Mono11 2014

Nadkarni
Sulfur
Dr. R.A. Kishore Nadkarni received his
Analysis of Fossil Fuel Products

Sulfur: Chemistry and
Ph.D. in analytical chemistry at the University of Bombay.
Since then he has worked as a research associate at
the University of Kentucky, manager of the Materials
Science Center Analytical Facility at Cornell University,
and analytical leader in the ExxonMobil Company.
In his last position he was responsible for technical
quality management of the Paramins Division’s global
plant laboratories.
Chemistry and Analysis of
Fossil Fuel Products
He has authored more than 140 technical publications
including 21 new ASTM standards in the area of
analytical chemistry and quality management. He is a member of the American
Chemical Society and ASTM International. He is very active in ASTM and ISO in
the petroleum products and lubricant field, holding the position of immediate past
chairman of ISO/TC28, chairman of ASTM’s D02.03 on Elemental Analysis, vice-
chairman of D02.92 on Proficiency Test Programs, D02.94 on Quality Assurance and R.A. Kishore Nadkarni
Statistics.
Dr. Nadkarni has received the Award of Appreciation (1991) and Awards for Excellence
(1998, 1999, and 2013) from ASTM’s D02 Committee for his contribution to the oil
industry, the Award of Merit (2005) and the George Dyroff Award of Honorary D02
membership (2006), and the Sydney Andrews D02 Scroll of Achievement Award (2005).
He is the author or editor of STP 1109, Modern Instrumental Methods of Elemental

Analysis of Petroleum Products and Lubricants (1991); STP 1468, Elemental Analysis of
Fuels and Lubricants (2005); Manual 44, Guide to ASTM Test Methods for the Analysis
of Petroleum Products and Lubricants (2007); Manual 61, Guide to ASTM Test Methods
for the Analysis of Coal and Coke (2008); Monograph 9, Spectroscopic Analysis of
Petroleum Products and Lubricants (2011); and Monograph 10, “Elemental Analysis of
Fossil Fuels and Related Materials” (2014).
www.astm.org
ISBN: 978-0-8031-7052-0
Stock #: MONO11
R. A. Kishore Nadkarni
Sulfur: Chemistry and Analysis

of Fossil Fuel Products
ASTM Stock Number: MONO11
ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959
Printed in the U.S.A.
BK-AST-MONO11-140027-FM.indd 1 5/23/2014 6:43:37 PM

Library of Congress Cataloging-in-Publication Data
Nadkarni, R. A.
Sulfur : chemistry and analysis of fossil fuel products / R.A. Kishore Nadkarni.
pages cm. – (ASTM International’s monograph series ; 11)
“ASTM Stock Number: MONO 11.”
Includes bibliographical references and index.
ISBN 978-0-8031-7052-0
1. Petroleum–Sulfur content. 2. Petroleum products–Analysis. I. Title.
TP692.4.S9N33 2014
665.5’38–dc232013036927
Copyright © 2014 ASTM International, West Conshohocken, PA. All rights reserved. This material may
not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other
distribution and storage media, without the written consent of the publisher.
ASTM Photocopy Rights

Authorization to photocopy items for internal, personal, or educational classroom use of specific
clients, is granted by ASTM International provided that the appropriate fee is paid to ASTM International,
100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, Tel: 610-832-9634; online:
http://www.astm.org/copyright/
ASTM International is not responsible, as a body, for the statements and opinions advanced in the
publication. ASTM International does not endorse any products represented in this publication.
Printed in City, State

Date

Foreword
THIS PUBLICATION, Sulfur: Chemistry and Analysis of Fossil Fuel Products, was
sponsored by Committee D02 on Petroleum Products and Lubricants. This is
Monograph 11 in ASTM International’s monograph series.

Acknowledgments
I have to thank my former employers who provided facilities and allowed me to pursue my
research interests in analytical chemistry: Exxon Research and Engineering Company; Exxon
Chemical Company—Paramins Manufacturing Technology Division; ExxonMobil Research and
Engineering Company; and Infineum USA, LLC.
I am indebted to the following colleagues in the above companies: Kevin Bly, Alex Lau,
Dr. Richard Ledesma, and Dr. Kelly Mason. I also thank the following colleagues from the oil
industry involved in ASTM work: John Crnko of ASI, Dr. Keith Dahnke of ConocoPhillips,
Dr. Mike Pohl of Horiba Instruments, and Bill Tanguay of Metrotech Systems. All of them were
key players in our efforts to develop the best regulatory test methods for sulfur in petroleum prod-
ucts. All of them helped me in this work and know far more about the subject than I do.
Special thanks are due to various ASTM staff members, principal among them Kathy
Dernoga, Managing Editor, and Monica Siperko, Publishing Specialist. Also, Rebecca Edwards
(senior project manager) at Cenveo Publisher Services for her work during the publication
process.
I am, of course, eternally grateful to my beloved wife, Nancy Joanne, for her unfailing sup-
port while I was busy with writing, teaching, and traveling around the world.

Contents
Forewordiii
Acknowledgments iv
1. Introduction1
2. Analytical Techniques for Sulfur Determination9
3. Analysis of Coal and Coke Products35
4. Analysis of Oil Shales53
5. Analysis of Petroleum Products59
6. Analysis of Lubricants and Additives153
7. Analysis of Gaseous Fuels163
8. Analysis of Biofuels195
9. Proficiency Testing Programs for Sulfur in Petroleum Products and Lubricants207
Appendix 1 ASTM Standards Cited243
Appendix 2 Index of Description of ASTM Test Methods245
Index249

Chapter 1 | Introduction
Sulfur is a ubiquitous element present in almost all living organisms and in the
environment. Many studies have been conducted, especially in recent times, to
evaluate the effect of sulfur compounds on the environment, particularly from the use
of fossil fuels by combustion or otherwise. Sulfur is spelled “sulphur” in British English
used throughout the British Commonwealth, although IUPAC spells it “sulfur.”
Sulfur has been known since antiquity. In the Bible, it was called brimstone
(stone that burns). The word comes from the Latin word sulphurium or the Sanskrit
word sulvere or shulbari, meaning enemy (ari) of copper (shulba). The last observation
implies that ancient Indians (~3,000 years ago) knew about the reaction of sulfur with
metals such as copper. The name may also have been derived from the Arabic sufra,
meaning yellow. Alchemists regarded sulfur as essential in combustion because of its
flammability. Ancient Greeks knew about the use of burning sulfur for fumigation.
In Homer’s The Odyssey, which is approximately 2,800 years old, Odysseus says, “. . .
bring sulfur, old nurse, that cleanses all pollution, and bring me fire, that I may purify
the house with sulfur. . . .” In the year 808 ad, a Chinese text provides possibly the
first recipe for gunpowder, containing saltpeter, sulfur, and c arbon. Sulfur is also
believed to have been a component of “Greek Fire,” a weapon similar to a flame-
thrower used in the Byzantine Empire. In Shakespeare’s Othello, one possible punish-
ment he suggests is “. . . roast me in sulfur!” Antoine Lavoisier included sulfur in his
list of elements in 1789.
Sulfur occurs in the free state and in combination, mainly as sulfides and various
sulfates. It ranks 16th in abundance and makes up approximately 0.05 % of the Earth’s
crust. It is found widely distributed in free and combined states. It occurs in metallic
sulfides, including lead sulfide (galena), zinc blend (ZnS), copper pyrite (Cu·Fe)S2,
cinnabar (HgS), stibinite (Sb2S3), and iron pyrite (FeS2). It also combines with other
elements and occurs as sulfates, including barite (BaSO4), celestite (SrSO4), epsomite
(MgSO4·H2O), and gypsum (CaSO4·2H2O). In the free state, it is found in volcanic
regions such as Iceland, Sicily, Mexico, and Japan. Vast subterranean deposits are found
in the United States in many parts of Louisiana (salt domes along the Gulf Coast),
BK-AST-MONO11-140027-Chp01.indd 1 5/22/2014 12:16:45 PM

2 Sulfur: Chemistry and Analysis of Fossil Fuel Products
Table 1.1 Typical Sulfur Content of Some Important Oil Fields
Country Sulfur, mass % Country Sulfur, mass %
Abu Dhabi 0.62–0.77 Nigeria 0.10–0.26

Algeria 0.02–0.31 Saudi Arabia 1.25–3.91
Canada 0.20–3.67 United States
Colombia 0.25–1.11 Alaska (N. Slope) 1.07
Egypt 0.84–2.06 California 0.2–1.2
Indonesia 0.07–0.18 Louisiana 0.1–0.8
Iran 0.76–3.68 Oklahoma 0.2–1.8
Iraq 1.36–2.10 Texas 0.1–2.4
Kuwait 1.82–2.58 Wyoming 0.1–0.44
Libya 0.13–1.04
Texas, Colorado, Nevada, Wyoming, and California. It exists in several allotropic

modifications.
The typical sulfur content of crude oils from some giant oil fields in the world
is shown in Table 1.1. Nearly 25 % of the sulfur produced today is recovered from
petroleum refining operations and as a byproduct of extracting other materials
from sulfur-containing ores. Organosulfur compounds present in petroleum are
upgraded by subjecting them to hydrodesulfurization, which cleaves the carbon–
sulfur bonds.
R-S-R + 2 H2  2 RH + H2S (1.1)
where R is an organic ligand.

The resulting hydrogen sulfide (H2S) from this process as well as the H2S origi-
nally present in natural gas is converted into elemental sulfur by the Claus process,
which involves oxidation of some H2S to sulfur dioxide (SO2) and then the compropor-
tionation of the two.
3 O2 + 2 H2S  2 SO2 + 2 H2O (1.2)
SO2 + 2 H2S  3 S + 2 H2O (1.3)
Because of the high sulfur content of the Athabasca Oil Sands, bright yellow
stockpiles of sulfur from this process can be seen throughout Alberta, Canada. This is
also a common sight in most refineries processing high-sulfur crude oil.
The typical sulfur content of some petroleum products is given in Table 1.2. In
many products, the values listed may be completely different depending on the manu-
facturer and the intent of the product usage.

Introduction 3
Table 1.2 Typical Sulfur Content of Petroleum Products
Product Sulfur, mass % Product Sulfur, mass %
Diesel fuel oil grade 1D, 2D 0.50 Automatic transmission fluid 0.1–0.3
Diesel fuel oil grade 4D 2.0 Gear oils 1.5–2.0
Kerosine 0.12 Lubricating oils 0.3–0.7
Premium diesel 0.0015 Automotive 0.5–3.5
lubricant additives
Railroad diesel 0.05 Marine distillate fuel 0.05
Compound Types Range

Class in General Formulas Number of Types
Sulfur compounds CnH2n+2S to CnH2n-42S 23

CnH2n-12S2 to CnH2n-30S2 11
Sulfur-oxygen CnH2n-10SO to CnH2n-30SO 11

compounds CnH2n-10SO2 to CnH2n-18SO2 5
CnH2n-10SO3 to CnH2n-20SO3 6
Sulfur is present in petroleum not only as elemental sulfur but also in various
organic molecular forms. Various researchers have identified many compounds using
sophisticated analytical techniques such as nuclear magnetic resonance spectrometry,
gas chromatography, gas chromatography–mass spectrometry, high resolution–mass
spectrometry (HR-MS), etc. Mendez and Colin provide the following types of organo-
sulfur compounds present in petroleum [1]:
Sulfur is a tasteless, odorless, light yellow solid. Sulfur is insoluble in water and
most organic solvents. It is sparingly soluble in ether and alcohol, but it is soluble in
carbon disulfide (1 g per 2 mL). It combines with hydrogen and metallic elements
in the presence of heat to form H2S. Most of the sulfides and similar organosulfur
compounds are odorous.
Sulfur originates in crude oil from natural sources from its marine animal and veg-
etative origins deposited with sediments in coastal waters in ancient times. Over the
millennia, sulfur, oxygen, nitrogen, and other volatile compounds evolved out of this
primordial mixture because of bacterial actions and thermal and environmental pres-
sure, leaving behind a mixture of hydrocarbons containing some of these elements, met-
als, and other compounds. Sulfur and its compounds are present in virtually all petroleum
products and lubricants. The sulfur levels vary from the highest amounts in crude oils
and some lubricants to trace levels in the current road fuels. When combusted in internal
combustion engines, sulfur oxides cause damage to engine parts. Acids of sulfur oxides
increase rusting and corrosion of engine parts, piston rings, and cylinder walls.
Sulfur is removed from refinery streams by a hydrodesulfurization process with
high pressure and catalysts. The process also affects the low diesel characteristics of

density, aromatics, cetane number, and cloud point. Some refractory sulfur com-
pounds are not easily removed (e.g., 4,6-dimethyl dibenzothiophene). As consumers of
fuel products none of us should have a problem supporting government regulations to
reduce sulfur emissions and to improve the environmental quality of life. However,
what concerns many analysts and chemists is how well can these ultralow-sulfur fuels
be accurately analyzed?
Because of the deleterious effects of sulfur emissions from automobiles, several
governmental agencies, particularly in the United States, Europe, and elsewhere,
have vigorously controlled the sulfur emission levels and have gradually reduced the
sulfur levels of fuels used for vehicles [2]. Although at one time the U.S. Environmental
Protection Agency (EPA) mandated the test method to be used (D6428) to determine
sulfur in gasoline and diesel, over the years, through litigation and negotiations, the
rules have been changed to allow alternative test methods for such analysis. The
alternative methods allowed are (1) those developed by voluntary consensus-based
standard bodies such as ASTM International, or (2) oil company methods for which
the data must be provided to EPA to establish their provenance under the perfor-
mance-based measurement system, or (3) both. The most widely used test methods
for such work in the oil industry are D2622 (wavelength-dispersive X-ray fluores-
cence [WD-XRF]), D4294 (energy-dispersive X-ray fluorescence [ED-XRF]), D5453
(ultraviolet fluorescence), and D7039 (monochromatic wavelength-dispersive X-ray
fluorescence [MWD-XRF]) [3].
When burned in air, sulfur forms SO2, a heavy, colorless gas with suffocating odor.
In moist air it slowly oxidizes to sulfuric acid (H2SO4). SO2 is released into the atmo-
sphere in the combustion of fossil fuels such as coal, gas, and petroleum products. This
poisonous gas is responsible for respiratory illnesses in humans and damage to vegeta-
tion, buildings, and corrosion in general by forming “acid rain.” H2S in very small
concentrations can be metabolized, but in higher concentrations it can quickly cause
death by respiratory paralysis. It is insidious in that it quickly deadens the sense of
smell. Humans can smell H2S at a concentration of 0.03 ppm, but it is regarded as safe
for up to 8 h of exposure. At a level of 4 ppm, H2S may cause eye irritation. Exposure to
H2S at 20 ppm for more than 1 min causes severe injury to optical nerves; breathing
stops at 700 ppm. Death will result if there is not a quick rescue.
Several methods exist for the extraction of free sulfur from the ground. The most
common extraction method used is the Frasch process, in which sulfur is extracted
from underground without mining it. The underground deposits of sulfur are forced
to the surface using superheated water and steam (160°C at 16 atm to melt the sulfur)
as well as compressed air (25 atm). This produces molten sulfur, which is allowed to
cool in large basins. Purity can reach 99.5 %.
H2S is an important impurity in natural gas that must be removed before the
gas can be used; a modified Claus process achieves this. In the Claus process,
absorption and regeneration are conducted to concentrate the H2S, followed by

Introduction 5
a catalytic oxidation using porous catalysts such as aluminum oxide (Al2O3) or

iron(III) oxide (Fe2O3).
8 H2S + 4 O2  S8 + 8 H2O (1.4)
Sulfur is used in the manufacture of H2SO4, carbon disulfide, sulfites, insecticides,

dyes, drugs, plastics, enamels, batteries, metal-glass cements, lubricants, and fertiliz-
ers. It is also used in vulcanizing rubber; in the synthesis of dyes; in making gunpow-
der and matches; and in bleaching wood pulp, straw, wool, silk, felt, and linen.
Sulfur is essential for living organisms. In humans it is part of the amino acid
methionine, which is an absolute dietary requirement for humans. The amino acid
cysteine also contains sulfur. In metabolic reactions, sulfur compounds serve as fuels
and respiratory materials for simple organisms. Sulfur in organic form is present in the
vitamins biotin and thiamine. Sulfur is an important part of many enzymes and in
Table 1.3 Physicochemical Properties of Sulfur
Parameter Value
CAS registry ID 7704-34-9

Atomic weight 32.066 ± 0.003 amu
Atomic number 16
Atomic volume 15.5 cmj/mol
Electronic configuration Ne 3s2 3p4
Electronegativity 2.58
Ionization energy 10.360 eV

van der Waals radius 0.127 nm
Ionic radius 0.184 (–2) nm; 0.029 (+6)
Energy of first ionization 999.3 kJ/mol
Periodic table group Via
Valences –2, +4, and +6
Naturally occurring isotopes 32 (95.0 %), 33 (0.76 %), 34 (4.22 %), and 36 (0.014 %)
Artificial radioactive isotopes 29, 31, 35, 37, and 38
Melting point 119°C (246.3°F)
Boiling point 444.6°C (832.28°F)
Hardness 2 Mohs
Crystal structure Orthorhombic
Density at 293 K 2.07 g/cm3
Source: Merck Index, 10th ed., Merck & Company, Rahway, NJ, 1983; Funk & Wagnalls New
Encyclopedia, Vol. 24, 1986; and Wikipedia, 2012.

antioxidant molecules such as glutathione and thioredoxin. The average person takes
in approximately 900 mg of sulfur per day, mainly in the form of protein. Organically
bonded sulfur is a component of all proteins as the amino acids cysteine and methion-
ine. Disulfide bonds are largely responsible for the mechanical strength and insolubil-
ity of the protein keratin, found in the outer skin, hair, and feathers, and the element
contributes to their pungent odor when burned.
There are several articles and books published by ASTM International and the
American Chemical Society, among others, dealing with the analysis of inorganic ele-
ments in fossil fuels [4–10]. However, this is the first book that deals with the analytical
test methods that are used for the determination of only sulfur in various fossil fuel
matrices and related products. Chapter 2 describes the various fundamentals of the
analytical techniques that are used for these analyses. There are several monographs
that have described these techniques in greater detail, but all of that information will
not be repeated here. However, to keep proper context, the principal techniques used
are briefly described here. Chapters 3–8 describe the ASTM Test Methods used for
coal and coke, oil shales, petroleum products, lubricants, gaseous fuels, and biofuels,
respectively. All relevant ASTM Test Methods published through 2012 are included
here. Chapter 9 describes the ASTM Proficiency Testing Program for the determina-
tion of sulfur in various petroleum products and lubricants.
References
[1] Mendez, A. and Colin, T. B., “Applications of Mass Spectrometry in the Petroleum and
Petrochemical Industries,” Spectroscopic Analysis of Petroleum Products and Lubricants,
MONO9, R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA, 2011,
pp. 287–348.
[2] U.S. Environmental Protection Agency, Federal Register, 62(133), 40CFR Part 80 Part II,
page 37337 [July 11, 1997]; 64(92), 40 CFR Parts 80, 85 and 86, Page 26055 [May 13,
1999]; 65(28), 40 CFR Part 80, pages 6752–6774 [February10, 2000]; and 66(12),
40 CFR Part 80, pages 5002–5141, January 18, 2001.
[3] Nadkarni, R. A., “The Challenge of Sulfur Analysis in the Fuels of the Future,” ASTM
Standardization News, June 2004, pp. 32–35.
[4] Nadkarni, R. A., “Advances in Elemental Analysis of Hydrocarbon Products,” Analytical

Advances for Hydrocarbon Research, C. S. Hsu, Ed., Kluwer/Academic/Plenum Publishers,
New York, 2003, pp. 27–56.
[5] Nadkarni, R. A., “Elemental Analysis,” Fuels and Lubricants Handbook: Technology,
Properties, Performance, and Testing, MNL37, G. E. Totten, S. R. Westbrook, and
R. J. Shah, Eds., ASTM International, West Conshohocken, PA, 2001, pp. 707–716.
[6] Nadkarni, R. A., “A Review of Modern Instrumental Methods of Elemental Analysis of

Petroleum Related Materials: Occurrence and Significance of Trace Elements in Petroleum
and Lubricants; Analytical Techniques,” Modern Instrumental Methods of Elemental
Analysis of Petroleum Products and Lubricants, STP1109, R. A. Nadkarni, Ed., ASTM
International, West Conshohocken, PA, 1991, pp. 5–51.

Introduction 7
[7] Nadkarni, R. A., “Determination of Inorganic Species in Petroleum Products and

Lubricants,” Significance of Tests for Petroleum Products, MNL1, 8th ed., S. J. Rand, Ed.,
ASTM International, West Conshohocken, PA, 2010, pp. 283–298.
[8] Nadkarni. R. A., “Trace Levels of Sulfur in the Fuels of the Future: Analytical Perspective,”
Elemental Analysis of Fuels and Lubricants: Recent Advances and Future Prospects,
STP1468, R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA, 2005,
pp. 85–97.
[9] Nadkarni, R. A., Spectroscopic Analysis of Petroleum Products and Lubricants, MONO9,
ASTM International, West Conshohocken, PA, 2011.
[10] Nadkarni, R. A., Elemental Analysis of Fossil Fuels and Related Materials, MONO10, ASTM
International, West Conshohocken, PA, 2014.

Chapter 2 | Analytical Techniques
for Sulfur Determination
In the first part of the last century, elemental determinations were essentially confined
to the use of wet chemistry with measurement ends using gravimetry or titrimetry. In
the late 1940s to 1950s, this scenario started changing with the introduction of
colorimetry, polarography, and optical emission spectroscopy. As the last century pro-
gressed, wet chemical techniques were replaced by atomic absorption spectroscopy
(AAS), inductively coupled plasma–atomic emission spectroscopy (ICP-AES), induc-
tively coupled plasma–mass spectrometry, ion chromatography (IC), X-ray fluorescence
spectroscopy (XRF), neutron activation analysis (NAA), etc. These later techniques are
mature, but advances are still being made in these techniques, and they are in wide use
in many industrial laboratories, including those in the energy sector.
Sulfur has been a particularly difficult element to determine given that it is a non-
metal and is not necessarily amenable to all spectroscopic techniques. In addition to
XRF, many test methods are available for sulfur using microelemental techniques,
which involve combustion followed by diverse detection and quantitation techniques.
The “micro” in this context of analysis refers to the sample preparation using only very
small quantities of sample taken for analysis. Along with sulfur, carbon, hydrogen,
nitrogen, oxygen, and halogens fall in this category of microchemical determinations.
The end detection methods include thermal ionization, chemiluminescence, ultrav
iolet (UV) fluorescence, coulometry, electrochemistry, infrared, and others.
Some of the favorable criteria in choosing a particular technique for sulfur (or any
other analysis) are high sensitivity and selectivity, broad linear dynamic range, high
precision, no matrix interference, inexpensive to acquire and operate, applicable to all
elements in all matrices, needing minimal sample preparation, microsampling capa-
bility, rapid turnaround, nondestructive nature, etc. [1]. Unfortunately, no single tech-
nique can qualify as a success on every one of these criteria, but a judicious choice
needs to be made as to which method is best suited and beneficial for a specific analyt-
ical task at hand.
Diverse analytical techniques have been used for the determination of sulfur in
fossil fuel products. These have changed from classical wet chemistry techniques to
modern instrumental methods. The emphasis has also moved from the determination

of sulfur present in bulk quantities to that present in trace amounts. Several earlier
books have described many of these analytical techniques in detail [2,3], and all such
information will not be necessarily repeated here. However, to clarify the context of
these techniques, brief descriptions of them are included in this chapter. Individual
test method standards published by ASTM International are listed in each of the fol-
lowing chapters: test methods for coal, coke, and fly ash in Chapter 3; test methods for
oil shales and its products in Chapter 4; test methods for petroleum products in
Chapter 5; test methods for lubricants in Chapter 6; test methods for gaseous fuels in
Chapter 7; and test methods for biofuels in Chapter 8. Some of the same analytical
techniques are used for various products and these are identified in Table 2.1.
Some of these standard test methods, at least for petroleum products and lubri-
cants, have their international counterpart standards issued by other national orga-
nizations such as the Energy Institute (United Kingdom), the ISO (International
Organization for Standardization), DIN (Deutsche Institut für Normung), JIS (Japan
Industrial Standards), CEN (Center for European Normalization), and AFNOR
(Association FranÇaise de Normalisation). Where available, these equivalent test
Table 2 .1 Analytical Techniques Used for Sulfur Determination in Fossil Fuel

Products
Analytical Technique Coal and Coke Petroleum Products Gaseous Fuels
Combustion–chemical D129, D1266, D6920

analysis
Combustion–infrared D4239 D1552
D5016
Combustion–microcoulometry D3120, D3246
Combustion–UV fluorescence D5453, D6667, D7620 D7551, D6667
ICP-AES D4951, D5185, D7040, D7111
IC D7319, D7328, D7359, D7318
Gas chromatography D5303, D5623, D7041, D3712, D5305
XRF–Energy dispersive D4294, D6481, D7212,
D6445, D7212,
D7220
D6481,
D7212, D7220
XRF–Wavelength dispersive D2622, D4927,
D7039, D6334, D6443,
D7039
Other methods D2492 D1662, D2420, D2784, D3227, D1072, D1988,
D4045, D6920, D4952, D5705 D4084, D4468,
D4810

Analytical Techniques for Sulfur Determination 11
Table 2.2 International Standards for Sulfur Determination in Petroleum Products

and Lubricants
Analysis ASTM IP ISO DIN JIS AFNOR
Bomb Method D129 61 51577 T60-109

Lamp Method D1266 107 M07-031
High-Temperature Combustion D1552 M07-025
H2S in LPG D2420 401 8819 51855T3 M41-011
Wickbold Method D2485 4260
WD-XRF D2622 447 14596 51400T6 K 2541
Wickbold Combustion D2785 243 4260 T60-142
Oxidative Microcoulometry D3120 16591
Mercaptan Sulfur D3227 342 3012 K 2276 M07-022
Oxidative Microcoulometry D3246 373 M07-052
ED-XRF D4294 336 8754 M07-053
WD-XRF D4927 407 51391T2
Doctor Test D4952 30 5275
UV-Fluorescence D5453 20846 M07-059
H2S in Fuel Oil D7621 570
H2S: hydrogen sulfide; LPG: liquefied petroleum gasoline; WD-XRF: wavelength-dispersive X-ray
fluorescence; ED-XRF: energy-dispersive X-ray fluorescence.
Source: Excerpted from [4].
methods are listed in Table 2.2. It is not claimed that all of these test methods are
exactly identical, just that if properly followed, in all probability they will produce
equivalent results.
Given the plethora of test methods available for sulfur determination in fossil
fuel products, the choice for a particular analysis would normally depend on eco-
nomic considerations, the fuel matrix of interest, the sulfur concentration present,
and the precision of the analysis required. Each method has its advantages and draw-
backs. Certain individual laboratories have demonstrated impressive measurement
capabilities for individual methods. An intelligent choice must be made on the basis
of a method’s accuracy and precision before deciding which method to use for a par-
ticular product. Because the method precision is often dependent on the analyte
level and the product matrix, the choice of an optimal test method can be a critical
decision for measurement and control. Arbitrarily using a method without these con-
siderations can only result in producing data without much reliability, which does not
help in settling disputes in commercial transactions or in regulatory affairs. Although
earlier the U.S. Environmental Protection Agency (EPA) had mandated which test
method be used for the sulfur analysis of fuels, this rule has been now withdrawn and
replaced with an optional performance-based measurement system (PBMS) [5].

Importance of Sulfur Analysis in Fossil Fuel Products

Much work has been published in the area of sulfur analysis because of the interest in
elucidating the occurrence and the effects of sulfur in various products. One of the
most important analyses, particularly for petroleum products and coal and coke, is for
low levels of sulfur. Government regulations on sulfur emissions from automobiles
and other c ombustion sources such as coal-fired power plants have steadily increased—
hence the increasing interest in devising precise and accurate methods for trace and
ultratrace amounts of sulfur in fuels.
Complexity and expenses of the refining operations increase significantly as the
sulfur content of crude oils increases from nearly zero to several mass percent. During
distillation, hydrogen sulfide (H2S) is evolved and other sulfur compounds concen-
trate in the heavier distillation residues. The residual fuel oils with more than very
small amounts of sulfur have to pay a higher penalty in the marketplace. Some local,
state, and federal government environmental laws ban them all together. Sulfur com-
pounds are objectionable in refined solvents because they impart odor and may cause
darkening of cooked varnishes and resins [6].
The sulfur oxides formed during gasoline or diesel burning in internal combus-
tion engines can be converted to acids that promote rusting and corrosion of engine
parts, piston rings, and cause catalyst wall wear. Sulfur oxides emitted in car exhausts
are obviously atmospheric pollutants. Sulfur in diesel fuels causes wear because of the
corrosive nature of the combustion products, and it increases the amount of deposits
in the combustion chamber and pistons. Low-speed diesel engines can tolerate more
sulfur than high-speed diesel engines [7].
High-boiling-range fractions and residual fuel usually contain high amounts of
sulfur, which creates corrosion and pollution problems. Conversion of sulfur to sulfur
trioxide (SO3) during combustion and later reaction with water will form sulfuric acid,
corroding the metal surfaces of equipment. Combining with sodium and vanadium
complexes, sulfur forms deposits on the external surfaces of superheater tubes, etc.,
causing equipment corrosion and loss of thermal efficiency [8].
High levels of sulfur in fuels adversely affect the carbon-forming tendency in gas
turbine combustion chambers, and large amounts of sulfur oxides in the combustion
gases promote corrosion. Sodium and potassium combine with vanadium to form
low-melting eutectics (565°C), and they combine with sulfur in the fuel to yield sul-
fates with melting points in the operating range of gas turbines. They produce severe
corrosion. Hence, sodium and potassium in the gas turbine fuels must be limited [9].
In aviation gasoline, sulfur compounds have a deleterious effect on the anti-
knock efficiency of the alkyl lead compounds. If the sulfur content was not limited,
then specified antiknock values would not be reached for highly leaded grades of
aviation fuel. Some sulfur compounds corrode various metal parts of the engine
system, with effects varying according to the sulfur compounds present [10].
The total sulfur content of aviation gasoline is limited to 0.05 mass % maximum.
Some sulfur compounds can have a corroding action on the various metals in the

engine system. Effects vary according to the chemical types of the sulfur compounds
present. Elemental sulfur and H2S are particularly implicated [10].
Most of the sulfur compounds in crude petroleum are removed during refining.
The maximum amount of sulfur as specified in ASTM D4814 is 0.0080 mass %, which
is the U.S. federal per-gallon maximum limit. The federal regulations also have a refin-
ery annual average maximum limit of 0.0030 mass %. The limit on sulfur content is
included to protect against engine wear, deterioration of engine oil, corrosion of
exhaust system parts, and exhaust catalyst deactivation.
Sulfur oxides formed during combustion may be converted to acids that promote
rusting and corrosion of engine parts and exhaust systems. Sulfur oxides formed in the
exhausts are undesirable atmospheric pollutants. However, the contribution of auto-
motive exhaust to total sulfur oxide emission is negligible compared with emissions
from coal combustion. Sulfur also reduces the effectiveness of exhaust gas catalytic
converters. In 1996, California set an average maximum limit of 0.0030 mass % and
then at the end of 2003 lowered it to 0.0015 mass %.
The sulfur content of a fuel depends on the origin of the crude oil from which the
fuel is made and on the refining methods used. Sulfur can be present in several forms—
as mercaptans, sulfides, disulfides, or heterocyclic compounds such as thiophenes—all
of which affect wear and deposits. Fuel sulfur tolerance in a diesel engine depends largely
whether the engine is of the low- or high-speed type and the prevalent operating condi-
tions. Low-speed engines can tolerate more sulfur than their high-speed counterparts
because they operate under relatively constant speed and load conditions. Under these
conditions, lubricating oils, cooling water, and combustion zone temperatures show lit-
tle fluctuation. These steady temperatures make low-speed engines more tolerant to
sulfur present in the fuel [9].
High-sulfur fuels for diesel engines are undesirable from a purely technical
standpoint regardless of engine type. However, less harm will occur from fuel sulfur
when engines are operated at high-power outputs and operating temperatures than
at lower temperatures. Under the lower-temperature conditions that result from
stopping and starting or decrease of load or speed or both, moisture condensation is
apt to occur within the engine. The sulfur in the fuel then combines with water to
form acid solutions that corrode metal components and increase wear of moving
parts. Active sulfur in fuel tends to attack and corrode injection system components.
Sulfur compounds also contribute to combustion chamber and injection system
deposits [9].
Concern for sulfur levels in liquefied petroleum gasoline (LPG) is the same as
those in other petroleum products. For decades, LPG had much lower sulfur levels than
gasoline or diesel fuel. However, most gasolines now contain less than 30 mg/kg sulfur
and many diesel fuels now contain less than 15 mg/kg sulfur, making LPG higher in
sulfur content than other major fuels. Thus, HD-5 propane, with up to 123 mg/kg
sulfur, could not be used with current gasoline or diesel engine emission control tech-
nologies, which cannot tolerate such high-sulfur fuels. If LPG were to be used in

engines with current emission control technologies, then the sulfur content would
have to be significantly reduced and a new warning mechanism would be needed to
replace the current sulfur-containing odorants [11].
Throughout the evolution of base oil refining and processing technology, the sulfur
content has been used as an indicator of product quality and a predictor of lubricant per-
formance. Very low sulfur content is the most desirable for base oil; slightly higher sulfur
levels directionally improve base oil oxidation stability as well as friction and wear perfor-
mance. Current domestic base oil sulfur concentrations typically range from less than
0.005 mass % to 0.4 mass % for heavier viscosity grades. In other regions of the world, it is
not uncommon to see sulfur levels in excess of 1.0 mass %. How the organosulfur content
affects lubricant performance is very complex and depends, to a large extent, on the ulti-
mate application and the nature of the additives used in the formulation [12].
Sulfur compounds present in crude oil can contribute to corrosion of refinery
equipment and poisoning of catalysts, they can cause corrosiveness in refined prod-
ucts, and they can contribute to environmental pollution through emission of sulfur
oxides from combustion of fuel products. Sulfur compounds are more abundant in the
heavier fractions of crude oil. In some crude oils, thermally reactive sulfur compounds
can decompose on heating to produce the toxic and corrosive gas H2S. The thiols (mer-
captans) present in crude oil can impart a foul odor. Butanethiol is a compound natu-
rally present in crude oils and is added as an odorant to natural gas [13]. The
concentration of sulfur contributes to the complexity of the crude oil refining step.
Sulfur compounds impart odor and may react with end-product container vessels.
Sulfur is removed from the refinery streams by a hydrodesulfurization process with
high pressure and catalysts.
H2S occurs naturally in some but not all crude oils. Even crude oils that do
not contain H 2S can form this compound on heating or during distillation by
thermal decomposition of elemental sulfur and thiols. H2S can also be produced
by reduction of bisulfite chemicals used as oxygen scavengers, by thermal decom-
position of sulfur compounds, or by dissolution of iron sulfide. It can also be
produced by microbiological reactions [13].
The sulfur compounds are objectionable in refined solvents because they impart
odor and may cause darkening of cooked varnishes and resins [6]. In aviation gasoline,
sulfur compounds have a deleterious effect on the antiknock efficiency of the alkyl lead
compounds. If the sulfur content was not limited, then specific antiknock values would
not be reached for highly leaded grades of aviation fuel. Acidic sulfur compounds may
also corrode the metallic parts of internal combustion engines. The severity of such cor-
rosion is dependent on the types of sulfur compounds present in the fuel used. In addi-
tion, sulfur oxides formed during gasoline combustion can hinder the performance of
catalytic converters in automobiles. Some sulfur compounds corrode various metal parts
of the engine system, with effects varying according to the sulfur compounds present [6].
Emission of sulfur oxides formed during the combustion of fuel oils in commer-
cial or domestic applications is one of the main causes of “acid rain,” which affects

vegetation and quality of life in general. Some typical sulfur concentrations reported
in diesel fuels are as follows [6]:
• Diesel fuel oil grade 1D and 2D 0.50 mass %
• Diesel fuel oil grade 4D 2.0 mass %
• Kerosine 0.12 mass %
• Premium diesel 0.30 mass %
• Railroad diesel 0.50 mass %
• Marine distillate diesel 1.2 mass %
Thiols or mercaptans are considerably more prevalent in crude oils than H2S.
They are very unstable compounds, and many decompose on heating to H2S. See Giles
and Mills for a detailed discussion of sulfur compounds in crude oils [13]. Mercaptans
are toxic sulfur compounds with an objectionable odor, they occur in crude oils, and
they are removed from most petroleum products by refining. Because of the adverse
effect on fuel system components or kerosine burner equipment, or both, mercaptans
are limited to preclude undesirable side reactions and to minimize the unpleasant
odor. The Doctor test (ASTM D4052) is an indirect indication of mercaptan levels [8].
Sulfur levels certainly have decreased over the years because of increasing regula-
tions set by national bodies. The following are the decreases in sulfur maximum limits
(in mg/kg) issued for European diesel specifications:
1984 1993 1996 2000 2005 2009

3000 2000 500 350 10 10
Refineries, plants, and pipeline operators are increasingly focusing on obtaining

quick turnaround for sulfur analysis rather than wait for time-delayed laboratory
analysis. Many such installations are being operated in the petroleum and gaseous
fuels industry around the world. XRF or other techniques such as UV-fluorescence or
chemiluminescence detection techniques are typically used for such work [14].
Knowledge of sulfur concentration is necessary for processing purposes. These
test methods provide a means of monitoring the sulfur levels of various petroleum
products and additives. This knowledge can be used to predict performance, handling,
or processing properties. In some cases, the presence of sulfur components is benefi-
cial to the product, and monitoring the depletion of sulfur compounds provides useful
information. In other cases, the presence of sulfur compounds is detrimental to the
processing or use of the product.
In distillate fuels and solvents, sulfur can be present as mercaptans or as H2S. These
can attack many metallic and nonmetallic materials in fuel and other distribution
systems. A negative test in the Doctor test (D4052) ensures that the concentration of
these compounds is insufficient to cause such problems in normal use. In LPGs, the
presence of sulfur can result in corrosion of metal surfaces. Sulfur can be poisonous to
catalysts in subsequent processing.

Marine fuels generally have an average sulfur content of 2.7 mass % compared
with gasoline, which has less than 50 mg/kg sulfur. To reduce the contribution of sulfur
to atmospheric pollution, the European Union (EU) has decreased the sulfur level to
1.5 % for all seagoing vessels on the high seas under its jurisdiction.
Because of the deleterious effects of sulfur emissions from motor vehicles, several
government regulatory agencies, principally in North America and the EU, have vig-
orously controlled the sulfur emission levels and gradually reduced the sulfur levels in
fuels, (gasoline and diesel) from a high at one time of approximately 300 mg/kg to
10–15 mg/kg today. Over the years, through litigation and discussions with the indus-
try, the mandatory test method for sulfur rules of EPA have been modified so as alter-
native methods can now be used for sulfur determination. The alternative methods
allowed would be (1) those developed by voluntary consensus-based standard bodies
such as ASTM International or (2) oil company methods for which the data must be
provided to EPA to establish their provenance under the PBMS, or (3) both [15].
Unlike the other petroleum products discussed above, lubricant additives and
lubricating oils, including automatic transmission fluids, gear oils, turbine oils, etc.,
contain additional amounts of sulfur in the form of metal sulfonates, particularly
zinc dialkyldithiophosphate, which are usually added to enhance the performance
characteristics of oils in internal combustion engines. Some typical sulfur levels
found in lubricants are as follows:
• Automatic transmission fluids 0.1–0.3 mass %
• Gear oils 1.5–2.0 mass %
• Lubricating oils 0.3–0.7 mass %
• Automotive lubricant additives 0.5–3.5 mass %
ASTM Test Methods for the determination of sulfur in fossil fuels can be roughly
divided into wet chemistry methods, ICP-AES methods, XRF methods, and other
instrumental technique methods (Table 2.3). Some of these are widely used in industry
laboratories whereas others have seen their share of utilization decline. On the basis of
their usage in oil industry laboratories, these test methods can be grouped as follows [16]:
• Not widely used: D129, D1266, D4045, D6920, D7212, and D7220
• Some use: D1552, D3120, D3246, D6334, D6443, and D6445
• Widely used: D2622, D4294, D4927*, D4951*, D5185*, D5453, D7039, and D7041
Asterisks indicate that the test method is primarily used for the determination of other
metals.
Inductively Coupled Plasma—Atomic Emission Spectrometry

Although determination of sulfur is not the principal reason to choose an ICP-AES
analysis technique for fuel analysis, it is one of the elements, along with a multitude of
metals, that can be simultaneously determined by this technique in fuel samples,
whether petroleum products, lubricants, coal, coke, fly ash, or oil shales. The most
significant development in the analytical atomic spectroscopy area in the last 40 years
has been the development of the technique of ICP-AES. This technique is widely used

Table 2.3 ASTM Test Methods for Sulfur Determination in Fossil Fuels, Petroleum
Products, and Lubricants
Wet Chemistry ICP-AES XRF Other Instruments
Petroleum Products and Lubricants

D129 Bomb Combustion D4951–Additives D2622–WD-XRF D3120–Coulometric
D1266 Lamp Combustion D5185–Lube Oils D4294–ED-XRF D3246–Coulometric
D1552 High-Temperature D7691–Crude Oil D4927–WD-XRF D4045–Hydrogeneolysis
Combustion
D2784 Oxyhydro Combustion D6334–WD-XRF D5453–UV-Fluorescence
D6443–WD-XRF D6920–Electrochemical
D6445–ED-XRF D6667–UV-Fluorescence
D7039–MWD-XRF D7041– GC-FPD Online
D7212–ED-XRF D7620– UV-Fluorescence
D7220–ED-XRF
D7751–ED-XRF
Coal and Coke
D1757– Sulfate D5016–Combustion and
IR Detection
D2492– Sulfur Forms
D3177–Combustion
D4239–High-Temperature
Furnace Combustion
Gaseous Fuels
D1072–Combustion and BaCl2 D5504–
Titration Chemiluminescence
D1988–Mercaptans Using D6228–GC-FPD
Length-of-Stain Detector Tubes
D4084–Lead Acetate Reaction D6868–GC-AED
Rate
D4468–Hydrogeneolysis D7165– Online
D4810–Length-of-Stain D7166– Online
Detector Tubes
ED-XRF: energy-dispersive X-ray fluorescence; WD-XRF: wavelength-dispersive X-ray fluorescence;

MWD-XRF: monochromatic wavelength-dispersive X-ray fluorescence; GC: gas chromatography;
GC-AED: gas chromatography–atomic emission detection; GC-FPD: gas chromatography–flame
photometric detection; IR: infrared; BaCl2: barium chloride.
in oil industry laboratories for the determination of metals, and in many cases it has
essentially replaced the use of AAS or graphite furnace–atomic absorption spectroscopy
(GF-AAS). Its main advantages are its wide dynamic range, simultaneous multiele-
ment capability, and extremely low detection limits. Argon is the most commonly used
gas to produce a plasma, which is an electrically neutral, highly ionized gas consisting
of ions, electrons, and neutral particles. However, in the ICP-AES technique, the plasma
is ionized by a strong electric field by radiofrequency (RF). The RF discharge at

27.12- or 40.68-MHz frequency causes the flowing argon gas to become electrically
conductive and reach a temperature up to 15,000°C. The sample solution is sprayed
into this plasma through a nebulizer, where the elements of interest are vaporized,
atomized, or ionized and electronically excited. While returning to their ground
states, the electrons emit photons at wavelengths characteristic of an element. This
emitted light is measured by a polychromator in a simultaneous spectrometer or it is
measured by a single photomultplier in a scanning or sequential spectrometer. A sche-
matic diagram of an ICP-AES system is shown in Fig. 2.1. ASTM standards using ICP-
AES for the determination of sulfur along with other metals in oil analysis are listed
below. Because solid materials such as coal, coke, fly ash, or oil shale samples need to
be brought into acidic aqueous solutions before ICP-AES measurements, this tech-
nique is not applicable for sulfur determination in these materials because during the
combustion of these products all sulfur in them will be lost by decomposition.
A vacuum spectrometer and measurement in the UV region are typically used for
sulfur determination in ICP-AES. Sulfur is measured at 190.00-, 180.73-, or 182.04-nm
Fig. 2.1 Schematic Diagram of Inductively Coupled Plasma — Atomic Emission

Spectrometer.

wavelengths. Its detection limit is approximately 0.05 mg/kg, and the upper dynamic
range is approximately 100 mg/kg. Several crosschecks have shown equivalent results for
sulfur in oils using ICP-AES or XRF, the primary technique used for sulfur determination.
More data on this subject are supplied in this book in Chapter 9 on proficiency testing.
D4951 Additive Elements by ICP-AES Lubricants and Additives

D5185 Additive Elements by ICP-AES Lubricating Oils and Base Oils
D7260 Standard Practice for ICP-AES Petroleum Products and Lubricants
Nadkarni, Hwang, and Young have determined sulfur along with other trace
elements in crude oils using ICP-AES [17]. On the basis of an ASTM interlaboratory
study using 18 crude oil samples including 3 National Institute of Standards and
Technology (NIST) Standard Reference Materials (SRMs), the following precision for
sulfur was obtained in the concentration range of 400 mg/kg to 5.0 mass %. The sulfur
measurement was made at 180.731-, 182.04-, or 182.62-nm wavelengths.
Repeatability 0.01971X1.1606
Reproducibility 0.06360X1.1606
Where X is the mean of two values.

