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: D2622 − 24a

Standard Test Method for

Sulfur in Petroleum Products by Wavelength Dispersive
X-ray Fluorescence Spectrometry1
This standard is issued under the fixed designation D2622; 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* match can be caused by C/H ratio differences between samples

1.1 This test method covers the determination of total sulfur and standards or by the presence of other interfering heteroa-
in petroleum and petroleum products that are single-phase and toms or species (see Table 1).
either liquid at ambient conditions, liquefiable with moderate 1.6 The values stated in SI units are to be regarded as
heat, or soluble in hydrocarbon solvents. These materials can standard. No other units of measurement are included in this
include diesel fuel, jet fuel, kerosene, other distillate oil, standard.
naphtha, residual oil, lubricating base oil, hydraulic oil, crude 1.7 This standard does not purport to address all of the
oil, unleaded gasoline, gasoline-ethanol blends, and biodiesel. safety concerns, if any, associated with its use. It is the
1.2 The range of this test method is between the PLOQ responsibility of the user of this standard to establish appro-
value (calculated by procedures consistent with Practice priate safety, health, and environmental practices and deter-
D6259) of 3 mg/kg total sulfur and the highest level sample in mine the applicability of regulatory limitations prior to use.
the round robin, 4.6 % by weight total sulfur. 1.8 This international standard was developed in accor-
dance with internationally recognized principles on standard-
NOTE 1—Instrumentation covered by this test method can vary in
sensitivity. The applicability of the test method at sulfur concentrations ization established in the Decision on Principles for the
below 3 mg ⁄kg may be determined on an individual basis for WDXRF Development of International Standards, Guides and Recom-
instruments capable of measuring lower levels, but precision in this test mendations issued by the World Trade Organization Technical
method does not apply. Barriers to Trade (TBT) Committee.
1.2.1 The values of the limit of quantitation (LOQ) and
method precision for a specific laboratory’s instrument depends 2. Referenced Documents
on instrument source power (low or high power), sample type, 2.1 ASTM Standards:2
and the practices established by the laboratory to perform the D4057 Practice for Manual Sampling of Petroleum and
method. Petroleum Products
1.3 Samples containing more than 4.6 % by mass sulfur D4175 Terminology Relating to Petroleum Products, Liquid
should be diluted to bring the sulfur concentration of the Fuels, and Lubricants
diluted material within the scope of this test method. Samples D4177 Practice for Automatic Sampling of Petroleum and
that are diluted can have higher errors than indicated in Section Petroleum Products
15 than non-diluted samples. D4294 Test Method for Sulfur in Petroleum and Petroleum
1.4 Volatile samples (such as high vapor pressure gasolines Products by Energy Dispersive X-ray Fluorescence Spec-
or light hydrocarbons) may not meet the stated precision trometry
because of selective loss of light materials during the analysis. D4927 Test Methods for Elemental Analysis of Lubricant
and Additive Components—Barium, Calcium,
1.5 A fundamental assumption in this test method is that the Phosphorus, Sulfur, and Zinc by Wavelength-Dispersive
standard and sample matrices are well matched, or that the X-Ray Fluorescence Spectroscopy
matrix differences are accounted for (see 13.2). Matrix mis- D6259 Practice for Determination of a Pooled Limit of
Quantitation for a Test Method
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
2
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2024. Published December 2024. Originally contact ASTM Customer Service at www.astm.org/contact. For Annual Book of
approved in 1967. Last previous edition approved in 2024 as D2622 – 24. DOI: ASTM Standards volume information, refer to the standard’s Document Summary
10.1520/D2622-24A. page on 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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 D2622 − 24a
TABLE 1 Concentrations of Interfering Species Test Method D4294. Consult the Index to ASTM Standards for alternative
Species Mass % Tolerated test methods.
Phosphorus 0.3
Zinc 0.6 6. Interferences
Barium 0.8
Lead 0.9 6.1 When the elemental composition (excluding sulfur) of
Calcium 1 samples differs significantly from the standards, errors in the
Chlorine 3
Oxygen 2.8
sulfur determination can result. For example, differences in the
FAME (see Note 16) 25 carbon-hydrogen ratio of sample and calibration standards
Ethanol (see Note 16) 8.6 introduce errors in the determination. Some other interferences
Methanol (see Note 16) 6
and action levels are listed in Table 1. If a sample is known
from its history or another analysis to contain any of the
species listed in Table 1 at or above the values listed there, that
D6299 Practice for Applying Statistical Quality Assurance sample should be diluted with blank sulfur solvent to reduce
and Control Charting Techniques to Evaluate Analytical the interferent concentration below the value to mitigate the
Measurement System Performance effect of this interference.
NOTE 3—The concentrations of the first seven substances in Table 1
D7343 Practice for Optimization, Sample Handling, were determined by the calculation of the sum of the mass absorption
Calibration, and Validation of X-ray Fluorescence Spec- coefficients times mass fraction of each element present. This calculation
trometry Methods for Elemental Analysis of Petroleum was made for dilutions of representative samples containing approxi-
Products and Lubricants mately 3 % of interfering substances and 0.5 % sulfur. Refer to Note 16
E29 Practice for Using Significant Digits in Test Data to for additional information regarding FAME, ethanol, and methanol.
Determine Conformance with Specifications 6.2 Fuels containing large quantities of FAME, ethanol, or
methanol (see Table 1) have a high oxygen content leading to
3. Terminology significant absorption of sulfur Kα radiation and low sulfur
3.1 For definitions of terms used in this test method, refer to results. Such fuels can, however, be analyzed using this test
Terminology D4175. method provided either that correction factors are applied to
the results (when calibrating with white oils) or that the
4. Summary of Test Method calibration standards are prepared to match the matrix of the
4.1 The sample is placed in the X-ray beam, and the peak sample. See 12.5.
intensity of the sulfur K-L2,3 (Kα) line at 0.5373 nm is 6.3 In general, petroleum materials with compositions that
measured. The background intensity, measured at a recom- vary from white oils as specified in 10.1 can be analyzed with
mended wavelength of 0.5190 nm (0.5437 nm for a Rh target standards made from base materials that are of the same or
tube) is subtracted from the peak intensity. The resultant net similar composition. Thus a gasoline may be simulated by
counting rate is then compared to a previously prepared mixing isooctane and toluene in a ratio that approximates the
calibration curve or equation to obtain the concentration of expected aromatic content of the samples to be analyzed.
sulfur in milligrams per kilogram (mg/kg) or mass percent (see Standards made from this simulated gasoline can produce
Section 13). results that are more accurate than results obtained using white
oil standards.
5. Significance and Use
6.4 Test Method D4927 is the recommended test method for
5.1 This test method provides rapid and precise measure- the determination of sulfur >100 mg ⁄kg in lubricating oils and
ment of total sulfur in petroleum and petroleum products with lubricating oil additives because method D4927 implements
a minimum of sample preparation. A typical analysis time is inter-element correction factors. Test Method D2622 is not
1 min to 2 min per sample. suitable because it does not encompass the measurement of the
5.2 The quality of many petroleum products is related to the additional elements present in lubricating oils and their addi-
amount of sulfur present. Knowledge of sulfur concentration is tives making matrix correction impossible.
necessary for processing purposes. There are also regulations
promulgated in federal, state, and local agencies that restrict 7. Apparatus
the amount of sulfur present in some fuels. 7.1 Wavelength Dispersive X-Ray Fluorescence Spectrom-
5.3 This test method provides a means of determining eter (WDXRF), equipped for X-ray detection in the wavelength
whether the sulfur content of petroleum or a petroleum product range from about 0.52 nm to about 0.55 nm (specifically at
meets specification or regulatory limits. 0.537 nm). For optimum sensitivity to sulfur, the instrument
5.4 When this test method is applied to petroleum materials should be equipped with the following items:
with matrices significantly different from the white oil calibra- 7.1.1 Optical Path, vendor specified, helium preferred, am-
tion materials specified in this test method, the cautions and bient air or nitrogen are inferior.
recommendations in Section 6 should be observed when 7.1.2 Pulse-Height Analyzer, or other means of energy
interpreting results. discrimination.
NOTE 2—The equipment specified for Test Method D2622 tends to be 7.1.3 Detector, for the detection of X-rays with wavelengths
more expensive than that required for alternative test methods, such as in the range of interest (from about 0.52 nm to about 0.55 nm).

