ASTM D4294-08a
(Test Method)Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry
Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry
SIGNIFICANCE AND USE
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 to 5 min per sample.
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.
This test method provides a means of determining whether the sulfur content of petroleum or a petroleum product meets specification or regulatory limits.
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, gasohol, 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 wt %) 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 17.0 mg/kg as calculated by the procedures in Practice D 6259. 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 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.
1.5 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.
TABLE 1 Concentrations of Interfering SpeciesA ElementMass % Tolerated Phosphorus0.3 Zinc0.6 Barium0.8 Lead0.9 Calcium1 Chlorine3 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 calculation of the sum of the mass absorption coefficients times mass fraction of each element present. This calculation was made for diluti...
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Designation:D4294–08a
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 Department of Defense.
A
TABLE 1 Concentrations of Interfering Species
1. Scope*
Element Mass % Tolerated
1.1 This test method covers the determination of total sulfur
Phosphorus 0.3
in petroleum and petroleum products that are single-phase and
Zinc 0.6
either liquid at ambient conditions, liquefiable with moderate
Barium 0.8
heat, or soluble in hydrocarbon solvents. These materials can
Lead 0.9
Calcium 1
include diesel fuel, jet fuel, kerosine, other distillate oil,
Chlorine 3
naphtha, residual oil, lubricating base oil, hydraulic oil, crude
Ethanol (Note 11)8.6
oil, unleaded gasoline, gasohol, biodiesel (see Note 2), and
Methanol (Note 11)6
Fatty Acid Methyl Ester (FAME) 5
similar petroleum products.
A
The concentrations of substances in this table were determined by the
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceed-
calculation of the sum of the mass absorption coefficients times mass fraction of
ingthelimitsgiveninTable1canbedealtwithusingthistestmethod,but
each element present. This calculation was made for dilutions of representative
the precision and bias statements do not apply (see Appendix X3). samples containing approximately 3 % of interfering substances and 0.5 % sulfur.
NOTE 2—For samples with high oxygen contents (>3 wt %) sample
dilution as described in 1.3 or matrix matching must be performed to
1.5 Afundamental assumption in this test method is that the
assure accurate results.
standard and sample matrices are well matched, or that the
1.2 Interlaboratory studies on precision revealed the scope
matrix differences are accounted for (see 5.2). Matrix mis-
tobe17mg/kgto4.6mass %.Anestimateofthistestmethod’s
match can be caused by C/H ratio differences between samples
pooled limit of quantitation (PLOQ) is 17.0 mg/kg as calcu-
and standards (see Section 5) or by the presence of other
lated by the procedures in Practice D6259. However, because
heteroatoms.
instrumentation covered by this test method can vary in
1.6 The values stated in SI units are to be regarded as
sensitivity, the applicability of the test method at sulfur
standard. No other units of measurement are included in this
concentrations below approximately 20 mg/kg must be deter-
standard.
mined on an individual basis. An estimate of the limit of
1.7 This standard does not purport to address all of the
detection is three times the reproducibility standard deviation,
safety concerns, if any, associated with its use. It is the
2
and an estimate of the limit of quantitation is ten times the
responsibility of the user of this standard to establish appro-
reproducibility standard deviation.
priate safety and health practices and determine the applica-
1.3 Samples containing more than 4.6 mass % sulfur can be
bility of regulatory limitations prior to use.
diluted to bring the sulfur concentration of the diluted material
2. Referenced Documents
within the scope of this test method. Samples that are diluted
3
can have higher errors than indicated in Section 16 than
2.1 ASTM Standards:
non-diluted samples.
D4057 Practice for Manual Sampling of Petroleum and
1.4 Volatile samples (such as high vapor pressure gasolines
Petroleum Products
or light hydrocarbons) may not meet the stated precision
D4177 Practice for Automatic Sampling of Petroleum and
because of selective loss of light materials during the analysis.
Petroleum Products
D6259 Practice for Determination of a Pooled Limit of
Quantitation
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
3
Current edition approved Oct. 15, 2008. Published November 2008. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1983. Last previous edition approved in 2008 as D4294–08. DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D4294-08A. 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 Sta
...
This document is not anASTM standard and is intended only to provide the user of anASTM 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.
An American National Standard
Designation:D4294–08 Designation:D4294–08a
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 D 4294; 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 Department of Defense.
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, kerosene,kerosine, other distillate oil, naphtha, residual oil, lubricating base oil, hydraulic oil, crude oil,
unleaded gasoline, gasohol, 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 X2Appendix X3).
NOTE 2—For samples with high oxygen contents (>3 wt %) 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 17.0 mg/kg as calculated by the procedures in Practice D 6259. 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.
1.5 Afundamental 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.
2. Referenced Documents
3
2.1 ASTM Standards:
D 4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D 4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D 6259 Practice for Determination of a Pooled Limit of Quantitation
D 6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
D 7343 Practice for Optimization, Sample Handling, Calibration, and Validation of X-ray Fluorescence Spectrometry Methods
for Elemental Analysis of Petroleum Products and Lubricants
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.03 on
Elemental Analysis.
Current edition approved March 1,Oct. 15, 2008. Published AprilNovember 2008. Originally approved in 1983. Last previous edition approved in 20032008 as
D 4294–038.
2
Analytical Chemistry, Vol 55, 1983, pp. 2210-2218.
3
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes
...
This document is not anASTM standard and is intended only to provide the user of anASTM 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.
An American National Standard
Designation:D4294–08 Designation:D4294–08a
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 D 4294; 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 Department of Defense.
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, kerosene,kerosine, other distillate oil, naphtha, residual oil, lubricating base oil, hydraulic oil, crude oil,
unleaded gasoline, gasohol, 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 X2Appendix X3).
NOTE 2—For samples with high oxygen contents (>3 wt %) 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 17.0 mg/kg as calculated by the procedures in Practice D 6259. 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.
1.5 Afundamental 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.
2. Referenced Documents
3
2.1 ASTM Standards:
D 4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D 4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D 6259 Practice for Determination of a Pooled Limit of Quantitation
D 6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
D 7343 Practice for Optimization, Sample Handling, Calibration, and Validation of X-ray Fluorescence Spectrometry Methods
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.03 on
Elemental Analysis.
Current edition approved March 1,Oct. 15, 2008. Published AprilNovember 2008. Originally approved in 1983. Last previous edition approved in 20032008 as
D 4294–038.
2
Analytical Chemistry
2
Analytical Chemistry, Vol 55, 1983, pp. 2210-2218.
3
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this s
...
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