An American National Standard

Designation: D 4294 – 08

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 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 (e) 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* TABLE 1 Concentrations of Interfering SpeciesA

1.1 This test method covers the determination of total sulfur Element Mass % Tolerated

in petroleum and petroleum products that are single-phase and Phosphorus 0.3
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
include diesel fuel, jet fuel, kerosene, other distillate oil, Calcium 1
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
similar petroleum products. Fatty Acid Methyl Ester (FAME) 5
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
ing the limits given in Table 1 can be dealt with using this test method, but each element present. This calculation was made for dilutions of representative
the precision and bias statements do not apply (see Appendix X2). 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
assure accurate results. 1.5 A fundamental assumption in this test method is that the
1.2 Interlaboratory studies on precision revealed the scope standard and sample matrices are well matched, or that the
to be 17 mg/kg to 4.6 mass %. An estimate of this test method’s matrix differences are accounted for (see 5.2). Matrix mis-
pooled limit of quantitation (PLOQ) is 17.0 mg/kg as calcu- match can be caused by C/H ratio differences between samples
lated by the procedures in Practice D 6259. However, because and standards (see Section 5) or by the presence of other
instrumentation covered by this test method can vary in heteroatoms.
sensitivity, the applicability of the test method at sulfur 1.6 The values stated in SI units are to be regarded as
concentrations below approximately 20 mg/kg must be deter- standard. No other units of measurement are included in this
mined on an individual basis. An estimate of the limit of standard.
detection is three times the reproducibility standard deviation, 1.7 This standard does not purport to address all of the
and an estimate of the limit of quantitation2 is ten times the safety concerns, if any, associated with its use. It is the
reproducibility standard deviation. responsibility of the user of this standard to establish appro-

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1.3 Samples containing more than 4.6 mass % sulfur can be priate safety and health practices and determine the applica-
diluted to bring the sulfur concentration of the diluted material bility of regulatory limitations prior to use.
within the scope of this test method. Samples that are diluted
can have higher errors than indicated in Section 16 than 2. Referenced Documents
non-diluted samples. 2.1 ASTM Standards: 3
1.4 Volatile samples (such as high vapor pressure gasolines D 4057 Practice for Manual Sampling of Petroleum and
or light hydrocarbons) may not meet the stated precision Petroleum Products
because of selective loss of light materials during the analysis. D 4177 Practice for Automatic Sampling of Petroleum and
Petroleum Products
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
3
D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved March 1, 2008. Published April 2008. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1983. Last previous edition approved in 2003 as D 4294–03. 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.

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 D 4294 – 08
D 6259 Practice for Determination of a Pooled Limit of TABLE 2 Matrix Diluents
Quantitation Matrix Matrix Diluent Alternate Diluent
D 6299 Practice for Applying Statistical Quality Assurance #2 Diesel #2 Diesel Kerosine
and Control Charting Techniques to Evaluate Analytical Naphtha Kerosine —
Kerosine Kerosine #2 Diesel
Measurement System Performance Residuals Lube Oil MOWHA
D 7343 Practice for Optimization, Sample Handling, Cali- Lubricating Base Oils Lube Oil MOWLB
bration, and Validation of X-ray Fluorescence Spectrom- Hydraulic Oils Lube Oil MOWLB
Crude Oil Lube Oil MOWHA
etry Methods for Elemental Analysis of Petroleum Prod- Jet Fuels Kerosine —
ucts and Lubricants Gasoline Gasoline —
E 29 Practice for Using Significant Digits in Test Data to A
MOWH = mineral oil white heavy
Determine Conformance with Specifications B
MOWL = mineral oil white light