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 D2622 − 24a
7.1.4 Analyzing Crystal, suitable for the dispersion of sulfur
K-L2,3 (Kα) and background X-rays within the angular range
of the spectrometer employed. Germanium or pentaerythritol
(PET) are generally found to be acceptable. Other crystals may
be used, consult with the instrument vendor.
7.1.5 X-ray Tube, capable of exciting sulfur K-L2,3 (Kα)
radiation. Tubes with anodes of rhodium, chromium, and
scandium are most popular although other anodes can be used.
NOTE 4—Exposure to excessive quantities of high energy radiation such
as those produced by X-ray spectrometers is injurious to health. The
operator needs to take appropriate actions to avoid exposing any part of
their body, not only to primary X-rays, but also to secondary or scattered
radiation that might be present. The X-ray spectrometer should be
operated in accordance with the regulations governing the use of ionizing
radiation. FIG. 1 Relative Sulfur Sensitivity versus C/H Ratio
7.2 Analytical Balance, capable of weighing to the nearest
0.1 mg and up to 100 g.
8. Reagents
time of analysis (see 11.1). These counting rates are used to
8.1 Purity of Reagents—Reagent grade chemicals shall be calculate a drift correction factor (see 12.1).
used in all tests. Unless otherwise indicated, it is intended that 8.3.1 Drift correction is usually implemented automatically
all reagents conform to the specifications of the Committee on in software, although the calculation can readily be done
Analytical Reagents of the American Chemical Society where manually. For X-ray instruments that are highly stable, the
such specifications are available.3 Other grades may be used, magnitude of the drift correction factor may not differ signifi-
provided it is first ascertained that the reagent is of sufficiently cantly from unity.
high purity to permit its use without lessening the accuracy of
the determination. 8.4 Polysulfide Oil, generally nonyl polysulfides containing
a known percentage of sulfur diluted in a hydrocarbon matrix.
8.2 Di-n-Butyl Sulfide (DBS), a high-purity material with a (Warning—May cause allergic skin reactions. Warning—
certified analysis for sulfur content. Use the certified sulfur Solutions prepared in a volatile or un-stabilized matrix may not
content and the material purity when calculating the exact be stable several months after preparation.)
concentrations of the calibration standards (see 10.1). NOTE 6—Polysulfide oils are high molecular weight oils that contain
(Warning—Di-n-butyl sulfide is flammable and toxic. high concentrations of sulfur, as high as 50 % by weight. They exhibit
Warning—Solutions prepared in a volatile or un-stabilized physical properties such as low viscosity, low volatility, and durable shelf
matrix may not be stable several months after preparation.) life while being completely miscible in white oil. The sulfur content of the
NOTE 5—It is essential to know the concentration of sulfur in the polysulfide oil concentrate is determined via mass dilution in sulfur-free
di-n-butyl sulfide, not only the purity, since impurities may also be sulfur white oil followed by a direct comparison analysis against NIST (or other
containing compounds. The sulfur content may be determined via mass primary standards body) reference materials.
dilution in sulfur-free white oil followed by a direct comparison analysis 8.5 Mineral Oil, White (MOW), ACS Reagent Grade con-
against NIST (or other primary standards body) reference materials. taining less than 2 mg/kg sulfur or other suitable base material
8.3 Drift Correction Monitor(s) (Optional), Several differ- containing less than 2 mg/kg sulfur. When low level
ent materials have been found to be suitable for use as drift (<200 mg ⁄kg) measurements are anticipated, then the sulfur
correction monitors. Appropriate drift monitor samples should content, if any, of the base material needs to be included in the
be permanent materials that are stable with respect to repeated calculation of calibration standard concentration (see 10.1).
exposure to X-rays. Stable liquids like polysulfide oils, glass, When the sulfur content of the solvent or reagent is not
or metallic specimens are recommended. Liquids, pressed certified, verify the absence of sulfur. Use the purest grades for
powders, and solid materials that degrade with repeated expo- the preparation of calibration standards. It is also important to
sure to X-rays should not be used. Examples of sulfur measure the C/H ratio (see Section 13 and Fig. 1).
containing materials that have been found to be suitable
8.6 X-ray Transparent Film—Any film that resists attack by
include a renewable liquid petroleum material, a metal alloy, or
the sample, is free of sulfur, and is sufficiently X-ray transpar-
a fused glass disk. The monitor’s counting rate, in combination
ent can be used. Film types can include polyester,
with count time, shall be sufficient to give a relative counting
polypropylene, polycarbonate, and polyimide. However,
error of less than 1 %. The counting rate for the monitor sample
samples of high aromatic content can dissolve polypropylene
is determined during calibration (see 10.4) and again at the
and polycarbonate films.
3
8.7 Helium Gas, minimum purity 99.9 %.
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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 D2622 − 24a
8.9 Sample Cells, compatible with the sample and the TABLE 2 Suggested Sulfur Standard Calibration Ranges
geometry requirements of the spectrometer. Disposable cells 0–1000 0.10–1.00 1.0–5.0
are preferred over reusable ones for ultra low (<50 mg/kg) mg/kg % mass % mass

