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
Dispersive X-ray Fluorescence Spectrometry1
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 A fundamental assumption in this test method is that the

1.1 This test method covers the determination of total sulfur standard and sample matrices are well matched, or that the
in petroleum and petroleum products that are single-phase and matrix differences are accounted for (see 6.2). Matrix mis-
either liquid at ambient conditions, liquefiable with moderate match can be caused by C/H ratio differences between samples
heat, or soluble in hydrocarbon solvents. These materials can and standards (see Section 6) or by the presence of other
include diesel fuel, jet fuel, kerosine, other distillate oil, heteroatoms.
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.
NOTE 1—Oxygenated fuels with ethanol or methanol contents exceed- 1.7 This standard does not purport to address all of the
ing the limits given in Table 1 can be dealt with using this test method, 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
to assure accurate results. mine the applicability of regulatory limitations prior to use.
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’s pooled limit of quantitation (PLOQ) is 16.0 mg ⁄kg as
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
detection is three times the reproducibility standard deviation, 2.1 ASTM Standards:3
and an estimate of the limit of quantitation2 is ten times the D4057 Practice for Manual Sampling of Petroleum and
reproducibility standard deviation. Petroleum Products
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
diluted can have higher errors than indicated in Section 17 than
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
approved in 1983. Last previous edition approved in 2016 as D4294 – 16ɛ1. DOI: contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
10.1520/D4294-21. 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

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 D4294 − 21
TABLE 1 Concentrations of Interfering SpeciesA TABLE 2 Matrix Diluents
Element Mass % Tolerated Matrix Matrix Diluent Alternate Diluent
Phosphorus 0.3 #2 Diesel #2 Diesel Kerosine
Zinc 0.6 Naphtha Kerosine —
Barium 0.8 Kerosine Kerosine #2 Diesel
Lead 0.9 Residuals Lube Oil MOWHA
Calcium 1 Lubricating Base Oils Lube Oil MOWLB
Chlorine 3 Hydraulic Oils Lube Oil MOWLB
Ethanol (Note 11) 8.6 Crude Oil Lube Oil MOWHA
Methanol (Note 11) 6 Jet Fuels Kerosine —
Fatty Acid Methyl Ester (FAME) 5 Gasoline Gasoline —
A
The concentrations of substances in this table were determined by the calcula- A
MOWH = mineral oil white heavy
tion of the sum of the mass absorption coefficients times mass fraction of each B
MOWL = mineral oil white light
element present. This calculation was made for dilutions of representative samples
containing approximately 3 % of interfering substances and 0.5 % sulfur.
a result, the lines produce spectral peaks that overlap with each
other. Spectral interferences may arise from samples contain-
Calibration, and Validation of X-ray Fluorescence Spec- ing lead alkyls, silicon, phosphorus, calcium, potassium,
trometry Methods for Elemental Analysis of Petroleum halides, and catalyst particles if present at concentrations
Products and Lubricants greater than one tenth of the measured concentration of sulfur,
E29 Practice for Using Significant Digits in Test Data to or more than a few hundred milligrams/kilogram (parts per
Determine Conformance with Specifications million—mass ppm). Follow the manufacturer’s operating-
guide to compensate for the interferences.
3. Terminology
6.2 Matrix effects are caused by concentration variations of
3.1 For definitions of terms used in this test method, refer to the elements in a sample. These variations directly influence