3. Summary of Test Method

3.1 The sample is placed in the beam emitted from an X-ray heavy metal additives, lead alkyls, and elements such as
tube. The resultant excited characteristic X radiation is mea- silicon, phosphorus, calcium, potassium, and the halides,
sured, and the accumulated count is compared with counts especially if present at concentrations greater than one tenth of
from previously prepared calibration samples to obtain the the measured concentration of sulfur, or more than a few
sulfur concentration in mass % and/or mg/kg. A minimum of hundred milligrams/kilogram (parts per million—ppm). These
three groups of calibration samples are required to span the types of interferences are always present in X-ray fluorescence
concentration range: 0.0 to 0.1 mass %, 0.1 to 1.0 mass %, and analysis and are completely unrelated to spectral interferences.
1.0 to 5.0 mass % sulfur. (See Practice D 7343.) 5.3 The interferences mentioned in 5.1 and 5.2 may be
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compensated for in contemporary instruments with the use of

4. Significance and Use built-in software for spectra deconvolution or overlap correc-
4.1 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 5.4 In general, petroleum materials with compositions that
to 5 minutes per sample. vary from oils as specified in 9.1 may be analyzed with
4.2 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
4.3 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
4.4 When this test method is applied to petroleum materials water, it is recommended that the water be removed before testing or that
with matrices significantly different from the calibration mate- the sample be thoroughly homogenized and immediately tested. The
rials specified in 9.1, the cautions and recommendations in interference is greatest if the water creates a layer over the transparent film
as it will attenuate the X-ray intensity for sulfur. One such method to
Section 5 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
5. Interferences compromised.
5.1 Spectral interferences are caused by the closeness of the
X-ray characteristic lines of the elements present in a sample 6. Apparatus
and the limited detector ability to completely resolve them. As 6.1 Energy-dispersive X-ray Fluorescence Analyzer—
a result, the lines produce spectral peaks that overlap with each Energy dispersive X-ray fluorescence analyzer may be used if
other. Spectral interferences may arise from samples contain- its design incorporates, as a minimum, the following features
ing lead alkyls, silicon, phosphorus, calcium, potassium, ha- and if test results from it are shown to be equivalent on the
lides and catalyst particles if present at concentrations greater samples of interest. Required design features include:
than one tenth of the measured concentration of sulfur, or more 6.1.1 Source of X-ray Excitation, X-ray tube with excitation
than a few hundred milligrams/kilogram (parts per million— energy above 2.5 keV.
mass ppm). Follow the manufacturer’s operating-guide to 6.1.2 Removable Sample Cup, equipped with replaceable
compensate for the interferences. X-ray transparent plastic film windows and providing a sample
5.2 Matrix effects are caused by concentration variations of depth of at least 4 mm and a diameter of at least 10 mm.
the elements in a sample. These variations directly influence 6.1.3 X-ray Detector, with high sensitivity and a resolution
X-ray absorption and change the measured intensity of each value (Full Width at Half Maximum, FWHM) not to exceed
element. For example, performance enhancing additives, such 800 eV at 2.3 keV.
as oxygenates in gasoline, may affect the apparent sulfur 6.1.4 Filters or other means of discriminating between
reading. Other matrix related interferences may arise from sulfur Ka radiation and other X-rays of higher energy.

