ASTM D4294-16e1

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

SIGNIFICANCE AND USE
4.1 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.  
4.2 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.  
4.3 This test method provides a means of determining whether the sulfur content of petroleum or a petroleum product meets specification or regulatory limits.  
4.4 When this test method is applied to petroleum materials with matrices significantly different from the calibration materials specified in 9.1, the cautions and recommendations in Section 5 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). (A) The concentrations of substances in this table were determined by the calculation 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.
Note 2: For samples with high oxygen contents (>3 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 %. 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 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 16 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 5.2). Matrix mismatch can be caused by C/H ratio differences between samples and standards (see Section 5) 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 and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 31-Dec-2015
• 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)

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
´1
Designation: D4294 − 16
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* 1.4 Volatile samples (such as high vapor pressure gasolines
or light hydrocarbons) may not meet the stated precision
1.1 This test method covers the determination of total sulfur
because of selective loss of light materials during the analysis.
in petroleum and petroleum products that are single-phase and
1.5 Afundamental assumption in this test method is that the
either liquid at ambient conditions, liquefiable with moderate
heat, or soluble in hydrocarbon solvents. These materials can standard and sample matrices are well matched, or that the
matrix differences are accounted for (see 5.2). Matrix mis-
include diesel fuel, jet fuel, kerosine, other distillate oil,
naphtha, residual oil, lubricating base oil, hydraulic oil, crude match can be caused by C/H ratio differences between samples
and standards (see Section 5) or by the presence of other
oil, unleaded gasoline, gasoline-ethanol blends, biodiesel (see
Note 2), and similar petroleum products. heteroatoms.
1.6 The values stated in SI units are to be regarded as
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceed-
ingthelimitsgiveninTable1canbedealtwithusingthistestmethod,but standard. No other units of measurement are included in this
the precision and bias statements do not apply (see Appendix X3).
standard.
NOTE 2—For samples with high oxygen contents (>3 weight %) sample
1.7 This standard does not purport to address all of the
dilution as described in 1.3 or matrix matching must be performed to
safety concerns, if any, associated with its use. It is the
assure accurate results.
responsibility of the user of this standard to establish appro-
1.2 Interlaboratory studies on precision revealed the scope
priate safety and health practices and determine the applica-
to be 17 mg⁄kg to 4.6 mass %. An estimate of this test
bility of regulatory limitations prior to use.
method’spooledlimitofquantitation(PLOQ)is16.0 mg⁄kgas
calculated by the procedures in Practice D6259. However,
2. Referenced Documents
because instrumentation covered by this test method can vary
3
2.1 ASTM Standards:
in sensitivity, the applicability of the test method at sulfur
D4057 Practice for Manual Sampling of Petroleum and
concentrations below approximately 20 mg/kg must be deter-
Petroleum Products
mined on an individual basis. An estimate of the limit of
D4177 Practice for Automatic Sampling of Petroleum and
detection is three times the reproducibility standard deviation,
2
Petroleum Products
and an estimate of the limit of quantitation is ten times the
D6259 Practice for Determination of a Pooled Limit of
reproducibility standard deviation.
Quantitation for a Test Method
1.3 Samples containing more than 4.6 mass % sulfur can be
D6299 Practice for Applying Statistical Quality Assurance
diluted to bring the sulfur concentration of the diluted material
and Control Charting Techniques to Evaluate Analytical
within the scope of this test method. Samples that are diluted
Measurement System Performance
can have higher errors than indicated in Section 16 than
D7343 Practice for Optimization, Sample Handling,
non-diluted samples.
Calibration, and Validation of X-ray Fluorescence Spec-
trometry Methods for Elemental Analysis of Petroleum
Products and Lubricants
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 Jan. 1, 2016. Published February 2016. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1983. Last previous edition approved in 2010 as D4294 – 10. DOI: contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
10.1520/D4294-16E01. Standards volume information, refer to the standard’s Document Summary page on
2
Analytical Chemistry, Vol 55, 1983, pp. 2210-2218. the ASTM website.
*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
1

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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 − 16
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 %) 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 %. 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
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 % 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 16 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
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, 2016. Published February 2016. Originally approved in 1983. Last previous edition approved in 2010 as D4294 – 10. DOI:
10.1520/D4294-16.10.1520/D4294-16E01.
2
Analytical Chemistry, Vol 55, 1983, pp. 2210-2218.
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
1

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D4294 − 16
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 5.2). Matrix mismatch can be caused by C/H ratio differences between samples and standards
(see Section 5) 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 and health practices and determine the applica
...