sulfur levels. 0.0A,B 0.100 1.0

5B 0.250 2.0
8.10 Calibration Check Samples, portions of one or more 10B 0.500 3.0
100B 1.000 4.0
liquid petroleum or product standards of known or certified 250 5.0
sulfur content (including polysulfide oils, di-n-butyl sulfide, 500
thiophenes, etc.) and not used in the generation of the calibra- 750
1000
tion curve. The check samples shall be used to determine the
A
precision and accuracy of the initial calibration (see 10.5). Base material.
B
Analyze these standards in duplicate and use both values or the average value
8.11 Quality Control Samples, stable petroleum or product in the calibration.
samples or solids representative of the samples of interest that
are run on a regular basis to verify that the system is in standards are listed in Table 2 for the sulfur concentration
statistical control (see Section 14). ranges of interest. Take into account any sulfur in the base
NOTE 7—Verification of system control through the use of QC samples
and control charting is highly recommended. It is recognized that QC
material when calculating the concentration of standards below
procedures are the province of the individual laboratory. 0.02 % by mass (200 mg/kg), as shown in Eq 1:
NOTE 8—Suitable QC samples can often be prepared by combining S 5 @ ~ DBS × S DBS! 1 ~ WO × S WO! # / ~ DBS1WO! (1)
retains of typical samples if they are stable. For monitors, solid materials
are recommended. QC samples must be stable over long periods. where:
9. Sampling and Specimen Preparation S = mass percent sulfur of the prepared standards,
DBS = actual mass of DBS, g,
9.1 Samples shall be taken in accordance with the instruc- SDBS = mass percent sulfur in DBS, typically 21.91 %,
tions in Practices D4057 or D4177 when applicable. WO = actual mass of white oil, g, and
9.2 When reusable sample cells are used, clean and dry cells SWO = mass percent sulfur in the white oil.
before each use. Disposable sample cells shall not be reused. NOTE 9—If desired, additional standards can prepared and analyzed
For each sample, an unused piece of X-ray film is required for with concentrations between those listed in Table 2, see 10.1.1.
the sample cell. Avoid touching the inside of the sample cell, 10.1.1 Calibration standards can also be prepared by careful
the portion of the window film in the cell, or the instrument mixing of certified reference materials (CRM) of the same
window (if the instrument is so equipped) that is exposed to matrix, so long as the sulfur values of the resulting blends and
X-rays. Oil from fingerprints can affect the reading when their uncertainties are characterized by the certifying body.4
analyzing for low levels of sulfur. Wrinkles in the film will 10.1.2 Alternatively, standards may be prepared by mass
affect the intensity of the sulfur X-rays transmitted. Therefore, serial dilution of polysulfide oils (Note 6) with sulfur-free
it is essential that the film be taut and clean to ensure reliable white oil. A freshly prepared calibration curve should be
results. The analyzer may need recalibration if the type or verified using CRMs traceable to a national measurement
thickness of the window film is changed. After the sample cell institution that has demonstrated proficiency for measuring
is filled, create a small vent hole except when the cell is of the sulfur in the matrix of interest.
sealed type. NOTE 10—Commercially available standards may be used provided
9.3 Employ adequate storage, mixing, and sampling proce- their sulfur concentrations are accurately known and they approximate the
nominal concentrations listed in Table 2.
dures. Refrigerate gasolines or other similar volatile materials
to retain sample integrity in storage, but allow them to return to 10.2 Establish calibration curve data by carefully determin-
room temperature before testing. Expose these materials to ing the net intensity of the emitted sulfur radiation from each
ambient conditions only as long as necessary to obtain a of the standards by the procedures described in Sections 11 and
sample for analysis. 12.
10.2.1 Analyze standards containing 100 mg/kg total sulfur
9.4 Impurities or thickness variations, which may affect the or less in duplicate. Either both of the individual values or the
measurement of low levels of sulfur, have been found in average value of these measurements may be used in the
polyester films and may vary from lot to lot. Therefore, the calibration. All samples in this sulfur concentration range must
calibration should be checked after starting each new lot of also be analyzed in duplicate, as in 11.12, and reported as in
film. 13.1.1.
9.5 See Practice D7343 for more detailed sample handling 10.3 Construct a calibration model by using the software
and preparation information. and algorithms supplied by the equipment vendor. The calibra-
10. Calibration tion model typically takes one of the following forms (refer to
the equipment vendor’s software documentation to determine
10.1 Prepare calibration standards by careful mass dilution the exact form):
of the certified di-n-butyl sulfide with a sulfur-free white oil or
other suitable base material (see 8.5). The concentrations of the 4
Kelly, W. R., MacDonald, B. S., and Leigh, S. D., “A Method for the
unknown samples must lie within the calibration range that is Preparation of NIST Traceable Fossil Fuel Standards with Concentrations Interme-
used. Approximate recommended nominal sulfur concentration diate to SRM Values,” Journal of ASTM International, Vol 4, No. 2, 2007.

