ASTM D4294-21

Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry

SIGNIFICANCE AND USE
5.1 This test method provides rapid and precise measurement of total sulfur in petroleum and petroleum products with a minimum of sample preparation. A typical analysis time is 1 min to 5 min per sample.  
5.2 The quality of many petroleum products is related to the amount of sulfur present. Knowledge of sulfur concentration is necessary for processing purposes. There are also regulations promulgated in federal, state, and local agencies that restrict the amount of sulfur present in some fuels.  
5.3 This test method provides a means of determining whether the sulfur content of petroleum or a petroleum product meets specification or regulatory limits.  
5.4 When this test method is applied to petroleum materials with matrices significantly different from the calibration materials specified in 10.1, the cautions and recommendations in Section 6 should be observed when interpreting results.
SCOPE
1.1 This test method covers the determination of total sulfur in petroleum and petroleum products that are single-phase and either liquid at ambient conditions, liquefiable with moderate heat, or soluble in hydrocarbon solvents. These materials can include diesel fuel, jet fuel, kerosine, other distillate oil, naphtha, residual oil, lubricating base oil, hydraulic oil, crude oil, unleaded gasoline, gasoline-ethanol blends, biodiesel (see Note 2), and similar petroleum products.
Note 1: Oxygenated fuels with ethanol or methanol contents exceeding the limits given in Table 1 can be dealt with using this test method, but the precision and bias statements do not apply (see Appendix X3).
Note 2: For samples with high oxygen contents (>3 % by weight) sample dilution as described in 1.3 or matrix matching must be performed to assure accurate results.  
1.2 Interlaboratory studies on precision revealed the scope to be 17 mg/kg to 4.6 % by mass. An estimate of this test method’s pooled limit of quantitation (PLOQ) is 16.0 mg/kg as calculated by the procedures in Practice D6259. However, because instrumentation covered by this test method can vary in sensitivity, the applicability of the test method at sulfur concentrations below approximately 20 mg/kg must be determined on an individual basis. An estimate of the limit of detection is three times the reproducibility standard deviation, and an estimate of the limit of quantitation2 is ten times the reproducibility standard deviation.  
1.3 Samples containing more than 4.6 % by mass sulfur can be diluted to bring the sulfur concentration of the diluted material within the scope of this test method. Samples that are diluted can have higher errors than indicated in Section 17 than non-diluted samples.  
1.4 Volatile samples (such as high vapor pressure gasolines or light hydrocarbons) may not meet the stated precision because of selective loss of light materials during the analysis.  
1.5 A fundamental assumption in this test method is that the standard and sample matrices are well matched, or that the matrix differences are accounted for (see 6.2). Matrix mismatch can be caused by C/H ratio differences between samples and standards (see Section 6) or by the presence of other heteroatoms.  
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
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.

General Information

• Status: Published
• Publication Date: 30-Nov-2021
• ICS: 75.080 - Petroleum products in general
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

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: D4294 − 21
Standard Test Method for
Sulfur in Petroleum and Petroleum Products by Energy
1
Dispersive X-ray Fluorescence Spectrometry
This standard is issued under the fixed designation D4294; 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* 1.5 Afundamental assumption in this test method is that the
standard and sample matrices are well matched, or that the
1.1 This test method covers the determination of total sulfur
matrix differences are accounted for (see 6.2). Matrix mis-
in petroleum and petroleum products that are single-phase and
match can be caused by C/H ratio differences between samples
either liquid at ambient conditions, liquefiable with moderate
and standards (see Section 6) or by the presence of other
heat, or soluble in hydrocarbon solvents. These materials can
heteroatoms.
include diesel fuel, jet fuel, kerosine, other distillate oil,
naphtha, residual oil, lubricating base oil, hydraulic oil, crude 1.6 The values stated in SI units are to be regarded as
oil, unleaded gasoline, gasoline-ethanol blends, biodiesel (see standard. No other units of measurement are included in this
Note 2), and similar petroleum products. standard.
1.7 This standard does not purport to address all of the
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceed-
ingthelimitsgiveninTable1canbedealtwithusingthistestmethod,but safety concerns, if any, associated with its use. It is the
the precision and bias statements do not apply (see Appendix X3).
responsibility of the user of this standard to establish appro-
NOTE 2—For samples with high oxygen contents (>3 % by weight)
priate safety, health, and environmental practices and deter-
sample dilution as described in 1.3 or matrix matching must be performed
mine the applicability of regulatory limitations prior to use.
to assure accurate results.
1.8 This international standard was developed in accor-
1.2 Interlaboratory studies on precision revealed the scope
dance with internationally recognized principles on standard-
to be 17 mg⁄kg to 4.6 % by mass. An estimate of this test
ization established in the Decision on Principles for the
method’spooledlimitofquantitation(PLOQ)is16.0 mg⁄kgas
Development of International Standards, Guides and Recom-
calculated by the procedures in Practice D6259. However,
mendations issued by the World Trade Organization Technical
because instrumentation covered by this test method can vary
Barriers to Trade (TBT) Committee.
in sensitivity, the applicability of the test method at sulfur
concentrations below approximately 20 mg/kg must be deter-
2. Referenced Documents
mined on an individual basis. An estimate of the limit of
3
2.1 ASTM Standards:
detection is three times the reproducibility standard deviation,
2
D4057 Practice for Manual Sampling of Petroleum and
and an estimate of the limit of quantitation is ten times the
Petroleum Products
reproducibility standard deviation.
D4175 Terminology Relating to Petroleum Products, Liquid
1.3 Samples containing more than 4.6 % by mass sulfur can
Fuels, and Lubricants
be diluted to bring the sulfur concentration of the diluted
D4177 Practice for Automatic Sampling of Petroleum and
material within the scope of this test method. Samples that are
Petroleum Products
dilutedcanhavehighererrorsthanindicatedinSection17than
D6259 Practice for Determination of a Pooled Limit of
non-diluted samples.
Quantitation for a Test Method
1.4 Volatile samples (such as high vapor pressure gasolines
D6299 Practice for Applying Statistical Quality Assurance
or light hydrocarbons) may not meet the stated precision
and Control Charting Techniques to Evaluate Analytical
because of selective loss of light materials during the analysis.
Measurement System Performance
D7343 Practice for Optimization, Sample Handling,
1
This test method 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.
3
Current edition approved Dec. 1, 2021. Published December 2021. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
ɛ1
approved in 1983. Last previous edition approved in 2016 as D4294 – 16 . DOI: contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
10.1520/D4294-21. Standards volume
...