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6.1.5 Signal conditioning and data handling electronics that 7.3.1 Drift correction is usually implemented automatically
include the functions of X-ray intensity counting, a minimum in software, although the calculation can readily be done
of two energy regions, spectral overlap corrections, and con- manually. For X-ray instruments that are highly stable, the
version of sulfur X-ray intensity into mass percent sulfur magnitude of the drift correction factor may not differ signifi-
concentration. cantly from unity.
6.1.6 The analyzer shall have the sensitivity under opti- 7.4 Polysulfide Oil, generally nonyl polysulfides containing
mized measurement conditions to measure the concentration of a known percentage of sulfur diluted in a hydrocarbon matrix.
sulfur at the 0.05 % level with a demonstrated error due to (Warning—May cause allergic skin reactions.)
counting statistics with one standard deviation not greater than
0.5 percent relative at the 500 mg/kg level. This requirement NOTE 6—Polysulfide oils are high molecular weight oils that contain
pertains to sample measurements of less than 1000 mg/kg. high concentrations of sulfur, as high as 50 weight percent. They exhibit
excellent physical properties such as low viscosity, low volatility, and
6.1.7 Display or Printer that reads out in mass % sulfur
durable shelf life while being completely miscible in white oil. Polysulfide
and/or mg/kg sulfur. oils are readily available commercially. The sulfur content of the polysul-
6.2 Analytical Balance, with an accuracy and resolution of fide oil concentrate is determined via mass dilution in sulfur-free white oil
0.1 mg and capable of weighing up to 100 g. followed by a direct comparison analysis against NIST reference materi-
als.
NOTE 4—Operation of analyzers using X-ray tube sources is to be
conducted in accordance with the manufacturer’s safety instructions. 7.5 Mineral Oil, White (MOW), ACS Reagent Grade con-
taining less than 2 mg/kg sulfur or other suitable base material
7. Reagents
containing less than 2 mg/kg sulfur. When low level (<200
7.1 Purity of Reagents—Reagent grade chemicals shall be mg/kg) measurements are anticipated, then the sulfur content,
used in all tests. Unless otherwise indicated, it is intended that if any, of the base material needs to be included in the
all reagents conform to the specifications of the Committee on calculation of calibration standard concentration (see 9.1).
Analytical Reagents of the American Chemical Society (ACS) When the sulfur content of the solvent or reagent is not
where such specifications are available.4 Other grades may be certified, verify the absence of sulfur. Use the purest available
used, provided it is first ascertained that the reagent is of grades for chemicals to be used for preparing calibration
sufficiently high purity to permit its use without lessening the standards.
accuracy of the determination.
7.6 X-ray Transparent Film—Any film that resists attack by
7.2 Di-n-Butyl Sulfide (DBS), a high-purity standard with a
the sample, is free of sulfur, and is sufficiently X-ray transpar-
certified analysis for sulfur content. Use the certified sulfur
ent can be used. Film types can include polyester, polypropy-
content and the material purity when calculating the exact
lene, polycarbonate, and polyimide. However, samples of high
concentrations of the calibration standards (see 9.1).
aromatic content can dissolve polypropylene, polycarbonate
(Warning—Di-n-butyl sulfide is flammable and toxic.)
and polyester films.
NOTE 5—It is essential to know the concentration of sulfur in the 7.7 Helium Gas, minimum purity 99.9 %.
di-n-butyl sulfide, not only the purity, since impurities may also be sulfur
containing compounds. 7.8 Counting Gas, for instruments equipped with flow
proportional counters. The purity of the counting gas should be
7.3 Drift Correction Monitor(s) (Optional)—Several differ-
in agreement with the specification provided by the instrument
ent materials have been found to be suitable for use as drift
manufacturer.
correction monitors. Appropriate drift monitor samples should
be permanent materials that are stable with respect to repeated 7.9 Sample Cells, compatible with the sample and the
exposure to X-rays. Stable liquids like polysulfide oils, glass or geometry requirements of the spectrometer. Disposable cells
metallic specimens are recommended. Liquids, pressed pow- are preferred over reusable ones for ultra low (<50 mg/kg)
ders, and solid materials that degrade with repeated exposure to sulfur levels.
X-rays should not be used. Examples of sulfur containing 7.10 Calibration Check Samples, portions of one or more
materials that have been found to be suitable include a liquid petroleum or product standards of known or certified
renewable liquid petroleum material, a metal alloy, or a fused sulfur content (including polysulfide oils, di-n-butyl sulfide,
glass disk. The monitor’s counting rate, in combination with thiophenes, etc.) and not used in the generation of the calibra-
count time, shall be sufficient to give a relative counting error tion curve. The check samples shall be used to determine the
of less than 1 %. The counting rate for the monitor sample is precision and accuracy of the initial calibration (see Section 9).
determined during calibration (see 9.2.1) and again at the time 7.11 Quality Control (QC) Samples, stable petroleum or
of analysis (see 12.2). These counting rates are used to product samples or solids representative of the samples of
calculate a drift correction factor (see 15.6). interest that are run on a regular basis to verify that the system
is in statistical control (see Section 15).