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 D2622 − 24a
C S 5 a1bI linear calibration (2) are set correctly. Before performing a calibration of the
goniometer angles carry out pulse height discriminator settings
C S 5 ~ a1bI! ~ 11 (α C !
ij j correction for matrix effects (3)
(PHD’s) for each element and background to be used. The
C S 5 a1bI~ 11 (α C !
ij j alternative correction for matrix effects angle should be checked first, then the PHD, then the angle
(4) re-checked if the PHD settings are changed significantly. A
C S 5 a1bI1cI 2
2nd order polynomial (5) very poor angle calibration may lead to bad PHD. The only
reasonable alternate line is the sulfur K-M2,3 (Kβ) with
where: significantly less than 10 % of the sensitivity of the K-L2,3
CS = mass fraction of sulfur. The concentration units depend (Kα); this will only be practical for samples with high sulfur
on the fitted calibration constants a, b and c, concentrations.
I = measured net intensity for the sulfur radiation,
a = fitted calibration line offset (intercept), 11.3 Account for observations of known instrument inter-
b = fitted calibration line slope, ferences. These include crystal fluorescence, tube line overlaps
c = fitted calibration line 2nd order polynomial, and any element spectral contamination from the materials
aij = correction factor for the effect of an interfering element within the instrument construction. Lead is a particularly bad
(j) on sulfur (i). The interfering element can be sulfur interference for sulfur measurement. A number of these inter-
when “matrix eliminated alphas” or empirical correc- ferences can be avoided by careful selection of window
tions are used, and settings during PHD set-up and for element interference the
Cj = concentration of the interfering element (j). selection of an alternative line or minimizing overlap using
NOTE 11—The aij factors can be determined empirically through higher resolution collimators and crystal selection.
multiple regression, or theoretically through fundamental parameters.
Equipment vendors typically have provisions in their software for 11.4 When the factor F' is used in Eq 8, regularly analyze a
calculating theoretical a’s. blank sample to determine the factor F'. On a sulfur free
10.3.1 Fit the calibration data over several ranges if sample, such as the base material, determine the counting rate
necessary, depending on the sulfur concentrations to be cov- at the appropriate sulfur peak and background angles.
ered. For example (Table 2): 0 % to 0.10 % by mass sulfur, 11.5 Place the sample in an appropriate cell using tech-
0.10 % to 1.0 % by mass sulfur, and 1.0 % to 5.0 % by mass niques consistent with good practice for the particular instru-
sulfur. ment being used. Although incident radiation may penetrate a
NOTE 12—Calibration curves are typically linear to about 0.10 % by
significant distance into the sample, sulfur radiation will escape
mass sulfur. The analyst should choose a linear calibration model when from only a small distance into the sample, and scatter from the
fitting within this range. One of the other calibration models (correction sample cell and the sample can vary. Ensure that the sample
for matrix effects or a 2nd order polynominal) should be chosen when cell is filled above a minimum depth, beyond which additional
fitting to higher concentrations of sulfur. sample does not significantly affect the counting rate.
10.4 When using drift correction monitors, determine the Generally, fill the sample cell to a minimum of two-thirds of
intensity of the drift correction monitor sample(s) during the the cell’s capacity. Provide a small vent hole in the sample cell
calibration procedure. The value determined corresponds to the unless using a sealed cell.
factor A in Eq 7 in 12.1.
11.6 Place the sample in the X-ray beam and allow the
10.5 Immediately after completing the calibration, deter- X-ray optical path to come to equilibrium.
mine the sulfur concentration of one or more of the calibration
11.7 Determine the intensity of the sulfur K-L2,3 (Kα)
check samples (8.10). The differences between two measured
radiation at 0.5373 nm by making counting rate measurements
values shall be within the repeatability of this test method (see
at the precise angular settings for this wavelength.
15.1.1). When this is not the case, the stability of the instru-
NOTE 13—It is suggested that a sufficient number of counts be taken to
ment and the repeatability of the sample preparation are satisfy an expected coefficient of variation (% rsd) of 1.0 % or less when
suspect and corrective measures should be taken. The degree of practical. When sensitivity or concentration, or both, make it impractical
matrix mismatch between samples and standards should also to collect a sufficient number of counts to achieve a 1.0 % coefficient of
be considered when evaluating a calibration. Statistical quality variation, accepted techniques, which will allow the greatest statistical
control charts may be prepared for these materials to establish precision in the time allotted for each analysis, should be used.
if the method is in statistical control, as described in Section 11.8 The coefficient of variation, CV, is calculated as
14. follows:
11. Procedure CV 5 ~ 100~ N p 1N b ! 1/2 ! / ~ N p 2 N b ! (6)

11.1 Instrument Setup—Before using any WDXRF where:

spectrometer, it is essential that the instrument is performing to CV = Coefficient of Variation, %,
the manufacturer’s specifications. Consult with the manufac- Np = number of counts collected at sulfur line peak,
turer on how to perform spectrometer quality control checks. 0.5373 nm, and
Practice D7343, Section 7 also provides more detailed infor- Nb = number of counts collected at background wavelength
mation in this area. in the same time interval taken to collect Np counts.
11.2 Place particular attention on goniometer settings for 11.9 Measure background counting rate at a previously-
sequential instruments, that is, ensuring goniometer positions selected fixed angular setting, adjacent to the sulfur Kα peak.

