ASTM D5059-14(2019)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D5059 − 14 (Reapproved 2019)
Standard Test Methods for
Lead in Gasoline by X-Ray 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 2. Referenced Documents
1.1 These test methods cover the determination of the total 2.1 ASTM Standards:
lead content of a gasoline within the following concentration D3341 Test Method for Lead in Gasoline—Iodine Mono-
ranges: chloride Method
D4057 Practice for Manual Sampling of Petroleum and
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
Petroleum Products
0.0026gPb⁄Lto1.32gPb⁄L
D6299 Practice for Applying Statistical Quality Assurance
1.1.1 Test Methods A and B cover the range of
and Control Charting Techniques to Evaluate Analytical
0.10 g Pb⁄US galto5.0 g Pb⁄US gal.TestMethodCcoversthe
Measurement System Performance
range of 0.010 g Pb⁄US gal to 0.50 g Pb⁄US gal.
D6792 Practice for Quality Management Systems in Petro-
1.1.2 These test methods compensate for normal variation
leum Products, Liquid Fuels, and Lubricants Testing
ingasolinecompositionandareindependentofleadalkyltype.
Laboratories
1.2 Test Method A (formerly in withdrawn Test Method
3. Summary of Test Method
D2599)—Sections5–9.
Test Method B (formerly in withdrawn Test Method
3.1 There are three alternative test methods, as follows.
D2599)—Sections10–14. 3.1.1 Test Method A (Bismuth Internal Standard Method
Test Method C (formerly in withdrawn Test Method
High Concentration)—One volume of sample is mixed thor-
D3229)—Sections15–19.
oughly with an equal volume of bismuth internal standard
solution. The mixture is placed in the X-ray beam and the
1.3 The values stated in SI are to be regarded as the
intensitiesofthelead L-α radiationat1.175 Åandthebismuth
standard. For reporting purposes the values stated in grams per
L-α radiation at 1.144 Å are determined. The lead concentra-
U.S. gallon are the preferred units in the United States. Note
tion of the sample is measured by comparing the ratio of gross
that in other countries, other units can be preferred.
counting rate at 1.175 Å with the gross counting rate at 1.144 Å
1.4 This standard does not purport to address all of the
to a previous prepared calibration curve of concentration
safety concerns, if any, associated with its use. It is the
versus the same ratios.
responsibility of the user of this standard to establish appro-
3.1.2 Test Method B (Scattered Tungsten Radiation
priate safety, health, and environmental practices and deter-
Method)—The ratio of the net X-ray intensity of the lead L-α
mine the applicability of regulatory limitations prior to use.
radiation to the net intensity of the incoherently scattered
For specific hazard statements, see Sections 5, 6, 11, and 18.
tungsten L-α radiation is obtained on a portion of the sample.
1.5 This international standard was developed in accor-
The lead content is determined by multiplying this ratio by a
dance with internationally recognized principles on standard-
calibration factor obtained with a standard lead solution of
ization established in the Decision on Principles for the
known concentration.
Development of International Standards, Guides and Recom-
3.1.3 Test Method C (Bismuth Internal Standard Method,
mendations issued by the World Trade Organization Technical
Low Concentration)—Twenty millilitres of sample is mixed
Barriers to Trade (TBT) Committee.
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
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, 2019. Published June 2019. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1990. Last previous edition approved in 2014 as D5059 – 14. DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D5059-14R19. Standards volume information, refer to the standard’s Document Summary page on
Initially published as D2599 – 67T and D3229 – 73, now withdrawn. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5059 − 14 (2019)
1.175 Å, the bismuth L-α radiation at 1.144 Å, and a back- muth 2-ethylhexoate is used, add 2-ethylhexanoic acid as a
ground at 1.194 Å are determined. A blank, made with iso- stabilizer (see Note 3) to obtain a solution containing the
octane and bismuth internal standard, is run using the same following:
procedure. The lead concentration is measured by determining
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
the ratio of the net counting rate at 1.175 Å to the gross
0.793gBi⁄Lat15°C
counting rate at 1.144 Å for the sample, subtracting the
comparable ratio found for the blank, and comparing to a NOTE 3—Some stability difficulties have been experienced with bis-
muth 2-ethylhexoate internal standard solution. If the standard is blended
previously prepared calibration curve of concentration versus
to contain 5 % 2-ethylhexanoic acid, the standard has been found to last
the same ratios.
almost indefinitely. The 2-ethylhexanoic acid stabilizes iso-octane,
toluene, and benzene solutions of the bismuth 2-ethylhexoate which are
4. Significance and Use
otherwise stable for only a day or two. Normal octanoic acid does not
stabilize solution.
4.1 These test methods determine the concentration of lead
6.4 Iso-octane. (Warning—Extremely flammable.)
(from alkyl addition) in gasoline. These alkyl additives im-
prove the antiknock properties.
6.5 Solvent, capable of dissolving the bismuth internal
standard. Mixed xylenes and dodecane have been found
4.2 Test Method C is used to ensure compliance of trace
suitable to use.
lead as required by federal regulations for lead-free gasoline
(40 CFR part 80).
6.6 Hydrocarbon-Soluble Lead—Either tetraethyllead
(TEL) or a lead-containing compound (for example, lead
naphthenate) with a certifiable lead concentration.