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.
´1
Designation: D4294 − 16 D4294 − 21
Standard Test Method for
Sulfur in Petroleum and Petroleum Products by Energy
1
Dispersive X-ray Fluorescence Spectrometry
This standard is issued under the fixed designation D4294; 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
ε NOTE—The overall layout of the Appendix sections was editorially corrected in February 2016.
1. Scope*
1.1 This test method covers the determination of total sulfur in petroleum and petroleum products that are single-phase and either
liquid at ambient conditions, liquefiable with moderate heat, or soluble in hydrocarbon solvents. These materials can include diesel
fuel, jet fuel, kerosine, other distillate oil, naphtha, residual oil, lubricating base oil, hydraulic oil, crude oil, unleaded gasoline,
gasoline-ethanol blends, biodiesel (see Note 2), and similar petroleum products.
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceeding the limits given in Table 1 can be dealt with using this test method, but the
precision and bias statements do not apply (see Appendix X3).
NOTE 2—For samples with high oxygen contents (>3 weight %)(>3 % by weight) sample dilution as described in 1.3 or matrix matching must be
performed to assure accurate results.
1.2 Interlaboratory studies on precision revealed the scope to be 17 mg ⁄kg to 4.6 mass %. 4.6 % by mass. An estimate of this test
method’s pooled limit of quantitation (PLOQ) is 16.0 mg ⁄kg as calculated by the procedures in Practice D6259. However, because
instrumentation covered by this test method can vary in sensitivity, the applicability of the test method at sulfur concentrations
1
This test method 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 Jan. 1, 2016Dec. 1, 2021. Published February 2016December 2021. Originally approved in 1983. Last previous edition approved in 20102016
ɛ1
as D4294 – 10.D4294 – 16 . DOI: 10.1520/D4294-16E01.10.1520/D4294-21.
A
TABLE 1 Concentrations of Interfering Species
Element Mass % Tolerated
Phosphorus 0.3
Zinc 0.6
Barium 0.8
Lead 0.9
Calcium 1
Chlorine 3
Ethanol (Note 11) 8.6
Methanol (Note 11) 6
Fatty Acid Methyl Ester (FAME) 5
A
The concentrations of substances in this table were determined by the calcula-
tion of the sum of the mass absorption coefficients times mass fraction of each
element present. This calculation was made for dilutions of representative samples
containing approximately 3 % of interfering substances and 0.5 % sulfur.
*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
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D4294 − 21
below approximately 20 mg/kg must be determined on an individual basis. An estimate of the limit of detection is three times the
2
reproducibility standard deviation, and an estimate of the limit of quantitation is ten times the reproducibility standard deviation.
1.3 Samples containing more than 4.6 mass % 4.6 % by mass sulfur can be diluted to bring the sulfur concentration of the diluted
material within the scope of this test method. Samples that are diluted can have higher errors than indicated in Section 1617 than
non-diluted samples.
1.4 Volatile samples (such as high vapor pressure gasolines or light hydrocarbons) may not meet the stated precision because of
selective loss of light materials during the analysis.
1.5 A fundamental assumption in this test method is that the standard and sample matrices are well matched, or that the matrix
differences are accounted for (see 5.26.2). Matrix mismatch can be caused by C/H ratio differences between samples and standards
(see Section 56) or by the presence of other heteroatoms.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
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 safety,
...