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TABLE 3 2θ Angles for Most Common Crystals 11.13.3 Determine the sulfur content of the blend in the
S Kα Background normal manner as described in 11.5 – 11.9, and calculate the
Crystal
2d (0.5373 (0.5190 (0.5437 sulfur content of the original sample as described in Section 12.
(nm) nm) nm) nm)
Deg 2θ Deg 2θ Deg 2θ
12. Calculations
Pentaerythritol (002) 0.8742 75.85 72.84 76.92
GE (111) 0.6532 110.68 105.23 112.68 12.1 When using the drift correction monitor described in
8.3, calculate a correction factor for changes in daily instru-
ment sensitivity as follows:
NOTE 14—Suitability of any background setting will depend on the F 5 A/B (7)
X-ray tube anode employed. A wavelength of 0.5190 nm is recommended
where chromium or scandium is used whereas 0.5437 nm has been found where:
suitable for rhodium, 2θ, peak and background, angles for various crystals F = correction factor,
are listed in Table 3.
A = counting rate of the drift correction monitor as deter-
11.10 Determine the corrected counting rate and calculate mined at the time of calibration (see 10.4), and
the concentration of the sample as described in Section 12. B = counting rate of the drift correction monitor as deter-
11.11 When, from the measurements made in accordance mined at the time of analysis.
with 11.5 – 11.10, the counting rate is higher than that of the 12.2 Determine the corrected net counting rate (intensity) as
highest point of the calibration curve, dilute the sample with follows:
the base material used to prepare the calibration standards until
R 5 @ ~ N p /S 1 ! 2 ~ N b F'/S 2 ! # F (8)
the sulfur counting rate is within the limits of the calibration
curve and repeat the procedure described in 11.5 – 11.10. where:
11.12 For samples containing 100 mg/kg total sulfur or less, R = corrected net counting rate,
duplicate determinations are required. Each determination Np = total counts collected at 0.5373 nm,
must be made on a new portion of sample material and Nb = total counts collected at the background location
analyzed in accordance with 11.5 – 11.10. The difference chosen in 11.8,
between the duplicate analyses should be equal to or less than S1 and S2 = seconds required to collect Np and Nb counts,
the repeatability values indicated in 15.1.1. If the difference is respectively,
F' = the ratio of counts/s at 0.5373 nm to the counts/s
larger, investigate sample preparation to identify any possible
at background using a sample containing no
sources of sample contamination, and repeat the analysis. The
sulfur, and
reason for duplicate measurements is to identify problems
F = optional factor (see Note 17).
associated with sample contamination, leading to improved NOTE 17—The inclusion of the factor F in Eq 8 may not be necessary
results precision at the lower sulfur levels. or desirable with some instrumentation. In this case F is set to unity. It is
11.13 When the sample is known or believed to contain recommended that the user chart the F factor and develop criteria for its
application based on the stability of the instrumentation and standard SQC
concentrations of interfering substances higher than those principles.
listed in Table 1, dilute the sample by mass with base material
to concentrations below those listed. 12.2.1 The inclusion of the factor F' in Eq 8 is optional. In
11.13.1 The data collected (see Note 3) showed reasonable general it is needed for multi-channel spectrometers, which use
X-ray results when the calculated sum of mass absorption different spectrometer channels to measure peak and back-
coefficients times mass fractions for samples was not greater ground intensities.
NOTE 18—Charting the F' factor, even if it is not used in Eq 8, will alert
than 4 % to 5 % above the sum of mass absorption coefficients the user to changes in instrument operation due to contamination of
times mass fractions for the calibration standards. Absorption system elements, such as crystals, collimators, and fixed windows.
interferences are additive, and they are only minimized by
12.3 Calculate the sulfur content of the sample by inserting
dilution, not completely eliminated. Table 1 is therefore to be
the corrected net counting rate from Eq 8 in the chosen
used as a guide to concentrations that can be tolerated without
calibration model from Section 10. In many cases the instru-
significant error, not as an absolute quantity.
ment vendor will provide software for the required calcula-
NOTE 15—The effect of matrix interferences can also be corrected on an tions.
empirical or theoretical basis.
NOTE 16—The concentrations of ethanol and methanol were calculated 12.4 Calculate the concentration of sulfur in samples, which
assuming a theoretical mixture of hydrocarbons and di-butyl sulfide to have been diluted, as follows:
which ethanol (or methanol) was added until the sum of the mass
S 5 S b @ ~ W s 1W o ! /W s # (9)
coefficients times mass fractions increased by 5 %. In other words, the
amount of ethanol (or methanol) that caused a negative 5 % error in the where:
sulfur measurement was calculated. This information is included in Table
1 to inform those who wish to use Test Method D2622 for determining S = mass percent total sulfur in the sample,
sulfur in FAME blends (biodiesel), gasohol, M-85, or M-100 of the nature Sb = mass percent sulfur in diluted blend,
of the error involved. Ws = mass of original sample, g, and
11.13.2 Thoroughly mix the blend to ensure homogeneity Wo = mass of diluent, g.
(mixing method will depend on the matrix type), and transfer 12.4.1 The instrument vendor may have provided software
it to the instrument for measurement. to perform this calculation when required masses are input.