This translates into the following precisions at specific sulfur concentrations:
Sulfur Concentration, mg/kg Repeatability Reproducibility
400 20.6 66.6

1000 59.8 192.9
5000 387.0 1249
50,000 5601.6 18,075
Table 2.4 compares the results for NIST SRMs obtained using the ICP-AES
technique in good agreement with NIST certified values where available. A
Table 2.4 Comparison of ICP-AES Results for Sulfur in Crude Oils
NIST Materials Sulfur Found, mass% NIST Assigned Value, mass%
SRM 2721 1.688 ± 0.096 (4) 1.5832 ± 0.0044

SRM 2722 0.217 ± 0.009 (5) 0.21037 ± 0.00084
RM 8505 2.614 ± 0.300 (8) NA
ASTM Samples Sulfur Found, mass% D2622 WD-XRF Results, mass%
ASTM CO 0903 0.4397 ± 0.0097 (8) 0.4227 ± 0.0152 (26)
ASTM CO 0811 0.9165 ± 0.075 (8) 0.9319 ± 0.0363 (22)
ASTM CO 0807 2.622 ± 0.28 (8) 2.722 ± 0.126 (17)
Note: Values are expressed as average value ± standard deviation (number of valid results).

comparison between the sulfur results obtained using the wavelength-

dispersive X-ray fluorescence (WD-XRF) Test Method D2622 for the ASTM
Interlaboratory Crosscheck Program (ILCP) crude oil samples and the ICP-AES
results obtained in this study also shows good equivalence between the two sets
of results.
This work was later codified as ASTM Test Method D7691-11 “Multielement Analysis
of Crude Oils Using Inductively Coupled Plasma Atomic Emission Spectrometry” [17].
X-ray Fluorescence
The XRF technique rivals atomic spectroscopic techniques in its applicability, sensi-
tivity, ease of operation, nondestructive nature, and applicability to various matrices
without having to change the physical state of the sample. There are two principal
historic modes of XRF analysis: wavelength dispersive (WD) and energy dispersive
(ED). More recently, monochromatic wavelength dispersive (MWD) instruments
have achieved wide acceptability in the oil industry, particularly for sulfur determi-
nation. Vrebos and Glose have described the theory behind WD-XRF [18], Petiot and
Pohl have described the theory for ED-XRF [19], and Chen and Wei have described
the theory for MWD-XRF [20].
When a sample is bombarded with X rays, electrons are ejected from the various
energy levels of the target atoms. In the process, X rays of discrete characteristic energy
are emitted. This is called XRF. Every element has a unique electron distribution; thus,
every element produces a unique secondary X-ray spectrum for which the intensity is
proportional to the elemental concentration in the sample. XRF can be applied to all
elements with atomic numbers greater than 10 (i.e., neon). However, modern XRF
instruments with improved detector technology have the capability of determining
lower atomic number elements such as boron or magnesium. The basic components of
a XRF system are a source of excitation consisting of a high-energy X-ray tube, an optical
system for selecting characteristic X rays, and integrating or counting circuits for mea-
surements (see Fig. 2.2). The common X-ray tubes used are made of tungsten, molybde-
num, chromium, rhodium, or scandium, which have high energy output, spectral purity,
and long-term stability.
Because of numerous interelement matrix effects, standards identical in composi-
tion to the samples need to be used. Particle shape and size are also important; how-
ever, this may not be an important factor for liquid hydrocarbon samples. Many of
these interferences and matrix effects can be compensated by corrective techniques
such as standard addition, internal standard addition, matrix dilution, thin film
method, and mathematical correction methods.
In the WD-XRF technique, an X ray impinges on the sample and generates flu-
orescent X rays. These are then diffracted on a crystal. A goniometer selects the
geometry between the crystal and the detector. The geometry controls the detection
of X rays from the element of interest. Different crystals have different sensitivities.
ASTM methods available for WD-XRF analysis of petroleum products include

Fig. 2.2 Schematic Diagram of Wavelength Dispersive X-Ray Fluorescence Analyzer.
D2622 Sulfur by WD-XRF Gasoline and Diesel

D4927 Additive Elements by Wavelength Dispersive XRF Additives and Lubricating Oils
D6334 Sulfur by Wavelength Dispersive XRF Gasoline and Oxygenate Blends
D6443 Additive Metals by Wavelength Dispersive XRF Lubricating Oils and Additives
D6444 Sulfur in Gasoline by WD-XRF Gasoline
D7039 Sulfur by MWD-XRF Gasoline and Diesel
D7343 Standard Practice for XRF Petroleum Products and Lubricants
The ED-XRF technique uses a much less energetic X-ray tube. The emitted X-rays
from the sample impinge directly on a detector, typically a Si(Li) detector, which gen-
erates pulses on an incident beam, and these pulses are sorted and counted by a multi-
channel analyzer (Fig. 2.3). Simultaneous determination of elements with atomic
numbers greater than magnesium is possible. Optimization for specific elements is
accomplished through the use of secondary targets and filters. Radioisotope sources
can be used in place of X-ray tubes in instruments designed for limited element
applications. ASTM Test Methods available for ED-XRF analysis of petroleum prod-
ucts include:
D4294 Sulfur by ED-XRF Gasoline and Diesel

D6445 Sulfur by ED-XRF Gasoline
D6481 Additive Metals by ED-XRF Lubricating Oils
D7212 Sulfur by ED-XRF with Low Background Counter Gasoline and Diesel
D7220 Sulfur by Polarized ED-XRF Gasoline and Diesel
D7343 Standard Practice for XRF Petroleum Products and Lubricants

Fig. 2.3 Schematic Diagram of Energy Dispersive X-Ray Fluorescence Analyzer.
Fig. 2.4 Schematic Diagram of Monochromatic Wavelength Dispersive X-Ray

Fluorescence Analyzer (D7039).
In the MWD-XRF technique, a monochromatic X-ray beam with a wavelength

suitable to excite the K-shell electrons of an element is focused onto a test specimen
contained in a sample cell. The fluorescent K-alpha radiation emitted by sulfur is
collected by a fixed monochromator. The intensity of the sulfur X rays is measured
using a suitable detector (Fig. 2.4). Excitation by monochromatic X rays reduces

background, simplifies matrix correction, and increases the signal-to-background

ratio compared with the polychromatic excitation used in the conventional WD-XRF
instruments. This technique has been used for the determination of sulfur in gaso-
line and diesel samples (D7039).
Speed, convenience, minimal sample preparation, and its often nondestructive
nature are the main advantages of the XRF technique. It can determine sulfur concen-
trations from low milligram-per-kilogram to mass percentage levels. Irrespective of
the sulfur species present in the sample, XRF can determine the total amount of sulfur
in a sample. The method rivals the accuracy and the precision of wet chemistry tech-
niques for the analysis of major constituents provided that interferences and matrix
effects are accounted for.
Ion Chromatography
Until the advent of this technique in 1975, all anions in any matrices had to be deter-
mined by wet chemistry techniques such as gravimetry or titrimetry. IC is a combi-
nation of ion exchange chromatography, eluent suppression, and conductometric
detection. For anion analysis, a low-capacity anion exchange resin is used in the
separator column and a strong cation exchange resin in the H+ form is used in the
suppressor column. A dilute mixture of sodium carbonate and bicarbonate is used
as the eluent because carbonate and bicarbonate are conveniently neutralized to low-
conductivity species and the different combinations of carbonate-bicarbonate give
variable buffered pH values. This permits the ions of interest in a large range of affin-
ity to be separated. The anions are eluted through the separating column in the
background of carbonate-bicarbonate and are conveniently detected based on elec-
trical conductivity. See Fig. 2.5 for a schematic diagram of a basic IC system.
In practice, a dilute aqueous sample is injected at the head of the separator col-
umn. The anion exchange resin selectively causes the various sample anions of differ-
ent types to migrate through the bed at different respective rates, thus affecting the
separation. The effluent from the separator column then passes to the suppressor col-
umn where the H+-form cation exchange resin absorbs the cations in the eluent
stream. Finally, the suppressor column effluent passes through a conductivity cell. The
highly conductive anions in a low-background conductance of carbonic acid are
detected at high sensitivity by the conductivity detector. The nonspecific nature of
the conductometric detection allows several ions to be sequentially determined in the
same sample. At the same time, differential elution rates from the column make the
conductometric detection highly specific and relatively free from interferences.
Different stable valence states of the same element can be determined. See Fig. 2.6
for an example of a multianion ion chromatogram.
Because of the nonspecific nature of the conductivity detector, the chromato-
graphic peaks are identified by their retention times and using a standard anion mix-
ture to calibrate the retention time and the peak strength. Sometimes two ions having

Fig. 2.5 Schematic Diagram of Chemically Suppressed Ion Chromatography.
the same or close retention times will be detected as one broad peak, giving erroneous
results. Also, if one ion is present in vary large amount compared with its neighbor
ion in the chromatograph, the broad peak of the first major ion will change the base-
line and the shape of the second weaker ion.
ASTM standards using IC for fossil fuel sulfur species determination are given
below. Because IC is an aqueous analysis technique, organic and solid fuel samples
must be brought into solution before actual IC measurement. This is usually achieved
by oxygen bomb dissolution of the sample. Although only three ASTM standards are

Fig. 2.6 Typical Ion Chromatogram of a Solution Containing 1 mg/kg of Various

Anions in Water.
listed here, the IC technique can be frequently used for the determination of total
sulfur in coal, coke, or oil shale, as will be described in later chapters.
D7319 Total and Potential Sulfate by IC Biofuels

D7328 Total and Potential Inorganic Sulfate by IC Biofuels
D5987 Fluorine by Pyrohydrolytic Extraction and Coal and Coke
Ion-Selective Electrode or IC Method
Instrumentation for Sulfur Determination

Several different types of instrumental microchemical analyzers are available for sul-
fur determination in petroleum products and other fossil fuels.
Leco Induction Furnace

The sample is combusted in a stream of oxygen at a sufficiently high temperature in an
induction furnace to convert 95–98 % of the sulfur present to sulfur dioxide (SO2) with
virtually no SO3 being produced. The SO2 is then measured by passing the combustion
gases into an absorber containing an acid solution of potassium iodide (KI) and starch
indicator. Before the sample is combusted, a small amount of potassium iodate (KIO3)
is added to the absorber, producing elemental iodine.
KIO3 + 5 KI + 6 HCl  3 I2 + 6 KCl + 3 H2O (2.1)
This free iodine produces a blue color with starch. The SO2 from the combustion
gases reacts with free iodine and diminishes the intensity of blue color. A photoelectric

cell measuring the intensity of the blue color releases more KIO3 titrant as the blue
color intensity diminishes. When the SO2 production from the sample ceases and the
blue color remains constant, the titration is ended.
SO2 + I2 + 2 H2O  2 HI + H2SO4 (2.2)
High SO2 conversion and minimal SO3 production is favored at high temperature and
low oxygen partial pressure. At 1422°C or higher, the production is 98 % SO2 and is
almost independent of oxygen partial pressure. A correction or calibration factor is
applied to correct for the SO3 production. Sometimes the conversion of inorganic
sulfate to SO2 at temperatures exceeding 1315°C is incomplete, and vanadium pentox-
ide needs to be added to aid this conversion. Liquids with boiling points less than
200°C are not recommended for this analysis. Chlorine at levels less than 1 % does not
interfere, but nitrogen at levels greater than 0.1 % may depending on the types of
nitrogen compounds present. In a modification of the final measurement step, the
Leco IR-33 analyzer uses an infrared cell for selective SO2 determination.
Leco SC-32 Analyzer

The sample is combusted in a resistance furnace at 1370°C to convert sulfur to SO2.
Traps remove moisture and dust, and an infrared detector measures SO2. Approximately
2 min per sample is needed for analysis. The sensitivity of this instrument is 0.001 mass
% sulfur. The precision is approximately ±2 % relative standard deviation [21].
Carlo Erba 1106 Analyzer

After combustion in an analyzer, the gases are passed over an SO3 catalyst to convert
the sulfur compounds to SO2. Excess oxygen is removed with hot copper, and the gas
mixture is separated on a column of Poropak QS. The SO2 is measured with a thermal
conductivity detector. The sample size used is less than 1 mg, and a determination
takes approximately 5 min. The detection limit is 0.1 mass %. For ultra-micro sulfur
analysis, Kirsten and Nordenmark [22] modified this procedure so as to use nitrogen
as the carrier gas and electron capture detector. The detection limit is 0.0004 mass %
in a normal 0.5-mg sample.
Tracor Atlas Analyzer

This analyzer can be used for sub-part-per-million levels of sulfur. Multiple injections
of 100 µL are used. The light hydrocarbon liquid sample is injected into the hydrogena-
tion tube of a pyrolysis furnace at 1100°C. The hydrogenation products are passed
through an acetic acid solution over a lead-acetate-impregnated sensing tape. The H2S
from the gas stream reacts with lead acetate, darkening the tape; this change is detected
by a light beam from a tungsten lamp and is converted into the sulfur concentration.
The detection limit of this analyzer is 20 ng sulfur/mL.

Antek Sulfur Analyzer

This analyzer can be used alone or in conjunction with an Antek nitrogen analyzer
and with the same variable types of sample inlet systems. The sample is combusted in
a pyroreactor at a temperature greater than 1000°C in an oxygen atmosphere. Sulfur-
containing compounds are converted quantitatively to SO2. The combustion gases are
dried and then flow into a fluorescence chamber when they are exposed to UV radia-
tion. This fluorescent emission from Equation 2.3, which is specific for SO2, is mea-
sured with a photomultiplier tube. The linear range, detection limit, analysis time, and
precision are similar to those for the Antek nitrogen analyzer.
SO2 + hv  SO3 + hv1 (2.3)
Although detailed precisions and bias for ASTM sulfur test methods in various
fossil fuels are given in Chapters 3, 5, 6, 7, and 8 in this book, a summary of the
precision of all (~60) test methods is given in Table 2.5. Before choosing a test
method, the precision, the concomitant interferences, and other analytical
parameters should also be examined to find the best test method for a particular
product. This is true not just for sulfur determination but also for any analyte of
interest.
STANDARD REFERENCE MATERIALS FOR SULFUR [23]

Institutions such as NIST in the United States and other similar institutions in
other countries have issued several certified reference materials (CRMs) for sulfur
(and other elements) determination in various fossil fuel products. The CRMs
issued by NIST are called SRMs. Many of the gasoline and coal SRMs are certified
for sulfur because of the obvious interest in this element in fuels. A list of such
SRMs is given in Table 2.6 along with their certified sulfur values when available.
This is not necessarily a comprehensive list because NIST frequently revises exist-
ing SRMs and issues new SRMs; hence, their SRM catalog should be consulted for
up-to-date information. See NIST Special Publication 260-136 for details of NIST’s
certification program [24].
Proficiency Testing Program samples in the ASTM D02 Committees crosscheck
program can also be used as CRMs, although ASTM does not certify their values.
However, given the large database from which the assigned values are calculated, it is
reasonable to assume that the average mean values assigned are closest to the true
values in these materials. Once a crosscheck is completed, only limited residual quan-
tities of such materials are available from ASTM.
SRMs help a laboratory in the quality control of its analytical results and help
settle disputes between two or more laboratories’ analyses. They are also useful for
calibrating the analytical instruments in a laboratory. NIST recognizes three types of
values on their SRM certificates of analyses:

Table 2.5 Precision of ASTM Test Methods for Sulfur Determination in Fossil Fuels
Test Method Analysis Matrix Repeatability Reproducibility
Coal and Coke Products

D1757 Sulfate Sulfur Ash from coal and NA NA
coke
D2492 Forms of Sulfur Coal
• Sulfate 0.02 % 0.04 %
• Pyritic (referee) 0.08 + 0.09X 0.15 + 0.27X
• Pyritic (alternative) 0.06 + 0.11X 0.07 + 0.19X
D3177 Total Sulfur Coal 0.05–0.10 0.10–0.20
Coke 0.03 0.05
D4239 High-Temperature Tube Coal 0.02 + 0.03X 0.02 + 0.09X
Combustion Coke 0.02 0.08X
D5016 High-Temperature Tube Coal and coke 0.06X + 0.06 0.2X + 0.2
Combustion-IR Detection combustion residues
Gaseous Fuels
D1072 Combustion and BaCl2 Fuel gases NA NA
Titration
D1988 Mercaptans Natural gas NA NA
D4084 H2S using Lead-Acetate Gaseous fuels See test method See test method
Reaction Rate
D4468 Hydrogeneolysis and Gaseous fuels See test method See test method
Rateometric Colorimetry
D4810 H2S Using Length-of-Stain Natural gas 5–10 % NA
Detector Tube
D5504 Chemiluminescence Natural gas NA NA
D6228 GC and Flame Photometry Natural gas 0.06–0.16 NA
D6968 GC and AES Natural gas 0.23–53 NA
D7165 Online and At-Line Gaseous fuels NA NA
D7166 Total Sulfur Analyzer Natural gas NA NA
D7493 Online GC and EC Natural gas and 0.011–0.070 NA
Detection gaseous fuels
D7551 UV-Fluorescence Natural gas 0.036–0.18 NA
D7652 GC-Chemiluminescence Hydrogen fuel 0.005–0.037 NA
Detection
Petroleum Products and Lubricants
D129 General Bomb Method Petroleum products 0.04–0.08 0.06–0.27
D1266 Lamp Method Petroleum products 0.005 0.010 + 0.025X
D1552 High-Temperature Method Petroleum products 0.04–0.24 0.08–0.54

(Continued)
D1662 Active Sulfur Cutting oils

D2420 H2S by Lead Acetate LPG NA NA
D3120 Oxidative Light liquid See test method See test method
Microcoulometry petroleum products
D3227 Thiomercaptans by Gasoline, kerosine, 0.00007 + 0.00031 +
Potentiometry etc. 0.027X 0.042X
D3246 Oxidative Petroleum gases 0.4 5
Microcoulometry
D3712 Sulfonates by LC Petroleum liquids 0.63 % 0.92 %
D4045 Hydrogeneolysis and Petroleum products 0.16X0.5 0.26X0.5
D4294 ED-XRF Gasoline and diesel 0.4347X0.6446 1.9182X0.6446
D4952 Active Sulfur Species Fuels and solvents NA NA
D5303 Carbonyl Sulfide by GC Propylene 0.15X 1.0X
D5305 Ethyl Mercaptans LPG vapors 1 ppm 1.5 ppm
D5453 Combustion– Petroleum products 0.1788X0.75 0.5797X0.75
UV-Fluorescence
D5623 GC and Selective Ion Light petroleum See test method See test method
Detection products
D5627 GC
D5705 H2S in Vapor Phase Residual fuel oils 0.20X + 10 0.30X + 15
D6334 WD-XRF Gasoline 0.040(X + 0.1182(X +
97.29) 54.69)
D6443 WD-XRF Lube oils 0.02371X0.9 0.1623X0.9
D6481 ED-XRF Lube oils 0.01648(X + 0.01648(X +
0.0141)0.8 0.0141)0.8
D6667 UV-Fluorescence Gaseous 0.1152X 0.3130X
hydrocarbons
D6920 Oxidative Combustion and Petroleum products See test method See test method
ECD
D7039 MWD-XRF Gasoline and diesel See test method NA
D7041 Online GC and FPD Petroleum products 0.53 0.0657(X +
28.626)
D7212 ED-XRF Automotive fuels 1.6196X0.1 3.7668X0.1
D7220 Polarization ED-XRF Automotive fuels 0.6430X 0.504
1.1121X0.504
D7318 Inorganic Sulfate by Fuel ethanol 0.1711(X + 0.5807(X +
Potentiometry 0.1301)0.2678 0.1301)0.2678
(Continued )

(Continued)
D7319 Inorganic Sulfates by IC Fuel ethanol See test method See test method
D7328 Inorganic Sulfates by IC Fuel ethanol See test method See test method
D7620 Oxidation and Liquid hydrocarbons 0.180X 0.75
0.495X0.75
UV-Fluorescence
D7691 ICP-AES Crude oil 0.01971X1.1606 0.06360X1.1606
IR: infrared; BaCl2: barium chloride; GC: gas chromatography; AES: atomic emission spectrometry; EC:
electrochemistry; LC: liquid chromatography; ECD: electrochemical detection; FPD: flame photometric
detection; NA: not available; X: average of two determinations.
1. Certified value: A value for which NIST has the highest confidence in its accuracy
in that all known or suspected sources of bias have been fully investigated or
accounted for by NIST.
2. Reference value: A noncertified value that is the best estimate of the true value;
however, the value does not meet NIST criteria for certification and is provided
with an associated uncertainty that may reflect only measurement precision and
may not include all sources of uncertainty.
3. Information value: A value that may be of interest to the SRM user, but insufficient
information is available to assess the uncertainty associated with the value.
NIST uses seven models for value assignment of reference materials for chemical
measurements. NIST certified values are derived from certification at NIST using a
single primary method with confirmation by other method(s), or using two indepen-
dent critically evaluated methods, or using one method at NIST and different methods
by outside collaborating laboratories. NIST reference values are derived from the last
of the two models mentioned as well as from values that are based on measurements by
two or more laboratories using different methods in collaboration with NIST, from
values that are based on a method-specific protocol, from NIST measurements using a
single method or measurement by an outside collaborating laboratory using a single
method, or from values that are based on selected data from interlaboratory studies.
The last four means are used also for assigning NIST information values [24]. Reference
materials should be stored in a safe and environmentally clean environment so that
they do not degrade. The discussion of the above calibration standards also applies to
reference standards.
Quality Assurance in Sulfur Analysis of Materials

In a good laboratory, quality assurance (QA) of analysis results is considered an integral
part of the overall analytical process. Calibration, sample analysis, and quality control
(QC) should be repeated in cycles throughout the analytical cycle. The samples selected
for QC should be homogenous, stable, well characterized for the analyte of

Table 2.6 NIST Standard Reference Materials for Sulfur Analysis of Fossil Fuels
NIST SRM Number Matrix Sulfur Content Other Elements
1631 Bituminous coal

1632d Bituminous coal 1.5 mass % 18 + 17 + 5
1635a Subbituminous coal — 18 + 16 + 1
2682c Subbituminous coal 0.5 mass % 2+1
2683c Bituminous coal 2 mass % 2+1
2691 Coal fly ash — 20 + 19
2692 c Bituminous coal 1 mass % 2+1
2693 Bituminous coal 0.5 mass % 2+1
2718 Green petroleum coke 4.7032 ± 0.0079 mass % 6+5+4
2718a Green petroleum coke 5 mass % 10 + 3
2719 Calcined petroleum coke 0.8877 ± 0.0010 mass % 6+2+7
2775 Foundry coke 0.6 mass % 1+2
2776 Furnace coke 0.8 mass % 1+2
1633c Coal fly ash 0.1 mass % 20 + 16 + 8
2689 Coal fly ash — 9 + 3 + 19
2690 Coal fly ash 0.15 mass % 10 + 3 + 19
2691 Coal fly ash 0.8 mass % 10 + 3 + 19
1819 Base oil
2720 Di-n-butyl sulfide in base oil 1.583 mass %
2721 Crude oil 1.5832 ± 0.0044 mass %
2722 Crude oil 0.21037 ± 0.00084 mass %
2714b Diesel fuel oil 426.5 ± 5.7 mg/kg
2723a Diesel fuel 11.0 ±1.1 mg/kg
2724b Diesel fuel 426.5 ± 5.7 mg/kg
2770 Diesel fuel 41.57 ± 0.39 mg/kg
1619b Residual fuel oil 0.6960 ± 0.0077 mass %
1620c Residual fuel oil 4.561 ± 0.015 mass %
1621e Residual fuel oil 0.9480 ± 0.0057 mass %
1622e Residual fuel oil 2.1468 ± 0.0041 mass %
1623c Residual fuel oil 0.3806 ± 0.0024 mass %
1634c Residual fuel oil 2 mass %
2724, 8771 Diesel fuel
1624d Fuel oil distillate 0.3882 ± 0.0020 mass %
(Continued )

Table 2.6 NIST Standard Reference Materials for Sulfur Analysis of Fossil Fuels
(Continued)
NIST SRM Number Matrix Sulfur Content Other Elements
2294 Gasoline–RFG 40.9 ± 1.0 mg/kg
2295 Gasoline–RFG 308 ± 2 mg/kg

2298 High-octane gasoline 4.7 ± 1.3 mg/kg
1616a Kerosine 146.2 mg/kg
1616b Kerosine 8.41 ± 0.12 mg/kg
1617a Kerosine 0.17307 ± 0.00034 mass %
1819a Lubricating oils (×5) 0.04235–0.6135 mass %
1848 Lubricating oil additive 2.327 ± 0.0043 mass % 7
1619–1624, 1634 Residual fuel oil
2717a Residual fuel oil 2.9957 ± 0.0032 mass %
8590 Gas oil
1083 Used oils 980 mg/kg
1084a Used oils 1700 mg/kg
1085a Used oils 4500 mg/kg
1580 Shale oil
interest, available in sufficiently large quantities, and hopefully representative of the

actual samples being analyzed. It is not advisable to use the same sample for calibration
and QC. If the QC material appears to be degrading or changing in chemical or physical
properties, then this should be immediately investigated, and if necessary, a replacement
QC should be prepared for use.
The frequency of QC analysis will depend on the type of analysis and the instru-
ment involved. Many ASTM Test Methods specify the frequency of calibration or QC
intervals or both. At least one QC sample should certainly be analyzed with each set of
samples analyzed. Preferably, one QC sample should be analyzed before and after a set
of sample analyses to ensure that the sequence of sample analysis was under control
from beginning to end. Even better, a few QC samples should be included in the mid-
dle of samples so that continued QC surveillance is maintained. A rule of thumb gen-
erally used is one QC sample per five to ten samples. Special treatment of the QC
samples should be avoided because such practice seriously undermines the integrity of
precision and bias estimates.
If the QC samples indicate out-of-control results, then immediate remedial action
must be taken before analyzing further samples. Once the QC frequency is established

and the analysis appears to be in control over a long period of time, the QC frequency
may then be reduced. See ASTM Standard Guide D6792 for further guidance on QC in
the laboratory.
It is important that all QC data generated in a laboratory be manually or electron-
ically plotted promptly on a QC chart. The charts used could be individual, X, X bar,
moving average and moving range, exponentially weighted moving average (EWMA),
or cumulated sum (Cusum) charts. See a statistical textbook for the details of various
charting techniques. There are several statistical run rules that indicate when the pro-
cess may not be under statistical control. See ASTM D6300 or D6792 for discussion of
such rules. If the run rules show out-of-control data, remedial action should immedi-
ately be taken to bring the analysis back under control. The charts should periodically
be reviewed to identify the root causes of common out-of-statistical-control situations
so that they can be remedied.
References
[1] Hieftje, G. M., J. Anal. Atom. Spectrosc., Vol. 4, 1989, pp. 117.
[3] Nadkarni, R. A., Elemental Analysis of Fossil Fuels and Related Materials, MONO10,
[4] Nadkarni, R. A., “Atomic Absorption Spectrometry: Has It Gone or Is It Going?” Guide to
ASTM Test Methods for the Analysis of Petroleum Products and Lubricants, MNL44,
2nd ed., ASTM International, West Conshohocken, PA, 2007.
[5] Nadkarni, R. A., “Determining Trace Amounts of Sulfur in Petroleum Products,” World
Refining, Vol. 10, 2000, p. S-14.
[6] Rand, S. J., Significance of Tests for Petroleum Products, MNL1, 8th ed., ASTM
[7] Gibbs, L. M., Bonazza, B. R., and Fury, R. L., “Automotive Spark Ignition Engine Fuel,”
Significance of Tests for Petroleum Products, MNL1, 8th ed., S. J. Rand, Ed., ASTM International,
West Conshohocken, PA, 2010.
[8] Martin, C. J. and Hicks, L., “Burner, Lighting, and Heating Fuels,” Significance of Tests for
Petroleum Products, MNL1, 8th ed., S. J. Rand, Ed., ASTM International, West
Conshohocken, PA, 2010.
[9] Westbrook, S. W. and LeCren, R. T., “Fuels for Land and Marine Diesel Engines and for
Non-Aviation Gas Turbines,” Significance of Tests for Petroleum Products, MNL1, 8th ed.,
S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010.
[10] Rhodes, J., “Aviation Fuels,” Significance of Tests for Petroleum Products, MNL1, 8th ed.,
S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010.
[11] Pickard, A., “Gaseous Fuels and Light Hydrocarbons,” Significance of Tests for Petroleum
Products, MNL1, 8th ed., S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010.

[12] Hall, J. D., “Lubricant Base Oils,” Significance of Tests for Petroleum Products, MNL1,
8th ed., S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010.
[13] Giles, H. N. and Mills, C. O., Crude Oils: Their Sampling, Analysis, and Evaluation, MNL68,
[14] Nadkarni, R. A., “Trace Levels of Sulfur in the Fuels of the Future: Analytical Perspective,”
J. ASTM Int., Vol. 2, 2005, 12978.
Standardization News, Vol. 32, 2004, pp. 33–35.
[16] Nadkarni, R. A., “Recent Advances in the Determination of Sulfur in the Fuels of Today
and Tomorrow: A Report from the 2004 ASTM Symposium,” World Refining, Vol. 15,
2005, pp. 30–33.
[17] Nadkarni, R. A., Hwang, J. D., and Young, L., “Multielement Analysis of Crude Oils Using
Inductively Coupled Plasma-Atomic Emission Spectrometry,” J. ASTM Int., Vol. 8, 2011,
103837.
[18] Vrebos, B. A. R. and Glose, T. L., “Wavelength Dispersive X-Ray Spectrometry,”

Spectroscopic Analysis of Petroleum Products and Lubricants, MONO9, R. A. Nadkarni,
Ed., ASTM International, West Conshohocken, PA, 2011, pp. 349–373.
[19] Petiot, C. A. and Pohl, M. C., “Energy Dispersive X-Ray Fluorescence and Its Applications
in the Field of Petroleum Products and Lubricants,” Spectroscopic Analysis of Petroleum
Products and Lubricants, MONO9, R. A. Nadkarni, Ed., ASTM International, West
Conshohocken, PA, 2011, pp. 374–391.
[20] Chen, Z. W. and Wei, F., “Low-Power Monochromatic Wavelength Dispersive X-Ray
Fluorescence—Principle and Applications in Petroleum Products,” Spectroscopic Analysis
of Petroleum Products and Lubricants, MONO9, R. A. Nadkarni, Ed., ASTM International,
West Conshohocken, PA, 2011, pp. 392–409.
[21] Nadkarni, R. A., Hebel, M. T., and Taunton, J. W., “Laboratory Quality Assurance Through
the Analysis of Fossil Fuels Standard Reference Materials,” J. Coal Quality, Vol. 4, 1985,
pp. 72–79.
[22] Kirsten, W. J. and Nordenmark, B. S., “Determination of Sulfur Using a Micro-analyzer,”

Anal. Chim. Acta, Vol. 196, 1987, pp. 59–62.
[23] Nadkarni, R. A., “Calibration and Quality Control Standards and Reference Materials for
Spectroscopic Analysis of Petroleum Products,” ASTM International, West Conshohocken,
PA, 2011, pp. 112–131.
[24] May, W., Parris, R., Beck, C., Fassett, J., Greenberg, R., Guenther, F., Kramer, G., Wise, S.,
Gills, T., Gettings, R., and MacDonald, B., Definitions of Terms and Models Used at NIST for
Value-Assignment of Reference Materials for Chemical Measurements, NIST Special
Publication 260-136, National Institute of Standards and Technology, Gaithersburg, MD,
2000.

Chapter 3 | Analysis of Coal and
Coke Products
Sulfur occurs in coal as organically bound heterocyclics and as inorganic minerals

such as inorganic sulfates; as pyrite (disulfides); and as sulfides (small amounts of
galena, pyrhotite, etc.). What is referred to as pyrite are two different crystal forms of
FeS2: pyrite and marcasite. Pyrite is the most dominant sulfide mineral in coal.
Marcasite has also been reported in many different coals. Both are chemically FeS2, but
they differ in their crystalline forms. Pyrite is cubic whereas marcasite is orthorhom-
bic. Other sulfide minerals found in coals, sometimes in significant amounts, are
sphalerite (ZnS) and galena (PbS). Sulfates are usually not present in fresh and
unweathered coals unless formed by oxidation of the pyrite within them. Some other
sulfur minerals found in coal to a much smaller extent are gypsum (CaSO4∙7H2O) and
ferrous sulfate (FeSO4∙7H2O).
Organic sulfur and pyrites are the predominant forms of sulfur in most coals.
Sulfate sulfur is usually less than 0.1 mass %, except in weathered coal containing an
appreciable amount of pyrites or in coals high in alkaline sulfates. Pyrite is very sus-
ceptible to oxidation and decomposes to various phases of iron sulfate minerals at
room temperature. The following iron sulfate mineral phases are associated with
Illinois coals that have been subjected to oxidizing conditions. Sulfides and sulfate
minerals make up 25 % of the mineral matter content of Illinois coals [1].
• Szomolnokite FeSO4∙H2O
• Rozenite FeSO4∙4H2O
• Melanterite FeSO4∙7H2O
• Coquimbite Fe2(SO4)3∙9H2O
• Roemerite FeSO4.Fe2(SO4)3∙12H2O
• Jarosite (Na.K)Fe3(SO4)2(OH)6
The pyritic sulfur content varies considerably more than does the organic sulfur
content and is of greater interest because it is the form that can be most easily removed
from coal by current preparation practices. During high-temperature ashing, the
pyrite minerals are oxidized to ferric oxide and sulfur dioxide (SO2). Some of the SO2

may remain combined with calcium in the ash, but much of it is lost. If all of the SO2
was emitted during ashing, then there would be a 33 % weight loss with respect to the
weight of pyrite or marcasite in the original sample [1].
Most of the sulfur-containing organic compounds in coal are heterocyclic in
nature and are likely to be uniformly distributed throughout the coal matrix. Riley has
discussed direct determination of organic sulfur in coal [2]. An average range of sulfur
content of various classes of coal would generally be [2]
• Anthracite 0.5–2.5 mass %
• Bituminous 0.5–6 mass %
• Subbituminous 0.3–1.5 mass %
• Lignite 0.3–2.5 mass %
Given the importance of sulfur in coal and other fossil fuels because of its effect in
air pollution after fuel combustion, it is important to have precise and practical
methods available for such determination. Sulfur is a part of the ultimate analysis of
coal and coke (D3176). The results of sulfur analysis are used for the evaluation of coal
preparation and cleaning, the evaluation of potential sulfur emissions from coal and
coke combustion or conversion processes, and the evaluation of coal and coke quality
in relation to contractual specifications. There are several test methods published by
ASTM International Committee D05 on Coal and Coke that can be used for this
purpose.
Some of the coal, coke, and fly ash Standard Reference Materials (SRMs) issued by
the National Institute of Standards and Technology (NIST) and certified for their sul-
fur content include the following. These have proven to be quite useful in development
of new test methods and for quality control in laboratories.
• Bituminous coal NIST 1632 1.19 mass %
• Bituminous coal NIST 1632a 1.62 ± 0.03 mass %
• Subbituminous coal NIST 1635 0.33 ± 0.03 mass %
• Coal fly ash NIST 1633a 0.27 mass %
• Coal NIST 2682 0.47 ± 0.03 mass %
• Coal NIST 2683 1.85 ± 0.06 mass %
• Coal NIST 2684 3.00 ± 0.13 mass %
The sulfur test methods published by ASTM International are listed in Table 3.1.
Overall, all tests used for characterizing coal and coke and their ash products are
described by Nadkarni [3]. Given that coal or coke are solid products, the determina-
tion of sulfur in these materials cannot be done using instrumental methods such as
inductively coupled plasma–atomic emission spectroscopy (ICP-AES), which usually
needs dissolution of the sample, during which process all of the sulfur in the material
will be oxidized and lost from the sample as sulfur oxides. Hence, specific procedures
for this determination are designed that oxidize the sample and collect generated sulfur
oxides, which are then measured by specific detection techniques. There are three such

Analysis of Coal and Coke Products 37
Table 3.1 Sulfur ASTM Test Methods for Coal and Coke
ASTM Test Method Analysis Technique Matrix
D1757 Sulfate Sulfur Ash from coal and coke

D3176
D3177 Total Sulfur Coal and coke
D3682
D4239 Sulfur Using High-Temperature Tube Furnace Coal and coke
Combustion
D4326
D5016 High-Temperature Tube Furnace Combustion Coal and coke combustion
and Infrared Detection residues
ASTM test methods in use: D3177, D4239, and D5016. In addition, test methods D1757
and D2492 are used for determining the sulfur species in coal or coke. These test meth-
ods are described below, including the principles of analysis, test precision, and bias.
D1757: SULFATE SULFUR IN ASH FROM COAL AND COKE

Laboratory furnace temperature and furnace ventilation have an influence on sul-
fur trioxide (SO3) retention in laboratory ash. Consequently, sulfur in ash as deter-
mined in the laboratory cannot be assumed to be equivalent to the sulfur present in
the mineral matter in coal or to the retention of sulfur in ash produced under the
conditions of commercial utilization. The sulfate sulfur determined by these test
methods can be used to calculate the SO3 portion of ash so that the ash content or ash
composition can be reported on a SO3-free basis.
Test Method A is a modified British method in which a specified quantity of
ash is digested in boiling dilute hydrochloric acid (HCl) solution to which bromine
water is added to convert the sulfite that may be present to the sulfate form. After
neutralization and precipitation of iron with ammonium hydroxide, the mixture is
filtered to remove iron(III) hydroxide (Fe(OH)3), and the sulfate in the filtrate is
gravimetrically determined as barium sulfate (BaSO4).
In Test Method B, a specified quantity of the ash is ignited in air with Eschka
mixture. The sulfates are dissolved in hot water and separated from undissolved ash
residue and m agnesium oxide (MgO) by filtration. The sulfate in the filtrate is gravi-
metrically determined as BaSO4.
Interferences
Barium in coal ashes can result in incomplete recovery of sulfate sulfur. High iron
content can be encountered in coal and coke ash and can introduce error if, during the
sulfate precipitation, the iron is partially absorbed by the BaSO4 precipitate or co-
precipitated as iron sulfate.

Test Method Precision and Bias
British Method: British Method: Eschka Method: Eschka Method:

SO3 Range, % Repeatability Limit Reproducibility Limit Repeatability Limit Reproducibility Limit
<1 0.1 0.2 0.1 0.2

>1 to <5 0.2 0.3 0.3 0.4
>5 to <10 0.4 0.4 0.4 0.8
>10 to <20 0.6 1.0 0.5 1.0
Notes: The bias of this test method has not been determined. This test method was withdrawn in October
2009. The Eschka mixture, which is necessary to use for this test, is no longer commercially available.
D2492: FORMS OF SULFUR IN COAL

A knowledge of the forms and the concentrations of the sulfur present in coal is
necessary for determining the composition, heating value, thermal degradation
properties, and the eventual sulfur compounds formed in the coal byproducts.
Sulfur occurs in organic and inorganic forms, the latter consisting of pyrite, a small
amount of sulfate, and possibly some sulfide. Sulfur occurs in coal as inorganic
sulfates; as pyrites (disulfides); as sulfides (small amounts of galena, pyrhotite, etc.);
and in combination with the organic matter. Organic sulfur and pyrites are the
predominant forms of sulfur in most coals. Sulfate sulfur is usually less than
0.1 mass %, except in weathered coal containing an appreciable amount of pyrites
or in coals high in alkaline sulfates. The pyritic sulfur content varies considerably
more than does the organic sulfur content and is of more interest because it is the
form that can be most easily removed from coal by current preparation practices
[2]. Riley et al. have discussed direct determination of organic sulfur in coal [4].
The determination of sulfur species in coal is an important standard test routinely
performed on many coal samples. This test method applies to the determination of sul-
fate and pyritic sulfur in coal and calculates organic sulfur by difference. This test
method is not applicable to coke or other carbonaceous materials. Monosulfides (pyrites
and FeS2 are disulfides) of iron and elements such as cadmium, lead, vanadium, and zinc
can be present in coal. In the range of 0–100 ppm, these monosulfides do not contribute
significantly to the total inorganic sulfide content of coal.
In this test method, sulfate sulfur is extracted from the analysis sample with
dilute HCl. The sulfate sulfur in the extract is determined gravimetrically. Sulfates are
soluble in HCl, but pyrite and organic sulfur are not. Pyritic sulfur is calculated as a
stoichiometric combination with iron. For this purpose, in the referee method, the
iron combined in the pyritic state is extracted with dilute nitric acid from the coal
residue remaining after sulfate extraction. The extracted iron is determined by atomic
absorption spectrometry (AAS). The final iron determination can also be done using
ICP-AES at an interference-free iron wavelength. The sulfate extraction step also
removes HCl-soluble nonpyrite iron from the test specimen. A test specimen separate
from that used in the sulfate extraction could be used for the nitric acid extraction of

iron. In this case, nonpyritic and pyritic iron are extracted from the test specimen.
Because there is evidence that for some coals the extraction of nonpyritic iron by nitric
acid falls short of the amount extracted by HCl, the use of a separate test specimen for
the nitric acid extraction with subsequent correction for the contribution of nonpyritic
iron is not included in this test method [5,6].
In an alternative method to the referee method described above, which can
be used in routine analysis or when the concerned parties agree on this test method,
the iron originally combined in the pyrite state can be extracted with dilute HCl from
the ash obtained by incinerating the coal residue remaining after sulfate extraction.
The iron in the solution is determined by AAS or ICP-AES. The precision estimates
presented in Table 3.2 were obtained from an interlaboratory study (ILS) conducted for
this purpose.
Some difficulties encountered in determining the sulfur forms by the above pro-
cedure are adsorption of other materials on BaSO4 when it is precipitated, inability to
extract all of the pyritic sulfur from the coal during the extraction process, and possi-
ble oxidation of pyritic sulfur to sulfate in the pulverization and storage of the coal
sample. The first and the third difficulty can lead to high sulfate results. Iron ions are
readily adsorbed on the BaSO4 precipitate, which would be particularly objectionable
for coals containing large amounts of nonpyritic iron. Removal of the iron by precipi-
tation and filtration before the precipitation of BaSO4 minimizes the adsorption of
iron. Inadequate pulverization and mixing of the sample appear to be the major causes
of the incomplete extraction of pyritic sulfur from coal. A very small amount of
organic sulfur may also be extracted with the pyritic sulfur. For this reason, the
amount of pyritic iron extracted is used as a measure of the pyritic sulfur present. To
control the oxidation of pyritic sulfur to sulfates, exposure of the coal sample to the
atmosphere at elevated temperatures should be avoided and the samples should be
analyzed as soon as possible [2].
The barium perchlorate titration with thorin-methylene blue indicator can give
erratic results if it is not carefully performed. Also, it is a little hard to correctly judge
the end point. The sensitivity is poor; therefore, the low-sulfate coals end up with only
a “less than” value. Before the titration, two steps of evaporation to dryness to remove
most chloride, and ion exchange to remove all cations, need to be performed. These
Table 3.2 Precision of D2492 Test Method for Forms of Sulfur in Coal
Sulfur Form Range, mass % Repeatability Limit Reproducibility Limit
Sulfate sulfur 0.02 % 0.04 %

Pyritic sulfur 0.1–12
Referee method 0.08 + 0.09X 0.15 + 0.27X
Alternative method 0.06 + 0.11X 0.07 + 0.19X
Note: X is the mean of two single determinations.

difficulties can be avoided by using ion chromatography (IC) determination of sul-

fate. With using eluents such as 0.006 M sodium carbonate (Na2CO3) or 0.005 M
Na2CO3 + 0.004 M sodium hydroxide (NaOH), the retention time is reduced to 5 min.
The sulfate peak is resolved quite well from the chloride and nitrate peaks when the
concentrations of these three ions are roughly the same. However, when there is a
large amount of chloride or nitrate present compared with a small amount of sulfate,
the signal-to-noise ratio for sulfate is poor. Two ways of preventing this are
1. By removing the chloride as silver chloride (AgCl) with the addition of silver nitrate
or acetate. However, because the nitrate and acetate peaks are too close to the sulfate
peak, this offers no benefit.
2. By using a halide suppressor column in the ion chromatograph.
It is also feasible to use the chloride evaporation step from ASTM Test Method D2492
before subjecting the sample to IC. This will remove most of the chloride from the
sample.
The pyritic sulfur is conventionally determined after the nitric acid extraction
via iron determination by AAS or ICP-AES. Sulfate determination on this extract by
IC also gives results equivalent to the certified values or those by ICP-AES measure-
ments within the test method uncertainty. The results of determination of sulfur
forms in coal standards are given in Table 3.3. The coal standards used are from Alfa
Resources, Inc., and are certified for sulfur forms using the ASTM D2492 Test Method.
Agreement between the IC and the certified results is quite good. In addition, the
pyritic sulfur results obtained by IC and by iron determination by ICP-AES are also
in close agreement [7].
This test method provides for a separation of coal-associated sulfur into two com-
monly recognized forms: pyritic and sulfate. Organic sulfur is calculated by difference.
The results obtained by this test method are used to serve several interests, including
the evaluation of coal preparation and processing operations designed to reduce sulfur
Table 3.3 Determination of Sulfur Species in Coal
Sulfate Sulfur, mass % Pyritic Sulfur, mass %
Coal Certified Founda Certified Found IC Found ICP-AESb
AR 773 0.02 0.01 0.07 0.097 0.072

AR 778 0.03 0.03 0.49 0.62 0.60
AR 779 0.02 0.03 0.68 0.68 0.85
AR 780 0.13 0.15 ± 0.01c 0.74 0.52 0.84
AR 782 0.06 0.05 1.19 1.40 1.27
Illinois No. 6 0.53 0.57 0.63 0.56 0.66
IC.
a
Average of three measurements.

b
Calculated from iron values determined by ICP-AES.

c

levels in coal. The test method is not applicable to coke or other carbonaceous materials.
Monosulfides of iron and elements such as cadmium, lead, vanadium, and zinc can be
present in coal. In the concentration up to 100 ppm, these monosulfides do not contrib-
ute significantly to the total inorganic sulfide content.
In this test method, an analytical sample is used that has been pulverized to
pass a No. 60 (250-µm) sieve as prepared in accordance with Test Method D2013.
Moisture is determined by Test Method D3172 to permit calculations to other than
as-analyzed basis.
Sulfate sulfur is extracted from the analysis sample with dilute HCl. It is practi-
cal to limit the sample weight used to 2 g when the total sulfur level is 2 % or more
so as to avoid handling an excessive amount of iron in the pyritic extraction. The sul-
fate sulfur in the extract is gravimetrically determined as BaSO4. Sulfates are soluble
in HCl, but pyritic and organic sulfur are not. The sulfate extraction step also
removes HCl-soluble iron (nonpyritic form) from the test specimen. A test specimen
separate from that used for the sulfate extraction could be used for the nitric acid
extraction of iron. In this case, nonpyritic and pyritic iron are extracted from the
test specimen. Because there is evidence for some coals that the extraction of nonpy-
ritic iron by nitric acid falls short of the amount extracted by HCl, the use of a sepa-
rate test specimen for the nitric acid extraction of iron with subsequent correction
for the contribution of nonpyritic iron is not included in this test method. Pyritic
sulfur is calculated as a stoichiometric combination with iron using two different
methods:
1. The referee method can be used in cases of dispute or arbitration. The iron com-
bined in the pyritic state is extracted with dilute nitric acid from the coal residue
remaining after sulfate extraction. The iron is determined with AAS.
2. The alternative method can be used in routine practice or when the concerned par-
ties agree on this test method. The iron originally combined in the pyritic state can
be extracted with dilute HCl from the ash obtained by incinerating the coal residue
remaining after sulfate extraction. The HCl solution for extraction of iron should
be boiled for approximately 30 min for all iron compounds to dissolve completely.
The iron is determined by AAS. The following conditions are used in the AAS
determination of iron:
• A wavelength 248.3 nm for the 0- to 5-ppm iron
• A wavelength 372.0 nm for 5- to 100-ppm iron
• A wavelength 344.1 nm for greater than 100-ppm iron levels
• A lean air + acetylene flame.
Round-robin testing of the coal samples used to generate the precision and bias
statement of this test method indicates that the ICP-AES technique gives equivalent
results to those obtained by AAS in this test method for iron determination. Despite
the reservations cited in the test method standard, workers proficient in the ICP-AES

technique should have no problem in using this technique as long as proper wave-
length and linearity of calibration are maintained.
Because no suitable certified reference materials (CRMs) for these analyses are
available, absolute bias cannot be determined for this test method. However, on the
basis of matched pair comparison, the alternative method for pyritic sulfur was found
to be biased high with respect to the referee method, with the minimum detectable
bias being 0.06%.
Microwave-assisted dissolution of coal followed by ion chromatographic deter-
mination of sulfur species has been found to work well. Aqua regia was found to be a
more effective extractant than NaOH for the desulfurization of coal. Quantitative
recovery of sulfur can be obtained from the fly ash but not from the coal by microwave
heating with acids. When pyrite, FeS2, is treated with 6 M HCl or 3 M NaOH in the
microwave oven, only a small fraction of the original sulfur present is extracted.
However, when pyrite is treated with aqua regia + hydrofluoric acid (HF), almost all
sulfur is dissolved. An organic model compound such as benzyl disulfide that was
tested was not affected by microwave heating. Testing of an Illinois No. 6 coal treated
with acids and alkali in the microwave oven showed that approximately 56 % of the
sulfur present was extracted by acid leaching but very little by alkali leaching. Illinois
coals generally contain approximately 2 % pyritic sulfur; therefore, it appears that the
microwave action selectively removes pyritic and sulfatic sulfur, leaving only organic
sulfur in the residual coal. Thus, it is possible that the sulfur extracted in the acids by
microwave heating may give a good approximation of the pyritic plus sulfatic sulfur
present in coals.
Five different coal samples varying in their sulfur content from less than 1 to
greater than 7 % sulfur were analyzed for their sulfur forms by the ASTM D2492 pro-
cedure and the proposed microwave-assisted alternative procedure. The results in
Table 3.4 show that in all cases the amount of sulfur found by the microwave heating
Table 3.4 Determination of Sulfur Species in Coal Samples
Sulfur, mass % Illinois No. 6 NIST SRM 1632a Appalachian Wyodak
Totala
4.16 1.64 6.26 7.77 0.72
Sulfaticb 0.10 0.10 0.20 0.11 0.50
Pyritic c
1.14 0.81 4.85 6.70 0.17
Sulfatic + pyretic 1.75 0.91 5.05 6.81 0.67
Microwaved 1.89 0.86 5.00 6.36 0.49
Microwavee 1.81 ± 0.22 — — — 0.50 ± 0.04
a
Determined by Leco SC 32 method.
b
ASTM procedure: HCl Extraction and XRF Determination of Sulfur.
c
ASTM procedure: HNO Extraction and ICP-AES Determination of Iron.
d
Microwave oven—aqua regia extraction and X-ray fluorescence determination of sulfur.
e
Microwave oven procedure—five replicates each.