Terminology D4175. X-ray absorption and change the measured intensity of each
element. For example, performance enhancing additives, such
4. Summary of Test Method as oxygenates in gasoline, may affect the apparent sulfur
4.1 The sample is placed in the beam emitted from an X-ray reading. Other matrix related interferences may arise from
tube. The resultant excited characteristic X radiation is heavy metal additives, lead alkyls, and elements such as
measured, and the accumulated count is compared with counts silicon, phosphorus, calcium, potassium, and the halides,
from previously prepared calibration samples to obtain the especially if present at concentrations greater than one tenth of
sulfur concentration in mass percent or mg/kg, or both. A the measured concentration of sulfur, or more than a few
minimum of three groups of calibration samples are required to hundred milligrams/kilogram (parts per million—ppm). These
span the concentration range: 0.0 % to 0.1 % by mass, 0.1 % to types of interferences are always present in X-ray fluorescence
1.0 % by mass, and 1.0 % to 5.0 % by mass sulfur. (See analysis and are completely unrelated to spectral interferences.
Practice D7343.) 6.3 The interferences mentioned in 6.1 and 6.2 may be
5. Significance and Use compensated for in contemporary instruments with the use of
built-in software for spectra deconvolution or overlap correc-
5.1 This test method provides rapid and precise measure- tion and inter-element correction by multiple regression or by
ment of total sulfur in petroleum and petroleum products with other mathematical methods.
a minimum of sample preparation. A typical analysis time is
1 min to 5 min per sample. 6.4 In general, petroleum materials with compositions that
vary from oils as specified in 10.1 may be analyzed with
5.2 The quality of many petroleum products is related to the standards made from base materials that are of the same, or
amount of sulfur present. Knowledge of sulfur concentration is similar, composition. Thus, a gasoline may be simulated by
necessary for processing purposes. There are also regulations mixing isooctane and toluene in a ratio that approximates the
promulgated in federal, state, and local agencies that restrict true aromatic content of the samples to be analyzed. Standards
the amount of sulfur present in some fuels. made from this simulated gasoline will produce results that are
5.3 This test method provides a means of determining more accurate than results obtained using white oils. Sugges-
whether the sulfur content of petroleum or a petroleum product tions are given in Table 2.
meets specification or regulatory limits. NOTE 3—In the case of petroleum materials that contain suspended
water, it is recommended that the water be removed before testing or that
5.4 When this test method is applied to petroleum materials the sample be thoroughly homogenized and immediately tested. The
with matrices significantly different from the calibration mate- interference is greatest if the water creates a layer over the transparent film
rials specified in 10.1, the cautions and recommendations in as it will attenuate the X-ray intensity for sulfur. One such method to
Section 6 should be observed when interpreting results. accomplish the removal of water is to centrifuge the sample first under
ambient sealed conditions, taking care that the sample integrity is not
compromised.
6. Interferences
6.1 Spectral interferences are caused by the closeness of the 7. Apparatus
X-ray characteristic lines of the elements present in a sample 7.1 Energy-dispersive X-ray Fluorescence Analyzer—
and the limited detector ability to completely resolve them. As Energy dispersive X-ray fluorescence analyzer may be used if