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12.5 When analyzing fuels containing high levels of FAME, TABLE 4 Precision Values, All Sample Types
ethanol, or methanol (Table 1) with a calibration determined S,
Repeatability r, Reproducibility R,
with white oil based standards, divide the result obtained in mg/kg mg/kg
mg/kg
Eq 12 values Eq 14 values
12.3 as follows (see Note 16):
3.0 0.4 1.0
S Fuel 5 M/F (10) 5.0 0.5 1.6
10.0 0.9 2.7
where: 25.0 1.9 5.6
50.0 3.4 9.8
SFuel = mass percent sulfur present in the fuel sample, wt.%, 100.0 5.9 17.1
M = measured mass percent, wt.%, and 500 21 62
F = correction factor, for example, equals 0.59 for M-85 1000 37 108
5000 135 394
and 0.55 for M-100. 10 000 235 687
46 000 798 2333
12.5.1 This correction is not required if the standards are
prepared in the same matrix as the samples, as described in 6.2.
12.6 Additional information regarding regression calcula- Swhiteoil = sulfur concentration as derived from the
tions may be found in Practice D7343. calibration graph.
NOTE 19—There are multiple options for correcting the interference
from the presence of oxygenates in the determination of sulfur in fuels 13.2.1 The value for C/H mass ratio is input for each
using WD-XRF method. A survey of D02.SC 3 members conducted in unknown sample. The Swhiteoil will be corrected for the
December 2014 revealed that the majority of users of this test method use different C/H ratios. Accordingly, if standards are prepared
the option given in Section 2 (that is, use of fundamental parameter with a different solvent, the C/H ratio for that solvent should be
calculation which is built into the software. This is done automatically by
the instrument after the measurement is completed for each sample). Some used in place of (C/H)whiteoil. Any difference between the C/H
members use the option of matrix matching described in 6.2. This is a ratio between standards and samples will contribute to error in
challenging task due to the variability of the oxygen content in a series of the measured result (see Table 6 for examples). It is the
samples. Fewer members use the option of automatic correction of the analyst’s discretion as to when this error is large enough to be
final data done by an independent program, using the approach similar to
that given in 13.2. This would be similar to Fig. 1 depicted in the standard
corrected by Eq 11.
where the carbon/hydrogen ratio is being manually corrected. The option
given in 11.13 does not appear to be used by the members. 14. Quality Control
14.1 It is recommended that each laboratory establish a
13. Reporting program to ensure that the measurement system described in
13.1 For samples analyzed without dilution, report the result this test method is in statistical control. One part of such a
calculated in 12.3. For samples that have been diluted, report program might be the regular use and charting5 of quality
the result calculated in 12.4. Report the result as the total sulfur control samples (see 8.11). It is recommended that at least one
content, mass percent, to three significant figures for concen- type of quality control sample be analyzed that is representa-
trations greater than 0.1000 % by mass. Below 0.1000 % by tive of typical laboratory samples as defined in Practice D6299.
mass (1000 mg/kg) report results in mg/kg to three significant 14.2 In addition to running a quality control sample (8.11),
figures between 1000 mg/kg and 10 mg/kg, and to two it is strongly recommended that the calibration blank (for
significant figures below 10 mg/kg. For guidance in properly example, diluent oil) be analyzed on a daily basis.
rounding significant figures, refer to the rounding method in 14.2.1 The measured concentration for the blank should be
Practice E29. State that the results were obtained according to less than 2 mg/kg (0.0002 % by mass) sulfur. If the measured
Test Method D2622. concentration for the blank is greater than 2 mg/kg (0.0002 %
13.1.1 For samples containing 100 mg/kg total sulfur or by mass), re-standardize the instrument and repeat the mea-
less, average the duplicate determinations and report that value surement of the blank (use a fresh sample and fresh cell). If the
as in 13.1. result falls outside the acceptable range, carry out a full
calibration. If the sample loading port becomes contaminated,
13.2 The carbon/hydrogen (C/H) ratio correction formula, especially when analyzing <20 mg/kg sulfur level samples, it is
which is applicable when the base material used for the necessary to open and clean it according to manufacturer’s
calibration standards is white oil and is derived from the best recommendations before further use.
straight line shown in Fig. 1, is shown in Eq 11: 14.2.2 It should be noted that in order to obtain a good fit for
1.195 2 0.0164 ~ C/H ! whiteoil the calibration at low concentrations, it may be necessary to
S C/H 5 ·S whiteoil (11)
1.195 2 0.0164 ~ C/H ! change the weighting factor in the regression. It may also be
beneficial to change the weighting method used. Many soft-
where:
ware packages default to square root error weighting but have
SC/H = sulfur concentration corrected for C/H ratio the possibility of using linear error weighting or no error
matrix differences, weighting.
(C/H)whiteoil = mass ratio of carbon to hydrogen for white
oil, 5.7 from Fig. 1,
5
(C/H) = mass ratio of carbon to hydrogen for the ASTM MNL 7, Manual on Presentation of Data and Control Chart Analysis,
Section 3, Control Chart for Individuals, ASTM International, W. Conshohocken,
sample, and
PA.

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TABLE 5 Comparison of NIST SRM Data and ASTM Interlaboratory Study (RR) Measured Results
NIST Sulfur, RR Average Measured Measured Reproducibility Measured
Relative Measured
SRM mg/kg, Sample Matrix mg/kg Sulfur mg/kg Sulfur Bias
Bias, %
Number NIST Number ASTM RR ASTM RR mg/kg Sulfur
2298 4.7 1 Gasoline 6.0 2.9 1.3 27.7
2723a 11.0 5 Diesel 10.1 3.6 -0.9 -8.18
2299 13.6 3 Gasoline 14.2 3.8 0.6 4.41
2296 40.0 2 Gasoline 40.2 6.6 0.2 0.5
2770 41.6 7 Diesel 42.1 6.8 0.5 1.20
2724b 426.5 8 Diesel 420.9 42.5 -5.6 -1.31
2722 2103 10 Crude Oil 2054 181 -49 -2.33
1619b 6960 12 Residual Fuel Oil 6448 546 -512 -7.36
2721 15830 9 Crude Oil 15884 1170 54 0.34
1620c 45610 13 Residual Fuel Oil 44424 3123 -1186 -2.60

TABLE 6 Comparison of NIST SRM Data and ASTM Interlaboratory Study (RR) Results Corrected for C/H Ratio
Using Mineral Oil Standards
NIST Sulfur, C/H Average Measured Average C/H Corrected
Corrected Bias Relative Corrected
SRM mg/kg, Mass Matrix mg/kg Sulfur mg/kg Sulfur
mg/kg Sulfur Bias,%
Number NIST Ratio ASTM RR ASTM RR
2298 4.7 5.47 Gasoline 6.0 6.0 1.3 27.66
2723a 11.0 5.99 Diesel 10.1 10.2 -0.8 -7.27
2299 13.6 6.17 Gasoline 14.2 14.3 0.7 5.15
2296 40.0 6.42 Gasoline 40.2 40.6 0.6 1.50
2770 41.6 5.75 Diesel 42.1 42.4 0.8 1.92
2724b 426.5 7.18 Diesel 420.9 426.4 -0.1 -0.02
2722 2103 7.22 Crude Oil 2054 2105 2 0.10
1619b 6960 8.80 Residual Fuel Oil 6448 6804 -156 -2.24
2721 15830 7.17 Crude Oil 15884 16217 387 2.44
1620c 45610 7.93 Residual Fuel Oil 44424 46535 935 2.05

