one case in twenty:
by statistical examination of interlaboratory test results is as
follows:
30.1.1 Repeatability—The difference between successive r = 0.7054 x0.351
test results, obtained by the same operator with the same
apparatus under constant operating conditions on identical test where:
material, would in the long run, in the normal and correct x = the average of the two test results in mg Mn/L.
operation of the test method, exceed the following values only 30.3.2 Reproducibility—The difference between two single
in one case in twenty: and independent results, obtained by different operators work-
Test Method A Test Method B Test Method C ing in different laboratories on identical test material, would in
(Bismuth Internal (Scattered Tungsten (Low Lead
Standard) Radiation) Method) the long run, in the normal and correct operation of the test
Units of X method, exceed the following values only in one case in
0.029 + 0.008X 0.014 + 0.015X 0.007 + 0.14X g Pb ⁄US gal at twenty:
15.5 °C (60 °F)
0.035 + 0.008X 0.017 + 0.015X ... g Pb ⁄UK gal at
15.5 °C (60 °F)
0.008 + 0.008X 0.004 + 0.015X ... g Pb ⁄L at 15 °C
R = 0.5354 x0.7306
30.1.2 Reproducibility—The difference between two single
and independent results, obtained by different operators work- where:
ing in different laboratories on identical test material, would in x = the average of the two test results in mg Mn/L.
the long run, in the normal and correct operation of the test
30.4 Bias—The bias of Test Method D in this test method
method, exceed the following values only in one case in
has not been determined.
twenty:
31. Keywords
6
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1283 and Research Report 31.1 aviation gasoline; gasoline; lead; low lead; manganese;
RR:D02-1927. Contact ASTM Customer Service at service@[Link]. TEL, tetraethyllead; X-ray; X-ray fluorescence

6
 D5059 − 21
SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D5059 – 20) that may impact the use of this standard. (Approved April 1, 2021.)

(1) Revised title. (3) Revised subsections 9.1, 10.1, 15.1, 16.1, 21.1, 23.1, 28.1,
(2) Added Practice D4177 to Section 2. 29.1.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D5059 – 14 (2019)) that may impact the use of this standard. (Approved May 1, 2020.)

(1) Revised title. (4) Added new Test Method D in Sections 24 – 29.
(2) Revised subsections 1.1, 1.1.2, 1.2, 3.1, 30.1, and 31. (5) Added new Research Report RR:D02-1927 to footnote 6.
(3) Added new subsections 1.1.3, 2.2, 3.1.4, 4.3, 30.3, and
30.4.

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