4
NOTE 7—Verification of system control through the use of QC samples
Reagent Chemicals, American Chemical Society Specifications , American and control charting is highly recommended. It is recognized that QC
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
procedures are the province of the individual laboratory.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia NOTE 8—Suitable QC samples can often be prepared by combining
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, retains of typical samples if they are stable. For monitors, solid materials
MD. are recommended. QC samples must be stable over long periods.
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TABLE 3 Composition of Primary Standards MOW = actual mass of white oil, g, and
Sulfur Content, Mass of Matrix Mass of SMOW = mass % sulfur in the white oil.
mass % Diluent, g Di-n-Butyl Sulfide, g
For any generic source of sulfur use the following equation:
5 48.6 14.4
0.1 43.6 0.2 S 5 @~MSC 3 SSC! 1 ~MD 3 SD!# / ~MSC 1 MD! (2)

where:
S = mass % of sulfur in standard,
8. Sample Cell Preparation MSC = mass of sulfur compound, g,
SSC = mass % of sulfur in sulfur compound,
8.1 If you employ reusable cups, clean and dry cells before MD = mass of diluent, g, and
use. Disposable sample cups are not to be reused. Window SD = mass % of sulfur in diluent.
material usually is <10 µm polyester or polycarbonate film (see 9.1.1 Calibration standards can also be prepared by careful
7.6). Polycarbonate is preferred due to its high transmissivity mixing of certified reference materials (CRM) of the same
of sulfur X-rays. Renewal of the window of the sample cup is matrix, so long as the sulfur values of the resulting blends and
essential for the measurement of each sample. Avoid touching their uncertainties are characterized by the certifying body.5
the inside of the sample cup or portion of the window film in 9.1.2 Alternatively, standards may be prepared by mass
the cup or in the instrument window that is exposed to X-rays. serial dilution of polysulfide oils (Note 5) with sulfur-free
Oil from fingerprints can affect the reading when analyzing for white oil. A freshly prepared polysulfide oil calibration curve
low levels of sulfur. Wrinkles in the film will affect the number should be verified using CRMs traceable to NIST, or other
of sulfur X-rays transmitted. Therefore, the importance of the national metrology institute that has demonstrated proficiency
film’s smoothness and cleanliness cannot be over stressed to for measuring sulfur in the matrix of interest. Once a polysul-
ensure reliable results. The analyzer will need recalibration if fide oil calibration curve is established, the calibration stan-
the type or thickness of the window film is changed. dards are stored at room temperature, out of direct sunlight, and
8.2 Impurities which may affect the measurement of low in amber glass bottles. Polysulfide oil standards can be pre-
levels of sulfur have been found in polyester films and may pared over a wide concentration range from low mg/kg to high
vary from lot to lot. Therefore, if using a polyester film, the mass % levels of sulfur. They are easily prepared in quantity
calibration should be checked after starting each new roll. and make excellent quality control standards. Shaking polysul-
8.3 Samples of high aromatic content may dissolve polyes- fide oil standards before fresh aliquots are taken is recom-
ter, polypropylene and polycarbonate films. In these cases, mended to ensure the standard is uniformly blended. The high
other materials besides these films may be used for X-ray molecular weight of these sulfur compounds results in a very
windows, provided that they do not contain any elemental low vapor pressure that inhibits X-ray film diffusion. There-
impurities. An optional window material is 6 µm thick poly- fore, an autosampler can be employed during the measurement
imide foil. While polyimide foil absorbs sulfur X-rays more process. Calibration curves prepared from polysulfide also
than other films, it may be a preferred window material as it is demonstrate excellent linearity and help the analyst visualize
much more resistant to chemical attack by aromatics and the full dynamic range of their analytical method.
exhibits higher mechanical strength.
NOTE 9—Commercially available standards can be used provided their
9. Calibration sulfur concentrations are accurately known and they approximate the
nominal concentrations listed in Table 3.
9.1 Prepare Calibration Standards by careful mass dilution
9.1.3 Accurately weigh the appropriate quantity of matrix
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of the certified di-n-butyl sulfide with a sulfur-free white oil or