14.3 Results Validation—Once a standard or sample has limit of quantitation (PLOQ) of approximately 3 mg/kg S was
been measured, a procedure should be carried out to validate determined for all sample types. Precision for gasoline and
that measurement. This requires the operator to check for diesel samples for high-power source XRF instruments is
obvious signs of damage to the sample such as leaking sample included in Appendix X1. The ranges of sulfur concentrations
cells, crinkled sample cell window and inspection of any represented by the sample sets, together with the precisions, are
secondary film. listed in 15.1.1 and 15.1.2. These statistics apply only to
14.4 Observation of the Resultant Analysis—If a result is samples having less than the level of interfering materials
considered outside normal thresholds, a repeat of the analysis present shown in Table 1 (see also 1.4).
should be carried out to confirm anomalous results.
NOTE 20—The precision statement listed in this method does not match
14.5 Regular checks should be carried out to ensure that the statement listed in the cited research report, RR:D02-1622. Due to an
purging gas performance is within the instrument manufac- administrative oversight, the report did not include the complete data set
ture’s specification. from the ILS, so the precision statement was recalculated with the
complete data set in 2008. The precision statement given in this section is
14.6 Drift and quality control standards/monitors shall be based on the complete data set, while the report includes precision based
run on a regular basis. The tolerance levels of the checks made on incomplete data. The additional data is no longer accessible.
using these monitors should be such that a protocol of either 15.1.1 Repeatability—The difference between successive
drift correction or total recalibration is carried out if the results test results obtained by the same operator with the same
fall outside these levels. All measurements should be repeated apparatus under constant operating conditions on identical test
between the last accepted monitor result and point of non- material would, in the long run, in the normal and correct
compliance should a current monitor measurement prove to be operation of the test method exceed the following values only
outside acceptable levels. in one case in twenty. Repeatability (r) may be calculated as
15. Precision and Bias shown in Eq 12 or Eq 13 for all materials covering the full
scope of this method. See Table 4 for calculated values.
15.1 The precision of the test method was determined by
statistical analysis of results obtained an interlaboratory study6 Repeatability ~ r ! 5 0.1462·X 0.8015 mg/kg (12)
(see Note 20) that included 27 samples including gasolines, Repeatability ~ r ! 5 ~ 0.1462· ~~ Y·10000! !! /10000 %by mass
0.8015

distillates, biodiesel, residual oils, and crude oils. A pooled (13)

where:
6
Supporting data have been filed at ASTM International Headquarters and may X = sulfur concentration in mg/kg total sulfur, and
be obtained by requesting Research Report RR:D02-1622. Contact ASTM Customer
Y = sulfur concentration in mass % total sulfur.
Service at www.astm.org/contact.

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15.1.2 Reproducibility—The difference between two single 15.2 Bias—The interlaboratory study6 included ten NIST
and independent results obtained by different operators work- standard reference materials (SRMs). The certified sulfur
ing in different laboratories on identical test material would, in value, interlaboratory round robin (RR) value, measured C/H,
the long run, in the normal and correct operation of the test apparent bias, and relative bias are given in Table 5. Table 6
method exceed the following values only in one case in twenty. compares NIST value with sulfur concentrations corrected for
Reproducibility (R) may be calculated as shown in Eq 14 or Eq C/H ratio. The white oil was assumed to have a C/H mass ratio
15 for all materials covering the full scope of this method. See of 5.698 (C22H46).
Table 4 for calculated values. 15.2.1 The variation in relative sulfur sensitivity as a
function of C/H mass ratio is shown graphically in Fig. 1.
Reproducibility ~ R ! 5 0.4273·X 0.8015 mg/kg (14)
15.2.2 Based on the analysis of 10 NIST Standard Refer-
Reproducibility ~ R ! 5 ~ 0.4273· ~~ Y·10000! 0.8015
!! /10000 %by mass ence Materials (SRMs), there was no significant bias between
(15) the certified values and the results obtained in this interlabo-
where: ratory study for any SRM or sample type within measured
reproducibilities (R), especially after the C/H ratio corrections
X = sulfur concentration in mg/kg total sulfur, and
were applied (see Tables 5 and 6).
Y = sulfur concentration in mass percent total sulfur.
15.1.3 Repeatability and reproducibility values for gasoline 16. Keywords
and diesel in the aforementioned interlaboratory study6 may be 16.1 analysis; diesel; gasoline; jet fuel; kerosene; petro-
found in Appendix X1. Also, precision values and plots for leum; spectrometry; sulfur; wavelength dispersive x-ray fluo-
high power (>1KW source) instruments are also included. rescence; X-ray

APPENDIX

(Nonmandatory Information)

X1. ADDITIONAL PRECISION STATEMENTS

X1.1 Gasoline Precision—Five samples in the interlabora- TABLE X1.1 Precision Values, Gasoline
tory study6 were gasolines, they contained between approxi- S, Repeatability r, Reproducibility R,
mately 5 mg ⁄kg and 70 mg/kg total sulfur, the limits for these mg/kg mg/kg Eq X1.1 values mg/kg Eq X1.3 values