Table 3.5 Desulfurization of Coals with Acid & Microwave Radiation
Percentage of
Total Sulfur Present, Inorganic Sulfur Sulfur Found in Inorganic Sulfur
Coal mass % Present, mass % Solution, mass % Removal
Illinois No. 6 4.16 1.75 1.81 100

Pennsylvania 1.64 0.87 0.86 99
Appalachian 6.16 5.05 5.00 99
Wyodak 0.72 0.54 0.50 93
procedure is equivalent, within analytical errors, to the pyritic plus sulfatic sulfur
found by the ASTM procedure. Five replicate analyses of Wyodak and Illinois coals
gave precisions of approximately 10 %. Only approximately 10 min are needed for the
microwave procedure. Thus, rapid screening of coals for inorganic sulfur is possible by
the microwave heating procedure.
In a similar experiment, several coal types were analyzed for total sulfur and for
inorganic sulfur before treatment with the aqueous acid and microwave radiation. The
liquids recovered after the treatment were analyzed by X-ray fluorescence (XRF) for
their sulfur content. Prior experiments with model organic compounds had demon-
strated that organic sulfur is not removed by acid and microwave energy treatment.
Thus, all of the sulfur found in the liquids was assumed to be inorganic sulfur. The
results of these tests are presented in Table 3.5 [8].
Microwaves have the capability to heat one material much more rapidly than
another because materials vary greatly in their ability to absorb microwaves depend-
ing on their polarities. An example is the one given above of selective heating and
decomposition of the polar iron pyrite in coal, which might be expected to occur with-
out significant heating of the relatively less polar coal matrix. Although there certainly
would be a large difference in heating rate, it is not clear whether a temperature differ-
ential could be maintained between pyrite and coal over the time required for pyrite
decomposition. However, if this selective heating and decomposition of pyrites can be
attained, then it can open new methods of desulfurization. Because pyrites are being
selectively heated, the energy input for desulfurization might be minimized.
TOTAL SULFUR IN COAL AND COKE

Determination of total sulfur is, by definition, part of the ultimate analysis of coal. The
sulfur results obtained by these methods are used to serve several interests: evaluation
of coal preparation, evaluation of potential sulfur emissions from coal combustion or
conversion processes, evaluation of the coal quality in relation to contract specifica-
tion, and other purposes of commercial or scientific interest. There are three test meth-
ods available for the determination of total sulfur in coal and coke.
Riley notes the difficulties encountered in the analysis of coal for total sulfur
content [2]: nonuniform distribution of pyrite particles in coal, failure to recover all

of the sulfur as sulfate, and loss of sulfur as SO2 during the analysis. To overcome the
nonuniform distribution of pyrite particles in coal, many sample increments need to
be collected to ensure that the gross sample is representative of the lot of coal being
analyzed. Pyrite particles are hard, heavy, and have a tendency to segregate during
the preparation and handling of the samples. The sample must be reduced to the
point that 100 % of it can pass through a No. 60 sieve and be thoroughly mixed. Even
later as the pulverized sample is stored in bottles, heavy pyrite particles can segregate
themselves in the bottle; hence, thorough mixing of the analysis sample is necessary
before taking an aliquot for actual analysis [4].
Because the methods depend on the combustion of the sample, it is important
that the combustion products are completely oxidized. Failure to recover all of the
sulfur present in the sample as sulfate in the Eschka and bomb-washing methods
results in low total sulfur values. The combustion temperature used must be high
enough, the rate of burning must not be too fast, and sufficient time must be allowed
to complete the conversion of sulfur forms by oxidation. Riley gives several useful
instructions to help an analyst in obtaining accurate sulfur results through these wet
chemistry procedures [2]. When the gravimetric determination of sulfate is used in
the Eschka method, the final BaSO4 precipitate can create some difficulties in han-
dling. The precipitate is extremely fine and difficult to filter. Filter aids may have to be
used for help in filtration. BaSO4 can also occlude iron during the precipitation, and
this must be removed to avoid high biased results.
D3177: Total Sulfur in the Analysis Sample of Coal and Coke

The sample used in this test method is pulverized to pass a No. 60 (250-µm) sieve in
accordance with Test Method D2013 or D346. A separate portion of the sample is ana-
lyzed for moisture content using Test Method D3173 so that calculation to other than
the as-determined basis can be made. These test methods cover two alternative
procedures:
1. In the Eschka method, a weighed sample and the Eschka mixture are intimately
mixed and ignited together. The sulfur is dissolved in hot water and is then precip-
itated from the resulting solution as BaSO4. The precipitate is filtered, washed,
ashed, and weighed.
2. In the bomb-washing method, sulfur is precipitated as BaSO4 from oxygen-
bomb calorimeter washings and the precipitate is filtered, washed, ashed, and
weighed.
Range, % Repeatability Limit, % Reproducibility Limit, %
<2 0.05 0.10

>2 0.10 0.20
Coke 0.03 0.05
Note: There is no bias known for this method.

D4239: Sulfur in Coal and Coke Using High-Temperature

Tube Furnace Combustion
These test methods cover two alternative procedures using high-temperature tube
furnace combustion methods for the rapid determination of total sulfur in coal and
coke. When automatic equipment is used to perform either of these two methods, the
procedures can be classified as instrumental methods. There are several manufactur-
ers that offer such instruments. The instrumental methods are especially applicable
when results must be obtained rapidly for the successful completion of industrial,
beneficiation, trade, or other evaluations.
The sample for this analysis is pulverized to pass a No. 60 (250-µm) sieve and is
mixed thoroughly in accordance with practice D2013 or D346. A separate portion of
the analysis sample is taken for determining the moisture content using Test Method
D3173 or D7582 or ISO 11722 for calculation to other than the as-determined basis.
Test Method A
A weighed sample is burned in a tube furnace at a minimum temperature of 1350°C in
a stream of oxygen. During combustion, all sulfur present in the sample is oxidized to
gaseous oxides of sulfur, and the chlorine in the sample is released as gaseous HCl.
Moisture and particulates are removed from the gas by filters. The gas stream is passed
through a cell in which SO2 is measured by an infrared (IR) absorption detector. One
cell is used as a reference and a measurement chamber. Total sulfur as SO2 is detected
on a continuous basis.
Test Method B
The sample contained in a tin sample boat is combusted in a quartz combustion
tube furnace at a minimum temperature of 1150°C in a stream of oxygen with an
equal or excess amount of tungsten trioxide to oxidize the sulfur present in the sam-
ple. Moisture and particulates are removed from the gas by traps filled with anhydrous
magnesium perchlorate. The gas stream is passed through a cell in which SO2 is mea-
sured by an IR absorption detector. One cell is used as a reference and a measurement
chamber. Total sulfur as SO2 is determined on a continuous basis. This method is
empirical; therefore, the apparatus must be calibrated by using CRMs.
The schematics of these procedures are shown in Figs. 3.1 and 3.2.
Based on two interlaboratory studies conducted involving 12 laboratories for coal, and 48
laboratories using 24 coke samples, following precision estimates have been calculated.
Material Method Range, % Repeatability Limit, % Reproducibility Limit, %
Coal A 0.28 — 5.61 0.02 + 0.03 X 0.02 + 0.09 X

Coke A 0.52 — 0.84 0.02 0.08
Coal and Coke B 0.38 — 5.6 0.04 + 0.05 X 0.07 + 0.66 X
Note: X is the average of two single test results.

Fig. 3.1 Apparatus for Determination of Sulfur in Coal by Infrared Detection: D4239

Procedure A.
SOLENOID
VALVES COMBUSTION
PURGE TUBES
1350°C BOAT
LANCE STOP
COMBUSTION
BOAT
OXYGEN
TO SULFUR IR CELLS REAGENT
EXHAUST VACUUM TUBE
and/or
PUMP
CARBON IR CELLS PARTICLE
FILTER
SYSTEM ELECTRONICS
BALANCE
INPUT AND COMPUTER
Fig. 3.2 Apparatus for Determination of Sulfur in Coal by Infrared Detection: D4239

Procedure B.
The bias of this method is minimized when the instrument is calibrated with
certified reference materials.
D5016: Total Sulfur in Coal and Coke Combustion Residues Using a

High-Temperature Tube Furnace Combustion with IR Absorption
Method
This test method is similar to Test Method D4239 described above and it describes a
procedure using a high-temperature tube furnace and IR detection for the rapid deter-
mination of total sulfur in coal and coke combustion residues including laboratory ash
and residues from coal and coke combustion.

A weighed test portion is mixed with a promoting agent and ignited in a tube
furnace at 1450°C in a stream of oxygen. The combustible sulfur present in the sample
is oxidized to gaseous oxides of sulfur. Moisture and particulates are removed by traps
filled with anhydrous magnesium perchlorate. The gas stream is passed through a cell
in which SO2 is measured by an IR absorption detector. One cell is used as a reference
and a measurement chamber. Total sulfur as SO2 is detected on a continuous basis.
This test method is applicable for use with commercially available sulfur analyzers
equipped to automatically perform the above operations and must be calibrated using
CRMs covering the range of sulfur in the ash samples being analyzed.
Known interferences in this test method are some alkaline earth metal ions,
including barium and strontium, which form stable sulfate salts that are difficult to
decompose. To have an accurate analysis of the material, all sulfates must be decom-
posed to yield SO2. To minimize these interferences, a promoting agent is used to help
decompose these salts. These promoting agents can be an oxidizing agent, reducing
agent, or fluxing agent. Oxidizing and reducing agents help to decompose the metal
sulfates through the oxidation or reduction of sulfate or metal ions or both. The fluxing
agent helps decompose the metal sulfates by fusing the salt, which leads to the decom-
position of sulfates on further heating. Some promoting agents may contain sulfur,
which needs to be addressed with their use.
Ashing temperature, heating rate, and furnace ventilation have an important
influence on sulfur reaction; thus, observing the prescribed ashing conditions is
important. Sulfur in ash as determined by this test method cannot be strictly related
to the SO2 retained in ash produced under the combustion conditions in boiler fur-
naces or other commercial combustion processes. The following precision and bias
values were obtained based on an ILS:
Sulfur Range, wt % Repeatability Limit, % Reproducibility Limit, %
0.7–3.8 0.06X + 0.06 0.2X + 0.2
Note: X is the average of two single test results.
Compared against NIST SRM 1633b, this test method shows a –8.1 % relative bias.
Ion Chromatographic Determination of Sulfur

The Parr oxygen bomb can be used to determine the total sulfur in coal and oil shale
samples after combustion in an oxygen bomb and absorbing the gaseous products in
deionized water or very dilute Na2CO3. This is analyzed by an ion chromatograph,
where all anions present are separated chromatographically and detected by conduc-
tivity. Some typical results of coal samples for sulfur are given in Table 3.6. Where avail-
able, comparison is made with the known sulfur values for these samples. The average
precision for sulfur by ion chromatographic determination appears to be ~2 % [7].
Combustion followed by determination of sulfur (and other species) by other tech-
niques has been widely practiced. The Schoniger and Parr bomb methods are based on
such analysis. Because the Schoniger method generally uses only small quantities of

Table 3.6 Ion Chromatographic Determination of Total Sulfur in Coal and Oil Shale
Sample Sulfur Present, mass % [Ref.] Sulfur Found, mass %
Coal NIST 1632 1.35 [9] 1.22

Coal NIST 1632a 1.62 ± 0.03 [9] 1.37 ± 0.01 (5)
Coal NIST 1635 0.33 ± 0.03 [9] 0.33 ± 0.01 (3)
Coal NIST 2682 0.47 ± 0.03 [9] 0.37
Coal NIST 2683 1.85 ± 0.06 [9] 1.61
Coal NIST 2684 3.00 ± 0.13 [9] 2.54
Wyodak coal 0.596 a
0.591
Illinois No. 6 coal 4.10a 4.37
Value obtained using Leco SC-32 sulfur analyzer.

a
sample, it is sometimes not useful for trace determination. The Parr oxygen bomb
method is a standard test for the calorific value determination of fossil fuels. The method
involves the burning of a sample in a pressurized oxygen atmosphere within a closed
vessel that retains all combustion products. The organic compounds are oxidized to
carbon dioxide and water vapor whereas other volatile gaseous elements are absorbed in
the small amount of water placed in the bottom of the bomb. This solution can be ana-
lyzed for specific elements such as sulfur, nitrogen, and halogens. This technique has
been extensively used for the determination of sulfur in coal [10,11]. The end measure-
ment step of these procedures is usually gravimetric, turbidimetric, or volumetric titra-
tions. Many chemical manipulations, errors, and interferences associated with these
methods can be avoided by determining sulfur in the bomb solution using XRF spec-
trometry. The sulfur is determined through its K-alpha X ray, which is most strongly
absorbed by silica and phosphorus and enhanced by chlorine. However, in the bomb
combustion, practically no silicon goes into solution. Chlorine and phosphorus are nor-
mally present in coal at a fraction of the sulfur concentration and should not present an
absorption problem. Botto et al. have calculated the concentration of elements that will
cause the sulfur results to be low by 5 % when sulfur is determined in an aqueous solu-
tion containing the interfering element. The data were calculated from the mass absorp-
tion effects, and of 27 elements normally present in coal, none showed any significant
interference [12]. The results of the determination of sulfur in this fashion are given
below. All results are in agreement with the literature values where available [13,14].
Coal Sample Sulfur Present, mass % [Ref.] Sulfur Found, mass %b
NIST SRM 1632 1.35 [9] 1.32

NIST SRM 1632a 1.62 ± 0.03 [9] 1.48 ± 0.07 (6)
Wyodak coal 1.01a
1.06 ± 0.14 (3)
Value obtained by Leco method (D5016).

a
Results are expressed as mean ± standard deviation (number of replicates).

b

An alternative to the XRF determination of sulfur is to use IC after Parr bomb

combustion. Along with sulfur, other anions (e.g., fluorine, chlorine, and nitrogen) can
also be determined simultaneously [15]. The sulfur results are in fair agreement with the
NIST certificates of analysis values. From the replicate runs indicated in the table, the
precision of analysis appears to be approximately 2 %.
Sample Sulfur Present, mass % Sulfur Found, mass %
NIST SRM 1632 Coal 1.35 1.22

NIST SRM 1632a Coal 1.62 ± 0.03 1.37 ± 0.01 (5)
NIST SRM 1635 Coal 0.33 ± 0.03 0.33 ± 0.01 (3)
NIST SRM 1634a Fuel Oil 2.14 ± 0.02 2.12 ± 0.01(3)
Nadkarni and Botto have determined sulfur (and several other elements) in
NIST SRMs for coal and fly ash [16]. For sulfur determination, several alternative
methods were used: Leco SC 32 combustion–IR detection (D5016), oxygen bomb
combustion–IC, and XRF spectrometry. The results from this study for the anal-
ysis of several coal, fly ash, oil shale, and fuel oil standards are given in Table 3.7.
The number of replicate determinations ranges from 1 to 20. Analyses having
more than ten replicate determinations originate from ongoing laboratory
quality-assurance programs. Such analyses performed routinely for quality assur-
ance have greater variability built into them because of frequent changes in oper-
ator or instrumental conditions or both. Our results are compared with NIST
certified information or literature values where available. Overall, our results are
within ±5 to 10 % of NIST or literature values. The precision of the results varies
with the concentration levels, but the standard deviation is generally on the order
of ±5 %.
E775: Total Sulfur in the Analysis Sample of Refuse Derived Fuel

These test methods cover two alternative procedures for the determination of total
sulfur in prepared analysis samples of solid forms of refuse-derived fuel (RDF). These
Table 3.7 Analysis of NIST Fossil Fuel SRMs for Sulfur
NIST SRM # Analytical Technique Sulfur Found, mass % Sulfur Present, mass %
Coal 1632 D5016; IC 1.27 ± 0.05 (2) 1.19 [9]

Coal 1632a IC 1.51 ± 0.01 (20) 1.62 ± 0.03
Coal 1635 D5016; IC 0.33 ± 0.01 (6) 0.33 ± 0.03
Fly Ash 1633a D5016 0.169 ± 0.003 (4) 0.27 [9]
Fuel Oil 1634a WD-XRF; D5016; IC 3.00 ± 0.06 (10) 2.85 ± 0.05
Shale Oil 1580 WD-XRF 1.323 ± 0.004 (6)

test methods may be applicable to any waste material from which a laboratory sample
can be prepared.
1. In the Eschka procedure, a weighed sample and Eschka mixture are ignited together
and the sulfur is precipitated from the resulting solution as BaSO4. The precipitate
is filtered, ashed, and weighed.
2. In the bomb-washing procedure, sulfur is precipitated as BaSO4 from the oxygen-bomb
calorimeter washings, and the precipitate is filtered, ashed, and weighed.
RDF products are frequently nonhomogenous. Hence, significant care should be
taken to obtain a representative laboratory sample for the RDF to be characterized. The
sampling method used should be based on agreement between the involved parties.
The laboratory sample must be air-dried and the particle size reduced to pass a 0.5-mm
screen as described in practice E829.
The standard deviation of individual determinations in absolute percentage are as
follows on the basis of an ILS:
• Typical average value 0.35 %
• Within-laboratory 0.03 %
• Between laboratory 0.06 %
No bias has been determined because of the lack of availability of accepted RFD
reference material.
References
[1] Gluskoter, H. J., “Mineral Matter and Trace Elements in Coal,” Trace Elements in Fuel, S. P.
Babu, Ed., Advances in Chemistry Series No. 141, American Chemical Society, Washington,
DC, 1978, pp. 1–22.
[2] Riley, J. T., Routine Coal and Coke Analysis, MNL 57, ASTM International, West
Conshohocken, PA, 2007.
[3] Nadkarni, R. A., Guide to ASTM Test Methods for the Analysis of Coal and Coke, MNL61,
[4] Riley, J. T., Ruba, G. M., and Lee, C. C., “Direct Determination of Organic Sulfur,”
Geochemistry of Sulfur in Fossil Fuels, W. L. Orr and C. M. White, Eds., American Chemical
Society Symposium Series No. 429, American Chemical Society, Washington, DC, 1990.
[5] Edwards, A. H., Daybell, G. N., and Pringle, W. J. S., “An Investigation into Methods for the
Determination of Forms of Sulfur in Coal,” Fuel, Vol. 37, 1958, pp. 47–59.
[6] Burns, M. S., “Determination of Pyritic Sulfur in Australian Coals,” Fuel, Vol. 49, 1970,
pp. 126–133.
[7] Nadkarni, R. A., “Alternatives to ASTM Tests for Rapid Coal Analysis,” Proceedings of the
3rd International Coal Testing Conference, Lexington, KY, Vol. 3, 1983, pp. 135–142.
[8] Nadkarni, R. A. and Williams, R. B., “Coal and Oil Shale Beneficiation Process,” U. S.
Patent, 4,408,999, October 11, 1983.

[9] National Bureau of Standards Certificate of Analysis, 1978.
[10] Ahmed, S. A. and Whalley, B. J. P., Analytical Methods for Coal and Coal Products, C. Karr,
Ed., Academic Press, New York, 1978, Vol. 1, p. 263.
[11] Chakyabarti, J. N., Analytical Methods for Coal and Coal Products, C. Karr, Ed., Academic
Press, New York, 1978, Vol. 1, p. 279.
[12] Botto, R. I., White, B. H., and Karchmer, J. H., “Determination of Sulfur Species in Coal,”
Fuel, Vol. 59, 1979, pp. 157–160.
[13] Nadkarni, R. A., “Determination of Volatile Elements in Coal and Other Organic Materials,”
Amer. Lab., Vol. 13, 1981, pp. 22–29.
[14] Nadkarni, R. A., “Comprehensive Elemental Analysis of Coal and Fly Ash,” Coal and Coal
Products: Analytical Characterization Techniques, E. L. Fuller, Jr., Ed., ACS Symposium
Series No. 205, American Chemical Society, Washington, DC, 1982, pp. 147–162.
[15] Nadkarni, R. A. and Pond, D. M., “Application of Ion Chromatography for Determination of
Selected Elements in Coal and Oil Shale,” Anal. Chim. Acta, Vol. 146, 1983, pp. 261–266.
[16] Nadkarni, R. A. and Botto, R. I., “Analysis of National Bureau of Standards—Fossil Fuel
Standard Reference Materials,” J. Coal Quality, Vol. 5, 1986, pp. 67–71.

Chapter 4 | Analysis of Oil Shales
Oil shales do not have the same emphasis as coal or crude oil regarding their sulfur
content. That is mainly because oil shale is not directly combusted for power produc-
tion or any other public use, and the bulk of the chemical composition of oil shale is
made up of inorganic material. In technological usage, oil shale has to be liquefied to
shale oil by retorting under high pressure.
The total sulfur in oil shale is determined by combustion and infrared (IR) detec-
tion or other chemical means. Several commercial instruments are available for such
work. However, a knowledge of the forms of sulfur and the concentration of total sulfur
present is necessary for determining the composition, heating value, thermal degrada-
tion properties, and the eventual sulfur forms formed in the shale oil. In oil shale, sulfur
occurs in inorganic and organic forms, the former consisting of pyrite, small amounts
of sulfate, and possibly some sulfide. The quantitative determination of these forms first
needs quantitative chemical separation. The most widely used procedure for such work
is ASTM Test Method D2492, which was developed for application to coal. In this
method, a coal sample is digested with dilute hydrochloric acid (HCl) to dissolve sulfate
sulfur, which is subsequently determined by barium perchlorate titration or using X-ray
fluorescence (XRF). During the HCl dissolution, the gases produced are collected over-
head in a sodium hydroxide (NaOH) solution scrubber to collect the hydrogen sulfide
(H2S) produced by the decomposition of sulfides with HCl. The sulfide in the scrubber
is also determined using XRF. The filtered and washed residue of the HCl digestion is
treated with dilute nitric acid, which decomposes the pyrite FeS2. From this solution
after filtration, iron is determined by atomic absorption spectrometry (AAS) or induc-
tively coupled plasma–atomic emission spectrometry (ICP-AES) and is calculated to an
equivalent amount as FeS2. The total sulfur in the sample is separately determined by
the total combustion procedure or the Eschka fusion method. The difference between
the total sulfur and sulfate + sulfite + pyrite sulfur is considered as the organic sulfur.
This method is commonly used for the determination of sulfur species in coal and
coal products (see Chapter 3 in this book). However, when the method is applied to oil
shales, some difficulties are encountered. This is not unexpected because oil shales
contain much more inorganic material than does coal; hence, interferences are

probable. Blanco et al. [1] and Smith et al. [2] have reported on the determination of
sulfur forms in oil shales. Blanco et al. [1] compared two methods—one described
above and the other by Smith et al. [2]—on Mangrullo oil shale samples. The variation
in results obtained by these two procedures was not very significant according to this
study. In the Smith et al. procedure [2], the key to the determination is the decomposi-
tion of pyrite using lithium aluminum hydride (LiAlH4) reduction. The sample is first
refluxed with dilute perchloric acid to dissolve sulfate, which is then determined gravi-
metrically as barium sulfate. The residue is refluxed with LiAlH4 in tetrahydrofuran
(THF) to reduce pyrite to H2S, which is then trapped in cadmium sulfate solution. The
sulfuric acid (H2SO4) formed is titrated with NaOH to obtain the pyrite equivalent
value. The residue containing organic sulfur is fused with Eschka mixture—magne-
sium oxide (MgO) + sodium carbonate (Na2CO3)—and the sulfur is later determined
gravimetrically as barium sulfate. Smith et al. [2] have presented convincing evidence
about the validity of this procedure.
A Green River (Colorado) oil shale sample containing 0.88 wt % total sulfur, as deter-
mined by the combustion–IR method, was subjected to the ASTM D2492 procedure.
However, when the sample was continued to reflux for up to 7 h with dilute HCl, con-
tinual evolution of H2S was observed, with a slow increase in H2S formation from 45
min to 7 h (see Table 4.1). If the experiment was stopped after 45 min as suggested in the
D2492 procedure, then this sulfur would probably be reported as part of the errone-
ously high pyritic sulfur. On the other hand, there is no guarantee that the continued
release of H2S is solely from sulfide in the sample and is not due to the decomposition
of some other sulfur form in the oil shale sample.
The microwave oven dissolution followed by ion chromatographic determination
of sulfate ion has worked quite well for the coal samples tested, but the results obtained
were quite different when applied to Green River oil shale (Table 4.1). A similar
Table 4.1 Determination of Sulfur Species in Green River Oil Shale
Procedure Species Determined Sulfur, mass %
ASTM D2492 H2S —0.75 h 0.268

—3 h 0.329
—4 h 0.349
—5 h 0.365
—7 h 0.380
SO42— 0.217
FeS2 0.083
Microwave Dissolution + IC SO4 2—
0.094; 0.095; 0.095
FeS2 0.222; 0.183; 0.171
HF Treatment SO42— Not detected
FeS2 0.60
IC: ion chromatography; HF: hydrofluoric acid.

Analysis of Oil Shales 55
disparity was observed when analyzing Moroccan oil shales. Other reagents tested
included HF, hydrogen iodide (HI), and NaOH for the oil shale decomposition
purposes. In using 5 % HF and microwave heating, no sulfate sulfur was detected and
the pyritic sulfur result was higher than ever observed before.
Another suggested alternative for the determination of sulfur forms in oil shales
is demineralization to isolate the kerogen in the oil shale and then determining the
iron content of the kerogen fraction as a representative of the pyrite present. The
method was originally developed at the U.S. Bureau of Mines (USBM) to isolate kero-
gen from oil shale [3]. It consists of removing the carbonate minerals by dissolving in
HCl and the silicate minerals in HF, thus obtaining a kerogen material for which the
only mineral contaminant is pyrite because that mineral is insoluble in HCl and HF.
The isolated kerogen is dissolved in nitric acid, and the iron is determined in the
solution using AAS or ICP-AES.
A single analysis each performed by the above procedure on four oil shale sam-
ples gave results that were definitely lower than ones obtained by the ASTM D2492
procedure, but they were much closer to those obtained using the LiAlH4 procedure
(Table 4.2) [4].
Another alternative to the above procedures for total or forms of sulfur in oil
shales is to use Parr bomb combustion preparation and final measurement of sulfur in
the absorbent water by ion chromatography (IC). This procedure is described in this
book in Chapter 3 on coal analysis. Typical results for some oil shale samples are given
in Table 4.3. The sulfur results are means of triplicate analyses. The sulfur results are in
good agreement with the published results [4]. Oil shale standards have not been as
well characterized as National Institute of Standards and Technology (NIST) coal or
fly ash standards; hence, not a lot of information about their elemental content is avail-
able in the literature. However, the precision of results is not as good as that found
for coal analysis. This is suspected to be due to the heterogenous nature and high
inorganic content of oil shales.
IC can also be used for the anionic analysis of oil shale products such as aqueous
leachates from shale processing. Sulfur species such as sulfate, sulfite, thiosulfate, sul-
fide, and thiocyanate often present in oil shale aqueous streams can be determined by
IC, which avoids the tedious tasks of multiple wet chemistry titrations, etc., for the
Table 4.2 Determination of Pyrite in Oil Shales [4]
Method D2492 LiAlH4 Demineralization
Colorado Shale 0.68 ± 0.09 (11) 0.43 ± 0.02 (3) 0.41

Australian Shale 0.79 ± 0.07 (11) 0.64 ± 0.01 (3) 0.48
Moroccan Shale 0.74 0.64 0.43
Green River Shale 0.67 0.27 0.22
Note: All results are in mass % expressed as mean value ± standard deviation (number of replicates).

Table 4.3 Determination of Sulfur in Oil Shale Using IC
Oil Shale Sulfur Present, mass % Sulfur Found, mass %
USGS SGR-1 1.90 [5]; 1.64 [6] 1.71 ± 0.05 (3)

USGS SCO-1 0.12 [7]; 0.06 [5,6] 0.052 ± 0.001 (3)
Rundle oil shale 1.04a 0.86
Colorado oil shale 0.85a 0.86
Colorado kerogen 2.68 b
2.42
Paraho shale oil 0.74 [8] 0.74
Note: All results are expressed as mean value ± standard deviation (number of replicates).
Result by Leco SC-32 sulfur analyzer.

a
Results by ASTM D5016 Test Method.

b
determination of these sulfur species. Fig. 4.1 shows an ion chromatogram of Colorado
oil shale retort water. Table 4.4 shows the sulfur results from various stages of oil shale
processing [9].
Fig. 4.1 Ion chromatogram of Colorado oil shale retort water. Eluant: 2.4mM Na2CO3 +
3 mM NaHCO3. Flow rate: 1 mL min. Separator: Dionex HPIC-AS4 column.
Suppressor: Dionex AFS column. Injection loop: 100 µL.

Analysis of Oil Shales 57
Table 4.4 Sulfur Determination of Colorado Oil Shale Products by IC
Shale Material Sulfate Content, mg/kg
Colorado oil shale 2200

Kerogen 7.23 mass %
Fischer assay water 215
Spent shale leachate a
112
Shale oil 2.23 mass %
a
The spent shale leachate was prepared by U.S. Environmental Protection Agency procedure 43FR 58956.
Table 4.5 Sulfur Content of Shale Oil Types and Fractions [10]
Shale Oil Process Sulfur, mass % Shale Oil Fraction Sulfur, mass %
Green River Tosco process 0.7 Dewatered shale oil 0.69

Green River Paraho process 0.7 Distillation residuum 0.81
Geokinetics in situ 0.6 Heavy distillate 0.53
Occidental in situ 0.7 Light distillate 0.59
Rundle Lurgi aboveground 0.42 Naphtha 0.54
Shale Oil NIST SRM 1580 1.323 ± 0.004 Wax 0.0230
Kerogen in oil shale, which is the organic portion of the solid oil shale, can be
analyzed for sulfur by microchemical elemental analysis techniques, such as combus-
tion and IR detection of sulfur oxide. Different oil shale kerogens appear to have simi-
lar sulfur content, approximately 2 mass %.
• Green River 2.8 %
• Australian 2.0 %
• Brazilian 2.1 %
• Tennessee 2.9 %
Shale oil itself can be analyzed for its sulfur content either by XRF or by micro-
chemical techniques. It typically contains 0.5–1 mass % sulfur. Nadkarni sum-
marizes sulfur content of some shale oils and their fractions on the basis of earlier
literature reports (Table 4.5) [10].
References
[1] Blanco, F., Rodriguez, P., and Monteo, N., Inf. Invest. Cent. Invest. Technol. (Uruguay), 1011,
1978.
[2] Smith, J. W., Young, N. B., and Lawlor, D. L., “Direct Determination of Sulfur Forms in
Green River Oil Shale,” Anal. Chem., Vol. 36, 1964, pp. 618–622.

[3] Smith, J. W., U. S. Bureau of Mines Report Invest., 5725, 1961.
[4] Nadkarni, R. A., “Analytical Techniques for the Characterization of Oil Shales,”
Geochemistry and Chemistry of Oil Shales, F. P. Miknis and J. F. McKay, Eds., ACS
Symposium Series No. 230, American Chemical Society, Washington, DC, 1983,
pp. 477–492.
[5] Fabbi, B. P. and Espos, L. F., “X-Ray Fluorescence Analysis of 21 Selected Major, Minor, and
Trace Elements in Eight New U.S.G.S. Standard Rocks,” U.S. Geological Survey
Professional Paper No. 840, 1976, pp. 89–93.
[6] Evans, K. L., Tartar, J. G., and Moore, C. B., “Pyrohydrolytic Ion Chromatographic
Determination of Fluorine, Chlorine, and Sulfur in Geological Samples,” Anal. Chem., Vol.
53, 1981, pp. 925–928.
[7] Schultz, L. G., Pourtelot, H. A., and Flanagan, F. J., “Cody Shale SCO-1 from Natrona
County, Wyoming,” U.S. Geological Survey Professional Paper No. 840, 1976, pp. 21–23.
[8] Fruchter, J. S., Wilkerson, C. L., Evans, J. C., and Sanders, R. W., “Elemental Partitioning
in an Above Ground Oil Shale Retort Pilot Plant,” Environ. Sci. Technol., Vol. 14, 1980,
pp. 1374–1381.
[9] Nadkarni, R. A. and Brewer, J. M., “Applications of Ion Chromatography in Environmental

Analysis,” Amer. Lab., Vol. 19, 1987, pp. 50–59.
[10] Nadkarni, R. A., “Elemental Analysis of Oil Shales,” in Elemental Analysis of Fossil Fuels
and Related Materials, MONO10, ASTM International, West Conshohocken, PA, 2014,
pp. 395–456.

Chapter 5 | Analysis of Petroleum
Products
INTRODUCTION
As discussed in Chapter 1 of this book, sulfur occurs naturally in crude oil; it is
removed by hydrodesulfurization and other processes during refining crude oil to
gasoline and diesel. Thus, the latter products contain only trace amounts (ppm level) of
sulfur. However, even at such reduced levels, it is important to accurately measure the
amount of sulfur present in these fuels given the adverse effect any levels of sulfur has
on human health and the environment. In the United States, the U.S. Environmental
Protection Agency (EPA) and other state and federal bodies strictly regulate the
amount of sulfur present in fuels. Many petroleum products have ASTM specifications
in which sulfur is a critical component with the limits and test methods used to be
prescribed. See Table 5.1 for a summary of ASTM product specifications for sulfur con-
tent in petroleum products.
In addition to gasoline and diesel, other products originating from refining
process include lubricating additives and lubricating oils, fuel oils, automatic trans-
mission fluids, aviation jet fuel, base oil, gear oil, and general gas oil. Of these, the
lubricating oils and additives are discussed separately in Chapter 6 of this monograph.
The rest of the product slate uses similar test methods for sulfur determination.
No. 6 fuel oil D1552, D2622, D4294

Automatic transmission fluid D1552
Aviation jet fuel D1266, D1275, D2622, D4294, D5453
Base oil D2622, D4294
Gear oil D4294
General gas oil D1552, D2622, D4294
Fuel oils contain varying amounts of sulfur (as organic compounds) depending
on the source of crude oil, the refining processes used, and fuel grade. The high boiling
range fractions and the residual fuels usually contain higher amounts of sulfur, which
is generally regarded as an undesirable constituent because of its potential to create
corrosion and pollution problems. Various ASTM Test Methods are available for the
determination of sulfur.

Table 5.1 Petroleum Product Specifications for Sulfur Content
Product Specification Sulfur Limits Test Method
Fuel oil D396 (also 0.5 mass %—S5000 No. 1 and 2 D129
see Table 5.2) Grades
0.05 mass %—S500 No. 1 and 2 D2622
Grades
Aviation gasoline D910 0.05 mass % max D1266 or D2622
Diesel fuel oils D975 (also 15 ppm max No. 1D and No. 2D S15 D5453
see Table 5.3) 0.05 mass % No. 1D and No. 2D S500 D2622
0.50 mass % No. 1D and No. 2D D129
S5000; and 2.00 mass % No. 4D
Aviation turbine D1655 0.003 mass % max mercaptan sulfur D3227
fuel 0.30 mass % max total sulfur D1266, D2622,
D4294 or D5453
LPG D1835 123–185 ppm max D2784 or D6667
Gas turbine fuel oil D2880 0.001–0.8 mass % D129 (referee),
D1552, D2622,
D4294, or D5453
Kerosine D3699 Total sulfur 0.04 to 0.30 max mass % D1266
Mercaptan sulfur 0.003 max mass % D3227
Denatured fuel D4806 Sulfur 30 ppm max D2622, D3120,
ethanol D5453, or D7039
Sulfur 10 ppm max (CARB) D5453
Existent sulfate, ppm max D7318, D7319, or
D7328
Spark-ignition D4814 Sulfur max, mass % (unleaded) D1266, D2622,
engine fuel 0.0080; (leaded) 0.15 D3120, D5453,
D6920, D7039
Fuel methanol D5797 Sulfur max, mg/kg 160 (class 1), 200 D1266, D2622,
(class 2), 300 (class 3) D3120, D5453
Ethanol fuel blends D5798 Sulfur max, mg/kg D5453, D7039
MTBE for blending D5983 Sulfur max, mg/kg 300 D4045
Unleaded aviation D6227 Sulfur max, mass % 0.07 D1266, D2622,
gasoline D3120, D4294,
D5453
Industrial Burner D6448 Sulfur, mass %—report D129, D1266,
fuel D1552, D2622,
D4294, D5185
Jet B wide-cut D6615 Total sulfur, max 0.30 mass % D1266, D2622,
aviation turbine D4294, D5453
fuel Mercaptan sulfur, max 0.003 mass % D3227
Biodiesel fuel blend D6751 Sulfur max 0.0015–0.05 mass % D1266, D2622,
stock B100 D3120, D4294,
D5453, D7039

Analysis of Petroleum Products 61
Table 5.1 Petroleum Product Specifications for Sulfur Content (Continued )
Product Specification Sulfur Limits Test Method
Commercial boiler D6823 Sulfur mass %—report D129, D1266,

fuels D1552, D2622,
D4294
Aviation certification D7223 Total sulfur 0.30 mass % max D1266,
turbine fuel D2622, D4294,
D5453
Mercaptan sulfur 0.003 mass % max D3227
Report D4952
Biodiesel blend D7467 Sulfur 0.05–0.50 mass % max D129, D1266,
(B6-B20) diesel fuel oil D1552, D2622,
D3120, D4294,
D5453
Pyrolysis liquid biofuel D7544 Sulfur 0.05 mass % max D4294
Unleaded aviation D7547 Sulfur 0.05 mass % max D2622
gasoline
Aviation turbine fuel D7566 Total sulfur 0.30 mass % max D129, D1266,
with synthesized D2622, D4294,
hydrocarbons Mercaptan sulfur 0.003 mass % max D5453
Report D3227
D4952
Grade 94 unleaded D7592 Sulfur 0.05 mass % max D2622
aviation gasoline
certification
High-octane unleaded D7719 Sulfur 0.05 mass % max D1266, D2622
test fuel
LPG: liquefied petroleum gasoline; MTBE: methyl tert-butyl ether.
Table 5.2 Alternative Sulfur Test Methods for D396 Fuel Oil Specification
Test Method Range Grades Reporting Units
D129 (referee) >0.1 mass % No. 1 S5000, No. 2 S5000, No. 4 mass %
light, No. 5 heavy, No. 6
D1266 0.01–0.04 mass % No.1 S500, No. 2 S500 mass %
D1552 >0.06 mass % No. 1 S5000, No. 2 S5000, No. 4 mass %
light, No. 4, No. 5 heavy, No. 6
D2622 (referee for 0.0003–5.3 mass % All grades mass %
S500 grades)
D4294 0.0150–5.00 mass % All grades mass %
D5453 1.0–8000 mg/kg All grades mg/kg
D7039 4–17 mg/kg S500 grades if sulfur is <17 mg/kg mg/kg

Table 5.3 Alternative Sulfur Test Methods for D975 Diesel Fuel Oil Specifications
Test Method Range Grades Reporting Units
D129 (referee) >0.1 mass % No. 1D S5000; No. 2D, S5000; No. 4D mass %
D1266 0.0005–0.4 mass % No. 1D S500, No. 2D S500 mass %
D1552 >0.06 mass % No. 1D S5000, No. 2D S5000, No. 4D mass %
D2622 (referee 0.0003–5.3 mass % All grades mass %
for S500 grades)
D3120 3.0–100 mg/kg No. 1D S15, No. 2D S15, No. 1D S500, mg/kg
No. 2D S500
D4294 0.0150–5.00 mass % No. 1D S5000, No. 2D S5000, No. 4D mass %
D5453 (referee 0.0001–0.8 mass % All grades mg/kg
for S15 grades)
D7039 4–17 mg/kg No. 1D S15, No. 2D S15 mg/kg
Base oils are classified by the American Petroleum Institute (API) into five types
on the basis of their sulfur content and other parameters. The sulfur test methods for
analyzing base oils include D1552, D2622, D4294, D4927, or D3120. Sulfur limits are as
follows per API-defined base oil groups:
API Group Sulfur, mass % Saturates, % Viscosity Index
Group I >0.03 and <90 80–119

Group II ≤0.03 and ≥90 80–119
Group III ≤0.03 and ≥90 ≥120
Group IV All PAOs
Group V All basestocks not in Groups I–V (naphthenics, non-PAO synthetics)
PAO: polyalphaolefin.
Throughout the evolution of base oil refining and processing technology, the sul-
fur content has been used as an indicator of product quality and a predictor of lubri-
cant performance. Current domestic base oil sulfur concentrations typically range
from less than 0.005 to 0.1 mass % for light base stocks and up to 0.05–1.0 mass % for
heavier viscosity grades. In other parts of the world, the sulfur levels of base oils may
range in excess of 1.0 mass %.
The concentration of sulfur present in petroleum coke is a major factor in the
suitability of a coke for various uses. Sulfur contents are used to estimate the potential
formation of sulfur oxides (SOx). In some cases, sulfur is detrimental to production and
the use of artifacts produced from petroleum coke. Sulfur, even in the very low concen-
trations in graphite used in nuclear reactors, is of concern because of potential corro-
sion of metallic components. The specifications for green and calcined petroleum coke
differentiate between these two types on the basis of their sulfur and other elemental

contents. Sulfur levels in these materials can vary from 0.2 to 3 mass %. The test meth-
ods for sulfur determination of petroleum coke are C816, D1552, or D6376.
Obviously many test methods are used in the analyses of petroleum products. The
ASTM test methods used are included in Table 5.4. New tests for sulfur using newer
analytical technology continue to be added to this list by instrument manufacturers.
The most prominent analytical techniques used for this work are based on X-ray fluo-
rescence (XRF) and specific combustion-detection devices. Most test methods listed in
Table 5.4 are for fuels—gasoline and diesel—but there are also several for the analysis
of lubricating oils and additives. Sulfur is present as a trace element in fuels, but it is
present as a major constituent in crude oils and lubricants. Although an integral part
of the petroleum product area, lubricants are discussed separately in Chapter 6. Some
of the same or similar test methods are used for both of these types of products. There
Table 5.4 ASTM Test Methods for Sulfur in Petroleum Products and Lubricants
ASTM Test
Method Analysis Technique Matrix
D129 General Bomb Method Petroleum products
D1266 Lamp Method Petroleum products
D1275 Corrosive Sulfur Electrical insulating oils
D1552 High-Temperature Method Petroleum products
D2420 Hydrogen Sulfide by Lead Acetate Method LPG
D2622 Wavelength-Dispersive X-Ray Fluorescence Gasoline and diesel
D2784 Oxyhydrogen Burner or Lamp Method LPG
D3120 Oxidative Microcoulometry Method Light liquid petroleum
Hydrocarbons
D3227 Thiomercaptan Sulfur by Potentiometry Gasoline, kerosine, etc.
D3246 Sulfur by Oxidative Microcoulometry Petroleum gases

D3712 Oil Soluble Sulfonates by Liquid Petroleum liquids
Chromatography
D4045 Hydregenolysis and Rateometric Colorimetry Petroleum products
D4294 Energy-Dispersive X-Ray Fluorescence Petroleum products
D4927 Additive Elements by Wavelength-Dispersive Lubricants
X-Ray Fluorecence
D4951 Additive Elements by Inductively Coupled Lubricants
Plasma–Atomic Emission Spectrometry
D4952 Active Sulfur Species (Doctor Test) Fuels and solvents
D5185 Multielements by Inductively Coupled Plasma– Used and fresh oils
Atomic Emission Spectrometry
(Continued)

Table 5.4 ASTM Test Methods for Sulfur in Petroleum Products and Lubricants
(Continued)
ASTM Test
D5303 Carbonyl Sulfide by Gas Chromatography Propylene

D5305 Ethyl Mercaptans LPG vapors
D5453 Sulfur by Combustion Ultraviolet Fluorescence Petroleum products
D5623 Sulfur by Gas Chromatography and Selective Light petroleum liquids
Detection
D5705 Hydrogen Sulfide in Vapor Phase Residual fuel oils
D6334 Sulfur by Wavelength-Dispersive X-Ray Gasoline
Fluorescence
D6443 Sulfur by Wavelength-Dispersive X-Ray Lube oils and additives
Fluorescence
D6445 Sulfur by Energy-Dispersive X-Ray Fluorescence Gasoline
D6667 Total Volatile Sulfur by Ultraviolet-Fluorescence Gaseous hydrocarbons and
LPG
D6920 Sulfur by Oxidative Combustion and Petroleum products
Electrochemical Detection
D7039 Sulfur by Monochromatic Wavelength-Dispersive Petroleum products
X-Ray Fluorescence
D7041 On-Line Gas Chromatography and Flame Petroleum products
Photometric Detection
D7111 Trace Elements by Inductively Coupled Middle distillate fuels
Plasma–Atomic Emission Spectrometry
D7183 Total Sulfur by Ultraviolet-Fluorescence Aromatic hydrocarbons
D7212 Energy-Dispersive X-Ray Fluorescence with Low Automotive fuels
Background Proportional Counter
D7220 Polarization X-Ray Fluorescence Spectrometry Automotive fuels
D7318 Total Inorganioc Sulfate by Potentiometry Fuel ethanol
D7319 Total and Potential Sulfate by Ion Fuel ethanol
Chromatography
D7328 Total and Potential Inorganic Sulfate by Ion Fuel ethanol
Chromatography
D7359 Total Sulfur by Ion Chromatography Aromatic hydrocarbons
D7620 Total Sulfur by Oxidation and Ultraviolet- Liquid hydrocarbons
Fluorescence
D7621 Hydrogen Sulfide by Rapid Liquid Phase Fuel oils
Extraction
D7751 Additive Elements by Energy-Dispersive X-Ray Lubricating oils
Fluorescence
LPG: liquefied petroleum gasoline.