other suitable base material (see 7.5). The concentrations of the diluent, shown in Table 3, into a suitable, narrow-necked
unknown samples must lie within the calibration range that is container and then accurately weigh in the appropriate quantity
used. Approximate recommended nominal sulfur concentration of completely pure di-n-butyl sulfide. Mix thoroughly (a
standards are listed in Table 3 for the sulfur concentration polytetrafluoroethylene (PTFE)-coated magnetic stirrer is ad-
ranges of interest. Take into account any sulfur in the base visable) at room temperature.
material when calculating the concentration of standards below 9.1.4 Make calibration standards using one or more of the
0.02 mass % (200 mg/kg), as shown in Eq 1. Weigh the DBS three ranges suggested in Table 4, according to the expected
and matrix diluent to the recommended mass as closely as level of sulfur of the samples to be analyzed, by diluting
possible. It is important that the exact mass is known and thus primary standards with the applicable matrix diluent. Alterna-
the exact concentration of the prepared standards can be tively, standards may be prepared by mixing of certified
calculated and entered into the instrument for calibration reference materials (as in 9.1.1) or diluting polysulfide oils (as
purposes. The concentration of sulfur can be calculated using in 9.1.2).
the following equation: NOTE 10—If desired, additional standards can be prepared and analyzed
with concentrations between those listed in Table 4, see 9.1.1.
S 5 @~DBS 3 SDBS! 1 ~MOW 3 SMOW!# / ~DBS 1 MOW! (1)