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 D4294 − 21
its design incorporates, as a minimum, the following features correction monitors. Appropriate drift monitor samples should
and if test results from it are shown to be equivalent on the be permanent materials that are stable with respect to repeated
samples of interest. Required design features include: exposure to X-rays. Stable liquids like polysulfide oils, glass,
7.1.1 Source of X-ray Excitation, X-ray tube with excitation or metallic specimens are recommended. Liquids, pressed
energy above 2.5 keV. powders, and solid materials that degrade with repeated expo-
7.1.2 Removable Sample Cup, equipped with replaceable sure to X-rays should not be used. Examples of sulfur
X-ray transparent plastic film windows and providing a sample containing materials that have been found to be suitable
depth of at least 4 mm and a diameter of at least 10 mm. include a renewable liquid petroleum material, a metal alloy, or
7.1.3 X-ray Detector, with high sensitivity and a resolution a fused glass disk. The monitor’s counting rate, in combination
value (Full Width at Half Maximum, FWHM) not to exceed with count time, shall be sufficient to give a relative counting
800 eV at 2.3 keV. error of less than 1 %. The counting rate for the monitor sample
7.1.4 Filters or other means of discriminating between
is determined during calibration (see 10.2.1) and again at the
sulfur Kα radiation and other X-rays of higher energy.
time of analysis (see 13.2). These counting rates are used to
7.1.5 Signal conditioning and data handling electronics that
calculate a drift correction factor (see 16.6).
include the functions of X-ray intensity counting, a minimum
of two energy regions, spectral overlap corrections, and con- 8.3.1 Drift correction is usually implemented automatically
version of sulfur X-ray intensity into mass percent sulfur in software, although the calculation can readily be done
concentration. manually. For X-ray instruments that are highly stable, the
7.1.6 The analyzer shall have the sensitivity under opti- magnitude of the drift correction factor may not differ signifi-
mized measurement conditions to measure the concentration of cantly from unity.
sulfur at the 0.05 % level with a demonstrated error due to
8.4 Polysulfide Oil, generally nonyl polysulfides containing
counting statistics with one standard deviation not greater than
a known percentage of sulfur diluted in a hydrocarbon matrix.
0.5 % relative at the 500 mg ⁄kg level. This requirement
pertains to sample measurements of less than 1000 mg/kg. (Warning—May cause allergic skin reactions. Warning—
7.1.7 Display or Printer that reads out in mass percent Solutions prepared in a volatile or un-stabilized matrix may not
sulfur or mg/kg sulfur, or both. be stable several months after preparation.)
NOTE 6—Polysulfide oils are high molecular weight oils that contain
7.2 Analytical Balance, with an accuracy and resolution of high concentrations of sulfur, as high as 50 % by weight. They exhibit
0.1 mg and capable of weighing up to 100 g. excellent physical properties such as low viscosity, low volatility, and
NOTE 4—Operation of analyzers using X-ray tube sources is to be durable shelf life while being completely miscible in white oil. Polysulfide
conducted in accordance with the manufacturer’s safety instructions. oils are readily available commercially. The sulfur content of the polysul-
fide oil concentrate is determined via mass dilution in sulfur-free white oil
8. Reagents followed by a direct comparison analysis against NIST reference materi-
8.1 Purity of Reagents—Reagent grade chemicals shall be als.
used in all tests. Unless otherwise indicated, it is intended that 8.5 Mineral Oil, White (MOW), ACS Reagent Grade con-
all reagents conform to the specifications of the Committee on taining less than 2 mg/kg sulfur or other suitable base material
Analytical Reagents of the American Chemical Society (ACS) containing less than 2 mg/kg sulfur. When low level
where such specifications are available.4 Other grades may be (<200 mg ⁄kg) measurements are anticipated, then the sulfur
used, provided it is first ascertained that the reagent is of content, if any, of the base material needs to be included in the
sufficiently high purity to permit its use without lessening the
calculation of calibration standard concentration (see 10.1).
accuracy of the determination.
When the sulfur content of the solvent or reagent is not
8.2 Di-n-Butyl Sulfide (DBS), a high-purity standard with a certified, verify the absence of sulfur. Use the purest available
certified analysis for sulfur content. Use the certified sulfur grades for chemicals to be used for preparing calibration
content and the material purity when calculating the exact standards.
concentrations of the calibration standards (see 10.1).
(Warning—Di-n-butyl sulfide is flammable and toxic. 8.6 X-ray Transparent Film—Any film that resists attack by
Warning—Solutions prepared in a volatile or un-stabilized the sample, is free of sulfur, and is sufficiently X-ray transpar-
matrix may not be stable several months after preparation.) ent can be used. Film types can include polyester,
NOTE 5—It is essential to know the concentration of sulfur in the polypropylene, polycarbonate, and polyimide. However,
di-n-butyl sulfide, not only the purity, since impurities may also be sulfur samples of high aromatic content can dissolve polypropylene,
containing compounds.
polycarbonate, and polyester films.
8.3 Drift Correction Monitor(s) (Optional)—Several differ-
ent materials have been found to be suitable for use as drift 8.7 Helium Purge Gas (optional), Follow manufacturer’s
recommendations for corresponding specifications when use of
helium purge gas is required.
4
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
Standard-Grade Reference Materials, American Chemical Society, Washington, 8.8 Counting Gas, for instruments equipped with flow
DC. For suggestions on the testing of reagents not listed by the American Chemical proportional counters. The purity of the counting gas should be
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma- in agreement with the specification provided by the instrument
copeial Convention, Inc. (USPC), Rockville, MD. manufacturer.