Table 5.5 Analytical Techniques Used for Sulfur Determination in Petroleum Products
Analytical Technique ASTM Standard Test Method
Combustion–Chemical Analysis D129, D1266

Combustion–Infrared D1552
Combustion–UV-Fluorescence D5453, D6667, D7183, D7620
Combustion–Microcoulometry D3120, D3246
ICP-AES D4951, D5185, D7040, D7111
Ion Chromatography D7319, D7328, D7359
Gas Chromatography D5303, D5623, D7041
XRF–Energy Dispersive D4294, D6481, D7212, D7220
XRF–Wavelength Dispersive D2622, D4927, D6334, D6443, D7039
Other methods D1662, D2420, D2784, D3227, D3712, D4045,
D4952, D5305, D5705, D7318
UV: ultraviolet; ICP-AES: inductively coupled plasma–atomic emission spectrometry.
are several test methods that are used for identifying the sulfur species in these
materials, particularly crude oils (Table 5.5).
Each of these test methods is discussed below in terms of its applications, princi-
ple of analysis, and the test method precision and bias where available. For the sake of
convenience, the discussion is arranged in the order of the analytical techniques pre-
sented in Table 5.5.
In addition, there are several test methods for the determination of specific sulfur
compounds (Table 5.6). These are discussed at the end of this chapter.
Crude Oil
As the starting point of petroleum products and lubricants, the sulfur content of crude
oils is of great interest to the industry and to the regulators. The sulfur content varies
from less than 0.1 to over 5 mass %. Extensive data on the characteristics of crude oils
regarding sulfur content can be summarized as follows. Some typical data on the sul-
fur content of the world’s oil fields are given in Table 5.7.
Country Sulfur Characteristics
United States (Texas, Louisiana) Low metal, sulfur, and nitrogen content
United States (California) High metals, sulfur, and nitrogen content
Canada (Western) Medium-to-high sulfur and trace elements
Venezuela Medium-to-high sulfur
Colombia Low in sulfur and trace elements
Africa (Algeria, Libya, Nigeria, etc.) Low in sulfur and trace elements, high in nitrogen
Mid-East (Saudi Arabia, Iran, etc.) High in sulfur, moderate in trace elements
Indonesia Negligible trace elements
Source: [1].

Table 5.6 ASTM Test Methods for Sulfur Compounds in Petroleum Products
ASTM Test
Method Analysis Matrix

D2420 Hydrogen Sulfide by Lead Acetate Method LPG
D3227 Thiol Mercaptan Sulfur by Potentiometry Petroleum products
D3712 Oil-Soluble Petroleum Sulfonates by Liquid Chromatography Petroleum
D5303 Trace Carbonyl Sulfide by Gas Chromatography Propylene
D5305 Ethyl Mercaptan LPG vapors
D5623 Gas Chromatography and Sulfur-Selective Detection Light petroleum liquids
D5705 Hydrogen Sulfide in Vapor Phase Residual fuels
D7318 Inorganic Sulfate by Potentiometry Fuel ethanol
D7319 Total and Inorganic Sulfate by Ion Chromatography Fuel ethanol
D7328 Total and Potential Inorganic Sulfate by Ion Chromatography Fuel ethanol and butanol
D7621 Hydrogen Sulfide by Rapid Phase Liquid Extraction Fuel oils
LPG: liquefied petroleum gasoline.
Table 5.7 Sulfur Content of Crude Oils from the World’s Giant Oil Fields
Country Sulfur, mass % Country Sulfur, mass %
Abu Dhabi 0.62–0.777 Algeria 0.02–0.31

Canada 0.2–3.67 Colombia 0.25–1.11
Egypt 0.84–2.06 Indonesia 0.07–0.18
Iran 0.76–3.68 Iraq 1.36–2.1
Kuwait 1.82–2.58 Libya 0.13–1.04
Nigeria 0.10–0.26 Saudi Arabia 1.25–3.91
United States—Alaska N. Slope 1.07 United States—Arkansas 0.9–2.1
United States—California 0.2–1.2 United States—Louisiana 0.1–0.8
United States—Oklahoma 0.2–1.18 United States—Texas 0.1–2.4
United States—Wyoming 0.1–3.44
Source: [1].
Compared with high-sulfur Venezuelan Boscan crude oils, tar sands are also high
in their sulfur content [2]. Crude oils having a high sulfur content also usually have a
ratio of vanadium to nickel of greater than unity whereas for low-sulfur materials this
ratio is less than unity. See Table 5.8 for a comparison of Boscan crude oil with the same
parameters determined in various tar sands [3].

Table 5.8 Analysis of Various Tar Sand Bitumens [3]
Material V/Ni Ratio Sulfur, mass % Nitrogen, mass %
Boscan Crude Oil 1.1 2.5 —

Battle Creek, WY 3.5 5.7 0.6
Asphalt Ridge, UT 0.6 0.4 0.8
P. R. Spring. UT 0.6 0.6 1.3
Tar Sand Triangle, UT 3.2 4.5 0.6
Edna, CA 0.8 3.0 1.2
Santa Rosa, NM 1.2 2.3 0.2
Athabasca, Alta. 3.3 4.7 0.4
The determination of sulfur in crude oil is an integral part of the so-called crude
assay of oil because the sulfur concentration contributes to the complexity of the crude
oil refining step.
The sulfur content of a crude oil, which may vary from less than 0.1 to over 5 mass %,
is one of the most important quality attributes. Crude oils low in sulfur are labeled
“sweet” whereas those higher in sulfur are designated “sour.” The term derives mainly
from the foul or sour odor of one of the sulfur species, the mercaptans, as well as the
corrosiveness of hydrogen sulfide (H2S) and the mercaptans. The split between sweet
and sour was at 0.5 % when the average sulfur was much lower than today; now, the
crossover is more likely in the range of 0.5–1.5 % and is usually designated by each
refinery depending on its history and capability to process higher sulfur crude oils.
Barring the discovery of major low-sulfur crude oil deposits, it is expected that the
average sulfur will continue to modestly increase [4]. Sulfur compounds contribute to
the corrosion of refinery equipment and the poisoning of catalysts, cause corrosiveness
in refined products, and contribute to environmental pollution as a result of SOx
emission from the combustion of fuel products. Sulfur compounds may be present
throughout the boiling range of crude oils, although, as a rule, they are more abundant
in the heavier fractions. In some crude oils, thermally reactive sulfur compounds can
decompose on heating to produce H2S, which is very toxic and highly corrosive. Hence,
in reporting the H2S content of a crude oil, it is important to distinguish between that
which is dissolved and that which is evolved during heating or distillation. Butyl mer-
captan, a compound usually present in many crude oils, is the odorant commonly used
in natural gas [5].
Although inductively coupled plasma–atomic emission spectrometry (ICP-AES)
is not primarily used for the determination of sulfur in crude oils, it is used extensively
for the determination of many other elements [6]. Sulfur can be determined using the
emission wavelengths of 180.731, 182.04, or 182.62 nm. A new standard test method
for the multielement ICP-AES analysis of crude oil after dilution with an organic
solvent has been published as ASTM Standard D7691. This is based on a similar Test

Method D5185, which is widely used in the oil industry for the analysis of lubricating
oils, base oils, and used engine oils.
In this study, 18 crude oil samples including 3 ASTM Interlaboratory Crosscheck
Program (ILCP) crude oil samples and 3 National Institute of Standards and
Technology (NIST) reference materials were used. Twenty laboratories from seven
countries, including ten oil companies, four commercial, and three instrument vendor
laboratories, took part in this interlaboratory study (ILS). Nine of these laboratories did
not return the results. Each sample was analyzed in duplicate. The data were statistically
analyzed using ASTM D2PP software. Laboratories and samples with less than 20 %
data were removed a priori from consideration. Statistical outliers identified under
Cochran variances and Hawkins cells were rejected before calculating the final preci-
sion estimates. On the basis of this analysis, the average values ±1 standard deviation
obtained for these samples are given in Table 5.9. For NIST and ASTM ILCP crude oil
samples, the values assigned for these oils by these bodies are also listed in Table 5.9,
and they are in very good agreement with each other. All ASTM results were obtained
using the D2622 wavelength-dispersive X-ray fluorescence (WD-XRF) test method.
Table 5.9 Sulfur Determination in Crude Oils Using ICP-AES
Crude Oil Sulfur Found, mass %
#1: Venezuela 5.2891 ± 0.5348 (6)

#2: West Africa 491.1 ± 15.2 (8) mg/kg
#3: Central Asia 0.6668 ± 0.1148 (8)
#5: California 1.3274 ± 0.04353 (8)
#6: Argentina 0.5223 ± 0.02645 (8)
#7: Mexico 3.6960 ± 0.3227 (8)
#8: Southeast Asia 493.5 ± 21.4 (8) mg/kg
#9: North America 1.0199 ± 0.1767 (8)
#10: Brazil 1.8424 ± 0.1469 (6)
#11: China 0.2996 ± 0.04202 (8)
#12: West Africa 456.7 ± 28.7 (6) mg/kg
#13: NIST SRM 2721 Light Sour Texas NIST Value
1.6880 ± 0.0960 (4) 1.5832 ± 0.0044
#14: N
IST SRM 2722 Heavy Sweet Texas 0.21698 ± 0.00915 (5) 0.21037 ± 0.00084
#15: ASTM ILCP 0807 ASTM Value
2.6222 ± 0.2804 (8) 2.722±0.126 (17)
#16: ASTM ILCP 0811 0.9165 ± 0.0750 (8) 0.9319±0.0363 (22)
#17: ASTM ILCP 0903 0.4397 0.00974 (8) 0.4227±0.0152 (26)
#18: NIST RM 8505 Venezuela 2.6135 ± 0.3003 (8)
Note: Results are given as mean value ± standard deviation (number of valid results).

On the basis of this ILS, the pooled limit of quantitation (PLOQ) for sulfur deter-
mination was less than 457 mg/kg and the precision in the concentration range of
400–50,000 mg/kg was as follows:
Repeatability 0.01971X 1.1606

Reproducibility 0.06360X 1.1606
This translates into the following precision values at specific sulfur

concentrations:
400 20.6 66.6

1000 59.8 192.9
5000 387.0 1249
50,000 5601.6 18,075
This work has been documented in Reference 7, ASTM Test Method D7691-11, and
ASTM Research Report RR-D02-1760.
Crude Oil Reference Materials

To ensure that a laboratory is producing reliable and reproducible results, it is impor-
tant to include a sample of reference material of the same matrix as the samples. On the
basis of the certified values of such reference materials, the laboratory can satisfy itself
and its customers that the results are precise and accurate. There are some crude oil
certified reference materials (CRMs) commercially available. In addition, NIST cur-
rently provides two crude oil Standard Reference Materials (SRMs) that serve as the
definitive source of measurement traceability in the United States for the elements
certified. Both of these were included in the ILS mentioned earlier for an ICP-AES
method for trace elements.
SRM 2721 Light-Sour Crude Oil 1.5832 ± 0.0044 mass %

SRM 2722 Heavy-Sweet Crude Oil 0.21037±0.00084 mass %
Another source of reference materials is the residual quantities of crude oils from
the ASTM ILCP. Once the crosscheck is over, ASTM publishes the report of analysis
on the basis of the data from many laboratories. Unfortunately, only limited quantities
of these materials are available for a short period of time. They are more suited as
quality-control materials rather than as reference standards.
Mercaptans
H2S is a highly toxic and corrosive gas that occurs naturally in some crude oils. It can
be formed by thermal decomposition of elemental sulfur and thiols, and even crude

oils that do not naturally contain the compound may produce the gas on heating or
during distillation. Because H2S is highly volatile and reactive, strict procedures must
be observed in sample collection and handling to preserve their integrity before anal-
ysis. Samples having any headspace and not chilled will lose their H2S content in a
matter of days. Results for these samples undoubtedly provide a wide range of inaccu-
rate data and do not serve to validate the test procedures [8]. Thiols or mercaptans are
considerably more prevalent in crude oils than H2S. They are the least stable sulfur
compounds, and many decompose on heating to form H2S. Thiols may be distributed
across a wide boiling range. Free sulfur is known to occur in crude oils and it will also
decompose on heating to H2S [9].
Mercaptans in crude oils can be determined potentiometrically using ASTM Test
Method D3227 and its IP equivalent, Test Method 342. This test method can determine
mercaptan sulfur in gasolines, kerosines, aviation turbine fuels, and distillate fuels
containing from 0.0003 to 0.01 mass % of mercaptan sulfur. Elemental sulfur in
amounts less than 0.0005 mass % does not interfere. H2S will interfere if not removed.
In this test, the H2S-free sample is dissolved in an alcoholic sodium acetate titration
solvent and titrated potentiometrically with silver nitrate solution using as an indicator
the potential between a glass reference electrode and a silver/silver sulfide indicating
electrode. Under these conditions, the mercaptan sulfur is precipitated as silver
mercaptide, and the end point of the titration is shown by a large change in cell
potential. The repeatability and reproducibility of this procedure are estimated to be
0.00007 + 0.027X, and 0.00031 + 0.042X, respectively, where X is the average of
mercaptan sulfur in mass %.
Gasoline and Diesel

The natural progression in the analysis of petroleum products is from crude oil to
gasoline and diesel. These are the two products that are most significant in use and
in the number of test methods developed for them, particularly for their sulfur
content determination. Most of these test methods are discussed here with particu-
lar emphasis on XRF methods (D2622, D4294, and D7039 among others). Gasoline
has evolved continuously since it was first produced in quantities to meet the grow-
ing demand from the mass production of automobiles in the early 1900s. Since
then, it has become a carefully formulated mixture of hydrocarbons and additives,
seasonally blended to match local ambient conditions, providing good performance
and efficiency for a constantly changing vehicle fleet. More recently, gasoline has
been reformulated to reduce various emissions and minimize the effect of automo-
biles on urban air quality [10]. Gasoline is a complex mixture of relatively volatile
hydrocarbons that vary widely in their physical and chemical properties. It is a
blend of many hydrocarbons derived from the fractional distillation of crude petro-
leum and from complex refinery processes that increase either the amount or the
quality of gasoline. The hundreds of individual hydrocarbons in gasoline typically
range from those having just four carbon atoms to those having as many as eleven

carbon atoms. The types of hydrocarbons in gasoline are paraffins, isoparaffins,

naphthenes, olefins, and aromatics [11].
Among the inorganics present in gasoline are sulfur, nitrogen, and oxygen, which
are present in fuels at part-per-million levels. These can be present as ashless, combus-
tible additives. Sulfur levels are very much regulated and will be discussed later in this
chapter. There has recently been an ever-growing body of government regulations to
address concerns about the environment. The regulations aimed at the automobiles
have resulted in technologies that have significantly reduced vehicle emissions. Today
in the United States, nearly all automotive spark-ignition engine fuel contains
10 vol % ethanol. Some test methods do not contain gasoline-ethanol blends in their
scopes, and the precisions statements in such test methods may not be applicable to
gasoline-ethanol blends.
California’s Phase 2 reformulated gasoline specification limits the maximum sul-
fur content of the fuel to 30 ppm average with an 80-ppm cap. On December 31, 2003,
Phase 3 specifications lowered the sulfur maximum to 15 ppm average and the cap
limit to 60 ppm. The cap limits were further reduced to 30 ppm on December 31, 2005.
Federal Tier 2 regulations also have reduced the sulfur maximum levels allowed from
120 ppm in 2004 to 30 ppm average in 2006 with a cap limit of 80 ppm. With the
arrival of ultralow-sulfur diesels (ULSDs) in 2010, all earlier higher levels that were
allowed have expired [11].
Sulfur can cause wear in diesel engines as a result of the corrosiveness of its com-
bustion byproducts, and it can increase the amounts of deposits in the combustion
chamber and on the pistons. The sulfur content of a fuel depends on the origin of the
crude oil from which the fuel is made and on the refining methods used. Sulfur can be
present in several forms—as mercaptans, disulfides, or heterocyclic compounds such
as thiophenes—all of which affect wear and deposits.
Fuel sulfur tolerance by a diesel engine depends largely on whether the engine is
of the low- or high-speed type and the prevalent operating conditions. Low-speed engines
can tolerate more sulfur than their high-speed counterparts. High-sulfur fuels for diesel
engines are undesirable from a purely technical standpoint regardless of engine type [12].
The total sulfur content of aviation gasoline is limited to 0.05 mass % maximum
because most sulfur compounds have a deleterious effect on the antiknock effect of
alkyl lead compounds. If sulfur content were not limited, then specified antiknock
values would not be reached for highly leaded grades of aviation gasoline. Some sulfur
compounds can have a corroding action on the various metals in the engine system.
Effects vary according to the chemical type of the sulfur compound present. Elemental
sulfur and H2S are particularly implicated [13].
The refiners have struggled to settle on strategies that will provide flexible and
economical process investments to meet the government regulations for sulfur in
motor fuels. The U.S. federal gasoline sulfur limits are shown in the Federal Register
dated February 10, 2000, on pages 6824 and 6828, or see http://www.epa.gov/otaq/
standards/fuels.gas-sulfur.html. California Air Resources Board (CARB) regulations

are 15 ppm average starting in 2003, with various caps of 60, 30, and 20 ppm for 2003,
2004, and 2011, respectively. Diesel sulfur limits can be found at http://www.clean-diesel.
org/highway.html. As sulfur levels drop to unprecedented levels, what are the current
feasible measurement technologies for various refinery-of-the-future applications?
There are many test methods available, particularly for sulfur in fuel samples. An
intelligent choice must be made based on the precision and accuracy before deciding
which test method to use for a particular product. Because the test method precision is
often dependent on the sulfur concentration level and the product matrix, this can be
a critical decision for measurement and control managers. Arbitrarily using a test
method without these considerations can only result in producing data without much
reliability, which does not help in settling disputes in commercial transactions or in
regulatory affairs [9].
Nadkarni has reviewed the sulfur test methods for the analysis of gasolines and
diesels [9–17]. There are presently approximately four ASTM test methods that can
qualify for their usefulness at the expected low levels of sulfur in the future fuels. These
four techniques are D2622 WD-XRF, D3120 Microcoulometry, D5453 Ultraviolet-
Fluorescence, and D7039 MWD-XRF. Other than D3120, the other three test methods
are extensively used in the oil industry laboratories. All of these test methods are
described later in this chapter.
A BENCHMARK ASTM ILS [18]

In 1999 and 2002, EPA published requirements for the reduction of sulfur emissions of
future motor fuels—gasoline and diesel—and the test methods that would be required
to determine these low levels of sulfur [19,20]. In general, a modified version of D2622
was prescribed for the analysis of gasoline [19], and D6428 was prescribed for the anal-
ysis of diesel [20]. Alternative ASTM Test Methods such as D2622, D3120, or D5453
were allowed for diesel analysis if they were shown to be equivalent to the D6428 Test
Method [20]. Of this list of mandated test methods, oil industry laboratories had no
experience in using Test Method D6428. This method is written for the analysis of liq-
uid aromatic hydrocarbons as well as their derivatives and related chemicals and is
under the jurisdiction of ASTM Committee D16 on Aromatic Hydrocarbons and
Related Chemicals and not Committee D02 on Petroleum Products and Lubricants.
The precision quoted in D6428 was nonstatistically derived from a scant dataset.
Consequently, ASTM D02.SC 3 undertook the task of conducting a major ILS to com-
pare Test Methods D2622, D3120, D5453, and D6428 in terms of their precision and
applicability to gasoline and diesel samples.
There were a total of 16 samples each of gasoline and diesel obtained from a wide
variety of U.S. oil and allied companies. A total of 21 organizations supplied these
samples.
The samples included unleaded premium and regular gasolines, reformulated
gasolines, CARB Phase 2 gasolines, gasolines with methyl tert-butyl ether (MTBE),
diesels, CARB diesels, biodiesels, and NIST gasoline and diesel SRMs. They contained

varying levels of sulfur ranging from less than 1 to 100 mg/kg. A total of 56 laborato-
ries submitted the results on these samples. These included laboratories from the oil
industry, instrument vendor laboratories, and some commercial testing laboratories.
Overall, approximately 6000 data points were reported in this ILS. Each sample was
analyzed in duplicate by each of the participating laboratories. The statistical precision
was calculated using the D6300 protocol and ASTM D2PP software. The test method
correlations were calculated using the D6708 protocol.
Overall, it was found that the interlaboratory bias was a significant contributor
toward reproducibility (of course, this holds true for any analytical test method). The
correlation between the EPA-mandated method D6428 and the most widely used
industry method D5453 was as follows. Agreement between D6428 and D5453 can be
improved using relative bias correction (see Figs. 5.1–5.4).
• Predicted D6428 = 1.10 (D5453) – 0.9 for gasoline

• Predicted D6428 = 0.937 (D5453) for diesel
The proposed Test Method D6428 was found to have an interference from nitro-
gen present in the fuel samples. It appears that the adverse nitrogen effect is dependent
on the nitrogen-to-sulfur concentration ratio; the higher this number, the more severe
the negative bias. Later, the two vendors of D6428 instruments proposed an accessory
Fig. 5.1 Repeatability of Test Methods for Sulfur at 30 ppm in Gasoline.

Fig. 5.2 Reproducibility of Test Methods for Sulfur at 30 ppm in Gasoline.
Fig. 5.3 Repeatability of Test Methods for Sulfur at 15 ppm in Diesel.

Fig. 5.4 Reproducibility of Test Methods for Sulfur at 15 ppm in Diesel.
“gas converter” that can be used to reduce or eliminate this nitrogen interference in

Test Method D6428.
The sulfur repeatability and reproducibility for gasoline and the repeatability and
reproducibility for diesel obtained by these four test methods are illustrated by bar
charts in Figs. 5.1–5.4. The overall conclusions from this study were as follows:
• The PLOQ for the D2622 XRF method was the poorest among the four methods
tested. It was between 1 and 5 mg/kg for the other three methods.
• No significant difference was observed in the D2622 method precision obtained
using low- (i.e., <1 kW power) or high-powered XRF units.
• There was no dramatic difference between the conclusions that were based on this
study and a similar one conducted in Europe by CEN.
• Among the four test methods, D6428 had the poorest precision in terms of repeat-
ability and reproducibility in gasoline and diesel at sulfur levels of compliance
interest (Figs. 5.5–5.8).
• Test Method D6428 may not be precise enough for regulatory compliance at pro-
posed sulfur limits:
R gasoline = 30 ± 23 mg/kg
R diesel = 15 ± 16 mg/kg

Fig. 5.5 Relative Bias assessment of D5453 (X-method) vs. D6428-APS (Y-method)

for gasoline.
Fig. 5.6 Relative Bias assessment of D5453 (X-method) vs. D6428-APS (Y-method)

for diesel.

Fig. 5.7 Cross-Method Reproducibility.
Fig. 5.8 Cross-Method Reproducibility.

• None of the four methods could reproduce alleged ultralow-sulfur levels in samples
with certificates of analyses of less than 1 to 2 mg/kg (Table 5.10).
• There was no bias for NIST diesel SRMs. For gasoline samples, all three methods
had a bias at the 5-mg/kg level, and only D5453 has at an 11-mg/kg level.
A new standard, D6920, which is equivalent to D6428, was issued by the D02
Committee. The precision values of these test methods on the basis of this ILS are
presented in Table 5.11. These test methods were revised to reflect these new precision
estimates.
The results of this study summarized in Table 5.12 clearly showed that the man-
dated D6428 (and its D02 equivalent, D6920) was least precise in the repeatability and
Table 5.10 Precision at Sulfur Levels in Future Motor Fuels
Gasoline at 30 mg/kg Diesel at 15 mg/kg
Test Method Precision Current ILS Current ILS
D2622 r 7.4 3.77 5.7 NA

R 10.6 7.42 8.2 NA
D3120 r 8.4 3.85 4.2 1.33
R 11.4 17.7 5.7 8.07
D5453 r 1.59 1.95 1.03 1.20
R 5.07 11.7 2.68 6.26
D6428 r 4.72 6.26 3.06
R 22.8 15.6
NA: not applicable.
Table 5.11 Precisions for Test Methods Used in the ILS
Test Method Repeatability Reproducibility
D2622 (Gasoline) 0.02438 (X + 124.69) 0.04795 (X + 124.69)

D2622 (Diesel) NA NA
D3120 (Gasoline) 0.03194 (X + 7.4502) 1.3226
0.1470 (X + 7.4502)1.3226
D3120 (Diesel) 0.08520 (X + 0.65758) 0.5152 (X + 0.6758)
D5453 (Gasoline) 0.04356 (X + 14.844) 0.3170 (X + 6.8847)
D5453 (Diesel) 0.02777 (X + 28.158) 0.3659 (X + 2.1101)
D6428 (Gasoline) 0.3395 X0.7739 1.6384 X0.7739
D6428 (Diesel) 0.1960 (X + 0.61789) 1.3028 (X + 0.61789)0.9022
NA: not applicable.

Note: The concentration ranges of gasoline samples is 1–100 mg/kg sulfur and of diesel samples is
1–40 mg/kg sulfur.

Table 5.12 Methods for Analysis of Ultralow-Sulfur Fuels of the Future
30 mg/kg Gasoline 15 mg/kg Diesel

ASTM Test
Method Technique Sulfur Range r R r R
D2622 WD-XRF 3 mg/kg to 5.3 mass % 3.8 7.4 3.4 6.7

D3120 Microcoulometry 3–100 mg/kg 3.85 17.7 1.33 8.07
D5453 UV-fluorescence 1–800 mg/kg 1.95 11.7 1.20 6.26
D6920 Electrochemical 1–100 mg/kg 4.7 22.8 3.1 15.6
UV: ultraviolet.
reproducibility for gasoline and diesel at the sulfur levels of compliance interest and
was not useful for the precise determination of low levels of sulfur in the fuels of the
future. See Chapter 9 on proficiency testing programs in this monograph for further
discussion of the performance of alternative test methods for sulfur determination in
ULSD samples.
On the basis of the results of this historic study, EPA eventually withdrew the
requirement for use of the mandatory D6428 Test Method and allowed the industry
laboratories to use any of the alternative ASTM Test Methods if they are shown to be
adequate for compliance levels.
Among the many test methods available for sulfur determination, EPA had his-
torically designated specific test methods required for fuel certification. Only a few
alternative test methods were allowed as long as they were correlated to the designated
method. EPA allows any test method to be used for downstream quality assurance as
long as the method is correlated with the designated method. Since then, EPA adopted
a performance-based measurement system (PBMS) approach. There is no longer a
designated test method for ULSD analysis. Any voluntary consensus standardization
body (VCSB) or non-VCSB method that meets the specified accuracy and precision
criteria can be used. The requirements also include an ongoing laboratory quality-
control criterion (based on ASTM D6299). A laboratory has to qualify each individual
test method it wants to use on a laboratory-specific basis. This PBMS approach allows
for greater flexibility in instrument selection and encourages the development and use
of better instrumentation [21].
The qualification criteria for a test method to be approved include 20 replicate
tests over 20 days on samples taken from a single commercially available diesel fuel.
The standard deviation of these analyses must be less than 0.72 mg/kg for 15-mg/kg
sulfur diesel fuel and 9.68 mg/kg for 500-mg/kg sulfur diesel fuel. Two continuous
series of ten repeat tests on two commercially available gravimetric sulfur standards
need to be conducted. The mean of these test results may not deviate from the
accepted reference value of the standard by more than 0.54 mg/kg for 15-mg/kg sul-
fur and 7.26 mg/kg for 500-mg/kg sulfur diesel fuels. Ten tests are required on each

of two sulfur levels as follows: (1) 1–10 and 10–20 mg/kg for 15-mg/kg sulfur diesel
fuel, and (2) 100–200 and 400–500 mg/kg for 500-mg/kg sulfur diesel fuel. EPA
allows for a downstream enforcement tolerance of only 2 mg/kg, which is intended to
encompass all laboratory-to-laboratory variability. Pipelines may require a 6- to
8-mg/kg point of origin specification. Thus, it is critical that individual laboratories
perform to the best of their ability by using best practices, of which the proper test
method procedure is an important part. Another important parameter is the use of
reliable calibration standards. Possible reasons for laboratory-specific bias could be
due to improper use of standards. They should not be outside of the range of analysis,
they should not have aged, and they should be the correct standard with respect to
matrix effects [21].
EPA also spelled out the quality-control provisions during the course of this
sulfur testing [40 CFR 80.585(e)]. The laboratories are asked to abide by the mandatory
provisions of D6299 standard practice. Laboratories would be required to construct
quality-control charts using a designated quality-control sample. Check standards
using a reference material must be analyzed at least monthly or after a major change in
laboratory equipment or test procedure. Upon discovery of a quality-control testing
violation, the retained samples must be retested.
At the time of this EPA promulgation, most refinery laboratories did not have
much experience in measuring fuel sulfur at 15 ppm or less. The ASTM ULSD ILCP
established in January 2004 gave participants an opportunity to gain experience
measuring diesel sulfur at these very low levels. This was and is a monthly program.
Approximately 150 laboratories are currently participating, some using multiple
analysis techniques. The most dominant test methods used by the participants are
D2622 (WD-XRF), D5453 (Ultraviolet-fluorescence), and D7039 (monochromatic
wavelength-dispersive X-ray fluorescence [MWD-XRF]). On a monthly basis, the
average number of laboratories using these techniques varies around 90, 230, and 120,
respectively. Currently, the mean sulfur levels in ULS D fuels are approximately 5 ppm
or less.
In a very thorough research study done at the Southwest Research Institute
(SWRI) in San Antonio, TX, three sulfur test methods were compared for fitness for
use [22]. The three test methods studied were D2622 WD-XRF spectrometry, D4294
energy-dispersive X-ray fluorescence (ED-XRF) spectrometry, and D5453 combustion-
ultraviolet (UV) fluorescence for the analysis of fuels at less than 500 mg/kg sulfur
concentrations. All three test methods were found to be equivalent for measurements
in the range of 150–500 mg/kg. D5453 and D2622 demonstrated equivalent fitness for
use down to 20 mg/kg sulfur. Strong evidence was found that the D5453 Test Method
can be fit for use in multilaboratory situations down to the 1-mg/kg sulfur level. A
single isooctane matrix was used to minimize the well-known carbon-to-hydrogen
ratio interferences in the XRF test methods. All three test methods were then evaluated

for any bias with respect to 24 commonly occurring organosulfur compounds. No bias
was found, and the accuracy was within the precision limits for each of the test meth-
ods. Of these three test methods, the best low-level precision and accuracy were found
in Test Methods D2622 and D5453. Of these two, D5453 was found to generate better
data in the low (<50 mg/kg) sulfur regime. This work suggests that the D5453 Test
Method can be routinely used for the determination of sulfur in liquid hydrocarbons
at levels below 1 mg/kg.
In another very large round-robin study done in Europe, 69 laboratories from
9 countries participated in the determination of sulfur at levels between 5.0 and
500 mg/kg in 8 gasoline and 7 diesel samples [23]. Five test methods were principally
tested:
1. WD-XRF ISO 14596 D2622

2. ED-XRF IP/PM CX/00 D4294
3. UV-Fluorescence MO7-059 D5453
4. Microcoulometry ISO CD 16591 D3120
5. Wickbold Combustion EN 24260 D1266
At these levels, all five test methods were found to produce essentially equivalent
results, but the precision of different methods varied considerably (Table 5.13) The best
reproducibility was obtained for the WD-XRF and UV-fluorescence methods. Table 5.14
compares the reproducibility obtained in this crosscheck with those suggested in their
equivalent ASTM Test Methods. The best reproducibility appears to be those of the
Table 5.13 Precision Obtained in CEN Round-Robin Study
Material Test Method Repeatability Reproducibility
Gasoline WD-XRF 0.048X + 0.0002 0.147X + 0.0003

ED-XRF NA 0.0838X + 0.002
UV-Fluorescence 0.0417X + 0.0001 0.1573X + 0.0002
Microcoulometry 0.043X + 0.0003 0.1679X + 0.0008
Wickbold NA NA
Diesel WD-XRF 0.0293X + 0.0003 0.0725X + 0.0005
ED-XRF NA 0.0289X + 0.0016
UV-Fluorescence 0.0285X + 0.0002 0.1088X + 0.0002
Microcoulometry 0.043X + 0.0003 0.1679X + 0.0008
Wickbold NA NA
NA: not applicable.

Note: X is the average value of two results.

Table 5.14 Comparison of CEC and ASTM Reproducibility of Test Methods for Sulfur
Test Method CEN ILS Reproducibility ASTM Test Method Reproducibility
WD-XRF 10 12.8 (D2622)

ED-XRF 37 74 (D4294)
UV-Fluorescence 10 8.1 (D5453)
Microcoulometry 16 19 (D3120)
Wickbold 17 101 (D1266)
Note: All precision estimates are at 50 mg/kg sulfur in gasoline.
D2622 and D5453 Test Methods. As an outcome of this European round-robin study, it
was proposed that the Wickbold and ED-XRF methods be dropped from further con-
sideration for analyzing fuels at the 30-mg/kg level in the future. Only the
UV-fluorescence method was considered suitable for the determination of sulfur at
less than the 10-mg/kg concentration required in future European fuels.
Combustion—Chemical Analysis Methods
D129: Sulfur in Petroleum Products by High-Pressure Decomposition

This was the first test method for sulfur determination in petroleum products issued
by the ASTM D02 Committee in 1922. It is mainly used for high levels of sulfur in the
samples. It is applicable to petroleum products including lubricating oils containing
additives, additive concentrates, and lubricating greases that cannot be burned com-
pletely in a wick lamp. The test method is applicable to any petroleum product suffi-
ciently low in volatility that it can be weighed accurately in an open sample boat and
containing at least 0.1 mass % sulfur.
This test method is not applicable to samples containing elements that give
residues (other than barium sulfate) that are insoluble in dilute hydrochloric acid
and would interfere in the precipitation step. These interfering elements include
iron, aluminum, calcium, silicon, and lead, which are sometimes present in
greases, lube oil additives, or additive oils. Other acid insoluble materials that
interfere are silica, molybdenum disulfide, asbestos, mica, etc. The test method is
not applicable to used oils containing wear metals and lead or silicates from con-
tamination. The types of sample that are excluded here can be analyzed using Test
Method D1552 .
In this test method, a sample is oxidized by combustion in a high-pressure
decomposition device containing oxygen under pressure. To aid the combustion, a
small portion of white oil is added to the combustion boat. The sulfur, as sulfate in the
high-pressure decomposition device washings, is determined gravimetrically as bar-
ium sulfate. On the basis of an ILS that was conducted (RR-D02-1278), the following
precision values were obtained.

Sulfur, mass % Repeatability Reproducibility
0.1–0.5 0.04 0.05

0.5–1.0 0.06 0.09
1.0–1.5 0.08 0.15
1.5–2.0 0.12 0.25
2.0–2.5 0.18 0.27
D1266: Sulfur in Petroleum Products by the Lamp Method

This test method covers the determination of total sulfur in liquid petroleum products
in concentrations from 0.01 to 0.4 mass %. A modification of the basic procedure can
determine sulfur at concentrations as low as 5 mg/kg. The comparable lamp method
for the determination of sulfur in liquefied petroleum gasoline (LPG) is ASTM D2784.
For the determination of sulfur in heavier petroleum products that cannot be burnt in
a lamp, the pressure decomposition method, D129; the quartz tube method, IP 63; or
the high-temperature method, D1552, can be used.
The direct burning procedure is applicable to the analysis of such materials as
gasoline, kerosine, naphtha, and other liquids that can be burned completely in a wick
lamp. The blending procedure is applicable to the analysis of gas oils and distillate fuel
oils, naphthenic acids, alkyl phenols, high-sulfur-content petroleum products, and
many other materials that cannot be burned satisfactorily by the direct burning
procedure.
Phosphorus compounds normally present in commercial gasoline do not inter-
fere. A correction is given for the small amount of acid resulting from the combustion
of the lead antiknock fluids in gasoline. Appreciable concentrations of acid-forming or
base-forming elements from other sources interfere when the titration procedure is
used because no correction is provided in these cases.
In this test method, a sample is burned in a closed system using a suitable lamp
(Figs. 5.9 and 5.10) and an artificial atmosphere composed of 70 % carbon dioxide and
30 % oxygen to prevent formation of nitrogen oxides. The resultant oxides of sulfur are
absorbed and oxidized to sulfuric acid by means of hydrogen peroxide solution, which
is then flushed with air to remove dissolved carbon dioxide. Sulfur as sulfate in the
absorbent is determined acidimetrically by titration with standard NaOH solution or
gravimetrically by precipitation as BaSO4. Alternatively, the sample may be burned in
air, the sulfur as sulfate in the absorbent being determined by precipitation as BaSO4
for weighing. In the absence of acid-forming or base-forming elements, other than
sulfur, results by the volumetric and gravimetric finishes are equivalent within the
limits of precision of the method. For sulfur contents below 0.01 mass %, it is necessary
to turbidimetrically determine the sulfate content in the absorber solution as BaSO4.
The precision of this test method is given as a repeatability of 0.005 and a repro-
ducibility of 0.010 + 0.025X, where X is the sulfur content in mass %. When using the
turbidimetric method for trace amounts of sulfur, the following precision is expected.

Fig. 5.9 Schematics of Lamp Unit in Test Method D1266 for Sulfur.
Fig. 5.10 Schematics of CO2 Supply Manifold and Lamp System in Test Method D1266
for Sulfur.

Sulfur content, mg/kg Repeatability Reproducibility
5–80 0.116X
5–125 0.145X
>80 to 280 0.01X + 8.5
>125 to 280 0.508X – 45.4
Note: Where X is the sulfur concentration in mg/kg.
D1552: Sulfur in Petroleum Products by the High-Temperature Method

This test method covers three procedures for the determination of total sulfur in
petroleum products including lubricating oils containing additives as well as
additive concentrates. This test method is applicable to liquids boiling above 177°C
and containing not less than 0.06 mass % sulfur. Petroleum coke containing up to
8 mass % sulfur can be analyzed by this method. Two of three procedures use
iodate detection, one using an induction furnace and the other a resistance furnace.
The third procedure uses infrared (IR) detection after pyrolysis in a resistance
furnace.
• The sample is burned in a stream of oxygen at a sufficiently high temperature to

convert approximately 97 % of the sulfur to sulfur dioxide (SO2). A standardization
factor is used to obtain accurate results. The combustion products are passed into
an absorber containing an acid solution of potassium iodide (KI) and starch indicator.
A faint blue color is developed in the absorber solution by the addition of standard
potassium iodate solution. As the combustion proceeds, bleaching the blue color,
more iodate is added. The amount of standard iodate consumed during the com-
bustion is a measure of the sulfur content of the sample.
• The sample is weighed into a special ceramic boat, which is then placed into a
combustion furnace at 1371°C in an oxygen atmosphere. Most sulfur present is
combusted to SO2, which is then measured with an IR detector after moisture and
dust are removed by traps. A microprocessor calculates the mass percentage of
sulfur from the sample weight, the integrated detector signal, and a predetermined
calibration factor. The calibration factor is determined using standards approxi-
mating the material to be analyzed.
Figure 5.11 illustrates the combustion tube used and Figs. 5.12 and 5.13 show the sche-
matic diagrams of induction type and resistance type furnaces, respectively.
For the iodate systems, chlorine in concentrations less than 1 mass % does not
interfere. The IR system can tolerate somewhat higher concentrations. Nitrogen when
present in excess of 0.1 mass % may interfere with the iodate systems; the extent of such
interference may be dependent on the type of nitrogen compound as well as the com-
bustion conditions. Nitrogen does not interfere with the IR system. The alkali and alkaline
earth metals, as well as zinc, phosphorus, and lead, do not interfere with either system.

Fig. 5.11 Combustion Tube Used in Test Method D1552 for Sulfur.
Fig. 5.12 Schematics of Induction Furnace Used in Test Method D1552 for Sulfur.
On the basis of an ILS (RR-D02-1231), the precision values presented in Table 5.15
were obtained for the analysis of petroleum products and petroleum coke by iodate
and IR methods.
The bias of this test method has not been determined.

Fig. 5.13 Schematics of Resistance Furnace Used in Test Method D1552 for Sulfur.
D6920: Sulfur in Petroleum Products by Oxidative Combustion and

At one time this test method was under the jurisdiction of ASTM Committee 16 on
Aromatic Hydrocarbons and designated as Test Method D6428. EPA designated it as
the method of choice for determining low levels of sulfur in gasoline and diesel [U. S.
Federal Register 80.520(a)(1) Vol. 68, No. 100]. After concerted efforts by the oil
industry proving that this test method was the least precise among the test methods
available for sulfur determination, EPA withdrew its approval. See a detailed discus-
sion about this issue under the section A Benchmark ILS of this chapter.
This test method covers the determination of total sulfur in liquid hydrocarbons,
boiling in the range from approximately 25 to 400°C, with viscosities between
Table 5.15 Precision of Test Method D1552 for Petroleum Products
Repeatability Reproducibility
Sulfur Range, mass % Iodate IR Iodate IR
0.0–0.5 0.05 0.04 0.08 0.13

0.5–1.0 0.07 0.07 0.11 0.21
1.0–2.0 0.10 0.09 0.17 0.27
2.0–3.0 0.16 0.12 0.26 0.38
3.0–4.0 0.22 0.13 0.40 0.44
4.0–5.0 0.24 0.16 0.54 0.49
Petroleum coke 0.05X 0.22X
Note: X is the average of two test results.

approximately 0.2 and 10 cSt at room temperature. The test method is applicable to
naphthas, distillates, and motor fuels such as gasolines, reformulated gasolines, gaso-
hols, diesels, and biodiesels containing approximately 1–100 mg/kg total sulfur in
gasoline-type products and approximately 1–40 mg/kg sulfur in diesel-type products.
On the basis of an ILS, the PLOQ of this test method is 3 mg/kg for gasoline and less
than 0.5 mg/kg for diesel samples.
In this test method, the sample is injected at a controlled rate into a stream of
inert gas (helium or argon) or inert gas mixed with oxygen. The sample is vapor-
ized and carried into a high-temperature zone (>900°C) where oxygen is intro-
duced. Sulfur compounds, present in the test specimen, are converted to SO2,
which is reacted with the sensing electrode in a three-electrode electrochemical
cell. This reaction produces a measurable current that is directly proportional to
the amount of sulfur in the original sample material. The reactions that occur are
as follows:
Combustion at >900°C: R-S + O2  CO2 + H2 O + SO2 + oxides (5.1)
Detection: SO2 + 2H2O  H2SO4 + 2 H+ + 2e– (5.2)
Virtually all sulfur compounds will be detected by this technique. The detector
response for this technique within the scope of this test method is linear with sulfur
concentration. Moisture produced during the combustion step can interfere if not
removed before the detector. Equivalent amounts of nitrogen in the sample may also
interfere. Dibenzothiophene (C12H8S; CAS# 132650) is used as the sulfur calibrant in
this technique.
The precision and bias based on an ILS including 16 laboratories each analyzing
16 gasoline and diesel samples each in duplicate (RR-D02-1547) were found to be as
follows:
Gasoline Diesel
Total sulfur, mg/kg 3–100 1–40

Repeatability 0.3395X0.7739 0.1960 (X + 0.61789)0.9022
1.3028 (X + 0.61789)0.9022
Bias None None
Note: Where X is the average of two results in mg/kg.
Two instrument brands were used in this ILS: one from APS Technologies and
the other from Antek Instruments. Because the two sets of results were statistically
different from each other, precision statements were prepared for each type of
instrument.

Instrument
Brand Fuel Repeatability Reproducibility
APS Gasoline 0.2395X 0.5242

2.2331X0.5242
Diesel 0.002246 (X + 160.55) 0.6128(X + 3.6168)
Antek Gasoline 0.3302(X + 0.0001)0.8743 0.1826(X + 1.3086)
Diesel 0.1826(X + 1.3086) 0.7642(X + 3.2734)
On the basis of the analysis of NIST SRMs, there was no significant bias for the
test method on either instrument between the results by this test method and the
certified values by NIST for diesel SRM 2723a. For gasoline SRM 2299 containing
13.6 mg/kg sulfur there was no bias; however, for gasoline SRM 2298 containing
4.6 mg/kg total sulfur, there was a bias of –0.78 mg/kg for the test method on both
of the instruments.
On the basis of this pyroelectrochemical detection, an online ultralow sulfur
analyzer has been proposed [24]. The sensor is a small, low-cost, plug-in component,
leading to a greatly simplified detection subsystem compared with those of other
techniques. Nitrogen interference has been eliminated. It is claimed that the sensitivity,
repeatability, stability, linearity, and speed of response are equal to or better than those
of other online ULSD analyzers.
Combustion—Ion Chromatographic Methods
D7359: Total Sulfur in Aromatic Hydrocarbons by Oxidative

Pyrophydrolytic Combustion Followed by Ion Chromatography Detection
This test method covers the individual determinations of total fluorine, chloride, and
sulfur in aromatic hydrocarbons and their mixtures. Samples containing 0.1–50 mg/kg
of each element can be determined. It may also be possible to determine the elements
outside of this range by appropriate dilutions of the samples.
In this test method, a sample of known weight or volume is placed into a sample
boat and introduced at a controlled rate into a high-temperature combustion tube. The
sample is combusted in an oxygen-rich pyrohydrolytic environment. The gaseous
byproducts of the combusted sample are trapped in an absorption medium where the
hydrogen halides (HX) formed during combustion dissociate into their respective
ions, X–, whereas the SOx formed are further oxidized to sulfate (SO42–) in the presence
of an oxidizing agent. An aliquot of known volume of the absorbing solution is then
automatically injected into an ion chromatograph by means of a sample injection
valve. The halides (fluoride, chloride, and iodide) and SO42– are separated into individ-
ual elution bands on the separator column of the ion chromatograph. The conductivity
of the eluent is reduced with an anion suppressor device before the ion chromatograph’s
thermal conductivity detector, where the anions of interest are measured.
Substances that coelute with the anions of interest will interfere. A high concen-
tration of one anion can interfere with other constituents if their retention times are
close enough to affect the resolution of their peaks.

A ruggedness study was conducted by analyzing 3 toluene samples of 10 replicates

each and 1 toluene sample with 33 replicates over a 2-day period. The data for sulfur
are summarized below. No reproducibility has yet been determined. Because there is
no accepted reference material available for this analysis, bias cannot be determined.
Replicates Toluene Sample Expected Level, mg/kg Sulfur Found Average, mg/kg Repeatability
10 ~ 0.791 0.788 0.058
10 ~ 0.395 0.453 0.014

10 – 0.060 0.009
33 ~ 58 59.3 2.0
Combustion—Oxidative Microcoulometry Methods
D3120: Trace Quantities of Sulfur in Light Liquid Petroleum

Hydrocarbons by Oxidative Microcoulometry
This test method covers the determination of sulfur in the range from 3.0 to 1000 mg/kg
in light liquid hydrocarbons and fuels with oxygenates boiling in the range from 26 to
274°C. Other materials falling within the above stated distillation range but having
sulfur concentrations above 1000 mg/kg may be tested using appropriate dilutions to
bring them within the specified limit. In addition, sample types that may be outside of
the specified distillation range, such as diesels and biodiesels, may be analyzed by this
test method.
Preliminary data have shown that this test method is also applicable to the
determination of sulfur in denatured fuel ethanol (ASTM Specification D4806),
automotive spark-ignition engine fuel (ASTM Specification D4814), Ed75–Ed85
(ASTM Specification D5798), or gasoline-oxygenate fuel blends with greater than
10 % ethanol. However, the precision of analysis of such materials has not yet been
determined.
In this test method, a liquid sample is introduced into a pyrolysis tube maintained
at a temperature between 900 and 1200°C, having a flowing stream of gas containing
50–80 % oxygen and 20–50 % inert gas such as argon, helium, etc. Oxidative pyrolysis
converts the sulfur to SOx, which then flows into a titration cell where it reacts with the
triodide ion present in the electrolyte. The triodide ion consumed is coulometrically
replaced, and the total current required to replace it is a measure of the sulfur present
in the sample. The reaction occurring in the titration cell as SO2 enters is
I3 + SO–2 + H2O  SO3 + 3I– + 2 H+ (5.3)
The triodide ion consumed in the above reaction is generated coulometrically per this
equation:
3 I–  I3 + 2e– (5.4)

These microequivalents of triodide ion are equal to the number of microequivalents of

titratable SO2 ion entering the titration cell.
This test method is applicable in the presence of total halide concentrations of up
to 10 times the sulfur level and total nitrogen concentrations of up to 1000 times the
sulfur level. Stringent techniques should be applied to eliminate all possible sources of
sulfur contamination to attain the quantitative detectability capable with this test
method. This test method is not applicable in the presence of total heavy metal (e.g., Ni,
V, Pb, etc.) concentrations in excess of 500 mg/kg.
The configuration of the pyrolysis tube and furnace may be constructed as
is desirable as long as the operating parameters are met. Fig. 5.14 is typical of an
apparatus currently in use. A typical assembly and oxidative gas f low through
a coulometric apparatus for the determination of trace sulfur is shown in Fig. 5.15.
Dibenzothiophene, n-butyl sulfide, or thionaphthene (benzothiophene) diluted in
toluene, xylene, or isooctane can be used as the sulfur calibration standards. The
concentration ranges used for calibration solutions are 10, 50, and 500 µg/mL.
A correction for chemical impurity can be applied to the standards solutions if
deemed necessary. Not all of the sulfur in the sample exits the oxidation zone of
the furnace as titratable SO2 . In the strongly oxidative conditions of the pyroly-
sis tube, some of the sulfur is also converted to sulfur trioxide (SO3), which does
not react with the titrant. Accordingly, sulfur standards appropriate to the sam-
ple’s boiling range and sulfur type are recommended to guarantee adequate
calibration. Recoveries less than 75 % are to be considered suspect. In such
cases, it is recommended that the operator check that the coulometric system,
measuring parameters, and operating techniques are in proper order. If the
apparatus is being operated properly, then recoveries between 75 and 90 % are to
be expected.
Fig. 5.14 Pyrolysis Tube Used in Test Method D3120 for Sulfur.