where:
S = mass % sulfur of the prepared standards,
5
DBS = actual mass of DBS, g, Refer to Kelly, W. R., MacDonald, B. S., and Leigh, S. D., “A Method for the
Preparation of NIST Traceable Fossil Fuel Standards with Concentrations Interme-
SDBS = the mass % sulfur in DBS, typically 21.91 %, 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,
Mass % Seconds
0.0A,B 0.100 1.0
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
10. Preparation of Apparatus
A
Base material.
B
Analyze these standards in duplicate and use either both individual values or 10.1 Set up the apparatus in accordance with the manufac-
the average in the calibration. turer’s instructions. Whenever possible the instrument is left on
continuously to maintain optimum stability.
9.1.5 Alternatively, prepared standards for the above refer-
enced matrices are commercially available. 11. Sampling
9.1.6 If the matrix diluent being used for the preparation of 11.1 Obtain a test specimen in accordance with Practice
standards contains sulfur, add this value to the calculated sulfur D 4057 or D 4177. Samples should be analyzed immediately
content of the prepared standards as per Eq 1 (consult your after pouring into a sample cup and allowing for the escape of
supplier for an accurate sulfur concentration or test the mineral the air bubbles caused by mixing.
oil using some other low level sulfur analyzing method).
9.2 Certified Calibration Standards: 12. Procedure
9.2.1 Calibration standards which are certified by a respon- 12.1 A quality control sample is measured prior to analyzing
sible standards organization may be used when applicable to unknowns to verify that the test method is in control. If the
the sample of interest. Such standards included Standard chosen quality control sample’s repeatability varies by more
Reference Materials (SRM) prepared and certified by the than the repeatability value expected for that concentration
National Institute of Standards and Technology (NIST), and (acceptance value obtained from Table 6) then the procedure is
Standard Sample of Sulfur in Residual Fuel Oil certified by the deemed to be out of control and the instrument should be
Japan Petroleum Institute or other national metrology institute recalibrated before running any further analysis. A synthetic
that has demonstrated proficiency in measuring sulfur in the solid quality control sample may be used in lieu of liquid
matrix of interest. samples (see Section 15).
9.2.2 Standards containing 100 mg/kg total sulfur or less 12.2 Analysis of Unknown Samples—Fill the cup with the
must be analyzed in duplicate. Use either both individual sample to be measured to about 75 % of cup capacity. Before
values or the average value of these measurements in the filling the cell, it may be necessary to heat viscous samples so
calibration. that they are easy to pour into the cell. Ensure that no air
9.3 Instrument Calibration—Calibrate the instrument for bubbles are present between the cup window and the liquid
the appropriate range as listed in Table 4, following manufac- sample. Measure each sample once. If the concentration from
turer’s instructions. Typically, the calibration procedure in- the first analysis is less than 100 mg/kg, repeat the measure-
volves setting up the instrument for recording of net sulfur ment using a freshly prepared sample cup and a fresh portion
X-ray intensity, followed by the measurement of known of the sample, and obtain the average of the readings for the
standards. Obtain one reading on each standard using the sulfur content in the unknown sample.
recommended counting time for the instrument as per Table 5. 12.3 Measure a quality control sample at the end of each
In the case of calibration standards less than 100 mg/kg, repeat batch, but no less than every ten unknown samples, to verify
the measurement using a freshly prepared sample cup and a that the method is in control. In all situations where the quality
fresh portion of the sample. Immediately repeat the procedure control samples vary by more than the repeatability expected
using freshly prepared cells and fresh portions of samples. for that concentration (Table 6), the analysis must be discon-
Once all the standards have been analyzed, follow manufac- tinued and corrective action taken to find the source of error.
turers instructions for generating the optimum calibration curve Use a quality control sample close to the unknown samples’
based on the net sulfur counts for each standard. (Warning— sulfur concentration. Refer to Section 15.
Avoid spilling flammable liquids inside the analyzer.) 12.4 For samples containing 100 mg/kg total sulfur or less,
9.4 Quality Control Samples—Several additional standards duplicate determinations are required. Each determination
(quality control standards) may prove useful. Quality control must be made on a new portion of sample material and
standards, independently prepared as per 9.1, may be used as analyzed in accordance with 12.1 and 12.2. The difference
well as any appropriate certified standards as per 9.2. The between the duplicate analyses should be equal to or less than
concentration of the QC standards should be near the expected the repeatability values indicated in Table 6. If the difference is
concentration of the samples being analyzed. larger, investigate sample preparation to identify any possible
9.5 Storage of Standards—Store all standards in dark, glass sources of sample contamination, and repeat the analysis. The
bottles, with screw caps with a chemically resistant lining, in a reason for duplicate measurements is to identify problems
cool, dark place until required. As soon as any sediment or associated with sample contamination, leading to improved