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 D4294 − 21
8.9 Sample Cells, compatible with the sample and the TABLE 3 Composition of Primary Standards
geometry requirements of the spectrometer. Disposable cells Sulfur Content, Mass of Matrix Mass of
are preferred over reusable ones for ultra low (<50 mg/kg) mass % Diluent, g Di-n-Butyl Sulfide, g

sulfur levels. 5 48.6 14.4

0.1 43.6 0.2
8.10 Calibration Check Samples, portions of one or more
liquid petroleum or product standards of known or certified
sulfur content (including polysulfide oils, di-n-butyl sulfide, ranges of interest. Take into account any sulfur in the base
thiophenes, etc.) and not used in the generation of the calibra- material when calculating the concentration of standards below
tion curve. The check samples shall be used to determine the 0.02 % by mass (200 mg/kg), as shown in Eq 1. Weigh the
precision and accuracy of the initial calibration (see Section DBS and matrix diluent to the recommended mass as closely as
10). possible. It is important that the exact mass is known and thus
8.11 Quality Control (QC) Samples, stable petroleum or the exact concentration of the prepared standards can be
product samples or solids representative of the samples of calculated and entered into the instrument for calibration
interest that are run on a regular basis to verify that the system purposes. The concentration of sulfur can be calculated using
is in statistical control (see Section 16). the following equation:
NOTE 7—Verification of system control through the use of QC samples S 5 @ ~ DBS 3 S DBS! 1 ~ MOW 3 S MOW! # / ~ DBS1MOW! (1)
and control charting is highly recommended. It is recognized that QC
procedures are the province of the individual laboratory. where:
NOTE 8—Suitable QC samples can often be prepared by combining S = mass % sulfur of the prepared standards,
retains of typical samples if they are stable. For monitors, solid materials
are recommended. QC samples must be stable over long periods. DBS = actual mass of DBS, g,
SDBS = the mass % sulfur in DBS, typically 21.91 %,
9. Sample Cell Preparation MOW = actual mass of white oil, g, and
SMOW = mass % sulfur in the white oil.
9.1 If you employ reusable cups, clean and dry cells before
For any generic source of sulfur use the following equation:
use. Disposable sample cups are not to be reused. Window
material usually is <10 µm polyester or polycarbonate film (see S 5 @ ~ M SC 3 S SC! 1 ~ M D 3 S D ! # / ~ M SC1M D ! (2)
8.6). Polycarbonate is preferred due to its high transmissivity where:
of sulfur X-rays. Renewal of the window of the sample cup is
S = mass % of sulfur in standard,
essential for the measurement of each sample. Avoid touching
MSC = mass of sulfur compound, g,
the inside of the sample cup or portion of the window film in SSC = mass % of sulfur in sulfur compound,
the cup or in the instrument window that is exposed to X-rays. MD = mass of diluent, g, and
Oil from fingerprints can affect the reading when analyzing for SD = mass % of sulfur in diluent.
low levels of sulfur. Wrinkles in the film will affect the number
of sulfur X-rays transmitted. Therefore, the importance of the 10.1.1 Calibration standards can also be prepared by careful
film’s smoothness and cleanliness cannot be over stressed to mixing of certified reference materials (CRM) of the same
ensure reliable results. The analyzer will need recalibration if matrix, so long as the sulfur values of the resulting blends and
the type or thickness of the window film is changed. their uncertainties are characterized by the certifying body.5
10.1.2 Alternatively, standards may be prepared by mass
9.2 Impurities which may affect the measurement of low serial dilution of polysulfide oils (Note 6) with sulfur-free
levels of sulfur have been found in polyester films and may white oil. A freshly prepared calibration curve should be
vary from lot to lot. Therefore, if using a polyester film, the verified using CRMs traceable to a national measurement
calibration should be checked after starting each new roll. institution that has demonstrated proficiency for measuring
9.3 Samples of high aromatic content may dissolve sulfur in the matrix of interest.
polyester, polypropylene, and polycarbonate films. In these NOTE 9—Commercially available standards may be used provided their
cases, other materials besides these films may be used for sulfur concentrations are accurately known and they approximate the
X-ray windows, provided that they do not contain any elemen- nominal concentrations listed in Table 3.
tal impurities. An optional window material is 6 µm thick 10.1.3 Accurately weigh the appropriate quantity of matrix
polyimide foil. While polyimide foil absorbs sulfur X-rays diluent, shown in Table 3, into a suitable, narrow-necked
more than other films, it may be a preferred window material container and then accurately weigh in the appropriate quantity
as it is much more resistant to chemical attack by aromatics and of completely pure di-n-butyl sulfide. Mix thoroughly (a
exhibits higher mechanical strength. polytetrafluoroethylene (PTFE)-coated magnetic stirrer is ad-
visable) at room temperature.
10. Calibration 10.1.4 Make calibration standards using one or more of the
10.1 Prepare Calibration Standards by careful mass dilution three ranges suggested in Table 4, according to the expected
of the certified di-n-butyl sulfide with a sulfur-free white oil or level of sulfur of the samples to be analyzed, by diluting
other suitable base material (see 8.5). The concentrations of the
unknown samples must lie within the calibration range that is 5
Refer to Kelly, W. R., MacDonald, B. S., and Leigh, S. D., “A Method for the
used. Approximate recommended nominal sulfur concentration Preparation of NIST Traceable Fossil Fuel Standards with Concentrations Interme-
standards are listed in Table 3 for the sulfur concentration diate to SRM Values,” Journal of ASTM International, Vol 4, No. 2, 2007.