TEST METHOD A (BISMUTH INTERNAL
STANDARD) 6.7 Lead (Pb) Standard Solution—Dissolve tetraethyllead
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen-
5. Apparatus
ate (see Note 4), or other suitable lead containing compound in
iso-octane (Warning—Extremely flammable), toluene, or a
5.1 X-ray Spectrometer, capable of measuring radiations
mixture of these two solvents. This standard solution shall
mentioned in 3.1.1 and of being operated under the following
contain an accurately known lead concentration of approxi-
instrumental conditions or other giving equivalent results:
mately the following magnitude:
Tube Voltage 50 kV
Tube Current 20 mA to 45 mA
5 g Pb ⁄US gal at 15.5 °C (60 °F) or
Analyzing Crystal Lithium Fluoride (LiF) 6 g Pb ⁄UK gal at 15.5 °C (60 °F) or
Optical Path Air, Helium
1.3 g Pb ⁄L at 15.5 °C
(Warning—Compressed gas under pressure)
6.7.1 Keep the standard solution refrigerated when not in
Detector Proportional or Scintillation
use.
NOTE 1—The X-ray spectrometer and manner of use should comply
with the regulations governing the use of ionizing radiation or recommen-
NOTE 4—A lead naphthenate solution of same lead concentration has
dations of the International Commission of Radiological Protection, or
also proven satisfactory as a calibration material. ConcentratedTELis not
both.
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
6. Reagents and Materials
lead concentration can be determined with Test Method D3341.
6.1 Purity of Reagents—Reagent grade chemicals shall be
6.8 Toluene. (Warning—Flammable. Vapor harmful.)
used in all tests. Unless otherwise indicated, it is intended that
all reagents conform to the specifications of the Committee on
7. Calibration
Analytical Reagents of the American Chemical Society where
3 7.1 Make dilutions of the lead (Pb) standard solution to give
such specifications are available. Other grades may be used,
0.10 g Pb⁄US gal, 1.00 g Pb⁄US gal, 2.00 g Pb⁄US gal,
provided it is first ascertained that the reagent is of sufficiently
3.00 g Pb⁄US gal, 4.00 g Pb⁄US gal and 5.00 g Pb⁄US gal at
high purity to permit its use without lessening the accuracy of
15.5 °C (60 °F) or 0.10 g Pb⁄UK gal, 1.00 g Pb⁄UK gal,
the determinations.
2.50 g Pb⁄UK gal, 3.50 g Pb⁄UK gal, 5.00 g Pb⁄UK gal, and
6.2 Hydrocarbon-Soluble Bismuth.
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,
NOTE 2—Bismuth 2-Ethylhexoate has been found suitable to use. Other
bismuth containing materials that are hydrocarbon-soluble may also be 1.322 g Pb⁄L at 15 °C in toluene, iso-octane, or a mixture of
used when they are certified to conform to 6.1.
these solvents.
6.3 Bismuth Internal Standard Solution—Dilute the
7.2 Allow the lead standards and bismuth internal standard
hydrocarbon-soluble bismuth with a suitable solvent. If bis-
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
Reagent Chemicals, American Chemical Society Specifications, American
measured volume of the bismuth internal standard solution to
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory each one. Mix thoroughly.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
7.4 Place one of these solutions in the sample cell using
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. techniques consistent with good operating practice for the
D5059 − 14 (2019)
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.
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
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,
shortercountingtimesshouldbeusedconsistentwithacceptablestatistical 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
7.6 Plot a calibration curve relating R to the grams of lead
Tube Current 20 mA to 45 mA
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)
storethecalibrationcurve,slope,andrelatedinformationintheinstrument
Collimation Fine
computer system, as an alternative to hand-plotting this information.
Pulse Height Analyzer Threshold discrimination set as low as pos-
sible consistent with the removal of noise with
8. Quality Control Checks
respect to the detector employed.
Detector Proportional or Scintillation
8.1 Confirm the calibration of the instrument each day it is
Counting Technique Fixed Time
in use by analyzing a quality control (QC) sample containing a
11.1.1 Two restrictions are imposed upon the period of the
quantifiable concentration of lead, that is, independent of the
fixed time: namely, that it is 30 s or greater, and that it is such
calibration curve. It is advisable to analyze additional QC
that the count on the position of minimum intensity (back-
samples as appropriate, such as at the beginning and end of a
ground at A = 1.211 Å) should exceed 200 000.
batch of samples or after a fixed number of samples, to ensure
the quality of the results. Analysis of result(s) from these QC
NOTE 9—The X-ray spectrometer and manner of use should comply
samples can be carried out using control chart techniques.
with the regulations governing the use of ionizing radiation or recommen-
When the QC sample result causes the laboratory to be in an
dations of the International Commission of Radiological Protection, or
both.
out-of-control situation, such as exceeding the laboratory’s
control limits, instrument re-calibration may be required. An
12. Reagents and Materials
ample supply of QC sample material shall be available for the
intended period of use, and shall be homogeneous and stable
12.1 Iso-octane. (Warning—Extremely flammable.)
under the anticipated storage conditions. If possible, the QC
12.2 Lead (Pb) Standard Solution—Dissolve tetraethyllead
sample shall be representative of samples typically analyzed
(TEL) (Warning—TEL is toxic by ingestion), lead naphthen-
and the average and control limits of the QC sample shall be
ate (see Note 4), or other suitable lead containing compound in
determined prior to monitoring the measurement process. The
iso-octane (Warning—Extremely flammable), toluene, or a
QC sample precision shall be checked against the ASTM
mixture of these two solvents.WhenTELis used, refer to Note
method precision to ensure data quality. Further guidance on
5. This standard solution shall contain an accurately known
quality control can be found in Practices D6299 a
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