Fig. 5.15 Schematics of Coulometric Apparatus Used in Test Method D3230 for Sulfur.
On the basis of two separate ILS, the precisions and bias values presented in
Table 5.16 were found for this test method. These studies are documented in ASTM
Research Reports RR-D02-1036, RR-D02-1546, and RR-D02-1547.
Three NIST SRMs were analyzed to determine the bias. Gasoline SRMs 2298
(1.6 µg/g sulfur) and 2299 (13.6 µg/g sulfur) and diesel SRM 2723a (10 µg/g sulfur) were
used. There was no significant bias for SRMs 2299 and 2723a. However, there was a
bias of –1.25 for SRM 2298.
D3246: Sulfur in Petroleum Gas by Oxidative Microcoulometry

This test method is based on the same principle as Test Method D3120 described
above. This method is applicable in the sulfur range from 1.5 to 100 mg/kg in
hydrocarbon products that are gaseous at normal room temperature and pressure.
The principle of analysis technique, the calibrants used, interferences, and the
instrument operating parameters are similar to those described in Test Method
Table 5.16 Precision of Coulometric Method D3120 for Sulfur Determination
Study PLOQ Repeatability Reproducibility
RR-D02-1036 0.2802X 0.7901

0.5793X0.7901
RR-D02-1546 Gasoline: 3 ppm Gasoline: 0.03194 (X + 7.4502)1.3226 Gasoline: 0.1470 (X + 7.4502)1.3226
and Diesel: 5 ppm Diesel: 0.08520 (X + 0.65758) Diesel: 0.5152 (X + 0.65758)
RR-D02-1547
Note: X is the average of duplicate results in µg/g.

D3120 above. The precision of this test method has only been studied for high-purity
ethylene gas. At the 0- to 10-mg/kg sulfur level, the repeatability was found to be 0.4
mg/kg, and reproducibility was found to be 5 mg/kg. The precision and bias have
not been developed for other products.
D4045: Combustion—Hydrogeneolysis-Rateometric Colorimetry

This test method is based on the work developed by Drushel [25] and is similar to
ASTM Test Method D4468 described later for the determination of H2S in gaseous
fuels. This test method covers the range of sulfur from 0.02 to 10 mg/kg. It can be
extended to higher concentration by dilution of the sample. It is applicable to liq-
uids for which the boiling points are between 30 and 371°C. Materials that can be
analyzed include naphtha, kerosine, alcohol, steam condensate, various distillates,
jet fuel, benzene, and toluene. A liquid sample is injected at a constant rate into a
flowing hydrogen stream in a hydrogeneolysis apparatus (Fig. 5.16), The sample
and hydrogen are pyrolyzed at a temperature of 1300°C, or above, to convert sulfur
compounds to H2S. Readout is by the rateometric detection of the colorimetric
reaction of H2S with lead acetate (Fig. 5.17). Condensable components are con-
verted to gaseous products, such as methane, during hydrogeneolysis. Di-n-butyl
sulfide is used as the calibrant. Per an ILS conducted (RR-D02-1405), the following
Fig. 5.16 Flow Diagram of Hydrogeneolysis in Test Method D4045 for Sulfur.
DISPOSABLE CERAMIC
OR QUARTZ REACTION
TUBE
BALSTON CONTROLLED RATE SYRINGE
DFU FILTER INJECTION OF LIQUID
SEPTUM
OR GAS SAMPLE
GAS SAMPLE
TO 825R FOR
TOTAL SULFUR
READOUT
PYROLYZER®
HUMIDIFIER
GAS WASH BOTTLE
250 ml APPROX.
DISTILLED WATER
PURGE H2
CARRIER H2
Note: The humidifier gas wash bottle is optional.

Fig. 5.17 Photorateometric H2S Readout of Test Method D4045 for Sulfur.
precision for this test method has been found. The bias of this method is not
known.
Repeatability 0.16 X0.5

Reproducibility 0.26 X0.5
Where X is the average value of two results in mg/kg.

To prevent the adsorption impediment of H2S in the trace sulfur analyzer using
this method, a specially prepared pure ceramic tube has been developed to be the only
usable reactor for the hydrogeneolysis procedure. However, a conventional ceramic
tube becomes usable by inhibiting the H2S adsorption on the basic impurities by a
substitute adsorption of carbon dioxide that can be introduced continually with
hydrogen in the ceramic reactor. When the oxyhydro procedure was applied to reduce
the carbon deposit in the analysis of kerosine, a large overestimation error occurred in
the determination of a single part-per-billion of sulfur using even the specially pre-
pared pure ceramic tube. The overestimation error was completely eliminated by the
continuous introduction of carbon dioxide with hydrogen, even using conventional
ceramic reactors. By following procedures to suppress noise from the system, the

original limit of detection of 25 ppb sulfur for the analyzer was improved to 0.3 ppb.
However, the practical limit of detection or accuracy must be determined for each
instrument [26].
D7041: Total Sulfur in Petroleum Products by Online Gas

Chromatography and Flame Photometric Detection
This test method covers the determination of total sulfur in liquid hydrocarbons with
a final boiling point less than 450°C by gas chromatography (GC) using a flame pho-
tometric detector (FPD). The range of determination is from 0.5 to 100 mg/kg of sulfur.
The PLOQ is 1 mg/kg sulfur.
In this test method, a fixed amount of sample is injected into a gas chromatograph
where it is vaporized. The air carrier stream carries the vaporized sample into a
high-temperature zone (>900ºC) where the compounds present in the sample are
oxidized. Sulfur compounds are converted to SO2. The carrier stream carries the
oxidation components into a GC column where they are separated and the SO2 is
quantified by a FPD. A typical chromatogram obtained is shown in Fig. 5.18. Calibration
of the detector is achieved by the use of an appropriate external standard such as butyl
sulfide, thiophene, or thianaphthene.
Fig. 5.18 Typical Chromatogram of Flame Photometric Determination of Sulfur in

Test Method D7041.

In an interlaboratory study (RR-D02-1558), 9 laboratories analyzed 16 types of

hydrocarbon and hydrocarbon-oxygenate blends. The sample set consisted of eight
gasoline and diesel samples each. The gasolines contained between approximately 3
and 100 mg/kg of sulfur, and the diesel sample set contained between 2 and 85 mg/kg
sulfur. The following precisions were obtained:
Gasoline Diesel
Repeatability 0.53 0.2070 X0.2594

Reproducibility 0.0657 (X + 28.626) 1.9771 X0.2594
Where X is the average of two single determinations in mg/kg sulfur.
D5453: Combustion—UV-Fluorescence Detection

Test Method D5453 is a widely used method for the determination of trace amounts
of sulfur in fuels. It is an EPA-approved test method for such analysis. It covers the
determination of total sulfur (1–8000 mg/kg range) in liquid hydrocarbons that
boil in the range from approximately 25 to 400°C with viscosities between approxi-
mately 0.2 and 20 cSt at room temperature. This test method is applicable to petro-
leum products such as naphthas, distillates, engine oil, ethanol, fatty acid methyl
ester (FAME), and engine fuel such as gasoline, oxygen-enriched gasoline (ethanol
blends E-85, M-85), reformulated gasoline (RFG), diesel, biodiesel, diesel/biodiesel
blends, and jet fuel. Halogens in amounts less than 0.35 mass % do not interfere in
this determination. The PLOQ was found to be less than 1.0 and less than 5.0 mg/kg
sulfur.
In this test method, a liquid hydrocarbon sample is directly injected or placed in
a sample boat. The sample or boat (or both) is inserted into a high-temperature quartz
combustion tube where the sulfur is oxidized to SO2 in an oxygen-rich atmosphere.
The combustion tube must have side arms for the introduction of oxygen and carrier
gas. Figure 5.19 depicts conventional combustion tubes. Water produced during the
sample combustion is removed, and the sample combustion gases are next exposed to
UV light. The SO2 absorbs the energy from the UV light and is converted to excited
sulfur dioxide (SO2*). The fluorescence emitted from the SO2* as it returns to a stable
state, SO2, is detected by a photomultiplier tube, and the resulting signal is a measure
of the sulfur contained in the sample. Dibenzothiophene; butyl sulfide; or thionaph-
thene dissolved in toluene, xylene, isooctane or other appropriate solvents may be used
as calibration standards.
A direct-injection inlet system can also be used, which is capable of allowing
the quantitative delivery of the material to be analyzed into an inlet carrier stream,
which directs the sample into the oxidation zone at a controlled and repeatable rate
(Fig. 5.20). A syringe drive mechanism that discharges the sample from the

Fig. 5.19 Combustion Tube Design Used in Test Method D5453 for Sulfur.
Fig. 5.20 Direct Injection Syringe Drive Used in Test Method D5453 for Sulfur.

Fig. 5.21 Boat Inlet System Used in Test Method D5453 for Sulfur.
microlitre syringe at a rate of approximately 1 µL/s is required. Figure 5.21 shows a

boat inlet system where an extended combustion tube provides a seal to the inlet of
the oxidation area and is swept by a carrier gas. The system provides an area to
position the sample-carrying mechanism (i.e., the boat) at a retracted position
removed from the furnace. The boat drive mechanism fully inserts the boat into the
hottest section of the furnace inlet. Thus, a drive mechanism that advances and
withdraws the sample boat into and out of the furnace at a controlled and repeat-
able rate is required.
On the basis of the expected sulfur concentration in the sample, one of the three
calibration curves should be used (Table 5.17).
Table 5.17 Typical Sulfur Calibration Ranges and Standard Concentrations
Curve I Sulfur, ng/µL Curve II Sulfur, ng/µL Curve III Sulfur, ng/µL
0.50 5.00 100.00

1.00 25.00 500.00
2.50 50.00 1000.00
5.00 100.00
10.00
Injection size: 10–20 µL Injection size: 5–10 µL Injection size: 5 µL

Several ASTM Research Reports have documented the applicability of this tech-
nique to various petroleum products:
• RR-D02-1307 (1992): multiple matrices

• RR-D02-456 (1999): UV-fluorescence–XRF equivalence study
• RR-D02-1465 (1997): gasoline and RFG
• RR-D02-1475 (1998): low-level gasoline, diesel, and biodiesel
• RR-D02-1547 (2000–2001): low-level gasoline and diesels
• RR-D02-1633 (2008): biofuels
Overall, on the basis of these round robins, the following precisions have been
calculated.
< 400 0.1788X 0.75

0.5797X0.75
> 400 0.02902X 0.1267X
Note: Where X is the average of two test results.
There were several NIST SRMs analyzed by this method, and no significant bias
was found for any of the tested standards.
Tarkanic and Olstowski have demonstrated the utility of this technique for the
at-line process analysis of sulfur in liquid hydrocarbon streams [27]. The instrument
can complete a fast analysis in less than a minute. Thus, real-time data can be obtained
when refineries and terminals need to make rapid determination of sulfur levels for
process control and pipeline distribution decisions involving the new-generation
“clean” hydrocarbon fuels.
In one study, several organic compounds containing sulfur-oxygen bonds were
analyzed at a level of approximately 100 mg/kg sulfur in aqueous solutions and were
analyzed in five replicates [28]. The results are the recoveries are reported in Table 5.18.
Separately, sulfonate compounds were studied for their recovery in a hydrocarbon
Table 5.18 Recovery of Sulfur-Oxygen Compounds [28]
Expected Sulfur Sulfur Concentration Percentage

Compound Concentration, mg/kg Found, mg/kg Recovery
2-Thiophene carboxylic acid 125 110 88

Sodium sulfate 105 99 94
Benzene sulfinic acid 124 110 89
2-Methyl-2-propene-1-sulfonic acid 115 113 98
Benzene sulfonic acid 108 86 80

Table 5.19 Sulfonate Recovery Using D5453 Test Method [28]
Expected Sulfur Sulfur Concentration Percentage

Compound Concentration, mg/kg Found, mg/kg Recovery
Dodecylbenzene sulfonate 10.1 7.9 78

Dodecylbenzane sulfonate 25.3 19.2 76
Dodecylbenzene sulfonate 50.4 38.3 76
solution prepared in isopropyl alcohol and isooctane using dibenzothiophene in isooc-

tane as standard. The results in Table 5.19 are essentially identical to the results obtained
in aqueous solutions, and approximately 80 % of the sulfur is recovered [28].
In a research study done at SWRI in San Antonio, TX, three sulfur test methods
were compared for fitness for use for the analysis of fuels at levels less than
500 mg/kg sulfur: D2622, D4294, and D5453 [22]. All three test methods were found
to be equivalent for measurements in the range of 150–500 mg/kg sulfur; test meth-
ods D5453 and D2622 demonstrated equivalent fitness for use down to the 20-mg/kg
level. There is equivalency among these three test methods using ASTM labora-
tory crosscheck data. Strong evidence was found that D5453 can be fit for use in
multilaboratory situations down to the 1-mg/kg sulfur level. Test Method D2622 was
not found viable at levels less than 10 mg/kg. Test Method D2622 has the lowest stan-
dard deviation across the higher sulfur concentration ranges, and Test Method
D5453 has the lowest standard deviation at the lower (<50 mg/kg) ranges. Figures
5.22 and 5.23 and Table 5.20 demonstrate the standard deviation and percentage
relative standard deviation obtained across the concentration range of sulfur by
using these three test methods [18].
Fig. 5.22 Standard Deviations of Alternate Test Methods for Sulfur.

Fig. 5.23 Percent Relative Standard Deviations of Alternate Test Methods for Sulfur.
Table 5.20 Variability across Sulfur Concentration
D2622 D4294 D5453

Sulfur Concentration,
mg/kg SD %RSD SD %RSD SD %RSD
10 1.08 10.75 11.92 119.2 0.66 6.55

25 2.64 10.56 32.16 128.6 1.23 4.92
50 4.91 9.82 19.86 39.73 2.42 4.84
100 6.82 6.82 20.53 20.54 4.82 4.82
200 12.89 6.44 42.90 21.45 8.84 4.42
SD: Standard deviation; % RSD: percentage relative standard deviation.
To analyze for sulfur compound bias, a single isooctane matrix was used to
minimize the well-known carbon-to-hydrogen ratio interference in the XRF test
methods. All three test methods were then evaluated for any bias with respect to 24
commonly occurring organosulfur compounds. No bias was detected, and the accu-
racy was within the precision limits for each of the test methods. Of these three test
methods, the best low-level precision and accuracy was found in Test Methods D2622
and D5453. Of these two, Test Method D5453 was found to generate better data in the
low- (<50 mg/kg) sulfur regime. In fact, this work also suggests that Test Method
D5453 can be routinely used for determining sulfur in liquid hydrocarbons at levels
less than 1 mg/kg [18].
Crnko and Tarkanic have extended the application of Test Method D5453 for the
at-line measurement of sulfur in fuels [29]. High-speed real-time data on sulfur are
critical for decisions in refineries, blend plants, and pipelines regarding sulfur levels

in fuels being shipped. This decision is particularly critical when diverse fuel streams
use the same pipeline so as to prevent contamination of low-level sulfur streams by
those with high sulfur. It is of economic interest for the pipeline to keep the transmix
region to a minimum. Test methods such as API gravity or lead acetate paper tape have
historically been used for this purpose. However, there is not necessarily a correlation
between the gravity and the sulfur content of the fuels. The lead acetate tape test is not
sensitive enough for today’s low-level sulfur fuels. Other recent test methods for at- or
online sulfur analysis include oxidative combustion + GC separation + FPD detection
(D7041) and ED-XRF with proportional counter detector (D7212). They use analytical
cycle times of 2.5–10 min, which may be too long for real-time detection of small
changes in sulfur levels of fuel streams.
The proposed D5453 at-line analyzer has a fast analysis time of less than 1 min. A
5-µL sample is injected through a valve and pushed through an injection tube into the
combustion chamber. A sample conditioning system removes contaminants and
water, regulates sample pressure, and controls sample flow to ensure sample intro-
duction under constant conditions. The analysis does not have the matrix interfer-
ence problem of the XRF method, nor does it require the column switching and
back-flushing needed in the GC methods.
Interferences
The nitric oxide produced by combustion of nitrogen compounds in the sample will
fluoresce but at a reduced brightness compared with SO2. This will falsely increase the
detected sulfur result. The rejection ratio for N–O in a UV-fluorescence detector is
greater than 100:1, or possibly 50:1. Thus, for every 50-mg/kg nitrogen amount, sulfur
will increase by 1 mg/kg. Usually most hydrocarbon samples do not have high enough
nitrogen content to make this interference a concern. Another interferent is moisture,
which quenches the fluorescence reaction and will absorb SO2 when condensed. Using
a membrane dryer or keeping the sample path heated reduces humidity and prevents
water from condensing. After increasing for the first several injections, the moisture
content stabilizes. This quenching effect will reduce the overall detector sensitivity,
but the linearity is not affected. Chlorine will fluoresce, but it has a rejection ratio of
approximately 8000:1. Carbon dioxide can potentially quench the fluorescence reac-
tion, but experiments have shown no evidence of this effect on this analysis. Some data
on the analysis of gasoline samples spiked with sulfur are shown using the analyzer in
Table 5.21.
The precision of the analysis is better than 1 % of full scale, and the linearity is
better than 1 % at full scale at a sulfur level greater than 1 mg/kg. Recovery time
after an analysis is 15 min when switching from high (100 mg/kg) to low (15 mg/kg)
sulfur levels. Several ASTM ILCP ULSD samples were also analyzed by Test Method
D5453 using laboratory analysis and with the auto at-line analyzer. The comparative
results in Table 5.22 by both modes of analysis are in excellent accordance with each
other.

Table 5.21 Analysis of Spiked Gasoline with UV-Fluorescence Process Analyzer
Sulfur Spike, Sulfur Found, Percentage Relative

Number of Injections mg/kg mg/kg Standard Deviation
70 50 50 ± 0.47
20 30 30 ± 0.23
10 5 5 ± 0.14
79 h 78 77.45 ± 0.47 0.61

3048 (10 days) 11.8 11.7 ± 0.16 1.4
40 (3 h 20 min) 155.6 ± 1.70 1.09
195 (16 h 15 min) 71.2 ± 1.39 1.96
62 (5 h 10 min) 28.84 ± 0.66 2.30
Table 5.22 Analysis of ASTM ULSD ILCP Samples for Sulfur [29]
D5453 Laboratory On-Line Analyzer

ASTM ILCP # ASTM Consensus Valuesa Results (n = 2) Resultsa %RSD
0401 15.08 ± 1.27 (99) 14.5 15.63 ± 0.16 (12) 1.01

0402 1.58 ± 0.07 1.6 1.46 ± 0.12 (10) 7.98
0403 1.41 ± 0.07 (118) 1.6 1.51 ± 0.08 (10) 5.16
0404 14.92 ± 0.18 (104) 16.3 15.2 ± 0.27 (7) 1.75
0405 9.83 ± 0.13 (113) 7.9 9.66 ± 0.32 (7) 3.33
0406 0.66 ± 0.28 (101) 0.6 0.64 ± 0.08 (16) 12.8
%RSD: percentage relative standard deviation.

Results are expressed as mean value ± standard deviation (number of laboratory results).
a
The above data show that the D5453 analyzer can address the need for fast, accu-
rate analysis of fuel stream in refineries, blend terminals, and pipelines. Real-time,
high-speed sulfur data allow accurate delineation of boundary lines of the transmix
region of diverse fuel streams. There is minimal downtime between successive sample
switches. The accuracy of analysis is approximately 1 % with an analysis time of less
than 1 min. The injection volume used is 5 µL, and the range of analysis is 1–250 mg/kg
of sulfur. The procedure will enable the refinery or pipeline terminal operations to
achieve significant savings of time and money [29].
It has been reported in testing ULSD samples that there could be some interfer-
ence caused by iron sulfide corrosion product in the diesel sample. This causes a false
high reading when using the D2622 XRF method but not when using the D5453
method. Iron sulfide is not volatile. Hence, even if the particles did get into the syringe,
they would not be converted to a volatile form so that sulfur in the sulfide can be

analyzed. However, with the XRF analysis, the insoluble particles would accumulate in
the X-ray cup on the face of the analytical surface, making the sulfur reading higher
than actual. The issue is now more noticeable because of a significant decrease in sul-
fur content and because ULSD tanks are being circulated more than conventional
diesel tanks to improve sample homogeneity. The circulation could potentially stir fine
particles from tank bottoms as iron sulfide rust [30].
In an Alberta Research Council study, a set of 30 samples was analyzed using
Test Methods D5453 and D7039. The set included ULSD, gasolines, aviation gas-
oline, fuel oils, biodiesels, and aviation turbine fuel. The aviation gasoline sample
turned out to be a statistical outlier, possibly because of its lead content of
0.55 g/L. The sulfur content of this sample was very low—less than 5 mg/kg. A
statistical observable bias with all results combined over several calibration curves
(0–400 mg/kg nominal) was detected. However, no statistically observable bias
using independent t tests for three samples with greater than 200 mg/kg nominal
sulfur was observed. No statistically observable bias was detected for 0–100 mg/kg
in Test Method D7039. The conclusion was that Test Methods D5453 and D7039
should be considered as practically equivalent over all sample types studied
between 0 and 100 mg/kg if D7039 is calibrated using one equation for the above
range [31].
D7183: Total Sulfur in Aromatic Hydrocarbons and Related Chemicals

by UV-Fluorescence
Some process catalysts used in petroleum and chemical refining can be poisoned when
trace amounts of sulfur-bearing materials are contained in the feedstocks. This
method can be used in such cases for the determination of the total sulfur in these
products. This test method is applicable to samples with sulfur concentrations in the
range 0.5–100 mg/kg. The technical principle is the same as that of other combustion
UV-fluorescence methods described in this section. The interferences from halogens
and moisture are similar to that in other UV-fluorescence methods. Dibenzothiophene
diluted in methanol, isooctane, p-xylene, or other similar solvents is used as the sulfur
calibration standard. A correction for chemical impurity is required. Dibenzothiophene
is normally 98 % pure. Working standards should be remixed on a regular basis
depending on the frequency of use and age. The stock solutions typically have a useful
life of approximately 3 months.
In an ILS, 19 laboratories tested 5 different materials for sulfur concentrations
between 0.05 and 0.9 mg/kg. In a corresponding effort, 25 laboratories evaluated
3 materials with sulfur concentrations between 15 and 900 mg/kg. Each test result was
the average of three individual determinations. Laboratories reported three replicate
test results for each material. The repeatability and reproducibility obtained in this
study is summarized in Table 5.23. Because of the nonavailability of a suitable accepted
reference material, the bias has not been determined.

Table 5.23 Precision of Total Sulfur Measurement in Test Method D7183
Material Average, mg/kg Repeatability Limit Reproducibility Limit
Blank 0.051 — —
+0.498 0.500 0.083 0.216
+0.892 0.850 0.063 0.280
15 15.69 1.61 6.10
64.5 67.09 7.10 21.73
91 94.34 8.14 20.87
D7620: Total Sulfur in Liquid Hydrocarbon-Based Fuels by Continuous

Injection, Air Oxidation, and UV-Fluorescence Detection
This test method covers the determination of total sulfur in liquid hydrocarbon-based
fuels with a final boiling point of up to 450°C. It is applicable to the analysis of natural,
processed, and final product materials containing sulfur in the range of 4–830 mg/kg.
The samples should have less than 0.35 mass % halogen(s). Bound nitrogen at a concen-
tration greater than 150 mg/kg can cause a 1-mg/kg sulfur positive bias. Excessive
moisture produced during the sample combustion step will interfere if not removed
before detection.
This method is based on the same technical principles as Test Method D5453.
Figure 5.24 illustrates a basic block diagram of this process. Figure 5.25 shows a typical
combustion tube used in this analysis. A small, very controlled flow of hydrocarbon
sample is continuously injected during measurement. It is introduced via a syringe
into a high-temperature combustion tube containing air, where sulfur is oxidized to
SO2. Water produced during the sample combustion is removed, as required, and the
sample combustion gases are next exposed to UV light. The SO2 absorbs the energy
from the UV light and is converted to SO2*. Fluorescence emitted from the SO2* as it
returns to stable SO2 is detected by a photomultiplier tube, and the resulting signal is a
measure of the sulfur contained in the sample. Thiophene (or other sulfur compounds)
dissolved in solvents such as isooctane, toluene, xylenes, etc., is used as the calibration
standard.
Fig. 5.24 Block Diagram of Apparatus Used in Test Method D7620 for Sulfur.

Fig. 5.25 Typical Combustion Tube Used in Test Method D7620 for Sulfur.
The precision of this method was calculated in an ILS conducted by the

D02.SC 3 Committee, which included 14 sample sets each of gasoline, gasoline
with 10 % ethanol, diesel, biodiesel (B100), and jet fuel. Six laboratories participated
(RR-D02-1701).
The bias of this test method has not yet been determined.
XRF SPECTROMETRY
The principle behind XRF spectrometry was briefly explained in Chapter 2 of this
book and in much more detail in references 32 and 33. It is a widely used technique
in the fossil fuel industry for the determination of sulfur at high levels and at
part-per-million levels in various gaseous, solids, and liquid fuels. The XRF tech-
nique requires only a small amount of liquid sample, the analysis is rapid and
nondestructive, and it has very good precision. It is one of the primary methods
chosen by EPA for sulfur surveillance of U.S. refinery products such as gasoline
and diesel. However, there are some well-recognized interferences in the
technique.

• A fundamental assumption in XRF analysis is that the standard and sample matri-
ces are well matched or that that the matrix differences are accounted for. Matrix
mismatch can be caused by carbon-to-hydrogen ratio differences between samples
and standards or by the presence of other interfering heteroatoms or species.
• A second source of interference is spectral interference caused by the closeness of
the X-ray characteristic lines of the elements present in a sample and the detector’s
limited ability to completely resolve them. As a result, the lines produce spectral
peaks that overlap with each other. Spectral interferences may arise from samples
containing silicon, phosphorus, calcium, potassium, halides, etc., if present at con-
centrations greater than 0.1 times the measured sulfur concentration or more than
a few hundred milligrams per kilogram.
• Matrix effects are caused by concentration variations of the elements in a sample.
These variations directly influence X-ray absorption and change the measured
intensity of each element.
These interferences may be compensated for in modern XRF instruments with

the use of built-in software for spectra deconvolution or overlap correction and
interelement correction by multiple regression or by other mathematical methods.
For samples such as crude oils that may contain suspended water, it is recom-
mended that the water be removed before testing or that the sample be thoroughly
homogenized and immediately tested. The interference is greatest if the water creates a
layer over the transparent film because it will attenuate the X-ray intensity for the ele-
ments. One way to accomplish the removal of water is to centrifuge the sample first
under ambient sealed conditions.
Three principal ways of using this technique are WD-XRF, ED-XRF, and mono-
chromatic wavelength-dispersive X-ray fluorescence (MWD-XRF). The XRF test
methods used for the determination of sulfur in gasoline and diesel matrices are listed
in Table 5.24, and each is described below.
Table 5.24 XRF Test Methods for Sulfur Determination in Gasoline and Diesel
Technique ASTM Standard Number Analysis
WD-XRF D2622 Sulfur in Gasoline and Diesel

WD-XRF D6334 Sulfur in Gasoline
ED-XRF D6445 Sulfur in Gasoline and Oxygenated Blends
MWD-XRF D7039 Sulfur in Gasoline and Diesel
ED-XRF D4294 Sulfur in Petroleum Products
ED-XRF D7212 Sulfur in Fuels Using Low-Background
Proportional Counter
ED-XRF D7220 Sulfur in Fuels Using Polarization

Calibration in XRF Analysis [34]

In general, in XRF test methods for sulfur determination in petroleum products, the
calibration standards are prepared from pure organic sulfur or organometallic
compounds dissolved in base oils or other suitable organic solvents. Particular atten-
tion needs to be paid to the purity of the solvent used. Otherwise, a blank correction
may be necessary for the contaminants in the solvent.
Working calibration standards can be prepared by careful mass dilution of a
certified organic compound with an analyte-free white oil or other suitable base
material such as toluene, isooctane, or xylene. The concentration of the unknown
samples must lie within the calibration range that is used. Some of the calibration
standards suggested and widely used for XRF analysis include
• Di-n-butyl sulfide, thiophene, and 2-methyl thiophene.

• Polysulfide oil concentrates: Generally nonyl polysulfides containing a known
percentage of sulfur (as high as 50 mass %) diluted in pure hydrocarbon matrix,
they exhibit excellent physical properties such as low viscosity, low volatility, and
durable shelf life while being completely miscible in white oil. The sulfur content of
polysulfide oil concentrates is determined via mass dilution in sulfur-free white oil
followed by a direct comparison analysis against NIST (or other primary standards
body) reference materials.
The calibration and check standards should be stored in glass bottles in a cool,
dark place until required. The glass bottles should be of dark color or wrapped in
opaque material and closed with glass stoppers, inert plastic-lined screw caps, or other
equally inert, impermeable enclosures. If any sediment or change of appearance is
observed, then the standard should be discarded.
The calibration curve is established by determining the net intensity of the
emitted radiation from the element of interest in each of the standards. Five to ten
calibration standards may typically be used. These could be in the milligram per
kilogram or 0.x mass % levels depending on the level of the element of interest to be
determined in the samples. A calibration model is usually prepared by the software in
the modern XRF instruments. Immediately after the calibrations are completed, the
sulfur concentration of one or more of the calibration check samples is determined.
The difference between the two measured values should be within the repeatability of
the test method being used. When this is not the case, the stability of the instrument
and the reliability of the sample preparation may be suspect, and corrective measures
should be taken. The degree of matrix mismatch should also be considered when
evaluating a calibration.
Although every attempt is made during an analysis to use pure reagents and
maintain a clean working environment, there will often be contamination from an
unknown quantity of the analyte of interest in an analytical sequence. To minimize
such effects, a blank should always be subtracted from the sample and standard

measurement responses. The blank sample in such cases should contain the same
quantities of reagents or solvents that are added to the samples and undergo the same
processing steps to mimic the sample treatment.
D2622: Sulfur in Petroleum Products Using WD-XRF

For the determination of sulfur in liquid fossil fuels, this is probably the most impor-
tant test method and is widely used throughout the industry. The method has been
very thoroughly studied in the industry laboratories. The test method covers the deter-
mination of total sulfur in petroleum and petroleum products that are single phase
and liquid at ambient temperatures, liquefiable with moderate heat, or soluble in
hydrocarbon solvents. These materials can include diesel fuel, jet fuel, kerosine, other
distillate oil, naphtha, residual oil, lubricating base oil, hydraulic oil, crude oil, unleaded
gasoline, gasohol, and biodiesel. The test method is applicable to samples in the range
of 3 mg/kg to 4.6 mass % sulfur. Samples containing even higher levels of sulfur can be
diluted to bring the sulfur concentration of the diluted material within the scope of
the test method. Samples that are diluted can have higher errors than indicated in the
precision given for nondiluted samples. Volatile samples such as high-vapor-pressure
gasolines or light hydrocarbons may not meet the stated precision because of the
selective loss of the light materials during the analysis. A fundamental assumption of
this test method is that the standard and sample matrices are well matched or that
the matrix differences are accounted for. Matrix mismatch can be caused by the
carbon-to-hydrogen ratio differences between samples and standards or by the
presence of other interfering heteroatoms or species (Table 5.25).
In this test method, the sample is placed in the X-ray beam, and the peak intensity
of the sulfur K-alpha line at 0.5373 nm is measured. The background intensity,
Table 5.25 Concentration of Interfering Species in D2622 and D4294 Determination of

Sulfur
Interfering Species Mass Percentage Tolerated in D2622 Mass Percentage Tolerated in D4294
Phosphorus 0.3 0.3

Zinc 0.6 0.6
Barium 0.8 0.8
Lead 0.9 0.9
Calcium 1 1
Chlorine 3 3
Oxygen 2.8 —
FAME 25 5
Ethanol 8.6 8.6
Methanol 6 6

measured at a recommended wavelength of 0.5190 nm (0.5437 for a Rh target tube) is

subtracted from the peak intensity. The resultant net counting rate is then compared to
a previously prepared calibration curve or equation to obtain the concentration of
sulfur in milligrams per kilogram or mass percent. A high-purity di-n-butyl sulfide
with certified sulfur content is typically used as a calibration standard in this proce-
dure. It is essential to know the sulfur content of the di-n-butyl sulfide, not just the
purity, because impurities may also be sulfur-containing compounds.
There are significant interferences in this test method. When the elemental com-
position (excluding sulfur) of sample differs from the standards, errors in the sulfur
determination can result. For example, differences in the carbon-to-hydrogen ratio of
the sample and calibration standards introduce errors. Some other interferences and
action levels are listed in Table 5.25. In such cases, the sample should be diluted with a
blank sulfur solvent to reduce the interferent concentration below the value given in
the table to mitigate the effect of this interference.
Fuels containing large quantities of FAME, ethanol, or methanol have high
oxygen content, leading to significant absorption of sulfur K alpha radiation and low
sulfur results. However, such fuels can be analyzed using this test method provided
that correction factors are applied to the results or that the calibration standards are
prepared to match the matrix of the sample. In general, petroleum products with
compositions that vary from white oil used in calibrant solutions can be analyzed with
standards from base materials that are of the same or similar composition. Thus, a
gasoline sample may be simulated by mixing isooctane and toluene in a ratio that
approximates the expected aromatic content of the samples to be analyzed. Standards
made from this simulated gasoline can produce results that are more accurate than
results obtained using white oil standards.
Lubricating oils and additives containing greater than 100 mg/kg sulfur are better
analyzed using Test Method D4927 because that method implements interelement
correction factors. Test Method D2622 is not suitable for such work because it does not
encompass the measurement of the additional elements present in the lubricating oils
and their additives, making matrix correction impossible.
A major ILS conducted for obtaining the precision and bias of this test method
used 27 samples including gasolines, distillates, biodiesel, residual oils, and crude oils
[14]. The sulfur concentration range was 0.1 mg/kg to 4.6 mass %. A PLOQ of approx-
imately 3 mg/kg sulfur was obtained for all sample types. The overall repeatability and
reproducibility found for gasoline and diesel were as follows:
Repeatability = 0.1462(X0.8015 ) mg/kg

Repeatability = [0.1462(Y × 10,000)0.8015]/10,000 mass %
Reproducibility = 0.4273X0.8015 mg/kg

Reproducibility = [0.4273(Y × 10,000)0.8015]/10,000 mass %

Where X and Y are the sulfur concentrations in mg/kg and mass % total sulfur,
respectively.
On the basis of the analysis of ten NIST SRMs, there was no significant bias
between the certified values and the results obtained in the ILS for any SRM or sample
type within measured reproducibilities, especially after the carbon-to-hydrogen ratio
corrections were applied. See Table 5.26 for a comparison of the results obtained on
NIST SRMs in this ILS.
Table 5.27 presents the precision given above for all samples inclusive detailed by
product and instrument types. The power of the XRF source can affect the precision of
results measured by this method. Instruments having greater than 1000-W sources are
Table 5.26 Comparison of NIST SRM Data and ASTM ILS Measured Results
Sulfur Average Average

NIST C/H Measured Sulfur C/H-Corrected Corrected Relative
NIST SRM Value, Mass Found in ILS, Sulfur Found in Bias, Corrected
Number Matrix mg/kg Ratio mg/kg ILS, mg/kg mg/kg Sulfur Bias, %
2298 Gasoline 4.7 5.47 6.0 6.0 1.3 27.66

2723a Diesel 11.0 5.99 10.1 10.2 –0.8 –7.27
2299 Gasoline 13.6 6.17 14.2 14.3 0.7 5.15
2296 Gasoline 40.0 6.42 40.2 40.6 0.6 1.50
2770 Diesel 41.6 5.75 42.1 42.4 0.8 1.92
2724b Diesel 426.5 7.18 420.9 426.4 –0.1 –0.02
2722 Crude oil 2103 7.22 2054 2105 2 0.10
1619b Residual 6960 8.80 6448 6804 –156 –2.24
fuel oil
2721 Crude oil 15,830 7.17 15,994 16,217 387 2.44
1620c Residual 45,610 7.93 44,424 46,535 935 2.05
fuel oil
Table 5.27 Precision Values for Sulfur by Test Method D2622
NIST SRM Number Repeatability Reproducibility
Gasolines: 2298, 0.5006X 0.4377

mg/kg 1.4533X0.4377 mg/kg
2296, 2299;
gasoline with 5 %
ethanol; unleaded
regular gasoline [0.5006(Y × 10 000)0.4377]/10,000 mass % [1.4533(Y × 10,000)0.4377]/10,000 mass %
Diesels: 2723a, 0.1037X0.8000 mg/kg 0.3856X0.8000 mg/kg
2770, 2724b, [0.1037(Y × 10,000) 0.8000
]/10,000 mass % [0.3856(Y × 10,000)0.8000]/10,000 mass %
diesel, B-5 diesel
High-power 0.08681X0.8383 mg/kg 0.3086X0.8383 mg/kg
instruments [0.08681(Y × 10,000) 0.8383]
/10,000 mass % [0.3086(Y × 10,000)0.8383]/10,000 mass %

defined as high power whereas those having less than 1000-W sources are defined as
low power in this context.
There have been reports from some testing facilities that iron sulfide corrosion
particles interfere with the analysis of ULSD, particularly when using XRF methods
such as D2622, but not with D5453. Iron sulfide is nonvolatile and insoluble. With the
combustion technique D5453, even if the particles did somehow got into the syringe,
they would not be converted to a volatile form so that the sulfur in iron sulfide could
be analyzed. With the XRF technique, the insoluble particles would fall to the ana-
lytical viewing surface, making the sulfur concentration in the fuel appear higher
than in reality. This issue has become more noticeable because of the significant
decrease in the sulfur content and because the ULSD tanks are being circulated
more than conventional diesel tanks to improve sample homogeneity. The circula-
tion could potentially stir up the fine particulates such as iron sulfide (rust) from
tank bottoms [35].
D6334: Sulfur in Gasoline by WD-XRF

This is also a WD-XRF-based sulfur analysis method. It is applicable to gasoline and
gasoline-oxygenated blends. The PLOQ was determined to be 15 mg/kg. Therefore, the
practical range of this method is from 15 to 940 mg/kg sulfur. Below the 15-mg/kg
level, the reproducibility approaches 100 % of the concentration. In this test method,
the sample is placed in the X-ray beam, and the intensity of the sulfur K-alpha line at
5.373 Å is measured. The intensity of a corrected background measured at a recom-
mended wavelength of 5.190 Å, or if a rhodium tube is used, 5.437 Å, is subtracted
from this intensity. The resultant net count is compared to a previously prepared cali-
bration curve or equation to obtain the concentration of sulfur in milligram per
kilogram.
Fuels that vary in composition from those specified in the method may be ana-
lyzed with standards made from base materials that are of similar composition to
minimize matrix effects. Fuels containing oxygenates may be analyzed using stan-
dards prepared with similar amounts of the same oxygenate added to the standard
dilution matrix. However, round-robin studies conducted by the Western States
Petroleum Association have shown no significant bias in determining sulfur in gaso-
lines with and without oxygenate levels between 0 and 2.7 mass % oxygen. Methanol
fuels (M85 and M100) exhibit interferences at this level of detection (<100 mg/kg).
They can be analyzed using a calibration curve produced by diluting the standards in
a similar matrix of M85 or M100 or by using Test Method D2622. On the basis of an
ILS, the precision and bias values presented in Table 5.28 were obtained.
Studies done in conjunction with the Western States Petroleum Association and
CARB as well as ASTM round robins have shown that there is no significant bias
between this test method and others available for the analysis of sulfur in light fuels at
the appropriate levels. These include ASTM Test Methods D2622, D3210, D4045, D4294,
and D5453.

Table 5.28 Precision of Test Method D6334 for Sulfur in Gasoline
Sulfur Concentration, mg/kg Repeatability, mg/kg Reproducibility, mg/kg
15–940 0.0400(X + 97.29) 0.1182(X + 54.69)

15 4.6 8.2
50 5.9 12.4
100 7.9 18.3
500 23.9 65.6
940 41.5 117.6
Note: X is the average of duplicate analysis.
D7039: Sulfur in Gasoline and Diesel Fuel by MWD-XRF Spectrometry

This test method is based on the MWD-XRF technique. It has had singular success
in accurately analyzing trace quantities of sulfur in gasoline, naphtha, diesel, jet fuel,
kerosine, biodiesel, ethanol, and gasoline-ethanol blends. Its analysis range is from
0.5 to 2875 mg/kg sulfur. The PLOQ is 1.9 mg/kg. Volatile samples such as
high-vapor-pressure gasoline or light hydrocarbons might not meet the stated preci-
sion because of the evaporation of light components during the analysis. Gasoline
samples containing oxygenates may be analyzed by this test method provided that
the matrix of the calibration standards is matched to the sample matrices or
the matrix correction described in the test method is applied to the results. Fuels
containing sulfur above 3000 mg/kg can be analyzed after dilution with appropriate
solvent. However, the precision and bias of the diluted samples may not be the
same as that given in the test method. When the elemental composition of
the sample differs significantly from the calibration standards used to prepare the
calibration curve, the cautions and recommendations given in the test method
should be carefully observed.
In this test method, two doubly curved crystal (DCC) optics are used to
provide monochromatic excitation. An X-ray beam with a wavelength suitable to
excite the K-shell electrons of sulfur is focused onto a test specimen contained in
a sample cell. The fluorescent K alpha radiation at 0.5373 nm emitted by sulfur is
collected by a fixed monochromator (analyzer). The intensity counts per second of
sulfur X rays are measured using a suitable detector and converted to the concen-
tration of sulfur in the test specimen using a calibration equation. Excitation by
monochromatic X rays reduces background, simplifies matrix correction, and
increases the signal-to-background ratio compared with the polychromatic exci-
tation used in conventional WD-XRF techniques [36]. Di-n-butyl sulfide is used
as the calibration standard. A schematic of the MWD-XRF analyzer is shown
in Fig. 5.26.

Fig. 5.26 Schematic Diagram of D7039 MWD-XRF Sulfur Analyzer.
Differences between the elemental composition of test samples and the calibra-
tion standards can result in biased sulfur determinations. For diesels and gasolines
within the scope of this test method, the only important elements contributing to
bias resulting from differences in the matrices of calibrants and test samples are
hydrogen, carbon, and oxygen. A matrix correction factor, C, can be used to correct
this bias. For general analytical purposes, the matrices of test samples and the
calibrants are considered matched when the calculated correction factor C is
within 0.98–1.04. No matrix correction is required within this range. A matrix
correction is required when the value of C is outside of the range of 0.98–1.04. For
most testing, matrix correction can be avoided with a proper choice of calibrants.
For example, on the basis of the example graph (Fig. 5.27), a calibrant with 86 mass
% carbon and 14 mass % hydrogen can cover nonoxygen-containing samples with
carbon-to-hydrogen ratios from 5.4 to 8.5. For gasolines and oxygenates, up to
2.3 mass % oxygen (i.e., 12 mass % MTBE) can be tolerated for test samples with the
same carbon-to-hydrogen ratio as the calibrants.
To minimize any bias in the results, calibration standards prepared from sulfur-
free base materials of the same or similar elemental composition as the test sample
should be used. When diluting samples, diluent with an elemental composition the
same or similar to the base material should be used for preparing the calibration stan-
dards. A base material for gasoline can be approximately simulated by mixing isooc-
tane and toluene in a ratio that approximates the expected aromatic content of the
samples to be analyzed. Fuels containing oxygenates may be analyzed using calibra-
tion standards containing the same amount of the same oxygenate in the test fuel.
In the factory, for 20 D7039 analyzers, measurements made for 300 s gave a repeat-
ability of 1.2 ppm for a 10-ppm diesel standard and 4.4 ppm for a 300-ppm diesel sam-
ple. Analysis of NIST SRM 2723a on ten analyzers gave each result within the error bar
of the NIST-certified value of 11.0 ± 1.1 mg/kg sulfur [37].
The precisions of this test method found in various ILS (RR-D02-1552) conducted
in the last 5 years are summarized below.

Fig. 5.27 Matrix Correction for Oxygen Interference in Test Method D7039 for Sulfur.
ILS Study Sulfur Range, mg/kg Repeatability Reproducibility
Gasoline <500 0.555X 0.5
Diesel 4–17 0.23X0.5 0.5X0.5

Diesel 17–500 0.55X 0.5
Note: Where X is the average of two duplicate measurements.
The limit of detection for a single analyzer was found to be 0.36 mg/kg. On the basis of
several ILS, the following precision has been obtained for this test method [37]:
Repeatability = 0.2171X0.6783
Reproducibility = 0.3371X0.6783
Where X is the average sulfur concentration of two results in mg/kg.

Chen et al. show the following in-house variability for analyzing ULSD samples.
The samples used were from the ASTM ULSD ILCP program. Five benchtop ana-
lyzers were used with a different operator for each instrument. Calibration standards
from different commercial sources were used. There were a total of eight diesel sam-
ples from the crosscheck program. NIST SRM 2723a was also included in this study.