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TABLE 4 Suggested Sulfur Standard Calibration Ranges TABLE 5 Typical Counting Times For Sulfur Content
0–1000 0.10–1.00 1.0–5.0 Determination
mg/kg % mass % mass Sulfur Content Range, Counting Time,
0.0A,B 0.100 1.0 Mass % seconds
5B 0.250 2.0 0.0000 to 0.1000 200 to 300
10B 0.500 3.0 0.1 to 5.0 100
100B 1.000 4.0 1.0 to 5.0 100
250 5.0
500
750
1000
A
standards, independently prepared as per 10.1, may be used as
Base material.
B
Analyze these standards in duplicate and use both values or the average in the
well as any appropriate certified standards as per 10.2. The
calibration. concentration of the QC standards should be near the expected
concentration of the samples being analyzed.
10.5 Storage of Standards—Store all standards in dark,
primary standards with the applicable matrix diluent.
glass bottles, with screw caps with a chemically resistant
Alternatively, standards may be prepared by mixing of certified
lining, in a cool, dark place until required. As soon as any
reference materials (as in 10.1.1) or diluting polysulfide oils (as
sediment or change of concentration is observed, discard the
in 10.1.2).
standard.
NOTE 10—If desired, additional standards can be prepared and analyzed
with concentrations between those listed in Table 4, see 10.1.1. 11. Preparation of Apparatus
10.1.5 Alternatively, prepared standards for the above ref- 11.1 Set up the apparatus in accordance with the manufac-
erenced matrices are commercially available. turer’s instructions. Whenever possible the instrument is left on
10.1.6 If the matrix diluent being used for the preparation of continuously to maintain optimum stability.
standards contains sulfur, add this value to the calculated sulfur
content of the prepared standards as per Eq 1 (consult your 12. Sampling
supplier for an accurate sulfur concentration or test the mineral 12.1 Obtain a test specimen in accordance with Practice
oil using some other low level sulfur analyzing method). D4057 or D4177. Samples should be analyzed immediately
10.2 Certified Calibration Standards: after pouring into a sample cup and allowing for the escape of
10.2.1 Calibration standards which are certified by a respon- the air bubbles caused by mixing.
sible standards organization may be used when applicable to
the sample of interest. Such standards included Standard 13. Procedure
Reference Materials (SRM) prepared and certified by the 13.1 A quality control sample is measured prior to analyzing
National Institute of Standards and Technology (NIST), and unknowns to verify that the test method is in control. It is run
Standard Sample of Sulfur in Residual Fuel Oil certified by the identically to any unknown sample. If the chosen quality
Japan Petroleum Institute or other national metrology institute control sample’s repeatability varies by more than the repeat-
that has demonstrated proficiency in measuring sulfur in the ability value of this test method expected for that concentration
matrix of interest. (acceptance value obtained from Table 6) then the procedure is
10.2.2 Standards containing 100 mg/kg total sulfur or less deemed to be out of control and the instrument should be
must be analyzed in duplicate. Use either both individual recalibrated before running any further analysis. A synthetic
values or the average value of these measurements in the solid quality control sample may be used in lieu of liquid
calibration. samples (see Section 16).
10.3 Instrument Calibration—Calibrate the instrument for 13.2 Analysis of Unknown Samples—Fill the cup with the
the appropriate range as listed in Table 4, following manufac- sample to be measured to about 75 % of cup capacity. Before
turer’s instructions. Typically, the calibration procedure in- filling the cell, it may be necessary to heat viscous samples so
volves setting up the instrument for recording of net sulfur that they are easy to pour into the cell. Ensure that no air
X-ray intensity, followed by the measurement of known bubbles are present between the cup window and the liquid
standards. Obtain one reading on each standard using the sample. Measure each sample once. If the concentration from
recommended counting time for the instrument as per Table 5. the first analysis is less than 100 mg ⁄kg, repeat the measure-
In the case of calibration standards less than 100 mg/kg, repeat ment using a freshly prepared sample cup and a fresh portion
the measurement using a freshly prepared sample cup and a of the sample, and obtain the average of the readings for the
fresh portion of the sample. Immediately repeat the procedure sulfur content in the unknown sample.
using freshly prepared cells and fresh portions of samples. 13.3 When analyzing more than a single unknown sample,
Once all the standards have been analyzed, follow manufac- measure a quality control sample at the end of each batch of
turers instructions for generating the optimum calibration curve unknown samples, but no less than every ten unknown
based on the net sulfur counts for each standard. (Warning— samples, to verify that the method is in control. In all situations
Avoid spilling flammable liquids inside the analyzer.) where the quality control samples vary by more than the
10.4 Quality Control Samples—Several additional standards repeatability expected for that concentration (Table 6), the
(quality control standards) may prove useful. Quality control analysis must be discontinued and corrective action taken to