precision statement. 5.0 1.01 2.94

10.0 1.37 3.98
Number 1 NIST SRM 2298, high octane gasoline 25.0 2.05 5.95
Number 2 NIST SRM 2296, gasoline containing 13 % ETBE 70.0 3.21 9.33
Number 3 NIST SRM 2299, reformulated gasoline
Number 4 Gasoline containing 5 % ethanol
Number 11 Unleaded regular gasoline
X1.1.2 Reproducibility (R)—The difference between two
X1.1.1 Repeatability (r)—The difference between succes- single and independent results obtained by different operators
sive test results obtained by the same operator with the same working in different laboratories on identical test material
apparatus under constant operating conditions on identical test would, in the long run, in the normal and correct operation of
material would, in the long run, in the normal and correct the test method exceed the following values only in one case in
operation of the test method exceed the following values only twenty. Reproducibility (R) may be calculated as shown in Eq
in one case in twenty. Repeatability (r) may be calculated as X1.3 or Eq X1.4, which were derived from the interlaboratory
shown in Eq X1.1 or Eq X1.2, which were derived from the study6 data of five gasoline samples. See Table X1.1 for
interlaboratory study6 data of five gasoline samples. See Table calculated values and Fig. X1.2 for data plots.
X1.1 for calculated values and Fig. X1.1 for data plots.
Reproducibility ~ R ! 5 1.4533·X 0.4377 mg/kg (X1.3)
Repeatability ~ r ! 5 0.5006·X 0.4377 mg/kg (X1.1)
Reproducibility ~ R ! 5 ~ 1.4533· ~~ Y·10000! ! !/10000 %by mass
0.4377
Repeatability ~ r ! 5 ~ 0.5006 · ~~ Y·10000! 0.4377!! /10000 %by mass
(X1.4)
(X1.2)
where:
where:
X = sulfur concentration in mg/kg total sulfur, and
X = sulfur concentration in mg/kg total sulfur, and Y = sulfur concentration in mass percent total sulfur.
Y = sulfur concentration in mass percent total sulfur.

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FIG. X1.1 Repeatability of Gasoline, Diesel and All Sample Types versus Current ASTM Values

X1.2 Diesel Precision—Five samples in the interlaboratory twenty. Reproducibility (R) may be calculated as shown in Eq
study6 were diesels, they contained between approximately X1.7 or Eq X1.8 for five diesel samples used in the interlabo-
11 mg ⁄kg and 5500 mg/kg total sulfur, the limits for this ratory study.6 See Table X1.2 for calculated values and Fig.
precision statement: X1.2 for data plots.
Number 5 NIST SRM 2723a Reproducibility ~ R ! 5 0.3856·X 0.8000 mg/kg (X1.7)
Number 7 NIST SRM 2770
Number 8 NIST SRM 2724b Reproducibility ~ R ! 5 ~ 0.3856· ~~ Y·10000! !! /10000 %by mass
0.8000

Number 15 Diesel
Number 22 B-5 diesel containing 5 % biodiesel
(X1.8)

X1.2.1 Repeatability (r)—The difference between succes- where:

sive test results obtained by the same operator with the same X = sulfur concentration in mg/kg total sulfur, and
apparatus under constant operating conditions on identical test Y = sulfur concentration in mass percent total sulfur.
material would, in the long run, in the normal and correct
operation of the test method exceed the following values only X1.3 High Power Instrument Precision—The power of the
in one case in twenty. Repeatability (r) may be calculated as x-ray fluorescence source can affect the precision of results
shown in Eq X1.5 or Eq X1.6 for the five diesel samples. See measured by this method. Instruments having >1000 watt
Table X1.2 for calculated values and Fig. X1.1 for data plots. sources are defined as high power, while those having <1000
Repeatability ~ r ! 5 0.1037·X 0.8000 mg/kg (X1.5) watt sources are defined as low power. In this study6, five
participants used low power instruments and ten used high
Repeatability ~ r ! 5 ~ 0.1037 · ~~ Y·10000! 0.8000
! ! / 10 000 % by mass power instruments. The precision statements for the high
(X1.6)
power instruments follow, covering the full scope of this
where: method.
X = sulfur concentration in mg/kg total sulfur, and X1.3.1 Repeatability (r)—The difference between succes-
Y = sulfur concentration in mass percent total sulfur. sive test results obtained by the same operator with the same
X1.2.2 Reproducibility (R)—The difference between two apparatus under constant operating 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 X1.9 or Eq X1.10 derived from the interlaboratory

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FIG. X1.2 Reproducibility of Gasoline, Diesel and All Sample Types versus Current ASTM Values

TABLE X1.2 Precision Values, Diesel

S, Repeatability r, Reproducibility R,
mg/kg mg/kg Eq X1.5 values mg/kg Eq X1.7 values
11 0.71 2.63
25 1.36 5.06
100 4.13 15.35
500 15.0 55.6
1000 26.0 96.9
5500 102 379

study 6 data for the five gasoline samples. See Table X1.1 for the test method exceed the following values only in one case in
calculated values for gasoline, Table X1.2 for diesel, and Table twenty. Reproducibility (R) may be calculated as shown in Eq
X1.3 for all sample types using high-power instruments. X1.11 or Eq X1.12, which were derived from the ILS data for
Repeatability ~ r ! 5 0.08681·X 0.8383 mg/kg (X1.9) five gasoline samples. See Table X1.1 for calculated values for
gasoline, Table X1.2 for diesel, and Table X1.3 for all sample
Repeatability ~ r ! 5 ~ 0.08681 · ~~ Y·10000! 0.8383
!! /10000 %by mass
types using high-power instruments.
(X1.10)
Reproducibility ~ R ! 5 0.3086·X 0.8383 mg/kg (X1.11)
where:
Reproducibility ~ R ! 5 ~ 0.3086· ~~ Y·10000! 0.8383!! /10000 %by mass
X = sulfur concentration in mg/kg total sulfur, and
Y = sulfur concentration in mass percent total sulfur. (X1.12)

X1.3.2 Reproducibility (R)—The difference between two where:

single and independent results obtained by different operators X = sulfur concentration in mg/kg total sulfur, and
working in different laboratories on identical test material Y = sulfur concentration in mass percent total sulfur.
would, in the long run, in the normal and correct operation of

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TABLE X1.3 Precision Values, High Power Instruments, All
Sample Types
S, Repeatability r, Reproducibility R,
mg/kg mg/kg Eq X1.9 values mg/kg Eq X1.11 values
1.0 0.09 0.31
5.0 0.33 1.19
10.0 0.60 2.13
25.0 1.29 4.58
50.0 2.31 8.20
100.0 4.12 14.66
500 15.9 56.5
1000 28.4 101.0
5000 109.5 389.3
10000 196 696
46000 704 2501

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D2622 – 24) that may impact the use of this standard. (Approved Dec. 1, 2024.)

(1) Revised Note 20.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D2622 – 21) that may impact the use of this standard. (Approved July 1, 2024.)

(1) Revised subsection 15.1. (2) Added Note 20.

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