ASTM D4294-10
(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 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 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.
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Designation: D4294 − 10
StandardTest 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 5.2). 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 5) 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, gasohol, biodiesel (see Note 2), and standard. No other units of measurement are included in this
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 wt %) sample
priate safety and health practices and determine the applica-
dilution as described in 1.3 or matrix matching must be performed to
bility of regulatory limitations prior to use.
assure accurate results.
1.2 Interlaboratory studies on precision revealed the scope
2. Referenced Documents
tobe17mg/kgto4.6mass %.Anestimateofthistestmethod’s
3
2.1 ASTM Standards:
pooled limit of quantitation (PLOQ) is 16.0 mg/kg as calcu-
D4057 Practice for Manual Sampling of Petroleum and
lated by the procedures in Practice D6259. However, because
Petroleum Products
instrumentation covered by this test method can vary in
D4177 Practice for Automatic Sampling of Petroleum and
sensitivity, the applicability of the test method at sulfur
Petroleum Products
concentrations below approximately 20 mg/kg must be deter-
D6259 Practice for Determination of a Pooled Limit of
mined on an individual basis. An estimate of the limit of
Quantitation
detection is three times the reproducibility standard deviation,
D6299 Practice for Applying Statistical Quality Assurance
2
and an estimate of the limit of quantitation is ten times the
and Control Charting Techniques to Evaluate Analytical
reproducibility standard deviation.
Measurement System Performance
1.3 Samples containing more than 4.6 mass % sulfur can be
D7343 Practice for Optimization, Sample Handling,
diluted to bring the sulfur concentration of the diluted material
Calibration, and Validation of X-ray Fluorescence Spec-
within the scope of this test method. Samples that are diluted
trometry Methods for Elemental Analysis of Petroleum
can have higher errors than indicated in Section 16 than
Products and Lubricants
non-diluted samples.
E29 Practice for Using Significant Digits in Test Data to
Determine Conformance with Specifications
1.4 Volatile samples (such as high vapor pressure gasolines
or light hydrocarbons) may not meet the stated precision
3. Summary of Test Method
because of selective loss of light materials during the analysis.
3.1 The sample is placed in the beam emitted from an X-ray
1
tube. The resultant excited characteristic X radiation is
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 Feb. 15, 2010. Published March 2010. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
ε1
approved in 1983. Last previous edition approved in 2008 as D4294–08a . DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D4294-10. 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 Dr
...
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.
´1
Designation:D4294–08a Designation:D4294–10
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.
1
´ NOTE—NIST 2723a no longer appears in Appendix X1; deleted related Note X1.1 editorially in November 2009.
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, 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 17.016.0 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.
1.5 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:
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6259 Practice for Determination of a Pooled Limit of Quantitation
1
This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.03 on
Elemental Analysis.
Current edition approved Oct. 15, 2008. Published November 2008. Originally approved in 1983. Last previous edition approved in 2008 as D4294–08. DOI:
10.1520/D4294-08AE01.
´1
Current edition approved Feb. 15, 2010. Published March 2010. Originally approved in 1983. Last previous edition approved in 2008 as D4294–08a . DOI:
10.1520/D4294-10.
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 standard.
Copyright © ASTM International, 100 Barr
...
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