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TABLE 6 Precision Values, All Sample Types program might be the regular use and charting6 of quality
X, mg/kg
Repeatability r, mg/kg Reproducibility R, mg/kg control samples (see 8.11). It is recommended that at least one
Eq 3 Values Eq 5 Values type of quality control sample be analyzed that is representa-
16.0 2.6 11 tive of typical laboratory samples as defined in Practice D6299.
25.0 3.4 15
50.0 5.4 24 16.2 In addition to running a quality control sample (8.11),
100.0 8.5 37
500 24 105
it is strongly recommended that the calibration blank (for
1000 37 165 example, diluent oil) be analyzed on a daily basis.
5000 105 465 16.2.1 The measured concentration for the blank should be
10 000 165 727
46 000 440 1943
less than 2 mg ⁄kg (0.0002 % by mass) sulfur. If the measured
concentration for the blank is greater than 2 mg/kg (0.0002 %
by mass), re-standardize the instrument and repeat the mea-
surement of the blank (use a fresh sample and fresh cell). If the
result falls outside the acceptable range, carry out a full
find the source of error. Use a quality control sample close to calibration. If the sample loading port becomes contaminated,
the unknown samples’ sulfur concentration. Refer to Section especially when analyzing <20 mg ⁄kg sulfur level samples, it
16. is necessary to open and clean it according to manufacturer’s
recommendations before further use.
13.4 For samples containing 100 mg/kg total sulfur or less, 16.2.2 It should be noted that in order to obtain a good fit for
duplicate determinations are required. Each determination the calibration at low concentrations, it may be necessary to
must be made on a new portion of sample material and change the weighting factor in the regression.
analyzed in accordance with 13.1 and 13.2. The difference
16.3 Results Validation—Once a standard or sample has
between the duplicate analyses should be equal to or less than
been measured, a procedure should be carried out to validate
the repeatability values indicated in Table 6. If the difference is
that measurement. This requires the operator to check for
larger, investigate sample preparation to identify any possible
obvious signs of damage to the sample such as leaking sample
sources of sample contamination, and repeat the analysis. The
cells, crinkled sample cell window and inspection of any
reason for duplicate measurements is to identify problems
secondary film.
associated with sample contamination, leading to improved
results precision at the lower sulfur levels. 16.4 Observation of the resultant analysis. If a result is
NOTE 11—The concentrations of ethanol and methanol were calculated considered outside normal thresholds, a repeat of the analysis
assuring a theoretical mixture of hydrocarbons and di-butyl sulfide to should be carried out to confirm anomalous results.
which ethanol (or methanol) was added until the sum of the mass
coefficients times mass fractions increased by 5 %. In other words, the
16.5 Regular checks should be carried out to ensure that
amount of ethanol (or methanol) that caused a negative 5 % error in the purging gas performance is within the instrument manufactur-
sulfur measurement was calculated. This information is included in Table er’s specification.
1 to inform those who wish to use Test Method D4294 for determining
sulfur in gasohol (or M-85 and M-100) of the nature of the error involved. 16.6 Drift and quality control standards/monitors must be
run on a regular basis while drift monitors may also be run on
14. Calculation a regular basis. The tolerance levels of the checks made using
these monitors should be such that a protocol of either drift
14.1 The concentration of sulfur in the sample is automati- correction or total recalibration is carried out if the results fall
cally calculated from the calibration curve. outside these levels. All measurements should be repeated
between the last accepted monitor result and point of noncom-
15. Report pliance should a current monitor measurement prove to be
15.1 Report the results as total sulfur content mass percent outside acceptable levels.
to three significant figures for concentrations greater than
17. Precision and Bias7
0.01 %. For concentrations less than or equal to 0.01 %, report
results in milligrams per kilogram. Report results in milligrams 17.1 Precision—The precision of the test method was de-
per kilogram to two significant figures between 100 mg ⁄kg and termined by statistical analysis of results obtained in an
10 mg/kg, and to one significant figure below 10 mg/kg. Report interlaboratory study that included 27 samples including
that results were obtained according to Test Method D4294. distillates, gasoline with or without oxygenates, kerosine,
Use Practice E29 as a guide for rounding purposes. diesel, biodiesel E-85, residual oils, and crude oils. The
15.1.1 For samples containing less than 100 mg/kg total laboratory study on precision covered a variety of materials
sulfur, average the duplicate determinations and report that with sulfur concentrations ranging from approximately
value as in 15.1.
6
ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis,
16. Quality Control Section 3, Control Chart for Individuals, ASTM International, W. Conshohocken,
PA.
16.1 It is recommended that each laboratory establish a 7
Supporting data have been filed at ASTM International Headquarters and may
program to ensure that the measurement system described in be obtained by requesting Research Report RR:D02-1635. Contact ASTM Customer
this test method is in statistical control. One part of such a Service at [email protected].