Two successive repeat measurements were made for each sample on each analyzer.
The measurement results are given in Table 5.29 [37].
Using ASTM D6300 statistical protocol, the mean values, repeatability (r), and
reproducibility (R) were calculated and are included in Table 5.30. The repeatability
limits show improvement over those found in the 2002 crosscheck, although the
reproducibility limits are similar in both cases. However, it is clear that at very low
sulfur levels, such as samples ULSD 0406 or 0409 with submilligram-per-kilogram
sulfur levels, the results are not acceptable with variability greater than the mean
values.
Results for NIST SRMs analyzed in an ILS to measure the above precision values
resulted in the following data. No statistically significant bias was observed for this test
method using the NIST SRM 1616b kerosine sample.
Table 5.29 Analysis of ULSD Diesels with Multiple D7039 Analyzers
ULSD SRM
Number 0403 0404 0405 0406 0407 0408 0409 0410 2723A
A 1.26;1.33 14.5; 9.94; 0.39; 3.26; 14.30; 0.31; 15.51; 10.00;

13.92 9.74 0.47 4.11 14.42 0.17 15.77 9.80
B 1.70;1.55 14.33; 10.94; 0.63; 4.11; 15.16; 0.69; 15.42; 10.50;
13.66 11.13 0.68 4.14 15.54 0.48 15.32 10.40
C 1.24;1.40 13.77; 10.07; 0.11; 4.09; 16.30; 0.43; 15.28; 10.70;
13.33 10.55 0.23 4.55 16.18 0.23 15.52 10.40
D 2.00;1.95 13.85; 10.80; 0.80; 3.38; 16.03; 0.65; 15.25; 10.80;
14.58 10.85 0.63 3.68 16.88 0.65 13.93 9.80
E 1.40;1.70 14.6; 9.60; 1.00; 3.90; 14.00; 0.60; 15.80; 10.10;
15.5 10.30 1.10 4.10 13.40 0.60 16.30 10.90
Mean 1.55 14.20 10.39 0.60 3.93 15.22 0.48 15.41 10.34
r 0.44 1.75 1.03 0.29 1.19 1.29 0.38 1.68 1.53
R 1.05 2.33 2.05 1.21 1.45 4.40 0.72 2.28 1.45
Note: Semicolons denote duplicate values; bold values are the means of all ULSD replicate analyses.
Table 5.30 Analysis of NIST Fuel SRMs by MWD-XRF [37]
Certified Value, Measured Value, Measured Bias, Relative Measured

NIST SRM mg/kg mg/kg mg/kg Bias, %
Gasoline 2298 4.7 ± 1.3 4.6 ± 1.2 0.1 2.1

Gasoline 2299 13.6 ± 1.5 11.6 ± 0.6 –2.0
Diesel 2723a 11.0 ± 1.1 11.1 ± 1.2 –0.1 –0.9
Diesel 2724b 426.5 ± 57 431 ± 16 –5.0 –1.2
Kerosine 1616a 146.2 ± 1.8 149 ± 2.50 2.8

In an ILS, the Alberta Research Council investigated the precision of Test Method
D7039 [38]. Twenty-one laboratories analyzed 23 samples, including gasoline, ethanol,
aviation gasoline, fuel ethanol, biodiesel, kerosine, fuel oil, additive, and crude oil,
for their sulfur content using D7039 instruments. The precision values presented in
Table 5.31 were observed.
Results obtained from ASTM ILCP CS92 for Test Method D7039 for the period of
December 2005 through October 2006 were statistically examined for the purpose of
determining repeatability and reproducibility. Because in this proficiency testing
program each sample is analyzed in duplicate by each laboratory, it is possible to
calculate the repeatability of this exercise. Thirty-four laboratories participated in the
CS92 crosscheck program in this period.
A round-robin study was conducted by SWRI for EPA. The final report of this
investigation, “EPA 2005 Sulfur in Diesel Fuel Round Robin Test Plan and Data
Analysis” (SWRI Project No. 03.11382.02), was published in December 2005.
Sixteen laboratories participated in this study using Test Method D7039, and all
laboratories qualified their measurement method with EPA per 40 CFR 80.584.
This ILS involved a total of ten diesel fuel samples, five of which were sent to the
participating laboratories in July 2005 and five of which were sent in August 2005.
The 2-month EPA study included two blind samples of NIST SRM 1616b with a
certified sulfur value of 8.41 ± 0.12 mg/kg. The round-robin study reported that for
this sample, identical values of 8.49 mg/kg were obtained. The expanded uncer-
tainty (95 % confidence) is calculated at 0.27 mg/kg of the true value (i.e., 8.22–8.76
mg/kg). Because both confidence intervals of NIST and Test Method D7039 overlap,
there is statistically observable bas.
In the last ILS conducted in 2011, the following precisions were obtained, which
are considered as final for the time being.
Sample range = 1.10–2822.1 mg/kg

PLOQ = 3.2 mg/kg
Repeatability = 0.4998X0.54
Reproducibility = 0.7384X0.54
Table 5.31 Precision Obtained for D7039 in the Alberta Research Council Study
Parameter ULSD Motor Gasoline
Repeatability 0.53X0.5 0.2704X0.77

0.478X0.77
Sulfur range, mg/kg 4–17 4–1900
Total number of samples 4 13
Note: Where X is the average of two determinations in mg/kg.

Chen and Wei have compared the results and precision of ten ULSD samples ana-
lyzed in the ASTM ILCP crosschecks. All three test methods—D2622, D5453, and
D7039—gave comparable results (Table 5.32). D7039 shows better precision than D2622
in repeatability and reproducibility. D5453 has the best repeatability among these three
methods, whereas D7039 has the best reproducibility [36].
A version of Test Method D7039 has been suggested for the online determination
of sulfur in diesel fuels. Online measurement allows for the control of sample presen-
tation, which can hinder laboratory repeatability plus the delay in getting the labora-
tory analysis. Table 5.33 shows the precision that can be obtained using 15-min and
100-s measurement time with this analyzer [39].
D4294: Sulfur in Gasoline and Diesel Using ED-XRF

This is a widely used XRF test method for sulfur at low and high concentration levels
and is a less expensive alternative to Test Method D2622 instrumentation, although at
Table 5.32 Results of Major Sulfur Test Methods in ASTM ILCP Crosschecks
D2622 Results D5453 Results D7039 Results
ILCP Number Mean ± SD R r Mean ± SD R r Mean ± SD R r
ULSD 0801 10.99±1.14 3.18 1.25 10.93±0.76 2.11 0.23 11.03±0.63 1.76 0.62
ULSD 0802 5.13±0.72 2.01 0.56 4.63±0.47 1.31 0.20 4.94±0.47 1.31 0.41
ULSD 0803 8.93±1.06 2.96 0.41 8.87±0.69 1.92 0.20 8.83±0.51 1.42 0.62
ULSD 0804 10.58±1.35 3.76 0.84 10.91±0.79 2.19 0.31 11.13±0.75 2.09 0.82
ULSD 0805 8.54±1.00 2.79 0.82 8.93±0.66 1.83 0.22 8.78±0.59 1.64 0.64
ULSD 0806 5.06±1.20 3.34 0.70 5.31±0.49 1.36 0.20 5.56±0.44 1.23 0.39
ULSD 0807 10.44±1.62 4.51 0.84 10.93±0.76 2.11 0.27 10.99±0.47 1.31 0.82
ULSD 0808 5.24±0.94 2.62 0.66 5.28±0.47 1.31 0.18 5.53±0.41 1.14 0.53
ULSD 0809 7.80±0.79 2.20 0.60 7.66±0.54 1.50 0.20 7.76±0.53 1.48 0.39
ULSD 0810 10.90±0.92 2.56 0.53 10.86±0.70 1.94 0.31 11.09±0.57 1.59 0.39
Note: All results are in mg/kg of sulfur.
Table 5.33 Use of D7039 Test Method for Online Diesel Analysis
Sulfur Concentration, 15-min Measurement Time 100-s Measurement Time

mg/kg Sigma % RSD Sigma %RSD
200 6.7 3.3
100 1.5 1.5
20 0.37 1.9 1.3 6.5
15 0.34 2.2 1.0 6.3
10 0.28 2.8 0.90 8.4
5 0.22 4.1 0.66 11.7

very low levels of sulfur its precision is not very good. It is applicable to the analysis of
petroleum and petroleum products that are single phase and liquid at ambient condi-
tions, liquefiable with moderate heat, or soluble in hydrocarbon solvents. These materials
can include diesel fuel, jet fuel, kerosine, other distillate oils, naphtha, residual oil,
lubricating base oil, hydraulic oil, crude oil, unleaded gasoline, gasohol, biodiesel, and
similar petroleum products. The scope of the method is 17 mg/kg to 4.6 mass %. An
estimated PLOQ is 16 mg/kg. However, because the instruments covered by this test
method can vary in sensitivity, the applicability of the test method at sulfur concentra-
tions below approximately 20 mg/kg must be determined on an individual basis.
Samples containing more than 4.6 mass % sulfur can be diluted to bring the sulfur
concentration of the diluted material within the scope of this test method. Samples
that are diluted can have higher errors than the undiluted samples. Volatile samples
such as high-vapor pressure gasolines or light hydrocarbons may not meet the stated
precision because of selective loss of light materials during the analysis. A fundamental
assumption in this test method is that the standard and sample matrices are well
matched or that the matrix differences are accounted for. Matrix mismatch can be
caused by a carbon-to-hydrogen ratio difference between samples and standards or by
the presence of other heteroatoms.
In this test method, a sample is placed in the beam emitted from an X-ray tube,
the resultant characteristic X radiation is measured, and the accumulated count is
compared with counts from previously prepared calibration samples to obtain the
sulfur concentration in mass percent or milligrams per kilogram or both. A minimum
of three groups of calibration samples is required to span the concentration range.
Spectral and matrix interferences are generally encountered in XRF analysis.
Spectral interferences are caused by the closeness of the X-ray characteristic lines of the
elements present in a sample and the limited detector ability to completely resolve
them. As a result, the lines produce spectral peaks that overlap with each other.
Spectral interferences may arise from samples containing lead alkyls, silicon, phos-
phorus, calcium, potassium, halides, and catalyst particles present at concentrations
greater than one tenth of the measured concentration of sulfur or more than a few
hundred milligrams per kilogram. The manufacturer’s operating guide should be fol-
lowed to compensate for the interferences.
Matrix effects are caused by concentration variations of the elements in a sample.
These variations directly influence X-ray absorption and change the measured
intensity of each element. For example, performance-enhancing additives, such as
oxygenates in gasoline, may affect the apparent sulfur reading. Other matrix-related
interferences may arise from heavy metal additives; lead alkyls; and elements such as
silicon, phosphorus, calcium, potassium, and the halides, especially if present in con-
centrations greater than one tenth of the measured concentration of sulfur or more
than a few hundred milligrams per kilogram. These types of interferences are always
present in XRF analysis and are completely unrelated to spectral interferences.
The interferences mentioned above may be compensated for in contemporary
instruments with the use of built-in software for spectra deconvolution or overlap

correction and interelement correction by multiple regression or by other mathe-

matical methods. In general, petroleum materials with compositions that vary from
oils as specified in the method may be analyzed with standards made from base
materials that are of the same, or similar, composition. Thus, a gasoline may be simu-
lated by mixing isooctane with toluene in a ratio that approximates the true aromatic
content of the samples to be analyzed. Standards made up from this simulated gasoline
will produce results that are more accurate than results obtained using white oil.
In the case of petroleum materials that contain suspended water, it is recom-
mended that the water be removed before testing or that the sample be thoroughly
homogenized and immediately tested. The interference is greatest if the water creates a
layer over the transparent film because it will attenuate the X-ray intensity for sulfur.
One way to accomplish the removal of water is to centrifuge the sample first under
ambient sealed conditions, taking care that the sample integrity is not compromised.
A large ILS (RR-D02-1635) conducted to obtain the precision of this method
included 27 samples including distillates, gasoline with or without oxygenates, kerosine,
diesel, biodiesel E-85, residual oils, and crude oils. The sulfur concentrations ranged
from 1 mg/kg to 4.6 mass % [40]. The following precisions were found for all materials:
Repeatability: 0.4347X0.6446 mg/kg

Repeatability: [0.4347(Y × 10,000)0.6446 ]/10,000 mass %
Reproducibility: 1.9182X0.6446 mg/kg
Reproducibility: [1.9182 (Y × 10,000)0.6446]/10,000 mass %
On the basis of the NIST SRMs analyzed in this ILS, there did not appear to be
any significant bias between the values certified by NIST and those obtained in this
crosscheck (Table 5.34). Additional separate precision statements for gasolines and
diesels are given in Table 5.35.
Table 5.34 Analysis of NIST SRMs by D4294 ILS
NIST SRM Sulfur, NIST Sulfur Found, Apparent Bias, Relative

Number Matrix mg/kg mg/kg mg/kg Sulfur Bias, %
2296 RFG 40.0 46.3 +6.3 +15.6

2299 RFG 13.6 18.1 +4.5 +33.1
2770 Diesel 41.6 49.4 +7.8 +18.8
2724b Diesel 426.5 430.8 +4.3 +1.01
2721 Crude oil 15.832 16 118 +288 +1.82
2722 Crude oil 2104 2082 –21 –1.00
1619b Residual fuel oil 6960 6654 –306 –4.40
1620c Residual fuel oil 45,610 45,801 +191 +0.42

Table 5.35 Precision for Fuels Analysis Using Test Method D4294 for Sulfur
Samples Repeatability Reproducibility
Diesel: NIST 2770, 2724b, diesel, 1.6658X0.3300 mg/kg 8.9798X0.3300 mg/kg

diesel, diesel, B-5 diesel [1.6658(Y × 10,000)0.3300]/ [8.9798(Y × 10,000)0.3300]/
10,000 mass % 10,000 mass %
Gasoline: RFG, gasoline with 13 % 1.4477X0.3661 mg/kg 7.1295X0.3661 mg/kg
ETBE, gasoline with 5 % ethanol, E-85 [1.4477(Y × 10,000) ]/
0.3661
[7.1295(Y × 10,000)0.3661]/
10,000 mass % 10,000 mass %
ETBE: ethyl-tert-butyl ether.
Although per its scope statement this test method is not meant for measuring
sulfur less than 150 mg/kg in gasoline or diesel samples, it appears to be widely used in
the oil industry despite its poor reproducibility as seen in the ASTM ILCPs. The reason
for its widespread use is probably the low cost of purchase and maintenance of the
instrumentation used in this test method. Table 5.36 compares the results obtained on
several typical samples of petroleum products analyzed by three major methods used
in oil industry laboratories: D2622 WD-XRF, D4294 ED-XRF, and D5453
Table 5.36 Comparison of Test Methods for Sulfur Determination in Petroleum

Products
ASTM Sample D2622 WD-XRF D4294 ED-XRF D5453 UV-Fluorescence
JF 9811 6.1 ± 15.8 (34) 34 ± 83 (81) 2.85 ± 1.8 (16)

MG 9812 184 ± 39 (27) 195 ± 111 (52) 165 ± 68 (16)
MG 9904 96 ± 24 (30) 105 ± 94 (49) 79 ± 39 (15)
MG 0208 13.4 ± 4.8 (36) 31 ± 21 (39) 11.7 ± 1.9 (22)
RFG 9811 218 ± 39 (69) 235 ± 75 (42) 214 ± 68 (20)
RFG 9902 67 ± 24 (73) 72 ± 66 (39) 65 ± 20 (25)
RFG 9904 30 ± 19 (71) 42 ± 69 (39) 29 ± 7 (24)
RFG 9905 99 ± 27 (74) 114 ± 100 (44) 89 ± 22 (25)
RFG 9906 17 ± 17 (66) 29 ± 58 (31) 14 ± 4 (22)
RFG 0307 16.8 ± 3.5 (58) 31 ± 18 (28) 15.0 ± 2.7 (40)
RFG 0404 416 ± 16 (58) 438 ± 20 (35) 411 ± 30 (48)
DL 9810 441 ± 52 (63) 456 ± 102 (143) 440 ± 91 (16)
DL 9902 466 ± 53 (64) 487 ± 75 (142) 471 ± 152 (20)
DL 0202 32.6 ± 6 (80) 44 ± 43 (137) 32.0 ± 4.7 (45)
JF: jet fuel; MG: motor gasoline; DL: diesel fuel.

Note: All results are in mg/kg sulfur. Values are expressed as mean value ± reproducibility (number of
valid results).

UV-fluorescence. Despite the many laboratories using Test Method D4294, poor
reproducibility, sometimes approaching 100 % or more of the mean value, makes this
analysis of very little use, especially in settling quality disputes between a buyer and a
seller or in regulatory affairs. These false-positive results can indicate that the product
is exceeding the regulatory mandatory sulfur limits. Because of such poor quality of
data, EPA did not include D4294 as one of the preferred methods for determining sul-
fur in the fuels of the future. Again, below the 30-mg/kg sulfur level, D5453 has the best
precision among the three test methods compared here, and there is good equivalence
between the results from Test Methods D2622 and D5453.
When the sulfur levels are in the mass percent range, D4294 produces just as good
results as by other creditable test methods. See results for ASTM ILCP crosschecks in
Table 5.37.
However, at very low levels of sulfur, Test Method D4294 produces highly biased
false-positive results.
There is good agreement between Test Methods D2622 and D5453 results, but
erroneously very high results with extremely poor precision were obtained with Test
Method D4294 for these four matrices (Table 5.38).
Calculated precisions at various sulfur levels are given in Table 5.39 for Test
Methods D2622 and D4294. The precision of Test Method D2622 is superior at lower
levels of sulfur concentrations compared with that of D4294.
Table 5.37 Determination of Sulfur at Higher Concentrations
D5453
ASTM Sample D2622 WD-XRF D4294 ED-XRF D4951 ICP-AES UV-Fluorescence
CO 0403 1.008 ± 0.019 (14) 1.042 ± 0.038 (76)

CO 0711 0.1978 ±0.0072 (18) 0.202 ± 0.010 (73)
CO 0803 0.2003± 0.0092 (23) 0.2025±0.0065(82)
CO 0807 2.722 ± 0.126 (19) 2.832 ± 0.098 (89)
CO 0811 0.9319± 0.0363 (25) 0.9487±0.0324(89)
CO 0903 0.4227± 0.0152 (27) 0.4237±0.0132(92)
CO 0907 0.0645± 0.0314 (21) 0.0864±0.0159(70)
GO 0404 1.856 ± 0.069(6) 1.831 ±0.148(7)
GO 0312 1.832 ± 0.060 (8) 1.758± 0.038(4)
GG 0403 0.2089±0.0055(12) 0.2057±0.0098(22)
RFG 0404 0.0416 ± 0.0016(58) 0.0438±0.0022(35) 0.0411±0.003(48)
MG 0404 0.0271 ± 0.011 (30) 0.0276 ± 0.004(51) 0.0258±0.003(39)
RFG 0312 0.0238± 0.0013 (63) 0.0258±0.0029(38) 0.0230±0.002(44)
CO: crude oil; GO: gear oil; GG: general gas oil; MG: motor gasoline.
Note: All values are expressed in mass % as average value ± standard deviation (number of valid results).

Table 5.38 ASTM Crosschecks for Low Levels of Sulfur
Sample D2622 Results D4294 Results D5453 Results
MG 0312 6.3 ± 3.1 (24) 27 ± 31 (39) 3.74 ± 0.85 (37)

DL 0402 9.3 ± 4.3 (67) 26 ± 23 (91) 8.22 ± 1.86 (61)
JF 0403 9.6 ± 2.8 (60) 26 ± 20 (94) 9.0 ± 1.5 (56)
RFG 0403 10.8 ± 4.2 (60) 28 ± 19 (24) 9.31 ± 1.42 (54)
Note: All results are expressed as ppm ± standard deviation (number of valid results).
Table 5.39 C alculated Precision of XRF Test Methods for Sulfur
Sulfur Concentration, D2622 D4294

mg/kg Repeatability Reproducibility Repeatability Reproducibility
3 0.4 1.0
5 0.5 1.6
10 0.9 2.7
25 1.9 5.6 3.4 15
50 3.4 9.8 5.4 24
100 5.9 17.1 8.5 37
500 21 62 24 105
1000 37 108 37 165
5000 135 394 105 465
10,000 235 687 165 727
46,000 798 2333 440 1943
Table 5.40 shows the analyses of NIST crude oil SRMs and Table 5.41 shows the
analysis of ASTM ILCP crude oil crosscheck samples for sulfur using these two alter-
native XRF test methods. Both test methods give equivalent results for sulfur at the
high levels present in crude oils. Obviously many more industry laboratories use
D4294 compared with D2622 because of the low D4294 instrumenation and mainte-
nance costs and ease of operation.
Table 5.40 XRF Determination of Sulfur in NIST Crude Oil SRMs
XRF Results, mass %

Certified Sulfur
NIST SRM Concentration, mass% WDXRF EDXRF Relative Bias, %
2721 Light Sour 1.5832 ± 0.0044 1.5884 1.6118 0.33 1.81

Crude Oil
2722 Heavy Sweet 0.21037 ± 0.00084 0.2105 0.2082 0.06 –1.03
Crude Oil

Table 5.41 XRF Determination of Sulfur in ASTM ILCP Crude Oil Crosschecks
ASTM ILCP Number D2622 Results, mass % D4294 Results, mass %
CO 0911 1.76 ± 0.089 (19) 1.797 ± 0.055 (68)

CO 1003 0.737 ± 0.041 (26) 0.773 ± 0.03 (86)
CO 1011 2.625 ± 0.086 (25) 2.721 ± 0.084 (84)
All results are expressed as robust mean ± robust standard deviation (number of
valid results).
D6445: Sulfur in Gasoline and Oxygenates Using ED-XRF

Test Method D6445 also covers the determination of sulfur in unleaded gasoline and
gasoline-oxygenate blends in the sulfur range of 48–1000 mg/kg. The sample is
placed in the beam emitted from an X-ray source. The resultant excited characteristic
X radiation is measured, and the accumulated count is compared with counts from
previously prepared calibration standards to obtain the sulfur concentration of the
sample. One group of calibration standards is required to span the range covered by
this test method. The matrix effects in this test method are similar to those mentioned
above for Test Method D4294.
D7212: Low Sulfur in Automotive Fuels by ED-XRF Using a

Low-Background Proportional Counter
This test method determines the total sulfur in automotive fuels in the concentration
range of 7–50 mg/kg. The PLOQ is 7 mg/kg sulfur. In this test method, a sample is
placed in the beam emitted from an X-ray source with titanium target and primary
filtration so that the excitation is by essentially monochromatic radiation of 4.51 keV
and virtually no background at 2.3 keV. A low-background proportional counter
measures the intensity of the fluorescent sulfur K series and argon K series intensity
(from residual air), and the accumulated counts are compared with the counts from
previously prepared calibration standards to obtain the sulfur concentration in the
sample. If chlorine is expected to be present in the sample, then other regions of
the spectrum must be measured to provide compensation for the spectral overlap. One
group of calibration standards is required to span the concentration range from
0 to 150 mg/kg sulfur. High-purity di-n-butyl sulfide dissolved in sulfur-free mineral
oil is used as the calibrant. There could be interference in the method from overlapping
lines by lead alkyls, silicon, phosphorus, potassium, calcium, and halides if their
aggregate concentration is more than 10 mg/kg. The most likely interference is
chlorine found in biodiesels derived from recycled waste vegetable oil. The presence
of water or oxygenates may also alter the sensitivity for sulfur. The manufacturer’s
operating guide should be followed to compensate for the interferences. The precision
of this test method is given in Table 5.42.

Table 5.42 Precision of ED-XRF Sulfur Test Methods for Gasoline and Diesel
Test Method Sulfur Range Repeatability Reproducibility Bias
D4294 1 mg/kg to 4.6 mass % 0.5409X0.6154 2.4535X0.6154 No bias

D6445 48–1000 mg/kg 12.3(X + 10)0.1 36.26(X + 10)0.1 Not known
D6481 0.05–1.0 mass % 0.01648(X + 0.0141)0.8 0.1024 (X + 0.0141)0.8 Not known
D7212 7–50 mg/kg 1.6196X 0.1
3.7668X 0.1
No bias
D7220 6–50 mg/kg 0.6430X0.504 1.1121X0.504 No bias
Note: Where X is the mean sulfur result of two determinations.
D7220: Sulfur in Petroleum Products by Monochromatic ED-XRF

Spectrometry
This test method measures total sulfur in the range of 3–942 mg/kg in automotive,
No. 2 heating, and jet fuels. The PLOQ of this method is 3 mg/kg. This test method
is applicable to gasoline, oxygen-enriched gasoline (RFG), diesel, diesel/biodiesel
blends containing up to 20 vol % biodiesel, kerosine, jet fuel, jet fuel/biodiesel
blends containing up to 5 vol % biodiesel, and No. 2 home heating oil. A funda-
mental assumption of this method is that the standard and the sample matrix are
well matched. Matrix mismatch can be caused by a carbon-to-hydrogen ratio
difference between the samples and the standards or by the presence of other het-
eroatoms. In this method, the sample is placed in the monochromatic X-ray beam,
and the peak areas of the sulfur K-alpha line at 2.307 keV are measured. The back-
ground spectrum measured with a sulfur-free white oil or other matrix-matching
blank sample is adapted to the measured spectrum using the adjustment regions
following the instrument manufacturer’s instructions and then subtracted from the
measured spectrum [41]. The resultant net counting rate is then compared to a
previously prepared calibration curve or equation to obtain the concentration of
sulfur in the sample in milligrams per kilogram.
The interferences in this method are of the same type as discussed above for other
XRF test methods. M-85 and M-100 fuels have a high oxygen content, leading to
significant absorption of sulfur K alpha radiation. However, such fuels can be analyzed
with this test method provided that correction factors are applied to the results (when
calibrating with white oils) or that the calibration standards are prepared to match the
matrix of the sample. High-purity di-n-butyl sulfide dissolved in sulfur-free white oil
is used as the calibrant.
The precision and bias of this test method are given in Table 5.41 based on two ILS
(RR-D02-1592 and RR-D02-1736). Three NIST SRMs were included in the ILS, and on
the basis of the analysis, there was no significant bias between the certified values and
those obtained by this test method.

NIST Sulfur, NIST Average Measured Observed Statistically

SRM # Matrix Value, mg/kg Sulfur, mg/kg Difference, mg/kg Significant?
2770 Diesel 41.57 ± 0.39 41.8 0.2 No

2299 Gasoline 13.6 ± 1.5 12.5 -1.1 No
1616b Kerosine 8.4 ± 0.12 8.9 0.5 No
The precision and bias of these ED-XRF methods for gasoline and diesel are compared
in Table 5.42.
A CEN TC19 WG27 round-robin study utilized 102 laboratories for the determi-
nation of sulfur in gasoline and diesel samples. The repeatability and reproducibility
values presented in Table 5.43 were obtained for gasoline and diesel samples calculated
at two sulfur levels: 10 and 30 mg/kg.
X-Ray Transmission OnLine Determination of Sulfur

in Crude Oils
Fess has shown the applicability of X-ray transmission (XRT) technology for online
determination of sulfur in crude oils [42]. In this method, sulfur absorbs X rays trans-
mitted between an X-ray source and detector. The technique compensates for density
changes in the oil and minimizes the effects of variations in the carbon-to-hydrogen
ratio of the oil. When used online, the instrument obtains the sulfur measurement in
the high-pressure flow conditions required to pump crude oil, typically 800 psig in
pipelines. Automatic compensation for variation in oil density and temperature are
achieved using integrated densitometer and temperature sensor readings taken by the
instrument as the sulfur is being measured.
Possible interferences include the presence of chlorine in the oil in the ten-fold
ratio to sulfur and coating of the flow cell beryllium windows. The latter interference
has a negligible effect on the sulfur measurement. The precision values for the XRT
Table 5.43 Precision of Sulfur Determination in CEN Round-Robin Study [41]
Gasoline 10 mg/kg Diesel 10 mg/kg Gasoline 30 mg/kg Diesel 30 mg/kg
Technique r R r R r R r R
WD-XRF (IS-HP) 2.12 3.54 1.85 3.33 3.08 4.95 2.59 4.67
WD-XRF (IS-LP) 3.77 5.96 2.46 3.97 3.77 5.96 3.28 5.29
WD-XRF (HP) 1.92 3.45 1.92 2.99 2.57 5.74 2.16 4.97
WD-XRF (LP) 3.24 5.93 2.22 5.19 4.32 7.90 2.71 6.34
ED-XRF (nonpolarized) 6.29 10.05 7.38 10.4 7.87 12.56 7.95 11.2
ED-XRF (polarized) 2.00 2.28 1.59 2.14 3.00 3.43 1.59 2.14
UV-fluorescence 0.98 2.71 1.15 2.24 2.24 6.21 2.21 4.48
Microcoulometry 1.32 3.58 1.69 3.29 2.63 7.17 2.36 4.60
IS-HP: internal standard, high-powered instrument; IS-LP: internal standard, low-powered instrument

analyzer is equivalent to the repeatability value quoted in Test Method D4294 at sulfur
above 0.1 mass % concentrations.
D6376: WD-XRF Test Method for Sulfur in Petroleum Coke

Test Method D6376 determines several metals in raw or calcined petroleum coke using
WD-XRF. Detection limits, sensitivity, and optimal element ranges will vary with the
matrices, spectrometer type, analyzing crystal, and other instrument conditions and
parameters. The sample of petroleum coke is dried to constant weight at 110 ± 10°C
and then crushed to pass a 75-µm (No. 200 mesh) sieve. A weighed portion of this
powder is mixed with stearic acid or other suitable binder and then milled and com-
pressed into a small, smooth pellet suitable for analysis. An X-ray beam irradiates the
pellet. The characteristic X rays of the elements analyzed are excited, separated, and
detected by the WD-XRF instrument. The K alpha spectral lines are used for all of the
elements determined by this test method. Changes in the sulfur concentration in the
sample affect analyte X-ray intensities. Therefore, the magnitude of the sulfur effect on
each metallic element needs to be determined and appropriate correction needs to be
applied. Results are particle dependent, and erroneous data may be collected if analyt-
ical samples contain particles varying significantly in size from those in the reference
samples. The most difficult problems occur when there are coarse particles in the
petroleum coke samples and finely ground reference samples. In such cases, it is best
to grind the analytical sample, achieving a size distribution similar to the refer-
ence sample. The precision for sulfur determination by this test method in the con-
centration range of 0.10–7.0 mass % sulfur is a repeatability of 0.12 % and a
reproducibility of 0.22 %.
DETERMINATION OF SULFUR SPECIES IN PETROLEUM PRODUCTS

In addition to the test methods described above for the determination of total sulfur in
petroleum products, there are approximately a dozen test methods for the determina-
tion of sulfur compounds in petroleum products. These are listed in Table 5.6 above,
and their essential parameters are described below. The reason for the interest about
the knowledge of sulfur compounds as opposed to other metallic elements in which
only information on total amount present is usually satisfactory is because sulfur can
be present in a product in different forms and the sulfur compounds can behave in
different fashions in regards to their industrial, environmental, and physicochemical
contexts.
D1275: Corrosive Sulfur in Electrical Insulating Oils

This test method covers the detection of corrosive sulfur compounds (inorganic and
organic) in electrical insulating oils of petroleum origin. New and in-service mineral
insulating oils may contain substances that cause corrosion under certain conditions
of use. In most of their uses, insulating oils are continually in contact with metals that
are subject to corrosion. The presence of sulfur corrosive compounds will result in

deterioration of these metals. The extent of deterioration is dependent on the quantity

and type of corrosive agent and time and temperature factors. Detection of these unde-
sirable impurities, although not in terms of quantitative values, is a means for recog-
nizing the hazard involved.
This test method is designed to detect the presence of, or the propensity to form,
free (elemental) sulfur and corrosive sulfur compounds by subjecting copper in con-
tact with oil under prescribed conditions.
Two methods (A and B) are available. Method A has been in place since 1953. In
this method, 250 mL of oil is aged in a sealed flask for 19 h at 140°C in the presence of
a copper strip. Method B is more rigorous and is the preferred method. In this method,
220 mL of oil is aged in a sealed heavy-walled bottle for 48 h at 150°C in the presence
of a copper strip.
After the test, the oil is classified as corrosive or noncorrosive according to
Table 5.44. Classification of corrosive or noncorrosive is to be aided through the use of
ASTM copper strip corrosion standards as referenced in ASTM Test Method D130. A
description of the tarnish levels is only provided in Table 5.45 for reference.
The corrosive effects of unstable sulfur compounds present in the oil are reduced
when aged under strong oxidizing conditions such as when oxygen is present. It is
imperative to keep the reaction flask well sealed after nitrogen bubbling. If the oil
visibly darkens during testing, then most likely oxygen has entered the vessel and
oxidized the oil. In such cases, the test procedure has become compromised and must
be repeated.
No statement of precision or bias of this test method can be made because the
results merely state whether there is conformance to the criteria for success specified in
the procedure, and it is not quantitative.
D1662: Active Sulfur in Cutting Oils

This test method covers the determination of active sulfur in cutting oils and applies to
sulfur that is reactive with copper powder at a temperature of 150°C in cutting fluids
containing natural and added sulfur. Active sulfur is defined as the amount of sulfur
that will react with metallic copper at a temperature of 150°C under the prescribed
conditions. It has not been determined as to how the active sulfur content determined
by this method may relate to field performance of the cutting fluid.
Table 5.44 Copper Strip Classifications
Classification Description
Noncorrosive Orange, red, lavender, multicolored with lavender blue or silver, or both, overlaid
on claret red, silvery, brassy or gold, magenta overcast on brassy strip,
multicolored with red and green showing (peacock) but no gray.
Corrosive Transparent black, dark gray or dark brown, graphite or lusterless black, glossy
or jet black, any degree of flaking

Table 5.45 Copper Strip Tarnish Level Classifications
Classification Designation Description
Freshly polished — Unable to reproduce upon aging; therefore, no description

is provided.
1 Slight tarnish a. Light orange, almost the same as freshly polished strip
b. Dark orange
2 Moderate tarnish a. Claret red
b. Lavender
c. Multicolored with lavender blue or silver, or both
overlaid on claret red
d. Silvery
e. Brassy or gold
3 Dark tarnish a. Magenta overcast on brassy strip
b. Multicolored with red and green showing (peacock),
but no gray
4 Corrosion a. Transparent black, dark gray or brown with peacock
green barely showing
b. Graphite or lusterless black
c. Glossy or jet black
In this test method, a sample is treated with copper powder (>99 % pure) at 150°C.
The copper powder is filtered from the mixture. Active sulfur is expressed as the
difference between the sulfur contents of the sample as determined before and after
treatment with copper. Any accepted method for sulfur determination can be used if
the test method has a precision of ±0.15 % for sulfur.
The precision values presented in Table 5.46 were obtained based on an ILS
(RR-D02-1628) among nine laboratories using four cutting fluid samples of nominal
active sulfur levels of 0.9 %, 3.6 %, 0.3 %, and 2.1 %.
D3227: Thiol Mercaptan Sulfur in Fuels by Potentiometric Method

This test method is used for the determination of thiol mercaptan sulfur in gasoline,
kerosine, aviation turbine, and distillate fuels containing from 0.0003 to 0.01 mass %
Table 5.46 Precision for Active Sulfur Determination
Materials Average Concentration, wt % Repeatability Reproducibility
A 0.9454 0.0974 0.1976

B 3.3687 0.2862 1.6205
C 0.3902 0.2296 0.8312
D 1.9643 0.4343 1.3070

mercaptan sulfur. Organic sulfur compounds such as sulfides, disulfides, and

thiophene do not interfere. Elemental sulfur in amounts less than 0.0005 mass %
does not interfere. H2S will interfere if not removed. In this method, the H2S-free
sample is dissolved in an alcoholic sodium acetate titration solvent and titrated
potentiometrically with silver nitrate solution using as an indicator the potential
between a glass electrode and a silver/silver sulfide indicating electrode. Under these
conditions, the mercaptan sulfur is precipitated as silver mercaptide, and the end
point of the titration is shown by a large change in cell potential. See Fig. 5.28 for an
example of a potentiometric titration curve. The shape of the titration curve may
change with different instruments. The precision of this test method based on an ILS
is as follows:
Repeatability 0.00007 + 0.027X

Reproducibility 0.00031 + 0.042X
Where X is the average mercaptan result in mass %.

A precision curve for mercaptan sulfur determination in petroleum products is
shown in Fig. 5.29.
D3712: Oil-Soluble Petroleum Sulfonates by Liquid Chromatography

This test method covers the analysis of refined and crude natural and synthetic
oil-soluble sulfonate products. If present, resins are recovered with the oil phase and
Fig. 5.28 Potentiometric Titration Curvesin Test Method D3227 for Mercaptan Sulfur.

Fig. 5.29 Precision Curves for Analysis of Mercaptans Using Test Method D3227.
carboxylates are recovered as sulfonates. It is applicable to sodium and ammonium

sulfonate products. In this test method, the sample, except a sodium sulfonate product,
is dissolved in ethyl ether and converted to sulfonic acid using dilute hydrochloric
acid. The sulfonic acid after extraction is converted to sodium sulfonate, and the
isolated sodium sulfonate and mineral oil are dissolved in chloroform. An aliquot of
the chloroform solution or a sample of sodium sulfonate product, dissolved in chloro-
form, is placed on a silica gel column. The oil is eluted with chloroform, the sulfonate
with ethanol, and both are determined gravimetrically. The average molecular weight
is calculated from the average equivalent weight of the sodium sulfonate, which is
determined by ashing a portion of the isolated sodium sulfonate. Water is determined
using Test Method D95, base number by D2896 potentiometric titration, and relative
density by a pycnometer.
On the basis of an ILS, the precision of this test method for sulfonate determina-
tion is as follows:
Repeatability 0.63 mass %

Reproducibility 0.92 mass %
D4952: Active Sulfur Species in Fuels and Solvents (Doctor Test)

Sulfur present as mercaptan or as H2S in distillate fuels and solvents can attack many
metallic and nonmetallic materials in fuel and other distribution systems. A negative
result in the Doctor test ensures that the concentration of these compounds is insuffi-
cient to cause such problems in normal use.

This is a qualitative test for the analysis of active sulfur species in fuels and
solvents. It is colloquially called the “Doctor test.” It is intended primarily for the
detection of mercaptans in motor fuel, kerosine, and similar petroleum products. This
method may also provide information on H2S and elemental sulfur that may be
present in these sample types. In this test method, the sample is shaken with sodium
plumbite solution, a small quantity of sulfur powder is added, and the mixture is
shaken again. The presence of mercaptans or H2S or both is indicated by discoloration
of the sulfur floating at the oil-water interface or by discoloration of either of the
phases. If the solution is discolored, or if the yellow color of the sulfur film is noticeably
masked, then the result is reported as positive and the sample is considered as “sour.”
If the sample remains unchanged in color and the sulfur film is bright yellow or only
slightly discolored with gray or flecked with black, then the result is reported as
negative and the sample is considered as “sweet.” A negative result in the Doctor test
ensures that the concentration of mercaptans or H2S is insufficient to cause problems
in normal use. This examination must be made with extreme care. Sometimes the
sulfur layer will only be flecked with spots of gray or black, and if there is any change
in the color of either the sample or the Doctor solution these spots will be difficult
to detect.
This test cannot be used if there are more than trace amounts of peroxides in
the test sample. Peroxides can give false-positive results when mercaptans are at low
levels or are not even present.
Strictly speaking, the test will not reject the sample only on the basis of mer-
captans. The primary criterion for rejection is the appearance of the sulfur layer
after shaking, and small amounts of mercaptans will only discolor the sulfur.
However, samples that contain mercaptans will also normally contain small
amounts of sulfur in other forms that will discolor the layers at the interface. The
addition of pure, sublimed flowers of sulfur is required to indicate that a reaction
of mercaptan and sodium plumbite has occurred. When the sample contains
appreciable amounts of H2S, a heavy black precipitate may be formed during the
initial shaking and before the addition of the sulfur. If such a precipitate is noted,
then the test may be stopped at that point and the sample reported as “does not
pass.” However, if this observation is at all doubtful, then the test should be contin-
ued. If the sample darkens before the addition of sulfur is made, then this indicates
that the sample contains mercaptans and an excess of elemental sulfur that is
needed to drive the sample reaction with sodium plumbite. If the Doctor test
is positive, then mercaptan content may be determined using ASTM Test Method
D3227.
The relationship between the appearance of the sample and the type of sulfur
species present is shown in Table 5.47. No justifiable values of repeatability, reproduc-
ibility, or bias can be stated for this test method because the test only detects the
presence or absence of active sulfur species, such as H2S or mercaptan.

Table 5.47 Relationship between Sample and Sulfur
Appearance Type of Sulfur
Darkening of the sample before addition of sulfur Mercaptans and elemental sulfur present in the
sample
Black precipitate before addition of sulfur Appreciable amounts of H2S
Black color of sulfur after shaking Traces of H2S
Spots of discoloration in the sulfur layer plus H2S absent; mercaptans or elemental sulfur or
darkening of the sample both present
Clear yellow Doctor solution; no discoloration of H2S and elemental sulfur absent; traces of
sulfur mercaptans present
D5303: Trace Carbonyl Sulfide in Propylene by GC

In the processes producing propylene, carbonyl sulfide (COS) usually remains with the
C3 hydrocarbons and must be removed because it affects product quality. COS acts as
a poison to commercial polymerization catalysts, resulting in deactivation and costly
process downtime.
This test method covers the determination of traces of COS in propylene in
concentrations from 0.5 to 40 mg/kg. The lower limit of this test method is believed
to be below 0.1 mg/kg depending on the sample size and sensitivity of the instru-
mentation being used. H 2S and SO2 can be present in propylene and must be
separated from COS with a Carbopack BHT 100 column or with the Chromosil
300 column.
In this test method, a sample is removed from the sample cylinder, COS is
separated from propylene, and COS is detected calibrating the detector and quanti-
fying the COS content in the sample. A relatively large volume of sample is injected
into a gas chromatograph having a single packed column, operated isothermally at
10–50°C, that separates COS from propylene. COS is detected with a FPD. Calibration
is done using a known gas standard blend of COS in the range expected for the
sample. The COS peak area in the sample is measured, and the concentration of
COS is calculated. Figure 5.30 shows a calibration plot of COS measurement, and
Fig. 5.31 shows a chromatogram of COS in propylene.
On the basis of an ILS (RR-D02-1298), the following precision was obtained:
Repeatability 0.15X
Reproducibility 1.0X
Where X is the average of two results in mg/kg.

The bias of this method has not been determined because no acceptable reference
material suitable for determining the bias of this procedure is available.

Fig. 5.30 C alibration Plot for Carbonyl Sulfide Using Test Method D5303.
D5623: Sulfur Compounds in Light Petroleum Liquids by GC and

Sulfur-Selective Detection
GC with sulfur selective detection provides a rapid means to identify and quantify
sulfur compounds in various petroleum feeds and products. Often these materials
contain varying amounts and types of sulfur compounds. Many sulfur compounds
are odorous, corrosive to equipment, and inhibit or destroy catalysts deployed in
downstream processing. The ability to speciate sulfur compounds in various petro-
leum liquids is useful in controlling sulfur compounds in finished products and is
frequently more important than knowledge of the total sulfur content alone.
This test method is applicable to distillates, gasoline motor fuels (including those
containing oxygenates), and other petroleum liquids with a final boiling point of
approximately 230°C or lower at atmospheric pressure. The applicable concentration
range will vary to some extent depending on the nature of the sample and the instru-
mentation used. However, in most cases, the test method is applicable to the determi-
nation of individual sulfur species at levels of 0.1–100 mg/kg.

Fig. 5.31 Chromatogram of Carbonyl Sulfide in Propylene Using Test Method D5303.
This test method does not purport to identify all individual sulfur compounds.
Detector response to sulfur is linear and essentially equimolar to all sulfur compounds
within the scope of this test method. Thus, unidentified and known individual com-
pounds are determined. However, many sulfur compounds (e.g., mercaptans and H2S)
are reactive, and their concentrations in the sample may change during sampling and
analysis. The total sulfur content of the sample is estimated from the sum of the indi-
vidual compounds determined; however, this test method is not the preferred method
for the determination of total sulfur.
In this test method, the sample is analyzed by GC with an appropriate sulfur-
selective detector. Calibration is achieved by the use of an appropriate internal or
external standard (e.g., diphenyl sulfide, 3-chlorothiophene, or 2-bromothiophene).
All sulfur compounds are assumed to produce equivalent response as sulfur. As sulfur
compounds elute from the GC column, they are quantified by a sulfur-selective detec-
tor to produce a linear and equimolar response to sulfur compounds. For example, a
chemiluminescence or atomic emission detector is used in the sulfur channel. A typi-
cal chromatogram for the analysis of a typical gasoline sample containing approxi-
mately 85 ppm of total sulfur is shown in Fig. 5.32.

Fig. 5.32 Chromatogram of a Gasoline Sample Analyzed by Test Method D5623

for Sulfur.
On the basis of an ILS (RR-D02-1335) using chemiluminescent detector for sul-

fur, the following precision was obtained. There are not enough data to calculate statis-
tics for use of an atomic emission detector.
Sulfur Concentration,
Standardization Analysis mg/kg Repeatability Reproducibility
Internal Single stable component 1 to 100 0.11X 0.42X

Total sulfur 10 to 200 0.12X 0.33X
External Single stable component 1 to 100 0.31X 0.53X
Total sulfur 10 to 200 0.24X 0.52X
Note: Where X is the average sulfur concentration in mg/kg.
Gras et al. have demonstrated the determination of low sulfur levels in hydrocar-
bons using low thermal mass gas chromatography (LTMGC) and a dual plasma sulfur
chemiluminescent detector (DP-SCD). Highly sensitive total volatile sulfur measure-
ment can be made in less than 30 s with detection limits in the range of 20–30 ppb. The
response is linear over at least three orders of magnitude sulfur with excellent repeat-
ability. Taking advantage of LTMGC’s rapid temperature programming and cool
downtime, it is also possible to measure individual sulfur species, analogous to ASTM
Test Method D5623. Conditions have also been developed using the same analytical
apparatus to detect the major elemental sulfur allotropes (S2, S3, S6, S7, and S8) in gaso-
line at levels that can cause silver corrosion [43].
D5705: H2S in Vapor Phase Above Residual Fuel Oils

Excessive levels of H 2S in the vapor phase above residual fuel oil in storage
tanks may result in a health hazard, violation of Occupational Safety and Health

Administration (OSHA) limits, and public complaints about odors. Control mea-
sures to maintain safe levels of H2S in the tank atmosphere for those working in the
vicinity require a consistent method for assessment of potentially hazardous levels
of H2S in the fuel oils. This test method was developed to provide refineries, fuel
terminals, and independent testing laboratories, which do not have access to
analytical instruments such as a gas chromatograph, with a simple and consistent
field test method for the rapid determination of H2S in the vapor phase of residual
fuel oils.
This test does not necessarily simulate the vapor-phase H2S concentration of a
fuel storage tank. However, it does provide a level of consistency so that the test
result is only a function of the residual fuel oil sample and not the test method,
operator, or location. No general correlation can be established between this field
test and the actual vapor-phase concentration of H2S in residual fuel oil storage or
transports. However, a facility that produces fuel oil from the same crude source
under essentially consistent conditions might be able to develop a correlation for its
individual case.
This test method is applicable to liquids with a viscosity range of 5.5 mm2/s at
40°C to 50 mm2/s at 100°C. The test method is applicable to fuels conforming to ASTM
Specification D396 Grade Nos. 4, 5 (Heavy), and 6. The applicable range is from 5 to
4000 ppmv. In this test method, a 1-L H2S inert container (glass test bottle) is filled to
50 vol % with fuel oil from a filled H2S-inert container (glass sample bottle) just before
testing. In the test container, the vapor space above the fuel oil sample is purged with
nitrogen to displace air. The test container with the sample is heated in an oven to 60°C
and agitated on an orbital shaker at 220 rpm for 3 min. A typical assembly of the appa-
ratus used for this test is shown in Fig. 5.33.
A length-of-stain detector tube and hand-operated pump are used to measure the
H2S concentration in the vapor phase of the test container. The length-of-stain detector
tube should be close to but not in contact with the liquid surface.
SO2 and mercaptans typically may cause positive interferences. In some cases,
nitrogen dioxide can cause a negative interference. Most detector tubes will have a
precleanse layer designed to remove certain interferences up to some maximum inter-
ferant level. The manufacturer’s instructions should be followed for specific interfer-
ence information.
On the basis of an ILS (RR-D02-1358), the following precision can be expected. In
this study, eight participants in four locations tested four fuels each four times. These
fuels had a H2S content between 9 and 4000 ppm and a viscosity range between 80 and
700 mm2/s at 50°C.
Repeatability 0.20X + 10
Reproducibility 0.30X + 15
Where X is the average of the two results.