change of concentration is observed, discard the standard. results precision at the lower sulfur levels.
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TABLE 6 Precision Values, All Sample Types calibration. If the sample loading port becomes contaminated,
X, mg/kg
Repeatability r, mg/kg Reproducibility R, mg/kg especially when analyzing <20 mg/kg sulfur level samples, it is
Eq 3 Values Eq 4 Values necessary to open and clean it according to manufacturer’s
17.0 3.1 14 recommendations before further use.
25.0 3.9 18
50.0 6.0 27
15.2.2 It should be noted that in order to obtain a good fit for
100 9.2 42 the calibration at low concentrations, it may be necessary to
500 25 113 change the weighting factor in the regression.
1000 38 173
5000 102 463
15.3 Results Validation—Once a standard or sample has
10000 157 710 been measured, a procedure should be carried out to validate
46000 400 1816 that measurement. This requires the operator to check for
obvious signs of damage to the sample such as leaking sample
cells, crinkled sample cell window and inspection of any
NOTE 11—The concentrations of ethanol and methanol were calculated secondary film.
assuring a theoretical mixture of hydrocarbons and di-butyl sulfide to
which ethanol (or methanol) was added until the sum of the mass
15.4 Observation of the resultant analysis. If a result is
coefficients times mass fractions increased by 5 %. In other words, the considered outside normal thresholds, a repeat of the analysis
amount of ethanol (or methanol) that caused a negative 5 % error in the should be carried out to confirm anomalous results.
sulfur measurement was calculated. This information is included in Table 15.5 Regular checks should be carried out to ensure that
1 to inform those who wish to use Test Method D 4294 for determining purging gas performance is within the instrument manufac-
sulfur in gasohol (or M-85 and M-100) of the nature of the error involved. ture’s specification.
13. Calculation 15.6 Drift and quality control standards/monitors must be
run on a regular basis. The tolerance levels of the checks made
13.1 The concentration of sulfur in the sample is automati- using these monitors should be such that a protocol of either
cally calculated from the calibration curve. drift correction or total re-calibration is carried out if the results
14. Report fall outside these levels. All measurements should be repeated
between the last accepted monitor result and point of non-
14.1 Report the results as total sulfur content mass % to compliance should a current monitor measurement prove to be
three significant figures for concentrations greater than 0.01 %. outside acceptable levels.
For concentrations less than or equal to 0.01 %, report results
in mg/kg. Report results in mg/kg to two significant figures 16. Precision and Bias 7
between 100 and 10 mg/kg, and to one significant figure below
10 mg/kg. Report that results were obtained according to Test 16.1 Precision—The precision of the test method was
Method D 4294. Use Practice E 29 as a guide for rounding determined by statistical analysis of results obtained in inter-
purposes. laboratory study that included 27 samples including distillates,
14.1.1 For samples containing less than 100 mg/kg total gasoline, kerosene, diesel, biodiesel, residual oils, and crude
sulfur, average the duplicate determinations and report that oils. The laboratory study on precision covered a variety of
value as in 14.1. materials with sulfur concentrations ranging from approxi-
mately 1 mg/kg to 4.6 mass %. A pooled limit of quantitation
15. Quality Control (PLOQ) of 17.0 mg/kg sulfur, was determined for all sample
15.1 It is recommended that each laboratory establish a types. The precision for diesel samples is included in Appendix
program to ensure that the measurement system described in X1. The ranges of sulfur concentrations represented by the
this test method is in statistical control. One part of such a sample sets, together with the precisions, are listed in 16.1.1
program might be the regular use and charting6 of quality and 16.1.2. These statistics apply only to samples having less
control samples (see 7.11). It is recommended that at least one than the level of interfering materials present shown in Table 1.
type of quality control sample be analyzed that is representa- NOTE 12—Volatile materials may not meet the stated precision of the
tive of typical laboratory samples as defined in Practice method because selective loss of light materials is possible before and
D 6299. during analysis by this method. Another possible mechanism is the sulfur
15.2 In addition to running a quality control sample (7.11), enrichment of the sample cup window resulting in higher sulfur values.
it is strongly recommended that the calibration blank (for 16.1.1 Repeatability—The difference between successive
example, diluent oil) be analyzed on a daily basis. test results obtained by the same operator with the same
15.2.1 The measured concentration for the blank should be apparatus under constant operating conditions on identical test
less than 2 mg/kg (0.0002 mass %) sulfur. If the measured materials would, in the long run, in the normal and correct
concentration for the blank is greater than 2 mg/kg (0.0002 operation of the test method, exceed the following values only
mass %), re-standardize the instrument and repeat the measure- in one case in twenty. Repeatability (r) may be calculated as
ment of the blank (use a fresh sample and fresh cell). If the shown in Eq 3 for all materials covering the full scope of this
result falls outside the acceptable range, carry out a full method. See Table 6 for calculated values.