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 D4294 − 21
TABLE 7 Comparison of NIST and ASTM Interlaboratory Study (RR) Results
Sulfur, Apparent
NIST Sulfur, RR
mg/kg Bias Relative
SRM mg/kg, Sample Matrix Significant?
ASTM RR mg/kg Bias, %
Number NIST Number
avg Sulfur
2296 40.0 2 Reformulated Gasoline 46.3 +6.3 +15.8 No
(nominal 13 % ETBE)
2299 13.6 3 Reformulated Gasoline 18.1 +4.5 +33.1 No
2770 41.6 7 Diesel 49.4 +7.8 +18.8 No
2724b 426.5 8 Diesel 430.8 +4.3 +1.01 No
2721 15 832 9 Crude Oil (light-sour) 16 118 +288 +1.82 Yes
2722 2104 10 Crude Oil (heavy-sweet) 2082 -21 -1.00 No
1619b 6960 12 Residual Fuel Oil 6654 -306 -4.40 Yes
1620c 45 610 13 Residual Fuel Oil 45 801 +191 +0.42 No

1 mg ⁄kg to 4.6 % by mass. A pooled limit of quantitation method exceed the following values only in one case in twenty.
(PLOQ) of 16.0 mg ⁄kg sulfur, was determined for all sample Reproducibility (R) may be calculated as shown in Eq 5 or Eq
types. Separate precision statements for diesel and gasoline are 6 for all materials covering the full scope of this method. See
included in Appendix X1 and Appendix X2. The ranges of Table 6 for calculated values.
sulfur concentrations represented by the sample sets, together
Reproducibility ~ R ! 5 1.9182·X 0.6446 mg/kg (5)
with the precisions, are listed in 17.1.1 and 17.1.2. These
0.6446
statistics apply only to samples having less than the level of Reproducibility ~ R ! 5 ~ 1.9182· ~~ Y·10 000! !! /10 000 %by mass
interfering materials present shown in Table 1. (6)

NOTE 12—Volatile materials may not meet the stated precision of the where:
method because selective loss of light materials is possible before and
during analysis by this method. Another possible mechanism is the sulfur
X = sulfur concentration in mg/kg total sulfur, and
enrichment of the sample cup window resulting in higher sulfur values. Y = sulfur concentration in mass percent total sulfur.
17.1.1 Repeatability—The difference between successive 17.1.3 Repeatability and reproducibility values for diesel in
test results obtained by the same operator with the same the aforementioned interlaboratory study7 may be found in
apparatus under constant operating conditions on identical test Appendix X1 and for gasoline in Appendix X2.
materials would, in the long run, in the normal and correct
operation of the test method, exceed the following values only 17.2 Bias—The interlaboratory study7 included ten NIST
in one case in twenty. Repeatability (r) may be calculated as standard reference materials (SRM’s). The certified sulfur
shown in Eq 3 or Eq 4 for all materials covering the full scope value, interlaboratory round robin (RR) value, apparent bias,
of this method. See Table 6 for calculated values. and relative bias are given in Table 7. The white oil was
assumed to have a C/H mass ratio of 5.698 (C22H46). There
Repeatability ~ r ! 5 0.4347·X 0.6446 mg/kg (3)
was no apparent bias that could be attributed to C/H ratio.
Repeatability ~ r ! 5 ~ 0.4347· ~~ Y·10 000! 0.6446!! /10 000 % by mass
17.2.1 Based on the analysis of eight NIST Standard Ref-
(4) erence Materials (SRMs), there was no significant bias based
where: on D2PP calculations between the certified values and the
X = sulfur concentration in mg/kg total sulfur, and results obtained in this interlaboratory study for any sample
Y = sulfur concentration in mass percent total sulfur. type.
17.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work- 18. Keywords
ing in different laboratories on identical test material would, in 18.1 analysis; diesel; gasoline; jet fuel; kerosine; petroleum;
the long run, in the normal and correct operation of the test spectrometry; sulfur; X-ray

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 D4294 − 21
APPENDIXES

(Nonmandatory Information)