Fig. 5.33 Apparatus for Measurement of H2S in Vapor Phase of Residual Fuel Oil in
Test Method D5705.
D6021: H2S in Residual Fuels by Multiple Headspace Extraction and Sulfur

Specific Detection
Excessive levels of H2S in the vapor phase above residual fuel oils in storage tanks may
result in a health hazard, violation of OSHA safety limits, and public complaint. H2S
can also cause corrosion during refining and other production activities. Control

measures to maintain safe levels of H2S require a consistent method for the assessment
of potentially hazardous levels of H2S in fuel oils.
This test method covers a method suitable for measuring the total H2S in heavy
distillates, heavy distillates/residual fuel blends, or residual fuels as defined in ASTM
Specification D396 Grade 4, 5 (Light), 5 (Heavy), and 6 when the H2S concentration in
the fuel is in the range of 0.01–100 mg/kg.
In this test method, a representative sample of residual fuel oil is obtained in
sufficient quantity to completely fill the sample container. The sample is taken to the
laboratory, preferably within 1–4 h, within 24 h maximum, and placed in a refrigerator
until the H2S analysis can be run. A 0.05- to 5.0-g aliquot is placed in a headspace vial
and heated in an oven at 60°C for more than 5 but less than 15 min. The headspace gas
is sampled and injected into either of two types of apparatuses capable of measuring
the H2S concentration in the gaseous sample [44]. The two types of apparatuses are
those using the reaction of lead acetate with H2S (Test Method D4084 or D4323) and
those based on chemiluminescence (Test Method D5504). The remaining contents of
the headspace vial are cooled for 5 min and then again heated in the oven and sub-
jected to analysis as before. This step is then repeated a third time. This is called as
multiple headspace extraction (MHE) procedure. A schematic of headspace analysis
system is shown in Fig. 5.34. A linear plot of the natural logarithm of the area or peak
height difference of the instrument reading against the number of injections is
Fig. 5.34 Schematics of Head space Analysis System Used in Test Method D6021 for
Sulfur.

indicative of the correctness of the extraction procedure. Repeatability of this analysis

based on analysis done in a single laboratory was found to be as follows. Because gen-
erating reproducibility data is not practical, such data are not available.
H2S Concentration, mg/kg 0.022 0.24 37.3

Repeatability 0.004 0.07 1.9
D7621: H2S in Fuel Oils by Rapid Liquid-Phase Extraction

Excessive levels of H2S in the vapor phase above residual fuel oils in storage tanks can
result in health hazards, violation of local occupational health and safety regulations,
and public complaint. Corrosion can be caused by the presence of H2S during refining
or other activities. Control measures to maintain safe levels of H2S require a precise
method for the measurement of potentially hazardous levels of H2S in fuel oils.
H2S concentrations in the liquid and vapor phase attempt to reach equilibrium in
a static system. However, this equilibrium and the related liquid and vapor concentra-
tions can vary greatly depending on temperature and the chemical composition of the
liquid phase. The equilibrium of the vapor phase is disrupted the moment a vent or
access point is opened to collect a sample. Hence, during sampling operations, care
must be taken to ensure that the integrity of the material is maintained and the possi-
ble loss of H2S is kept to a minimum. The precision of analysis is critically dependent
on the sampling, thermal history, and handling of the test sample. Suitable containers
for keeping the sample aliquots include amber glass bottles and epoxy-lined contain-
ers. The latter should be examined visually to ensure that the lining has not been dam-
aged and that the containers are not dented. To ensure sample integrity, the containers
should be filled approximately 95 % full and capped immediately after filling. The
samples should be taken to the laboratory as soon as it is practical after sampling. The
test should be done immediately if possible. If the samples are not tested immediately,
then they should be stored in a cool place such as a refrigerator and should be analyzed
within 3 days after sampling. If a dedicated H2S sample cannot be taken, then the H2S
measurement should be the first test performed on the sample because any additional
handling of the sample can lead to loss of H2S and low results.
When samples are drawn in a manner that does not minimize vapor loss (e.g.,
continuous drip sampling), a dedicated sample should be drawn for H2S determina-
tion. When the samples cannot be drawn directly into the sample container, the sam-
ple should be transferred from the sampling device into the sample container, ensuring
that H2S loss is kept to a minimum.
This test method was developed so that refiners, fuel terminal operators, and
independent testing laboratory personnel can rapidly and precisely measure the
amount of H2S in residual fuel oils and distillate blend stocks with a minimum of
training in a wide range of locations.
Test Method D5705 (described above) provides a simple and consistent field test
method for the rapid determination of H2S in the residual fuel oil vapor phase.

However, it does not necessarily simulate the vapor phase H 2S concentration of

a fuel storage tank, nor does it provide any indication of the liquid-phase H2S
concentration.
Test Method D6021 (discussed above) also measures the H2S concentration in
the liquid phase; however, it requires a laboratory and a skilled operator to per-
form the complex procedure and calculations, and it does not offer any reproduc-
ibility data.
This test method covers a procedure for the determination of the H2S content of
fuel oils, such as marine residual fuels, marine distillate fuels, and blend stocks, in the
range 0.40–15.0 mg/kg as measured in the liquid phase. The test method is applicable
to materials with a viscosity up to 3000 mm2/s at 50°C. ASTM specification fuels fall-
ing within the scope of this test method are Specification D396 Grade Nos. 5 (light),
5 (heavy), and 6.
In this test method, a test specimen is introduced into a heated test vessel contain-
ing diluent base oil. Air is bubbled through the oil to extract the H2S gas. The H2S is
passed, with the air, via a vapor phase processor (Procedure A only) to an H2S-specific
electrochemical detector to enable the H2S content of the air to be measured and the
amount in the liquid phase to be calculated in milligrams per kilogram. The filter car-
tridge is not required in Procedure B. Thus, this test method offers a 15-min automated
test, simplicity, full precision, and a degree of portability. A schematic of the H2S appa-
ratus is shown in Fig. 5.35.
On the basis of an ILS conducted at the Energy Institute, United Kingdom, the
following precision was obtained. This study involved 7 instruments and individual
operators at a single location testing 15 samples in duplicate covering the H2S levels
from 0.01 to 15.3 mg/kg and viscosities up to 3000 mm2/s at 50°C. Figure 5.36 shows a
graphical illustration of the precision relationship with H2S levels.
Fig. 5.35 Schematics of Apparatus Used in Test Method D7621 for H2S Determination.

Fig. 5.36 Precision of Analysis Using Test Method D7621 for H2S Determination.
Repeatability 0.2970X0.6 mg/kg

Reproducibility 0.5232X0.6 mg/kg (Residual Fuels Procedure A)
0.4459X0.55 mg/kg (Distillate and Residual Fuels Procedure A)
0.2389X0.7 mg/kg (Distillate Fuels Procedure B)
Where X is the average of the results being compared.

The calculated repeatability and reproducibility for some typical H2S concentra-
tions are shown in Table 5.48. Because there are no accepted reference materials
suitable to determine the bias for the procedures in this method for measuring H2S,
bias not been determined.
D7318, D7319, and D7328: Determination of Sulfate in Fuel—Ethanol

Ethanol is used as a blending agent added to gasoline. Sulfates are indicated in filter-
plugging deposits and fuel injector deposits. When fuel ethanol is burned, sulfates may
contribute to sulfuric acid emissions. Ethanol acceptability for use depends on the
sulfate content.
These three test methods are used for the determination of sulfate species in eth-
anol and fuel-ethanol blends. Some terms are used specifically in these three test meth-
ods. These definitions are given here.
• Existent inorganic sulfate: Inorganic sulfate species actually present in the sample at
the time of the analysis with no oxidation treatment. In Test Method D7318, inor-
ganic sulfate is present as sulfate in ethanol.
• Inorganic sulfate: Sulfate (SO42–) species present as sulfuric acid, ionic salts of this
acid, or mixtures of these.

Table 5.48 C alculated Repeatability and Reproducibility for Typical H2S

Concentrations
Procedure A (Distillate and

Residual Fuels) Procedure B (Distillate Fuels) Procedure B (Residual Fuels)
Range 0.60–12.5 Range 0.4–9.7 Range 0.4–15.3
H2S, mg/kg r R r R r R
0.40 – – 0.11 0.13 0.17 0.30

0.60 0.25 0.34 0.15 0.17 0.22 0.39
1.00 0.33 0.45 0.21 0.24 0.30 0.52
1.50 0.42 0.56 0.28 0.32 0.38 0.67
2.00 0.49 0.65 0.34 0.39 0.45 0.79
3.00 0.71 0.82 0.45 0.52 0.57 1.01
5.00 0.81 1.08 0.65 0.74 0.78 1.37
10.0 1.18 1.58 1.05 1.20 1.18 2.08
12.5 1.34 1.79 – – 1.35 2.38
15.0 – – – – 1.51 2.66
• Potential sulfate: Inorganic sulfate species present after the sample has been reacted
with an oxidizing agent.
Test Method D7318 covers a potentiometric titration procedure for determining the
existent inorganic sulfate content of hydrous, anhydrous ethanol, and anhydrous
denatured ethanol, which is added as a blending agent with spark-ignition engine
fuels. Its range of analysis is between 1.0 and 2.0 mg/kg existent inorganic sulfate in
denatured ethanol samples.
In this test method, an ethanol sample containing inorganic sulfate is titrated in
ethanolic medium with a standard lead nitrate solution. Lead sulfate precipitate is
formed during the titration. Perchloric acid is added to remove possible interference
from carbonate. In the potentiometric titration, the end point is signaled by an increase
in lead ion activity, as measured by a lead-selective electrode. Typical examples of
potentiometric titration curves for sulfate standards in ethanol, and for existent inor-
ganic sulfate in commercial denatured ethanol samples, are given in Figs. 5.37 and
5.38, respectively.
On the basis of an ILS (RR-D02-1615), the following precision limits were obtained
for existent inorganic sulfate in the range of 1.0–20 mg/kg. The PLOQ was 1.0 mg/kg.
No statement of bias can be made because there are generally no accepted references
materials available for this analysis.
Repeatability 0.1711(X + 0.1301)0.2678

Reproducibility 0.5807(X + 0.1301)0.2678

Fig. 5.37 Potentiometric Titration Curve of Sulfate in Ethanol Standards Determined

by Test Method D7318.
Test Method D7319 covers a direct injection ion chromatographic method for deter-
mining existent and potential inorganic sulfate (and inorganic chloride) content in
hydrous and anhydrous denatured ethanol to be used in motor fuel applications. Its
range of analysis is between 1.0 and 20 mg/kg of the existent or potential inorganic
sulfate in ethanol samples. For existent inorganic sulfate, a small volume of an etha-
nol sample is directly injected into a suitably configured ion chromatograph. For
potential sulfate, 0.5 mL of 30 % hydrogen peroxide solution is added to 9.5 mL of the
ethanol sample and then injected into the ion chromatograph. Ions are separated
based on their affinity for exchange sites of the resin with respect to the resin’s affinity
for the eluent. The suppressor increases the sensitivity of the test method by increas-
ing the conductivity of the analytes and decreasing the conductivity of the eluent. It
also converts the eluent and the analytes to the corresponding hydrogen forms of
anions. Anions are quantified by integrations of their responses compared with an
external calibration curve and are measured as milligrams per litre and then con-
verted to milligrams per kilogram. The calibration standards are prepared in an
aqueous matrix.
A typical ion chromatogram of a solution containing 1 mg/L of various anions in
water is shown in Fig. 5.39, and a typical sulfate calibration plot is shown in Fig. 5.40.

Fig. 5.38 Potentiometric Titration Curve of Existent Inorganic Sulfate in Ethanol

Determined by Test Method D7318.
Fig. 5.39 Ion Chromatogram of Multiple Anionsin Test Method D7319.

Fig. 5.40 Typical Calibration Plot for Sulfate in Test Method D7319.
Interferences in this test method can be caused by substances with similar ion
chromatographic retention times, especially if they are in high concentration
compared with the analyte of interest. Sample dilution can be used to minimize or
resolve most interference problems. A water dip (system void, negative peak as shown
in Fig. 5.39) can cause interference with some integrators. For sulfate (and chloride)
determination, the water dip should usually not be a problem because these peaks are
far away from the water dip. Given the trace amounts of chloride and sulfate
determined in this test method, interferences can be caused by contamination of
glassware, eluent, reagents, and the like. For example, sodium leaching from glassware
can precipitate with sulfate giving low sulfate results. Care should be taken to ensure
that contamination is kept at the lowest possible levels. The use of powder-free gloves is
highly recommended to prevent sample contaminations.
On the basis of an ILS (RR-D02-1614), the following precisions were obtained for
existent inorganic sulfate and potential sulfate in the range 1.0–20 mg/kg. The PLOQ
was 0.01 mg/kg.
Sulfate Species Repeatability Reproducibility
Existent inorganic sulfate 0.09030(X + 1.000E-04)0.623 1.2291(X + 1.000E-04)0.623

Potential sulfate 0.09645(+0.59494)0.8642 0.9408(X + 0.59494)0.8642
Note: Where X is the average analyte concentration in mg/kg.
Test Method D7328 also covers the determination of existent and potential inor-
ganic sulfate (and total inorganic chloride) in hydrous and anhydrous denatured

fuel ethanol by IC using aqueous sample injection. It is applicable in the concentra-

tion range between 0.55 and 20 mg/kg for existent inorganic sulfate and 4.0–20.0
mg/kg of potential inorganic sulfate.
For existent inorganic sulfate (and chloride), a small volume of a sample is
evaporated to dryness; reconstituted to the initial sample volume with deionized
water; and injected into an ion chromatograph consisting of appropriate ion
exchange columns, a suppressor, and a conductivity detector. For potential sulfate, a
small volume of a sample is evaporated to dryness, reconstituted to initial volume
with 0.90 % aqueous hydrogen peroxide solution, and injected into an ion chroma-
tograph. Ions are separated based on their affinity for exchange sites of the resin with
respect to the resin’s affinity for the eluent. The suppressor increases the sensitivity of
the method by increasing the conductivity of the analyses and decreasing the
conductivity of the eluent. It also converts the eluent and the analytes to the corre-
sponding hydrogen forms of anions. Anions are quantified by integrations of their
responses compared with an external calibration curve, and measured as milligrams
per litre, and then converted to milligrams per kilogram. The calibration standards
are prepared in an aqueous matrix.
A typical ion chromatogram of a solution containing 1 mg/L of various anions
in water is shown in Fig. 5.39 and a typical sulfate calibration plot is shown
in Fig. 5.41.
Fig. 5.41 Typical Calibration Plot for Sulfate in Test Method D7328.

Table 5.49 Test Method Precision for Sulfate Species
Sulfate Species Test Method Range, mg/kg Repeatability Reproducibility
Existent inorganic D7318 1.0 0.18 0.60

4.0 0.25 0.85
20.0 0.38 1.30
4.0 0.21 2.92
20.0 0.58 7.95
Potential sulfate D7319 1.0 0.14 1.41
4.0 0.36 3.51
20.0 1.32 12.85
4.0 0.5 2.2
20.0 1.0 4.9
Potential sulfate D7328 4.0 0.4 1.8
20.0 0.6 3.5
Interferences in this test method are exactly the same as described above in Test
Method D7319. The precision of this test method on the basis of an ILS (RR-D02-1611)
is as follows:
Concentration Repeatability
Sulfate Species Range, mg/kg PLOQ Reproducibility
Existent inorganic 0.55–20 0.55 0.2319(X + 1.000E-04)0.50 1.0963(X + 1.000E-4)0.50

sulfate
Potential sulfate 4.0–50 4.0 0.1763X0.40 1.0505X0.40
Note: Where X is the average analyte concentration in mg/kg.
Table 5.49 shows the expected precision of these three test methods for sulfate
species at various concentrations on the basis of the precision equations given above.
References
[1] Magee, E. M., Hall, H. J., and Varga, G. M., Potential Pollutants in Fossil Fuels, EPA R2-73-
249, National Technical Information Service Publication PB 225-039, 1973.
[2] Branthaver, J. F. and Dorrence, S. M., “Organometallic Complexes in Domestic Tar Sands,”
Analytical Chemistry of Liquid Fuel Sources, P. C. Uden, S. Siggia, and H. B. Jensen, Eds.,
Advances in Chemistry Series No. 170, American Chemical Society, Washington, DC, 1978,
pp. 143–149.

[3] Uden, P. C., Siggia, S., and Jensen, H. B., Eds., Analytical Chemistry of Liquid Fuel Sources,
Advances in Chemistry Series No. 170, American Chemical Society, Washington, DC, 1978.
[4] Rakow, M. S., “Petroleum Oil Refining,” Fuels and Lubricants Handbook, MNL37, G. E.
Totten, Ed., ASTM International, West Conshohocken, PA, 2003, pp. 3–30.
[5] Giles, H. N., “Crude Oils,” Significance of Tests for Petroleum Products, MNL1, 7th ed., ASTM
[6] Nadkarni, R. A., “Determination of Sulfur in Petroleum Products and Lubricants: A Critical
Review of Test Performance,” Amer. Lab., Vol. 32, 2000, pp. 16–25.
[7] Nadkarni, R. A., Hwang, J. D., and Young, L., “Multielement Analysis of Crude Oils Using
Inductively Coupled Plasma Atomic Emission Spectrometry,” J. ASTM Int., Vol. 8, 2011,
103837.
[8] Giles, H. N., Personal Communication, February 2012.
[9] Giles, H. N. and Mills, C. O., Crude Oils: Their Sampling, Analysis, and Evaluation, MNL68,
[10] Hamilton, B. and Falkiner, R. J., “Motor Gasoline,” Fuels and Lubricants Handbook:
Technology, Properties, and Testing, MNL37, G. E. Totten, Ed., ASTM International, West
Conshohocken, PA, pp. 68–88.
[11] Gibbs, L. M., Bonazza, B. R., and Furey, R. L., “Automotive Spark Ignition Engine Fuel,”
Significance of Tests for Petroleum Products, MNL1, 8th ed., S. J. Rand, Ed., ASTM
[12] Westbrook, S. R. and LeCren, R. T., “Fuels for Land and Marine Diesel Engines and for
Non-Aviation Gas Turbines,” Significance of Tests for Petroleum Products, MNL1, 8th ed.,
S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010, pp. 33–52.
[13] Rhode, J., “Aviation Fuels,” Significance of Tests for Petroleum Products, MNL1, 8th ed.,
S. J. Rand, Ed., ASTM International, West Conshohocken, PA, 2010, pp. 80–105.
[14] Nadkarni, R. A., “Trace Levels of Sulfur in the Fuels of the Future: An Analytical
Perspective,” Elemental Analysis of Fuels and Lubricants: Recent Advances and Future
Prospects, STP1468, R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA,
2005, pp. 85–97.
[15] Nadkarni, R. A., A Review of Modern Instrumental Methods of Elemental Analysis of

Petroleum Related Materials: Part I—Occurrence and Significance of Trace Metals in
Petroleum and Lubricants; Part II—Analytical Techniques, STP 1109, ASTM International,
Standardization News, Vol. 32, 2004, p. 32.
[17] Nadkarni, R. A., “Recent Advances in the Determination of Sulfur in the Fuels of Today and
Tomorrow: A Report from the 2004 ASTM Symposium,” World Refining, Vol. 15, 2005,
pp. 30–33.
[18] Nadkarni, R. A. and Bly, K. J., The Report of the Interlaboratory Study for Low Level of
Sulfur Determination in Gasoline and Diesel Fuels, ASTM RR-DO2-1547, ASTM

[19] U.S. Environmental Protection Agency, Federal Register, 65(28), 6752–6774, 2000.
[20] U.S. Environmental Protection Agency, Federal Register, 66(12), 5002–5146, 2001.
[21] Schaefer, R. J., “Ultra Low Sulfur Diesel Measurement Challenges,” OPIS Ultra Low Sulfur
Diesel Summit, April 2005, Washington DC.
[22] Kohl, K., Fitness for Use Study of Test Method D5453, ASTM RR-D02-1456, ASTM
[23] Tittarelli, P., Round Robin Exercise for Sulfur Test Methods for EN 228 and EN 590 Fuel
Specifications, CEN/TC 19/WG 27, April 2000.
[24] Rhodes, J. R., “Pyro-Electrochemical On-Line Ultra Low Sulfur Analyzer,” Elemental
Analysis of Fuels and Lubricants: Recent Advances and Future Prospects, STP1468,
R. A. Nadkarni, Ed., ASTM International, West Conshohocken, PA, 2005, pp. 152–163.
[25] Drushel, H. V., “Trace Sulfur Determination in Petroleum Fractions,” Anal. Chem., Vol. 50,
1978, pp. 76–81.
[26] Tawara, K., Kawabata, Y., and Uno, Y., “Improvement of Sulfur Detection Limits in Petroleum
Products Using ASTM D4045,” ASTM J. Test. Eval., Vol. 31, 2003.
[27] Tarkanic, S. and Olstowski, F., Sulfur in 60 Seconds, PAC Preprint, Houston, TX.
[28] Nadkarni, R. A. and Crnko, J., Research Report in Support of 2007 Revisions to D5453-00
Test Method, ASTM RR-D02-1633, ASTM International, West Conshohocken, PA, 2007.
[29] Tarkanic, S. and Crnko, J., “Rapid Determination of Sulfur in Liquid Hydrocarbons for
At-Line Process Applications Using Combustion/Oxidation and UV-Fluorescence
Detection,” Elemental Analysis of Fuels and Lubricants: Recent Advances and Future
2005, pp. 137–151.
[30] Nadkarni, R. A., Personal communications from Hall, D., Schaefer, R. J., Brtko, K., and
Bain, S. S., June 2006.
[31] Wispinski, D., Statistical Comparison of Sulfur in Motor Gasoline, Aviation Gasoline & Diesel
Using ASTM D5453 and D7039 Test Methods, GO-2005-1026, Alberta Research Council.
[33] Nadkarni, R. A., Elemental Analysis of Fossil Fuels and Related Materials, MONO10, ASTM
[34] Nadkarni, R. A., “Calibration Protocols for Spectroscopic Measurements of Petroleum

Products,” Spectroscopic Analysis of Petroleum Products and Lubricants, MONO9, ASTM
[35] Bain, S. S., Brtko, K., and Schaefer, R. J., Personal communications, June 2006.
[36] Chen, Z. W. and Wei, F., “Low-Power Monochromatic Wavelength Dispersive X-Ray
Fluorescence—Principle and Applications in Petroleum Products,” Spectroscopic Analysis

[37] Chen, Z. W., Wei, F., Radley, I., and Beumer, B., “Low Level Sulfur in Fuel Determination
Using Monochromatic WD-XRF—ASTM D7039-04,” Elemental Analysis of Fuels and
Lubricants: Recent Advances and Future Prospects, STP1468, R. A. Nadkarni, Ed., ASTM
[38] Sarnelli, D. and Wispinski, D., Interlaboratory Study to Establish Precision Statements for
ASTM D7039 Test Method, GO-2007-FL 11087, November 2007, Alberta Research Council.
[39] Beumer, B., “On-Line Sulfur in Diesel Fuel Analysis,” Paper presented at ASTM D02.SC 3
Committee Meeting, 2001.
[40] Pohl, M. J., Sulfur Determination Using D4294 Energy Dispersive X-Ray Fluorescence,
ASTM RR-D02-1635, ASTM International, West Conshohocken, PA.
[41] Wissmann, D., “Latest Improvements on Using Polarized X-Ray Excitation EDXRF for the
Analysis of Low Sulfur Content in Automotive Fuel” Elemental Analysis of Fuels and
[42] Fess, S., “Determination of Sulfur Content in Crude Oil Using On-Line X-Ray Transmission
Technology,” Elemental Analysis of Fuels and Lubricants: Recent Advances and Future
2005, pp. 108–115.
[43] Gras, R. L., Luong, J. C., Mustacich, R. V., and Shearer, R. L., “DP-SCD and LTM-GC for
Determination of Low Sulfur Levels in Hydrocarbons,” Elemental Analysis of Fuels and
[44] Silva, B., Carvajal, N., and Gonzalez, A., “Determination of H2S in Residual Fuel Oils by
Multiple Headspace Extraction: A Critical Evaluation of Available Analytical Methods,”
Paper presented at the Eastern Analytical Symposium, sponsored by American Chemical
Society and American Microchemical Society, Somerset, NJ, November 16–20, 1992.

Chapter 6 | Analysis of Lubricants
and Additives
Although lubricating oils and additives are, of course, petroleum products, in this
book they are discussed separately from the former (Chapter 5) because the focus for
lubricants is to determine sulfur present in larger quantities versus in trace amounts in
most other petroleum products. Lubricating oils and additives are the only categories
of petroleum products in which sulfur compounds are generally added purposefully
to enhance the performance of the lubricants. These metal adducts are presented in
Table 6.1.
The ASTM test methods presented in Table 6.2, mainly using X-ray fluorescence
(XRF) or inductively coupled plasma–atomic emission spectrometry (ICP-AES) tech-
niques, are typically used for the determination of sulfur (and other elements) in lubri-
cants. Some of the sulfur test methods described in the previous chapter for gasoline
and diesel can also often be used by expanding the scope of the methods.
All of these methods are capable of simultaneously determining other elements in
addition to sulfur (Table 6.3). These test methods are actually really meant for other
metals and not just sulfur.
D4927: Elemental Analysis of Lubricant and Additive Components

by wavelength-dispersive X-ray fluorescence
This test method can be used for the determination of sulfur (and other elements) in
the range from 0.1 to 4.0 mass % in lubricating oils. The range can be extended to
higher concentrations by dilution of the sample specimens. Additives can also be ana-
lyzed after dilution with base oil. Two procedures can be used in this test method:
1. Procedure A: Internal standards are used to compensate for interelement effects of
X-ray excitation and fluorescence. For sulfur determination, the sample specimen
is mixed with a lead naphthenate (24 mass % lead) internal standard solution. Five
standards covering the range from 0.00 to 2.00 mass % sulfur are prepared in the
dilution solvent. Other internal standards are used for other elements of interest.
2. Procedure B: The measured XRF intensity for a given element is mathematically
corrected for potential interferences from other elements present in the sample.
Di-n-butyl sulfide of 97 % purity (21.9 mass % sulfur) is used as the calibration

Table 6.1 Additive Sulfur Compounds Added to Lubricants
Element Sulfur Compounds Performance
Antimony Dialkylphosphorodithionates Antiwear, extreme pressure, antioxidant

Barium Sulfonates Detergent inhibitors, corrosion inhibitors,
detergents, rust inhibitors, ATF, greases
Calcium Sulfonates Detergent inhibitors, dispersants
Magnesium Sulfonates Detergent inhibitors
Molybdenum Sulfide, dibutyldithiocarbamate Greases, extreme-pressure additives, antiwear
agents, improved lubrication and combustion
Nickel Dialkyldithiophosphates Detergents, antirusting agents
Zinc Dialkyldithiophosphates, Antioxidant, corrosion inhibitors, antiwear
dithiocarbamates additives, detergents, extreme-pressure additives,
crankcase oils
ATF: automatic transmission fluid.
Table 6.2 ASTM Test Methods for Sulfur in Lubricants and Additives
ASTM Standard
Number Analysis Matrix
D4927 Additive Elements by WD-XRF Lubricating oils and additives

D4951 Additive Elements by ICP-AES Lubricating oils and additives
D5185 Contaminants by ICP-AES Used oils and base oils
D6443 Additive Elements by WD-XRF Lubricating oils and additives
D6481 Additive Elements by ED-XRF Lubricating oils
D7751 Additive Elements by ED-XRF Lubricating oils
WD-XRF: wavelength-dispersive X-ray fluorescence; ICP-AES: inductively coupled plasma- atomic

emission spectrometry; ED-XRF: energy-dispersive X-ray fluorescence.
Table 6.3 Additional Elements Determined by Test Methods in Table 6.2
ASTM Standard
Number Analytical Technique Elements Determined
D4927 WD-XRF Ba, Ca, P, S, and Zn

D4951 ICP-AES B, Ba, Ca, Cu, Mg, Mo, P, S, and Zn
D5185 ICP-AES Ag, Al, B, Ba, Ca, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Pb, S,
Si, Sn, Ti, V, and Zn
D6443 WD-XRF Ca, Cl, Cu, Mg, P, S, and Zn
D6481 ED-XRF Ca, P, S, and Zn
D7751 ED-XRF Ca, Cl, Mg, Mo, P, S, and Zn
WD-XRF: wavelength-dispersive X-ray fluorescence; ICP-AES: inductively coupled plasma- atomic

emission spectrometry; ED-XRF: energy-dispersive X-ray fluorescence.

Analysis of Lubricants and Additives 155
standard for sulfur determination. Other sulfur-containing organic matrices (free

of metals and phosphorus) may be substituted provided that sulfur is stable in
solution and the concentration is equal to or greater than 7.5 mass % sulfur and
certified to better than ±0.1 % absolute.
The XRF spectrometer is initially calibrated with a suite of standards to deter-
mine by regression analysis the interelement correction factors and instrument
response factors. Subsequent calibration is achieved using a smaller number of stan-
dards because only the instrument response factors need to be determined. One of
these standards (or an optional synthetic pellet) can be used to monitor instrumental
drift when performing a high volume of analyses.
The additive elements found in the lubricating oils will affect the measured inten-
sities from the elements of interest to a varying degree. In general, for lubricating oils,
the X radiation emitted by the element of interest is absorbed by other elements in the
sample matrix. In addition, the X radiation emitted from one element can further
excite another element. These effects are significant at concentrations varying from
0.03 mass % because of the heavier elements to 1 mass % for the lighter elements. The
measured intensity for a given element can be mathematically corrected for the absorp-
tion of the emitted radiation by the other elements present in the sample specimen.
Suitable internal standards can also compensate for X-ray interelement effects. If an
element is present at significant concentrations and an intensity correction for that
element is not used, then the results can be low because of absorption or high because
of enhancement.
The precision and bias of this test method for determining sulfur on the basis of
an interlaboratory study (ILS; RR-D02-1259) are as follows. The bias of this test method
was not determined because at the time the ILS was conducted no suitable reference
materials of known composition were available.
Internal standard procedure 0.03966X 0.2098X

Mathematical correction procedure 0.05335(X + 0.001) 0.1669 (X + 0.001)
Where X is the average of two consecutive determinations.
D4951: Additive Elements in Lubricating Oils by ICP-AES

This test method can determine sulfur in lubricating oils and additives at concentration
ranges from 0.3 to 3.2 mass %. However, lower or higher concentrations can be deter-
mined by this test method. The low concentration limits are dependent on the sensitiv-
ity of the inductively coupled plasma (ICP) instrument and the dilution factor. The high
concentration limits are determined by the upper linear limit and the dilution factor.
Sulfur is determined if the instrument can operate in the ultraviolet (UV) range (with a
vacuum or inert gas purged optical path) at the recommended interference-free wave-
lengths of 180.73, 182.04, or 182.62 nm.

In this test method, a sample is weighed and diluted by mass with mixed xylenes
or other solvents such as o-xylene or kerosine. An internal standard, which is
required, is either weighed separately into the test solution or is previously combined
with the dilution solvent. Cobalt is recommended as the internal standard; however,
other elements have also been successfully used for this purpose (Ag, Be, Cd, La,
Mn, Pb, or Y). Calibration standards are prepared similarly. Some commercially
available organometallic standards are prepared from metal sulfonates and there-
fore contain sulfur. When sulfur is being determined, a separate sulfur standard is
required. A sulfur standard can be prepared by blending National Institute of
Standards and Technology (NIST) Standard Reference Material (SRM) 1622 with
white oil. Metal sulfonates can be used as sulfur calibration standards if the sulfur
content is known or determined by an appropriate test method such as D1552. The
solutions are introduced to the ICP instrument by free aspiration or an optional
peristaltic pump. By comparing emission intensities of elements in the test specimen
with emission intensities measured with the calibration standards and by applying
the appropriate internal standard correction, the concentrations of elements in the
sample are calculable.
There are no known spectral interferences between the elements covered by this
test method when using the recommended spectral lines. However, if spectral interfer-
ences exist because of other interfering elements or selection of other spectral lines,
then the interference can be corrected using the technique described in Test Method
D5185. Viscosity index improvers, which can be present in multigrade lubricating oils,
can bias measurements. However, the biases can be reduced to negligible proportion by
using the specified solvent-to-sample dilution and an internal standard [1].
The precision and bias of sulfur determination by this ICP-AES method on the
basis of an ILS (RR-D02-1349) is as follows:
Lubricating Oil Additive
Range, mass % 0.3–0.8 3.0–3.2

Repeatability, mass % 0.016 0.14
Reproducibility, mass % 0.061 0.372
D5185: Additive Elements, Wear Metals, and Contaminants

in Used Lubricating Oils and Base Oils by ICP-AES
This test method covers rapid determination of 22 elements in used lubricating oils
and in base oils, and it provides rapid screening of used oils for indication of wear.
Test times approximate a few minutes per test specimen, and detectability for most
elements is in the low milligram-per-kilogram range. Although this test method was
initially developed for the analysis of used oils, it can also be used for the analyses of
unused lubricating oils to complement test methods such as D4628, D4927, or
D4951. For determining sulfur, a vacuum or inert gas optical path is required with
the following recommended wavelengths: 180.73, 182.04, and 182.62 nm. This test

method uses oil-soluble metals for calibration and does not purport to quantitatively
determine insoluble particulates. Analytical results are dependent on particle size,
and low results are obtained for particles larger than a few micrometres. If sulfur
(or other elements) is present above the upper limit of the calibration curves, it can
be determined with additional appropriate dilutions and with no degradation of
precision. Sulfur concentrations in the range from 900 to 6000 mg/kg were deter-
mined in this ILS.
In this test method, similar to Test Method D4951 described above, a weighed
portion of a thoroughly homogenized used oil or base oil is diluted tenfold by weight
with mixed xylenes or other suitable solvent. Standards are prepared in the same man-
ner. An optional internal standard can be added to the solution to compensate for
variations in test specimen introduction efficiency. The solutions are presented to the
ICP instrument by free aspiration or an optional peristaltic pump. By comparing emis-
sion intensities of elements in the test specimen with emission intensities measured
with the standards, the concentrations of elements in the test specimen are
calculable.
Spectral interferences in this method can usually be avoided by judicious choice
of analytical wavelengths. When spectral interference cannot be avoided, the neces-
sary c orrections should be made using the computer software supplied by the instru-
ment manufacturer or the empirical method described in this standard.
Differences in the viscosities of the test specimen solutions and standard solutions
can cause differences in the uptake rates. These differences can adversely affect the
accuracy of the analysis. Using a peristaltic pump to deliver solution to the nebulizer
or the use of internal standardization, or both, can reduce this effect. When severe
viscosity effects are encountered, the test specimen and standard should be diluted
20-fold rather than 10-fold while maintaining the same concentration of the internal
standard [1–3].
Particulates in the solution, particularly used oils, can plug the nebulizer, thereby
causing low results. Use of a Babington-type high-solids nebulizer helps to minimize
this effect. In addition, the specimen introduction system can limit the transport of
particulates, and the plasmas can incompletely atomize the particulates, thereby caus-
ing low results. Although the use of an internal standard is given as optional in this test
method, it is strongly recommended that it be used as mandatory given the benefits of
this approach.
On the basis of an ILS (RR-D02-1282), the following precision for sulfur in the
concentration range of 900–6000 mg/kg using this test method can be expected:
Where X is the average concentration in mass %.

D6443: Determination of Metals in Unused Lubricating Oils

and Additives by Wavelength-Dispersive X-Ray Fluorescence
(Mathematical Correction Procedure)
This test method determines sulfur along with several other elements in unused lubricat-
ing oils, additives, and additive packages by wavelength-dispersive X-ray fluorescence
(WD-XRF) spectrometry. Matrix effects are handled with mathematical corrections. This
test method uses regression software to determine calibration parameters, which can
include influence coefficients (i.e., interelement effect coefficients) termed as alphas.
Alphas can also be determined from theory using relevant software.
In this test method, the XRF spectrometer is initially calibrated by determining
the slope and intercept of the calibration curve for each element by regressing con-
centration data and intensities measured on a set of physical standards. Empirical
alphas can also be determined by regression when the appropriate set of physical
standards is used for calibration. Theoretical alphas, calculated with special software,
can also be used. In addition, a combination of theoretical and empirical alphas can
also be used.
A sample is placed in the X-ray beam, and the intensities of the appropriate fluo-
rescence lines are measured. A similar measurement is made at a wavelength offset
from each fluorescence line to obtain a background correction. Enhancement or
absorption of the XRF of an analyte by an interfering element in the sample can occur,
and these effects can be handled in the data reduction by implementation of alphas.
Concentrations of the analytes are determined by comparison of net signals against
calibration curves, which include influence coefficients (i.e., alphas) calculated from
theory, empirical data, or a combination of theory and empirical data.
Molybdenum and lead in the sample can affect the determination of sulfur. This
can be compensated for by implementation of accurately determined alphas in the set of
calibration parameters. However, if lead or molybdenum are present in the sample at
significant concentrations and if accurate overlap corrections cannot be made, then this
method cannot be used for such determinations.
On the basis of an ILS (RR-D02-1450), the following precision for determining
sulfur with this test method was found:
Material Concentration, mass % Repeatability Reproducibility
Lube oils 0.030–0.800 0.02371X0.9 0.1623X0.9

Additives 1.00–5.00 0.02783X0.8 0.1744X0.8
Note: Where X is the average concentration in mass %.
D6481: Metals in Lubricating Oils by Energy-Dispersive

X-Ray Fluorescence SpectrOMETRY
This test method uses energy-dispersive X-ray fluorescence (ED-XRF) spectrometry
for the determination of sulfur and a few other elements in lubricating oils. The
concentration range for sulfur determination is from 0.05 to 1.0 mass %. This test
method uses interelement correction factors calculated from empirical calibration

data. This test method excludes lubricating oils that contain chlorine or barium as an
additive element.
The ED-XRF spectrometer is initially calibrated using a set of prepared standards to
collect the necessary intensity data. Each calibration line and any correction coefficient are
obtained by a regression of these data using the program supplied with the spectrometer.
The interferences encountered in this test method are similar to those experienced in
other XRF test methods discussed above. There can be spectral overlap of phosphorus
over sulfur, and the instrument must include correction procedures for any such
overlaps.
On the basis of an ILS conducted, the following precision for sulfur determina-
tion using this test method can be expected:
Repeatability 0.01648(X + 0.0141)0.8

Reproducibility 0.1024(X + 0.0141)0.8
Where X is the concentration of the element in mass %.

D7751: Additive Elements in Lubricating Oils by ED-XRF Analysis
Sulfur in the concentration range from 0.002 to 1.5 mass % can be determined by
this test method (along with six other additive elements). The pooled limit of quan-
titation of this test method for sulfur is 0.002 mass %. Concentrations higher than
this can also be determined by appropriate dilution of the samples with sulfur-free
base oil. This test method uses interelement correction factors calculated from
a fundamental parameters approach or from another matrix correction method.
Table 6.4 Sulfur Determination Using Alternate Test Methods
Product Certified Value ICP-AES WD-XRF D1552
NIST SRM 1848 Lubricant 2.327 ± 0.0043 2.223 ± 0.061a

2.236 ± 0.12b [6]
NIST SRM 1634b 2.80 ± 0.05 2.72a; 2.96b [6]
Fuel Oil
NIST SRM 1634c (2) 2.12a; 2.11b [6]
Fuel Oil
Additive Package 2.244 ± 0.030 2.35 ± 0.04
(Texaco) [4]
Motor Oil (Texaco) [4] 0.597 ± 0.011 0.629 ± 0.008
Additive Package 2.28 ± 0.05 2.40 ± 0.01
(Exxon) [5]
Lube Oil (Exxon) [5] 0.2490 ± 0.005 0.2520 ± 0.0010
Note: All results are in mass %. Values in parentheses are informational values. All results are given as
mean value ± standard deviation (number of laboratories or results).
a
ICP-AES after microwave digestion in acids.
b
ICP-AES after dilution in organic solvent.

Table 6.5 Proficiency Testing Sulfur Analysis of Lube Additives
Mean Value ± Standard Deviation

ASTM ILCP Number Test Method (number of results) TPI
ALA 1102 D4951 2.58 ± 0.068 (19)

D5185 2.60 ± 0.203 (16)
D1552 2.53 ± 0.18 (9) 0.75

ALA 1106 D4927A 1.606 ± 0.006 (3)
D4927B 1.62 ± 0.05 (4)
D4951 1.63 ± 0.04 (17)
D5185 1.636 ± 0.56 (11)
D1552 1.636 ± 0.060 (8) 1.63
ALA 1110 D4927A 2.20 ± 0.004 (3)
D4927B 2.30 ± 0.005 (5)
D4951 2.27 ± 0.058 (22)
D5185 2.26 ± 0.065 (10)
D1552 2.27 ± 0.081 (8) 1.70
ALA 1202 D4927A 2.515 ± 0.03 (3)
D4927B 2.602 ± 0.05 (4)
D4951 2.573 ± 0.102 (17)
D5185 2.610 ± 0.1426 (10)
D1552 2.509 ± 0.073 (8) 1.88
LU 1101 D129 0.297 ± 0.075 (7)
D4927A 0.3326 ± 0.024 (15)
D4951 0.3311 ± 0.019 (29)
D5185 0.3292 ± 0.038 (30)
D5453 0.2966 ± 0.0268 (12)
D6443 0.3237 ± 0.0186 (10)
D6481 0.3309 ± 0.040 (12)
LU 1105 D129 0.272 ± 0.042 (6)
D1552 0.266 ± 0.023 (6)
D4927A 0.2868 ± 0.060 (12)
D4951 0.2897 ± 0.024 (31)
D5185 0.2343 ± 0.0108 (70)
D5453 0.2378 ± 0.028 (13)
D6443 0.2821 ± 0.0089 (8)
D6481 0.303 ± 0.037 (12)
LU 1109 D129 0.266 ± 0.049 (7)
D4927A 0.2741 ± 0.008 (11)
D4951 0.2777 ± 0.015 (29)

Table 6.5 Proficiency Testing Sulfur Analysis of Lube Additives (Continued)
Mean Value ± Standard Deviation

ASTM ILCP Number Test Method (number of results) TPI
D5185 0.2753 ± 0.024 (28)

D5453 0.2314 ± 0.023 (9)
D6443 0.2667 ± 0.005 (8)
D6481 0.2889 ± 0.043 (12)
LU 1201 D4951 0.2566 ± 0.0122 (32)
D5185 0.2458 ± 0.0203 (26) 0.74
D4927A 0.2577 ± 0.0127 (6) 1.54
D6443 0.2543 ± 0.0086 (10) 1.99
D6481 0.2727 ± 0.0313 (11) 0.43
D129 0.26 ± 0.01 (5)
D5453 0.2199 ± 0.0294 (10) 0.34
ILCP: Interlaboratory Crosscheck Program; TPI: test performance index.

Note: All results are in mass %.
The algorithm used for the correction procedure is usually implemented in the
instrument manufacturer’s software. The interferences in this test method are simi-
lar to those described above in other XRF test methods.
On the basis of an ILS (RR-D02-1732), the repeatability of sulfur determination
using this test method was found to be 0.014X0.915, where X is the average concentration
of sulfur in mass percentage. The ILS included 11 laboratories analyzing 16 blended
lubricating oil samples in duplicate and sulfur in the concentration range of 0.002–1.5
mass %. The reproducibility or bias of this test method is not yet determined.
Alternative Test Methods for Sulfur in Lubricants

Many of the test methods described above and in Chapter 5 can be used for alternative
determination of sulfur in lubricating oils or additives. These alternative methods
include combustion methods D129 and D1552; WD-XRF Test Methods D2622, D6428,
and D7039; ED-XRF Test Method D4294; and UV-fluorescence Test Method D5453. In
general, the precision of these test methods is roughly equivalent for a given analysis.
Some of the typical results obtained for such analysis are illustrated in Table 6.4.
All results in Table 6.4 match each other very well between the ICP-AES (D4951 or
D5185 Test Methods) and WD-XRF (D4927 or D6443 Test Methods) methods for
analyzing lubricating oils or lube adpacks, thus demonstrating that several alternative
test methods are available for such elemental analysis and give virtually equivalent
results with comparable precision. This hypothesis about equivalency is also demon-
strated in the sulfur (and other elements) determination in ASTM interlaboratory
proficiency testing programs conducted by the D02 Committee. Some typical results
for sulfur determination in lubricating oils and additives for 2011 and 2012 are given
in Table 6.5.

References
[1] Bansal, J. G. and McElroy, F. C., Accurate Elemental Analysis of Multigrade Lubricating Oils
by ICP Method: Effect of Viscosity Modifiers, SAE Technical Paper 932694, Society
of Automotive Engineers, Warrendale, PA, 1993, pp. 61–68.
[2] Nadkarni, R. A., McElroy, F. C., and Bansal, J. G., “Effect of Viscosity Modifiers on Metal
Analysis of Lube Oils by ICP-AES,” Paper presented at the ASTM D02 Committee
Meeting, Kansas City, MO, June 16, 1993.
[3] Jansen, E. B. M., Knipscheer, J. H., and Nagtegaal, M., “Rapid and Accurate Element
Determination in Lubricating Oils Using Inductively Coupled Plasma Optical Emission
Spectrometry,” J. Anal. Atom. Spectr., Vol. 7, 1992, pp. 127–130.
[4] Sieber, J. R., Salmon, S. G., and Williams, M. C., “Analysis of Lubricant Additive Elements
by X-Ray Fluorescence and Supporting Methods,” Modern Instrumental Methods of
Elemental Analysis of Petroleum Products and Lubricants, STP1109, R. A., Nadkarni, Ed.,
ASTM International, West Conshohocken, PA, 1991, pp. 118–127.
[5] Nadkarni, R. A., Unpublished Results of NIST SRM 1848.
[6] Hwang, J. D., Horton, M., and Leong, D., “The Use of Microwave Digestion and ICP to
Determine Elements in Petroleum Samples,” Elemental Analysis of Fuels and Lubricants:
Recent Advances and Future Prospects, STP1468, R. A. Nadkarni, Ed., ASTM International,

Chapter 7 | Analysis of Gaseous Fuels
INTRODUCTION
Sulfur can be a contaminant in gas processing plants and must be removed before the
gas is introduced into gas pipelines. In petrochemical plants, sulfur is a poison for
many catalysts and must be reduced to acceptable levels, usually in the range from 0.01
to 1 ppmv. The sulfur content of the gaseous hydrocarbons, liquefied petroleum gas
(LPG), and liquefied natural gas (LNG) used for fuel purposes contributes to emission
of total sulfur oxides (SOx) and can lead to corrosion in engine and exhaust systems.
Natural gas, high-purity ethane, ethane/propane mixtures, LPG such as propane,
n-butane, isobutane, and their mixtures are considered as gaseous fuels.
Given the nature of the matrix, the interest in analysis of gaseous fuels such as
natural gas, LPG, LNG, etc., is for the determination of total sulfur as well as some
specific sulfur compounds in these fuels. However, there are no ASTM chemical spec-
ifications for natural gas. ASTM Test Methods available for such analyses are listed in
Table 7.1. These test methods can broadly be categorized as for
• Total sulfur: D1072, D2784, D4468, D6667, D7165, D7166, and D7551
• Specific sulfur compounds: Mercaptans (D1988) and H2S (D4084, D4810)
• Miscellaneous sulfur compounds: D5305, D5504, D6228, D6968, D7493, and D7652
Many of the techniques used here are similar to those used in the analysis of
petroleum products (Table 7.2). Some of them also have their International
Organization for Standardization (ISO) test method counterparts. These test methods
for natural gas can also be used as quality-control tests for sulfur determination in
finished products, such as propane, butane, ethane, and ethylene. Sulfur or its com-
pounds are often measured with at-line, online, and other near-real-time monitoring
systems. Such analyzers are prevalent in the natural gas and fuel gas industries. The
installation and operation of particular systems vary on the specific objectives, con-
tractual obligations, process type, regulatory requirements, and internal performance
requirements needed by the user. These test methods are discussed below by these
categories with regards to the principle of analysis, the precision of analysis, and other
analytical information.