6
ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis ,
7
Section 3, Control Chart for Individuals, ASTM International, W. Conshohocken, Supporting data have been filed at ASTM International Headquarters and may
PA. be obtained by requesting Research Report RR: D02-1635.

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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 15830 9 Crude Oil (light-sour) 16118 +288 +1.82 Yes
2722 2103 10 Crude Oil (heavy-sweet) 2082 -21 -1.00 No
1619b 6960 12 Residual Fuel Oil 6654 -306 -4.40 Yes
1620c 45610 13 Residual Fuel Oil 45801 +191 +0.42 No

Repeatability ~r! 5 0.5409 3 X 0.6154 mg/kg (3) 16.1.3 Repeatability and reproducibility values for diesel in
the aforementioned interlaboratory study7 may be found in
where: Appendix X1.
X = sulfur concentration in mg/kg total sulfur. 16.2 Bias—The interlaboratory study7 included ten NIST
16.1.2 Reproducibility—The difference between two single standard reference materials (SRM’s). The certified sulfur
and independent results obtained by different operators work- value, interlaboratory round robin (RR) value, apparent bias,
ing in different laboratories on identical test material would, in and relative bias are given in Table 7. The white oil was
the long run, in the normal and correct operation of the test assumed to have a C/H mass ratio of 5.698 (C22H46). There
method exceed the following values only in one case in twenty. was no apparent bias that could be attributed to C/H ratio.
Reproducibility (R) may be calculated as shown in Eq 4 for all 16.2.1 Based on the analysis of 10 NIST Standard Refer-
materials covering the full scope of this method. See Table 6 ence Materials (SRM’s), there was no significant bias between
for calculated values. the certified values and the results obtained in this interlabo-
ratory study for any sample type.
Reproducibility ~R! 5 2.4535 3 X 0.6154 mg/kg (4)
17. Keywords
where: 17.1 analysis; diesel; gasoline; jet fuel; kerosene; petro-
X = sulfur concentration in mg/kg total sulfur.
leum; spectrometry; sulfur; X-ray

APPENDIXES

(Nonmandatory Information)

X1. ADDITIONAL PRECISION STATEMENTS

X1.1 Diesel Precision—Six samples in the interlaboratory TABLE X1.1 Precision Values, Diesel
study7 were diesels; they contained between approximately 11 S, mg/kg
Repeatability r, mg/kg Reproducibility R, mg/kg
and 5500 mg/kg total sulfur: Eq X1.1 Values Eq X1.2 Values

Number 5 NIST SRM 2723a 25 5.1 26

Number 7 NIST SRM 2770 100 8.0 41
Number 8 NIST SRM 2724b 500 13 69
Number 15 Diesel 1000 17 87
Number 17 Diesel 5500 29 150
Number 22 B-5 diesel containing 5 % biodiesel

NOTE X1.1—NIST 2723a is a widely used standard that has a certified

value of 11 mg/kg which is below the PLOQ value. The average value in one case in twenty. Repeatability (r) may be calculated as
determined by the interlaboratory study was found to be 20 mg/kg, which shown in Eq X1.1 for the six diesel samples. See Table X1.1
is above the PLOQ and so it is included in this list.
for calculated values.
X1.1.1 Repeatability (r)—The difference between succes-
sive test results obtained by the same operator with the same Repeatability ~r! 5 1.8073·X 0.3221 mg/kg (X1.1)
apparatus under constant operation conditions on identical test X1.1.2 Reproducibility (R)—The difference between two
material would, in the long run, in the normal and correct single and independent results obtained by different operators
operation of the test method exceed the following values only working in different laboratories on identical test material

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would, in the long run, in the normal and correct operation of Reproducibility ~R! 5 9.3715·X 0.3221 mg/kg (X1.2)
the test method exceed the following values only in one case in
twenty. Reproducibility may be calculated as shown in Eq X1.2
for all materials covering the full scope of this method. See
Table X1.1 for calculated values.

X2. HANDLING OXYGENATED FUELS

X2.1 M-85 and M-100 are fuels containing 85 and 100% X2.2 When Analyzing M-85 or M-100 fuels with a cali-
methanol, respectively. E-85 contains 85% ethanol. As such, bration determined with white oil based standards, divide the
they have a high oxygen content, hence, absorption of sulfur result obtained in 12.3 as in the following equations. This
Ka 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 5.2.
to match the matrix of the sample. There may be a loss of
S ~in M285!, mass % 5 S, mass % / 0.59 (X2.1)
sensitivity and precision. The repeatability, reproducibility, and
bias obtained in this test method did not include M-85 and S ~in M2100!, mass % 5 S, mass % / 0.55 (X2.2)
M-l00 samples.

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D 4294–03) that may impact the use of this standard. (Approved March 1, 2008.)

(1) Significant changes to all parts of the test method.

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