X1. ADDITIONAL DIESEL PRECISION STATEMENTS

TABLE X1.1 Precision Values, Diesel Repeatability ~ r ! 5 1.6658·X 0.3300 mg/kg (X1.1)
Repeatability (r), mg/kg Reproducibility (R), mg/kg
S, mg/kg Repeatability ~ r !
Eq X1.1 Values Eq X1.3 Values
25 4.8 26 5 ~ 1.6658 · ~~ Y·10 000! 0.3300! / 10 000 % by mass
100 7.6 41 (X1.2)
500 13 70
1000 16 88 where:
5500 29 154
X = sulfur concentration in mg/kg total sulfur, and
Y = sulfur concentration in mass % total sulfur.
X1.1 Diesel Precision—Six samples in the interlaboratory X1.1.2 Reproducibility (R)—The difference between two
study7 were diesels; they contained between approximately single and independent results obtained by different operators
20 mg ⁄kg and 5500 mg/kg total sulfur: working in different laboratories on identical test material
Number 5 Diesel would, in the long run, in the normal and correct operation of
Number 7 NIST SRM 2770
Number 8 NIST SRM 2724b the test method exceed the following values only in one case in
Number 15 Diesel twenty. Reproducibility (R) may be calculated as shown in Eq
Number 17 Diesel
Number 22 B-5 diesel containing 5 %
X1.3 or Eq X1.4 for six diesel samples. See Table X1.1 for
biodiesel calculated values.
X1.1.1 Repeatability (r)—The difference between succes- Reproducibility ~ R ! 5 8.9798·X 0.3300 mg/kg (X1.3)
sive test results obtained by the same operator with the same Reproducibility ~ R ! 5 ~ 8.9798· ~~ Y·10 000! 0.3300
!! /10 000 %by mass
apparatus under constant operation conditions on identical test
(X1.4)
material would, in the long run, in the normal and correct
operation of the test method exceed the following values only where:
in one case in twenty. Repeatability (r) may be calculated as X = sulfur concentration in mg/kg total sulfur, and
shown in Eq X1.1 or Eq X1.2 for the six diesel samples. See Y = sulfur concentration in mass % total sulfur.
Table X1.1 for calculated values.

X2. ADDITIONAL GASOLINE PRECISION STATEMENTS

X2.1 Gasoline Precision—Five samples in the interlabora- TABLE X2.1 Precision Values, Gasoline
tory study7 were gasolines; they contained between approxi- S, mg/kg
Repeatability (r), mg/kg Reproducibility (R), mg/kg
mately 11 mg ⁄kg and 5500 mg/kg total sulfur: Eq X2.1 Values Eq X2.3 Values
50 6.0 30
Number 2 Gasoline with 13 % ETBE
100 7.8 38
Number 3 Reformulated gasoline
500 14 69
Number 4 Gasoline with 5 % ethanol
1000 18 89
Number 11 Gasoline
5500 34 167
Number 20 E-85
X2.1.1 Repeatability (r)—The difference between succes-
sive test results obtained by the same operator with the same X2.1.2 Reproducibility (R)—The difference between two
apparatus under constant operation conditions on identical test single and independent results obtained by different operators
material would, in the long run, in the normal and correct working in different laboratories on identical test material
operation of the test method exceed the following values only would, in the long run, in the normal and correct operation of
in one case in twenty. Repeatability (r) may be calculated as the test method exceed the following values only in one case in
shown in Eq X2.1 or Eq X2.2 for the five gasoline samples. See twenty. Reproducibility (R) may be calculated as shown in Eq
Table X2.1 for calculated values. X2.3 or Eq X2.4 for five gasoline samples. See Table X2.1 for
Repeatability ~ r ! 5 1.4477·X 0.3661 mg/kg (X2.1)
calculated values.
Repeatability ~ r ! 5 ~ 1.4477· ~~ Y·10 000! 0.3661 Reproducibility ~ R ! 5 7.1295·X 0.3661 mg/kg (X2.3)
!! /10 000 %by mass
0.3661
(X2.2) Reproducibility ~ R ! 5 ~ 7.1295· ~~ Y·10 000! !! /10 000 %by mass
(X2.4)
where:
X = sulfur concentration in mg/kg total sulfur, and where:
Y = sulfur concentration in mass % total sulfur. X = sulfur concentration in mg/kg total sulfur, and

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 D4294 − 21

Y = sulfur concentration in mass % total sulfur.

X3. HANDLING OXYGENATED FUELS

X3.1 M-85 and M-100 are fuels containing 85 % and 100 % X3.2 When analyzing M-85 or M-100 fuels with a calibra-
methanol, respectively. E-85 contains 85 % ethanol. As such, tion determined with white oil based standards, divide the
they have a high oxygen content, hence, absorption of sulfur result obtained in 13.3 as in the following equations. This
Kα radiation. Such fuels can, however, be analyzed using this correction is not required if the standards are prepared in the
test method provided that the calibration standards are prepared same matrix as the samples, as described in 6.2.
to match the matrix of the sample. There may be a loss of
sensitivity and precision. The repeatability, reproducibility, and S ~ in M 2 85! , mass % 5 S, mass %/0.59 (X3.1)
bias obtained in this test method did not include M-85 and S ~ in M 2 100! , mass % 5 S, mass %/0.55 (X3.2)
M-l00 samples.

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D4294 – 16ɛ1) that may impact the use of this standard. (Approved Dec. 1, 2021.)

(1) Added Terminology D4175 to Section 2. (4) Revised Note 9.

(2) Added Section 3. (5) Revised Footnote B of Table 4.
(3) Revised subsections 8.2, 8.4, and 10.1.2.

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