Table 7.1 ASTM Test Methods for Sulfur in Gaseous Fuels
ASTM Test
D1072 Combustion and BaCl2 Titration Fuel gases

D1988 Mercaptans Using Length-of-Stain Detector Tubes Natural gas
D2784 Combustion and BaCl2 Titration LPG
D4084 Hydrogen Sulfide Using Lead Acetate Reaction Rate Method Gaseous fuels
D4468 Total Sulfur by Hydregeneolysis and Rateometric Colorimetry Gaseous fuels
D4810 Hydrogen Sulfide Using Length-of-Stain Detector Tube Natural gas

D5305 Ethyl Mercaptan LPG vapor
D5504 Sulfur Compounds by Chemiluminiscence Detection Natural gas
D6228 Sulfur Compounds by GC and Flame Photometric Detection Natural gas
D6667 Total Volatile Sulfur by Combustion-UV-Fluorescence LPG
D6968 Sulfur Compounds by GC and Atomic Emission Detection Natural gas
D7165 Practice for Online/At-Line Sulfur Determination Gaseous fuels
D7166 Practice for Total Sulfur Analyzer Natural gas
D7493 Sulfur Compounds by Online GC and Electrochemical Detection Natural gas and
gaseous fuels
D7551 Total Volatile Sulfur by UV-Fluorescence Natural gas
D7652 Sulfur Compounds by GC and Chemiluminiscence Detection Hydrogen fuel
BaCl2: barium chloride; GC: gas chromatography; UV: ultraviolet.
Table 7.2 Equivalent Test Methods for Analysis of Gaseous Fuels, Coal, or Petroleum
Products
D03 Test Method D02 Test Method D05 Test Method ISO Test Method
D1072 D129; D1260 D3177

D4468 D4045
D6228 D7041
D6968 19739
D7166 D6920
D7493 D6920 19739; 6326-2
D7551 D6667
Sampling of Gaseous Fuels

A representative sample is necessary for accurate billing in custody transfer transac-
tions, accurate compositional analysis of the flowing stream, gravity determination
for flow calculations, and other desired information concerning the properties of
the stream contents. The sample handling and conditioning system must extract

Analysis of Gaseous Fuels 165
a representative sample from a flowing pipeline, transport the sample to the analyzer,
condition the sample to be compatible with the analyzer, switch sample streams and
calibration gases, transport excess sample to recovery (or disposal), and resist corro-
sion by the sample. Sampling of gaseous fuels is described in ASTM Standard Practices
D5287, D5503, and D7606.
Test Methods for Total Sulfur Determination
D1072 : Total Sulfur in Fuel Gases by Combustion

and Barium Chloride Titration
This test method is applicable to the determination of total sulfur in the range of approx-
imately 25–700 mg/m3 in natural gases, manufactured gases, mixed gases, and other
miscellaneous gaseous fuels. In this test method, a metered sample of gas is burned in a
closed system in an atmosphere of sulfur-free air. The oxides of sulfur produced are
absorbed in sodium carbonate solution, where they are oxidized to sulfate. The sulfate
in the absorbent solution is determined by titration with standardized barium chloride
(BaCl2) solution using tetrahydroxyquinone (THQ) as an indicator. There are no known
interferences for this analysis. However, if using BaCl2 titration after collection of sulfur
dioxide (SO2) by alternative procedures, then ammonia, amines, substances producing
water-soluble cations, and fluorides will interfere with the titration.
The burner used for combustion is specified in Fig. 7.1, the absorbers and spray
traps used in the chimneys are specified in Fig. 7.2, the suction system used
for sulfur determination is shown in Fig. 7.3, and the purified air system is depicted
in Fig. 7.4.
The accuracy of the results is dependent on the accuracy with which the sample
volume is metered and the accuracy of the titration procedures. When 1 m3 of gas is
burned, an absolute precision equivalent to ±0.06 mg/m3 should be attainable in the
BaCl2 titration independent of the total quantity of sulfate in the absorber. Therefore, the
overall accuracy should be between ±0.06 and ±0.42 mg/m3, if the metering accuracy of
±2 % is attained, over the concentration range to which the procedure is adaptable.
D2784: Sulfur in LPG by Oxygen-Hydrogen Burner or Lamp
This test method covers the determination of total sulfur in LPG containing more
than 1 µg/g. Specimens should not contain more than 100 µg/g of halogens. To
attain the quantitative detectability that the test method is capable of, stringent
techniques must be used and all possible sources of sulfur contamination must be
eliminated. In particular, cleaning agents, such as common household detergents
that contain sulfates, should be avoided.
In this test method, a sample is burned in an oxygen-hydrogen burner or in a lamp
in a closed system in a carbon dioxide–oxygen atmosphere. The latter is not recom-
mended for trace quantities of sulfur because of the inordinately long combustion
times needed. The oxides of sulfur are absorbed and oxidized to sulfuric acid in
a hydrogen peroxide solution. The sulfate ions are then determined by either of the
following finishes:

Fig. 7.1 Schematics of Test Method D1072 Combustion and Absorption Apparatus.
Note: All dimensions in millimetres. In the case of those dimensions for which no specific tolerences are
designated above, the permissible variation is 10% to the nearest 1mm, provided, however, that in no
case shall the deviation be greater than 5mm.
Fig. 7.2 Gas Burner for Sulfur Determination in Test Method D1072.
Note: All dimensions in millimetres.

Fig. 7.3 Suction System for Sulfur Determination in Test Method DI072.
Fig. 7.4 Purified Air System for Sulfur Determination in Test Method DI072.
• Barium perchlorate titration: The sulfate is titrated with barium perchlorate using
a thorin-methylene blue mixed indicator.
• Turbidimetric: The sulfate is precipitated as barium sulfate and the turbidity of a
suspension of the precipitate is measured with a photometer.
An oxy-hydrogen combustion assembly is depicted in Fig. 7.5 for a Wickbold-
type combustion apparatus and Fig. 7.6 for modified Beckman burner-type appara-
tus. This test method does not include the usual precision statement. This is in
recognition of the difficulty of shipping stable samples of LPG containing various

Fig. 7.5 Flow Diagram of a Typical Oxy-Hydrogen Combustion Apparatus Used in Test

Method D2784.
concentrations of sulfur to several cooperating laboratories. Studies have confirmed

that the sulfur species can change during transit.
D4468 : Total Sulfur in Gaseous Fuels by Hydrogenolysis

and Rateometric Colorimetry
This test method covers the determination of sulfur in gaseous fuels in the range from
0.001 to 20 ppmv. This test method can also be used for as a quality-control tool for
sulfur determination in finished products, such as propane, butane, ethane, and ethyl-
ene. This method is based on the same technical principles as used in ASTM Test

Fig. 7.6 Trace Sulfur Apparatus Flow Diagram Used in Test Method D2784.
Method D4045 for the determination of sulfur in petroleum products. The sample is
introduced at a constant rate into a flowing hydrogen stream in a hydrogeneolysis
apparatus. The sample and the hydrogen are pyrolyzed at a temperature of 1000°C or
above to convert sulfur compounds to hydrogen sulfide (H2S). Readout is by the rateo-
metric detection of the colorimetric reaction of H2S with lead acetate. Figures 5.16,
5.17, and 7.7 illustrate a hydrogeneolysis flow diagram, a photorateometric H2S readout,
and a flow system for gas sample and calibration reference, respectively. On the basis of
the information developed for determining H2S, the precision estimates presented in
Table 7.3 are expected.
D6667: Total Volatile Sulfur in Gaseous Hydrocarbons and LPG

by Combustion-Ultraviolet Fluorescence Detection
This test method covers the determination of total volatile sulfur in gaseous hydro-
carbons and LPG. It is applicable to the analysis of natural, processed, and final prod-
uct materials containing sulfur in the range of 1–100 mg/kg. This test method may
not detect sulfur compounds that do not vaporize under the conditions of the test.
The samples should not contain more than 0.35 mass % of halogen(s). This test
method is based on the same technical principles as Test Method D5453 discussed in
Chapter 5 in this book.
In this test method, a heated sample valve is used to inject gaseous samples. LPG
samples are injected by a sample valve connected to a heated expansion chamber.
The sample is combusted in a high-temperature quartz combustion tube where sul-
fur is oxidized to SO2 in an oxygen-rich atmosphere. The water produced during the
sample combustion is removed, and the sample combustion gases are next exposed
to ultraviolet (UV) light. The SO2 is converted to excited SO2 (SO2*) by interaction

Fig. 7.7 Flow Diagram for Gas Sample and Calibration in Test Method D4468.
Table 7.3 Precision for D4468 Test Method for Sulfur Determination in Gaseous Fuels
Full-Scale
Range Repeatability Reproducibility
Piston Cylinder PPM Generator Piston Cylinder PPM Generator

Reference Manual Reference Deviation Reference Manual Reference Automatic
Deviation Automatic Deviation Deviation
1.0 0.014 0.017 0.050 0.141
0.1 0.002 0.002 0.006 0.008
1.0 a
0.16 0.26
0.1a 0.051 0.082
Note: All units are in ppmv.

For sulfur compounds other than H2S.
a

with ozone. When this molecule comes back to its ground state, the fluorescence
emitted is measured by a photomultiplier and is converted to sulfur concentration.
The length of time required for detector response will depend on the type of the
pyrotube used, the carrier gas, and the sample size or sulfur concentration or both,
and from 20 s to 1 min can be typical. See Fig. 7.8 for the illustration of a typical
direct-injection quartz pyrolysis tube and Fig. 7.9 for a typical injection profile.
Dimethyl sulfide is used as the calibration standard diluted in n-butane, isobutane,
propylene, or propane. The precision of this test method on the basis of an interlab-
oratory study (ILS) was found to be as follows (RR-D02-1506):
Repeatability 0.1152X
Reproducibility 0.3130X
(X is the mean of two results)
D7165: Standard Practice for Gas Chromatography-Based Online/At-Line

Analysis for Sulfur Content of Gaseous Fuels
Online, at-line, inline, continuous fuel monitor system (CFMS), and other near-
real-time monitoring systems that measure fuel gas characteristics, such as the
sulfur content, are prevalent in the natural gas and fuel gas industries. The installa-
tion and operation of particular systems vary on the specific objectives, contractual
obligations, process type, regulatory requirements, and internal performance
requirements needed by the user.
This standard is intended to provide guidelines for standardized start-up proce-
dures, operating procedures, and quality-assurance practices for online, at-line, inline,
Fig. 7.8 Typical Direct Inject Quartz Pyrolysis Tube Used in Test Method D6667 for
Sulfur.

Fig. 7.9 Typical Injection Profile Obtained in Test Method D6667 for Sulfur.
CFMS, and other near-real-time gas chromatographic-based sulfur monitoring systems

used to determine fuel gas sulfur content.
This practice is for the determination of volatile sulfur-containing compounds in
high-methane-content gaseous fuels such as natural gas using online/at-line instru-
mentation and continuous fuel monitors. It has been successfully applied to other
types of gaseous samples including air, digester, landfill, and refinery fuel gas. The
detection range for sulfur compounds, reported as picograms of sulfur, on the basis of
the analysis of a 1-mL sample, is 0.1–1000 mg/m3. In this practice, a representative
sample of the gaseous fuel is extracted from a process pipe or pipeline and is trans-
ferred in a timely manner to an analyzer inlet system. The sample is conditioned with
minimal effect on the sulfur content. A precisely measured volume of sample is
injected into the analyzer. Excess process or pipeline sample is vented or returned to
the process stream dependent on application and regulatory requirements.
The sample containing the carrier gas is fed to a gas chromatograph (GC) where
the components are separated using a packed or capillary column. Measurement is
performed using a suitable sulfur detection system. Calibration, precision, calibration
error, performance audit tests, maintenance methodology, and miscellaneous quality-
assurance procedures are conducted to determine analyzer performance characteris-
tics and validate the operation and the quality of the generated results.
D7166: Total Sulfur Analyzer-Based Online/At-Line for Sulfur

Content of Gaseous Fuels
This practice is for the determination of total sulfur from volatile sulfur-containing
compounds in high methane or hydrogen content gaseous fuels using online/at-line

instrumentation. In this practice, a representative sample of the gaseous fuel is

extracted from a process pipe or pipeline and is transferred in a timely manner to a
total sulfur analyzer inlet system. The sample is conditioned with minimal, preferably
negligible, effect on the sulfur content. A precisely measured volume of sample is
injected, or allowed to flow continuously, directly into the analyzer, or into a carrier
gas, as required by the analyzer. Some total sulfur analyzers are configured such that
sample gas flows directly into the analyzer detection system. Excess process or pipeline
sample is vented to the atmosphere or returned to the process stream dependent on
application and regulatory requirements.
The sample containing the carrier gas is fed to a furnace o perating at an elevated
temperature where sulfur compounds are converted into detectable species. The con-
version reaction may be oxidative or reductive and may require the introduction of
additional carrier or other supply gases. Furnace exit gases are conditioned as required
with respect to temperature and water content and are introduced into the detector
where quantification of the total sulfur content occurs. Calibration, maintenance,
quality assurance, and performance protocols provide a means to validate the analyzer
operation and the generated results.
D7551 : Total Volatile Sulfur in Gaseous Fuels by UV-Fluorescence

This test method is based on the same technical principle as the one used for ASTM
Standard Test Method D5453 in the D02 Committee on Petroleum Products and
Lubricants. The method is applicable to the analysis of gaseous hydrocarbons,
LPG, LNG, natural gaseous fuels, process intermediates, final product hydrocar-
bons, and generic gaseous fuels containing sulfur in the range of 1–200 mg/kg.
Samples can also be tested at other total sulfur levels using preconcentration meth-
ods or sample dilution using a diluent gas. The diluent gas, such as ultrahigh-purity
nitrogen, zero nitrogen, or zero air, should not have a significant total sulfur
concentration. This test method may not detect sulfur compounds that do not
volatilize under the conditions of the test. The samples should contain less than
0.35 mol % halogen(s).
In this test method, a gaseous sample is injected into the analyzer by a sample
valve, by direct injection at a constant flow rate, or by syringe. A LPG or LNG sample
is vaporized in an appropriate expansion chamber and injected into the analyzer by a
sample valve, a syringe, or a sample valve connected to an expansion chamber. The
gaseous sample then enters into a high-temperature combustion tube where the
sulfur-containing compounds in the sample are oxidized to SO2. The water produced
during the sample combustion is removed, as required, and the sample combustion
gases are then exposed to a source of continuous or pulsed UV light. The SO2 absorbs
the energy from the UV light to form SO2*. The fluorescence emitted from SO2* as it
returns to SO2 is detected by a photomultiplier tube. The resulting signal is a measure
of the sulfur present in the sample.

Fig. 7.10 General Flow Diagram of Online Analyzer Used in Test Method D7551 for
Sulfur.
Figure 7.10 illustrates a general flow diagram applicable for an online/at-line pro-
cess analyzer. Sample collection and conditioning as well as sample introduction and
detection systems are depicted.
The following sulfur compounds, either singly or together, are suggested for
inclusion in a compressed gas standard: H2S, carbonyl sulfide (COS), and methyl mer-
captan. The following substances can also be included either singly or together: ethyl
mercaptan, 1-propanethiol, 2-propanethiol, and dimethyl sulfide. Dimethyl disulfide
and other disulfides are not recommended for inclusion in the mixed component stan-
dards because of their potential for promoting degradation.
Sulfur Compound Chemical Formula
Hydrogen sulfide H2S

Carbonyl sulfide COS
Methyl mercaptan CH3SH
Ethyl mercaptan CH3 CH2 SH
1-Propanethiol CH3 CH2 CH2 SH
2-Propanethiol CH3CHSCH3
Dimethyl sulfide CH3SCH3
Dimethyl disulfide CH3 SSCH3
Other disulfides Cx Hx Sx
Although no ILS has yet been conducted, the estimated repeatability for an online
UV-fluorescence total sulfur analyzer is expected to be as presented in Table 7.4.
Test Methods for Specific Sulfur Compounds

Among several test methods available for the determination of sulfur compounds in
natural gas are those based on gas chromatography and using an alternative means of

Table 7.4 Estimated Repeatability Standard Deviation for D7551 Analyzer
Nominal Sulfur Number of Results Repeatability

Material Concentration, mg/kg Number of Analyzers per Analyzer Standard Deviation
LPG (propane 5 5 6 0.038

or butane) 10 6 5 0.091
25 3 10 0.068
50 4 8 0.18
Methane 20 7 5 0.024
40 4 8 0.036
200 3 10 0.15
final detection. The analysis of gaseous sulfur compounds is challenging because of the
reactivity of these substances. They are difficult to sample and analyze. Analysis is
ideally performed onsite to eliminate sample deterioration as a factor in analysis.
Sampling must be performed using nonreactive containers such as Silcosteel-lined
vessels, Tedlar bags with polypropylene fittings, or an equivalent. Tedlar bags require
protection from light and heat. Laboratory equipment must be inert or passivated to
ensure reliable results. Sample containers should be filled and purged at least three
times to ensure representative sampling. Laboratory equipment must also be inert,
well conditioned, and passivated with a gas containing the sulfur compounds of inter-
est to ensure reliable results. Frequent calibration using stable standards is required.
Samples should be analyzed as quickly as possible not beyond the proven storage time
after collection to minimize sample deterioration. If the stability of analyzed sulfur
compounds is experimentally proven, then the time between the collection and analy-
sis may be lengthened.
Many sources of natural and petroleum gases contain sulfur compounds that are
odorous, corrosive, and poisonous to the catalysts used in gaseous fuel processing.
Low part-per-million amounts of sulfur compounds are added to natural gas and LPG
for safety purposes. Some odorants are unstable and react to form compounds having
lower odor thresholds. Quantitative analysis of these odorized gases ensures that odor-
ant injection equipment is performing to specification.
D1988 : Mercaptans in Natural Gas Using Length-of-Stain

Detector Tubes
The measurement of mercaptans in natural gas is important because mercaptans are
often added as odorants to natural gas to provide a warning property. The odor pro-
vided by the mercaptan serves to warn the consumers (e.g., residential users) of natural
gas leaks at levels that are well below the flammable or suffocating concentration levels
of natural gas in air. Field determinations of mercaptans in natural gas are important
because of the tendency of the mercaptan concentration to fade over time.
This test method provides inexpensive field screening of mercaptans. The sys-
tem design is such that it may be used by nontechnical personnel with a minimum

amount of training. Available detector tubes provide a total measuring range of

0.5–160 ppmv of mercaptans, although most applications will be on the lower end
of this range (i.e., <20 ppm). In addition to total mercaptans, detector tubes are also
available for methyl mercaptan (0.5–100 ppm), ethyl mercaptan (0.5–120 ppm), and
butyl mercaptan (0.1–8 ppm). Detector tubes are usually subject to interferences
from gases and vapors other than the target substance. Such interferences may vary
between brands because of the use of different detection principles. Many detector
tubes will have a precleanse layer designed to remove interferences up to some max-
imum level. H2S and other mercaptans are usually interferences on mercaptan
detector tubes.
The sample is passed through a detector tube filled with a specially prepared
chemical. Any mercaptan present in the sample reacts with the chemical to produce a
color change or stain. The length of the stain produced in the detector tube, when
exposed to a measured volume of sample, is directly proportional to the amount of
mercaptan present in the sample. A hand-operated piston or bellows-type pump is
used to draw a measured volume of sample through the tube at a controlled rate of flow.
The length of stain produced is converted to parts per million by volume mercaptan by
the manufacturer for each box of detection tubes. The system is direct reading, easily
portable, and completely suited to making rapid spot checks for mercaptans under field
conditions.
To overcome interferences by other gases in the sample, at least three detection
principles are used in this work. Palladium sulfate is used by at least one manufac-
turer. It has a positive interference from H2S, but H2S may be removed in a precondi-
tioning layer at the front of the tube. Propylene and hydrocarbons of five or more
carbon atoms will cause interfering discolorations, making the palladium sulfate
detection principle ineffective for LPG. Palladium chloride detector tubes also behave
the same way.
Mercuric chloride is used by some manufacturers. It also has a positive interfer-
ence from H2S, but it does not have the hydrocarbon interference that palladium sul-
fate does. This detector principle is preferred for LPG applications. H2S will produce a
stain on mercuric chloride tubes even if mercaptans are not present. H2S at 1 ppm will
produce a reading of 0.4–0.7 ppm mercaptans.
A two-stage copper salt/sulfate reaction is used by at least one manufacturer. This
detection principle has a positive interference from H2S with H2S being twice as sensi-
tive (i.e., 10 ppm H2S will appear as 20 ppm mercaptan). Ammonia or amines also
interfere with this principle, producing a second color.
A schematic of the apparatus used in this analysis is shown in Fig. 7.11. A detector
tube and pump together form a unit and must be used as such. Each manufacturer
calibrates detector tubes to match the flow characteristics of their specific pump.
Crossing brands of pumps and tubes is not permitted because considerable loss of
system accuracy is likely to occur. The accuracy of detector tube systems is generally
considered to be ±25 % of the reading.

Fig. 7.11 Schematics of Apparatus Used in Test Method D1988 for Sulfur.
D5305: Ethyl Mercaptan in LPG Vapor

LPG is a colorless and odorless gas and is not detectable by normal human senses.
To provide an olfactory warning in the event of a leak, LPG intended for domes-
tic or commercial use is intentionally odorized so as to be readily detectable well
below flammable or suffocating concentration levels of LPG in air. The most
common odorant for LPG is ethyl mercaptan. The field use of this test method
will rapidly determine the presence and concentrations of ethyl mercaptan in
LPG vapor without the necessity for complex laboratory equipment. Although
length-of-stain tubes are available to detect ethyl mercaptan concentrations in

the range of 0.5–120 ppmv, this test method is specifically applicable to systems
containing 5 ppmv or more of ethyl mercaptan in LPG vapor. A chromatographic
technique can be used for more precise quantitative determination of ethyl mer-
captan in LPG.
In this test method, using a manually operated vacuum pump, a sample of LPG is
drawn through a detector tube made specifically for detection of mercaptans. The
length of stain (color change) produced in the detector tube when exposed to a mea-
sured volume of sample is directly proportional to the amount of ethyl mercaptan
present in the sample being tested. The length of stain produced in the detector tube is
converted to concentration in parts per million by volume by comparison with a cali-
bration scale provided by the manufacturer of the stain tubes.
Detector tubes can be subject to interferences from materials other than the
target substances. Methyl mercaptan will likely interfere with tubes designed to
measure ethyl mercaptan. Interferences can vary because of different detection
chemistry by different manufacturers. Manufacturer’s instructions for specific
interference information for specific tubes should be followed. Propylene (pro-
pene) will cause an interfering gray discoloration with some tubes designed for
ethyl mercaptan. LPG from natural sources usually does not contain propylene.
However, LPG produced in refinery o peration often does contain propylene.
Detection tubes calibrated for t-butyl mercaptan eliminate this interference and
should be used if the presence of propylene is suspected.
On the basis of an ILS involving 12 laboratories that tested 5 samples of propane
with ethyl mercaptan concentrations ranging from 3.3 to 32 ppmv in the vapor phase,
the following precision of measurement was obtained:
Repeatability The larger of 1 ppm or ±15 % of the mean of the two results
Reproducibility The larger of 1.5 ppm or ±20 % of the mean of the two results
Determination of H2S in Gaseous Fuels

The measurement of H2S in natural gas is important because of the gas quality speci-
fications, the corrosive nature of the H2S on pipeline materials, and the effects of H2S
on utilization equipment. The potential personnel exposure hazards of H2S also make
the detection and measurement of H2S important, even in low concentrations.
D2420 : H2S in LPG by Lead Acetate Method

This test method covers the detection of H2S in LPG. The sensitivity of the test is
approximately 0.4 mg/m3. In this test method, vaporized LPG is passed over moist lead
acetate paper under controlled conditions. H2S reacts with lead acetate to form lead
sulfide, which p
roduces a coloration on the paper varying from yellow to black depend-
ing on the concentration of H2S present.
If present, methyl mercaptan produces a transitory yellow stain on the lead acetate
paper that will fade completely in less than 5 min. Other sulfur compounds present in

LPG do not interfere with this test. This is a pass-fail test. A concentration of H2S in
LPG of 4 mg/m3 or greater will give a positive result.
D4084: H2S in Gaseous Fuels Using Lead Acetate

Reaction Rate Method
This test method is useful in determining the concentration of H2S in gaseous samples
and in verifying compliance with the operational needs or environmental limitations
for H2S content or both. The automated performance operation of this method allows
unattended measurement of H2S concentration. This test method covers the determina-
tion of H2S in gaseous fuels such as natural gas, LPG, substitute natural gas, landfill gas,
sewage treatment offgases, recycle gas, flare gases, and mixtures of fuel gases. This test
method can also be used to measure H2S in carbon dioxide gas. Air does not interfere.
The applicable range is 0.1–16 ppmv and may be extended to 100 % H2S by manual or
automatic volumetric dilution.
In this test method, measurement of H2S is accomplished by rateometrically com-
paring a reading of an unknown sample with that of a known standard using a differ-
ential colorimetric detection. Pure H2S is used as a primary standard and mixed
volumetrically with a sulfur-free matrix gas that is ideally similar to the composition of
the sample gas. A gaseous sample at constant flow is humidified and passed over
lead-acetate-impregnated paper. H2S reacts with lead acetate to form a brown stain on
the paper. The rate of reaction and resulting rate of color change is proportional to the
concentration of H2S in the sample. The analyzer comprises an optical system, a photon
detection system, a signal differentiation system of first order, and a signal output sys-
tem (Fig. 7.12). When there is no change in the color or the tape, and no resulting change
in the photodetector output, E, the first derivative, dE/dt, is zero. This results in an ana-
lyzer that automatically zeroes when there is no H2S. The precision of this test method
is illustrated in Fig. 7.13.
D4810 : H2S in Natural Gas Using Length-of-Stain Detector Tubes

This test method provides a procedure for rapid and simple field determination of H2S
in natural gas pipelines. The system design is such that it may be used by nontechnical
personnel with minimal proper training. Available detection tubes provide a total
measuring range of 0.5 ppmv up to 40 % by volume, although most applications will
be on the lower end of this range (i.e., <120 ppm). Typically, SO2 and mercaptans may
cause positive interferences. In some cases, nitrogen dioxide can cause a negative
interference. Most detector tubes will have a “precleanse” layer designed to remove
certain interferences up to some maximum interferent level.
In this test method, a sample is drawn through a detector tube filled with a spe-
cially prepared chemical. Any H2S present in the sample reacts with the chemical to
produce a color change or a stain. The length of the stain produced in the detector tube,
when exposed to a measured volume of sample, is directly proportional to the amount
of H2S present in the sample. A hand-operated piston or bellows-type pump is used to

Fig. 7.12 Flow System for H2S Determination in LPG (D4084).
draw a measured volume of sample through the tube at a controlled rate of flow. The
length of stain produced is converted to parts per million by volume H2S by compari-
son to a calibration scale supplied by the manufacturer for each box of tubes. The sys-
tem is direct reading, easily portable, and completely suited for making rapid spot
checks for H2S under field conditions. A schematic diagram of the apparatus used in
this test method is shown in Figure 1 of Test Method D1988.

Fig. 7.13 Precision of H2S Determination Using Test Method D4084.
The accuracy of the detector tube system is generally considered to be ±25 %.

The repeatability is ±10 % between 3 and 120 ppm H2S and ±5 % between 0.05 and
5 % H2S.
Determination of Sulfur Compounds in Gaseous Fuels

The analysis of gaseous sulfur compounds is challenging because of the reactivity of
these substances. They are difficult to sample and analyze. Analysis is ideally per-
formed onsite to eliminate sample deterioration as a factor in analysis. Sampling must
be performed using nonreactive containers such as Silcosteel-lined vessels, Tedlar
bags with polypropylene fittings, or the equivalent. Tedlar bags require protection
from light and heat. Laboratory equipment must be inert or passivated to ensure reli-
able results. Sample containers should be filled and purged at least three times to
ensure representative sampling. Laboratory equipment must also be inert, well condi-
tioned, and passivated with a gas containing the sulfur compounds of interest to
ensure reliable results. Frequent calibration using stable standards is required. Samples
should be analyzed as quickly as possible not beyond the proven storage time after
collection to minimize sample deterioration. If the stability of analyzed sulfur com-
pounds is experimentally proven, then the time between the collection and analysis
may be lengthened.

Many sources of natural and petroleum gases contain sulfur compounds that are
dorous, corrosive, and poisonous to the catalysts used in gaseous fuel processing.
o
Low part-per-million amounts of sulfur compounds are added to natural gas and LPG
for safety purposes. Some odorants are unstable and react to form compounds having
lower odor thresholds. Quantitative analysis of these odorized gases ensures that odor-
ant injection equipment is performing to specification.
There are at least five ASTM test methods for identifying various other sulfur
compounds in gaseous fuels. All are based on gas chromatographic separation and
specific detection by various techniques such as chemiluminescence, flame photome-
try, atomic emission, electrochemistry, and UV-fluorescence.
D5504: Sulfur Compounds in Natural Gas and Gaseous Fuels by Gas

Chromatography and Chemiluminescence Detection
This test method determines speciated volatile sulfur-containing compounds in
high-methane-content gaseous fuels such as natural gas. It has been successfully
applied to other types of gaseous samples including air, digester, landfill, and
refinery fuel gas. The detection range for sulfur compounds is 10 to 1,000,000 pg, or
0.01–1000 mg/m3. This range can be extended to higher concentration by dilution
or by selection of a smaller sample loop. This test method is not claimed to identify
all sulfur species in a sample. Only the compounds that are eluted through
the selected column under chromatographic conditions chosen are determined. The
detector response to sulfur is equimolar for all sulfur compounds within the
scope of this test method. Thus, unidentified compounds are determined with
equal precision to that of identified substances. The total sulfur content is deter-
mined from the total of individually quantified components.
In this test method, a 1-mL sample is injected into a GC where it is eluted through
a megabore, thick-film, methyl silicone liquid phase, open tubular partitioning col-
umn or other suitable column and then separated into its individual constituents. As
sulfur compounds elute from the GC column, they are processed in a flame ioniza-
tion detector (FID) or a heated combustion zone. The products are collected and
transferred to a sulfur chemiluminiscence detector (SCD). The typical retention
times observed for some s ulfur compounds are listed in Table 7.5. There will also be
many non-sulfur-containing compounds in the chromatogram. This technique pro-
vides a sensitive, selective, and linear response to volatile sulfur compounds and may
be used while collecting hydrocarbon and fixed gas data from a FID. Other sul-
fur-specific detectors can be used provided they have sufficient sensitivity, respond to
all eluted sulfur compounds, do not suffer from interferences, and satisfy quality-
assurance criteria. Regulatory agencies may require demonstration of the equivalency
of alternative detection systems to the SCD. The precision of this test method is not
known at present.

Table 7.5 Retention Times for Sulfur Compounds Obtained in D5504 Analysis
Sulfur Compound Average Retention Time, min Sulfur Compound Average Retention Time, min
H2S 2.053 Carbon disulfide 9.617

COS 2.586 Methylethyl sulfide 11.779
SO2 2.815 ?-EtThiophene 16.983
Ethanethiol 8.583 Diethyl disulfide 18.767
Dimethyl sulfide 9.117 Benzothiophene 23.717
Note: A 4-µL capillary column of 30 m × 0.32 mm size was used.
D6228 : Sulfur Compounds in Natural Gas and Gaseous Fuels by GC and

Flame Photometric Detection
This test method is similar to D5504 in that it separates the sulfur compounds by
gas chromatography and determines the compounds with a flame photometric
detector (FPD) or a pulsed flame photometric detector (PFPD). Common sulfur
compounds found in gaseous fuels and their properties for using in calculations are
given in Table 7.6.
Table 7.6 Physical Properties of Common Sulfur Compounds
Vapor Pressure,
Compound Molecular Weight Percentage Sulfur Boiling Point, °C kPa at 37.78°C
H2S 34.08 94.09 –60.3

COS 60.08 53.37 –50.2
MeSH 48.11 66.65 6.2 214
EtSH 62.13 51.61 35.0 112
DMS 62.13 51.61 37.3 103
CS2 76.14 84.23 46.5
IprSH 76.16 42.10 52.6 61
TBM 90.19 35.55 64.0 41
NPrSH 76.16 42.10 67.0 35
MES 76.16 42.10 67.0 36
THT 88.17 36.37 120 4.6
di-EtS 90.19 35.55 92.0
DMDS 94.20 68.08 109,7
di-Et-DS 122.25 52.46 154.0
COS: carbonyl sulfide; CS2: carbon disulfide; di-Et-DS: diethyldisulfide; di-EtS: diethylsulfide; DMDS:
dimethyl disulfide; DMS: dimethyl sulfide; EtSH: ethanethiol; H2S: hydrogen sulfide; iPrSH:
2-propanethiol; MES: methylethyl sulfide; MeSH: methanethiol; nPrSH: 1-propanethiol; TBM: t-butyl
mercaptan; THT: tetrahydrothiophen.

Fig. 7.14 Chromatogram of a Natural Gas Acquired Using FPD in Test Method D6228.
A typical chromatogram of a composite odorized natural gas acquired using an

FPD is shown in Fig. 7.14. The retention times for sulfur compounds based on this
chromatogram are listed in Table 7.7.
The detection range for sulfur compounds is from 0.02 to 20 mg/m3 on the basis
of the analysis of a 1-mL sample. The precision (repeatability) for FPD and PFPD
obtained with a single operator and a single apparatus is shown in Table 7.8.
D6968: Sulfur Compounds and Hydrocarbons in Natural Gas

and Gaseous Fuels by Gas Chromatography
and Atomic Emission Detection
This test method also separates the volatile sulfur compounds by gas chromatography
but finishes the detection of components using atomic emission detection (AED). This
method uses a specific capillary GC column as an illustration for natural gas and
other gaseous fuel containing low percentages of ethane and propane. Alternative GC
columns and instrument parameters may be used in this analysis optimized for differ-
ent types of gaseous fuels provided that appropriate separation of the compounds of
interest can be achieved. The detection range for sulfur- and carbon-containing com-
pounds is approximately 0.04–200 mg/m3 sulfur or carbon on the basis of the analysis
of a 0.25-mL sample. This test method does not identify all individual sulfur species.
Unknown sulfur compounds are measured as monosulfur-containing compounds.
The total sulfur content of a sample can be calculated by summing up the sulfur

Table 7.7 Retention Times for Sulfur Components Shown in Fig. 7.6
Retention Retention Retention Time,

Compound Time, min Compound Time, min Compound min
H2S 2.45 Thiophene 7.80 M-tB-DS 11.90

COS 2.55 DES 8.25 DMTS 12.35
MeSH 3.52 DMDS 9.00 E-nPr-DS 12.87
EtSH 4.75 M-Thiophene 9.42 DiPr-DS 12.98
DMS 5.10 MEDS 10.37 iPr-tB-DS 13.50
CS2 5.50 C27-Thiophenes 11.00 iPr-nPr-DS 13.65
iPrSH 5.80 M-iPr-DS 11.23 DtB-DS 14.35
nPrSH 6.70 DEDS 11.62 DEt-TS 14.55
MES 6.80 M-nPr-DS 11.74 DtB-DS 17.15
COS: carbonyl sulfide; CS2: carbon disulfide; DMS: dimethyl sulfide; EtSH: ethanethiol; H2S: hydrogen
sulfide; iPrSH: 2-propanethiol; MES: methylethyl sulfide; MeSH: methanethiol; nPrSH: 1-propanethiol.
content present in all sulfur species. See Fig. 7.15 for typical chromatograms of C-179,
C0193, and S-181 in a composite natural gas containing H2S, COS, dimethylsulfide
(DMS), and tetrahydrothiophene (THT). Table 7.9 shows the retention times for some
typical sulfur compounds obtained using this test method.
An ILS has not yet been performed for this test method. Limited data show the
following repeatability:
Compound Concentration, ppmv % Relative Standard Deviation
COS 3.00 0.23

DMS 4.00 0.30
THT 6.00 0.29
COS: carbonyl sulfide; DMS: dimethylsulfide; THT: tetrahydrothiophen.
Table 7.8 Precision of Test Method D6228 for Sulfur Compounds
FPD Mode PFPD Mode
Sulfur Compound ppmv ± Repeatability ppmv ± Repeatability
COS 2.07 0.06 4.16 0.05

H2S 3.59 0.10
DMS 3.63 0.12 3.63 0.09
NPM 3.72 0.12
DMDS 2.00 0.06
nPrSH 3.22 0.05
THT 6.44 0.16 3.01 0.10
COS: carbonyl sulfide; DMDS: dimethyl disulfide; DMS: dimethyl sulfide; H2S: hydrogen sulfide; NPM:
n-propyl mercaptan; nPrSH: 1-propanethiol; THT: tetrahydrothiophen.

Table 7.9 Retention Times for Sulfur Compounds Using Test Method D6966
Retention Retention Retention

Compound Time, min Compound Time, min Compound Time, min
H2S 3.23 DMS 6.77 MES 8.87

COS 3.43 CS2 7.23 Thiophene 9.00
MeSH 4.67 IprSH 7.60 DES 10.45
EtSH 6.30 NprSH 8.63 DMDS 11.45
MEDS 13.55
COS: carbonyl sulfide; EtSH: ethanethiol; H2S: hydrogen sulfide; MeSH: methanethiol.
D7493: Sulfur Compounds in Natural Gas and Gaseous Fuels Using

Gas Chromatography and Electrochemical Detection
This is a test method for online measurement of sulfur compounds in natural gas and
gaseous fuels using gas chromatography, but the final measurement is done with an
electrochemical (EC) detector. This test method is applicable to H2S, C1–C4 mercap-
tans, sulfides, and THT. COS is not covered in this test method. The detection range
for sulfur compounds is approximately 0.1–100 ppmv. The detection range may vary
depending on the sample injection volume, the chromatographic peak separation, and
the sensitivity of the specific EC detector. In this test method, a fixed volume of the fuel
gas (normally 0.25 mL) is injected into an isothermal GC where it is passed through a
1.2-m, 1.6-mm inner diameter Chromosorb W column. A varying amount of sample
and other GC columns with or without column back-flush technique can be used for
the sensitive detection of sulfur species with optimal separation. Specific GC-separated
sulfur compounds are detected by an EC detector using chromic acid electrolyte.
Detectors with different physical designs are commercially available and may be used.
This test method may not identify and measure all individual sulfur species, and it is
mainly used for monitoring natural sulfur and sulfur deodorant compounds com-
monly found in fuel gases or used as an odorous warning agent in fuel gases. This test
method is normally used for repetitive online monitoring of sulfur components in fuel
gases with a single sulfur standard. This test method can also be used for measurement
of all listed sulfur compounds in air or other gases provided that no compound that
can interfere with gas chromatography separation and EC detection is present.
An EC detector using chromic acid chemistry is illustrated in Fig. 7.16. The detector
consists of a glass or methyl polymethacrylate container. The electrodes, two pieces of
platinum gauze as grids arranged vertically in parallel, are welded in a borosilicate glass
tube and separately connected to an amplifier for data acquisition. The electrolyte used
is a solution of chromium(VI) oxide in pure water. A tube with the electrodes dips into
the solution such that the liquid is retained by capillary action within the tube at a level
approximately midway between the two grids. The gas flow from the GC column is
discharged through a narrow glass or polytetrafluoroethylene tube immediately above

Fig. 7.15 Chromatograms of a Composite Natural Gas Using Test Method D6968.
the upper grid center. Each sulfur compound sequentially elutes and reacts with chromic
acid. The redox reaction occurs on the electrode surface, creating a potential difference
between the two electrodes, thus causing a current that is measured in a low-resistance
measuring circuit. One EC detector is normally used for measurement. A second EC
detector may be used for simultaneous detection of late-eluting sulfur compounds such
as THT using a shorter GC column or different optimal separation conditions or both.
Typical operating parameters for the GC are listed in Table 7.10. A typical GC-ED sulfur
chromatogram is shown in Fig. 7.17 for a mixed sulfur standard.
The retention times of selected sulfur compounds using different instrument
settings are listed for reference in Table 7.11. They may vary considerably depending on

Fig. 7.16 Typical Electrochemical Detection Cell Used in Test Method D7493.
the chromatographic conditions. The eluting sequence and spread of sulfur peaks
should remain roughly the same.
Table 7.12 presents the observed repeatability. Reproducibility has not yet been
determined.
Table 7.10 Typical Gas Chromatographic Operating Parameters
GC Parameter Conditions Used
Gas sample loop 0.25 mL at 10°C above GC column oven temperature

Injection type Sampling loop
Carrier gas Helium, air, or nitrogen at 12 mL/min with microelectrochemical detector
Column oven Isotherm, 65°C
Detector Reagent and instrument operating parameters as recommended by the
GC-ED manufacturer

Fig. 7.17 Typical GC-ED Sulfur Chromatogram of a Mixed Sulfur Standard in Test

Method D7493.
D7652: Trace Sulfur Compounds in Hydrogen Fuel by Gas

Chromatography and SCD
Low-operating-temperature power cells such as proton exchange membrane fuel
cells (PEMFCs) require high-purity hydrogen for maximal performance and life-
time. Sulfur compounds are present in many of the materials used in hydrogen
production, and small quantities typically remain after processing and purification.
Part-per-billion concentrations of sulfur gases such as H2S, COS, and mercaptans
diminish single fuel cell capacity.
This test method describes a procedure primarily used for the determination of
H2S, COS, methyl mercaptan, and carbon disulfide in hydrogen fuels for fuel cell
vehicles by gas chromatography with SCD. The reporting limit is 0.02 ppbv on the
basis of the analysis of a 500-mL hydrogen sample. This test method can be extended
to other sulfur species in hydrogen fuel that are eluted through a chromatographic
column. If any new sulfur compounds need to be analyzed in hydrogen fuel, then the
calibration or spiking sulfur standards must include these new compounds. Although
this test method is primarily written for the use of sulfur chemiluminiscent detectors,
other detectors can be used provided they can detect the species mentioned above at
the same sensitivity range with the same data quality.

Table 7.11 Typical Retention Times for Sulfur Components in Different Gas

Chromatography–EC Detection Runs
GC-ED Instrument #1 #2 #3
GC column and 1/8 in. ID × 70 cm L, 1.6 mm ID × 1200 mm L, 4 mm ID × 400 mm L,

parameters N2, 12 mL/min, 65°C N2, 100 mL/min, 20°C N2 100 mL/min, 20°C
Detector size 5 × 20 mm 5 × 20 mm 30 × 25 mm
Sulfur compound RT, s RT, s RT, s
H2S 30 30 30
Methyl mercaptan 70 66 60
Ethyl mercaptan 105 150 80
Dimethyl sulfide 120 200 80
i-Propyl mercaptan 160 240 160
t-Butyl mercaptan 220 342 240
n-Propyl mercaptan 265 426 290
i-Butyl mercaptan 440 560
n-Butyl mercaptan 585
Thiophene 900 720 2100
ID: inner diameter; RT: retention time.
The analysis of sulfur compounds at trace levels in hydrogen gas is challenging

because of the reactivity of these compounds, especially H2S. These substances can be
absorbed by, or out-gassed from, metal surfaces such as stainless steel. Absorption
and interaction with metals affects the sampling and analysis of sulfur compounds
in gaseous streams. The sampling cylinders used and the analytic systems must be
passivated against sulfur loss and reactivity. Passivation is provided by using tetra-
fluoroethylene (TFE)-fluorocarbon, silica, glass, or surface-treated metal in the ana-
lytic system as well as any transfer lines from the sample to the analysis system. The
trace level sulfur contaminants presented in Table 7.13 can be detected by this test
method.
Table 7.12 Repeatability of Specific Sulfur Compounds Measurement in Nitrogen
Compound ppmv ±Repeatability
H2S 5.55 0.047

MM 6.34 0.046
IPM 1.15 0.016
TBM 2.49 0.011
THT 4.91 0.070
H2S: hydrogen sulfide; IPM: i-propyl mercaptan; MM: methyl mercaptan; TBM: t-butyl mercaptan; THT:
tetrahydrothiophen.

Table 7.13 Trace Sulfur Compound Contaminates in Hydrogen Fuel
Sulfur Compound Formula CAS No. Molecular Weight Boiling Point, °C Melting Point, °C
Hydrogen sulfide H2S 7783-06-4 34.08 –61 –86

Carbonyl sulfide COS 463-58-1 60.07 –50 –139
Methyl mercaptan CH2SH 74-93-1 48.11 6 –123
Carbon disulfide CS2 75-15-0 76 46.5 –111.6
This test method uses a standard GC with the hardware necessary for interfac-
ing to a sulfur chemiluminescence detector possessing an inlet system and contain-
ing all other features necessary for measuring sulfur compounds in hydrogen. See
Fig. 7.18 for a schematic diagram of an instrument capable of determining sulfur
compounds in hydrogen fuel. A 500-mL sample of hydrogen is introduced into a
TFE-fluorocarbon tube that is suspended over a bath of liquid nitrogen using syringe
injection of the sample through an injection port. All sulfur compounds are trapped
whereas hydrogen is expelled through the vent valve of T-union 1 as shown in
Fig. 7.19. The trap is warmed to room temperature by immersing it into a water bath
at room temperature. Trapped sulfur compounds are desorbed onto a capillary col-
umn for separation. The sulfur compounds eluting from the capillary column are
detected by SCD. Alternative trapping methods and devices may be used provided
the sensitivity requirements are met.
Various chromatographic columns have been used successfully for the determina-
tion of trace sulfur compounds in hydrogen fuel. A 0.53-mm inner diameter fused sil-
ica open tubular column of bonded methyl silicone liquid phase is typically used. The
Fig. 7.18 Diagram for Analysis of Sulfur Compounds in Hydrogen in Test Method D7652.

Fig. 7.19 Chromatogram of a Sulfur Calibration Standard at 1 ppmv Used in Test

Method D7652.
selected column must provide baseline separation of H2S and COS at the reporting level
limit. An example of the chromatographic conditions used is listed in Table 7.14.
Figure 7.19 shows a chromatogram of a sulfur calibration standard at the detection limit
(10-µL i njection of 1 ppmv sulfur calibration standard).
Total sulfur can also be determined by this procedure except that a column is not
used. Instead, all sulfur compounds are trapped using liquid nitrogen followed
by injection into a SCD without chromatographic separation. This is accomplished
by replacing the analytical column with a short, uncoated silica column. Calibration
using this configuration can be accomplished by 10-µL injection of 1-ppmv standards.

Table 7.14 Typical Chromatographic Conditions Used in a Gas Chromatography-SCD
Operation GC
Column 75 m × 0.53 mm inner diameter 3-µm DB-624 fused silica

column
Carrier gas Nitrogen
Flow rate 4 cm3/min
Sample size 500 mL
Isothermal column temperature 35 or 40°C
Sulfur Chemiluminescence Detector
Detector hydrogen flow 40 mL/min
Air flow 65 mL/min
Detector temperature 800°C
Postanalysis drift assessment is performed by analysis of the same 10-µL injection of a

1-ppmv standard after sulfur analysis.
The reproducibility of this analysis is not known at present; however, the repeat-
ability on the basis of a limited study was found to be as follows:
H2S 0.037 at 0.10 ppbv

COS 0.015 at 0.02 ppbv
Methyl mercaptan 0.005 at 0.007 ppbv
Carbon disulfide 0.005 at 0.004 ppbv

Chapter 8 | Analysis of Biofuels
INTRODUCTION
As an alternative to gasoline and diesel procured from crude oil refining, biofuels
and biodiesels derived from plant or animal origins have been examined. Particularly,
in the United States, the European Union, and Brazil, considerable efforts are
underway to commercialize such petroleum substitute products.
The limit on sulfur content in fuels is included to protect against engine wear,
deterioration of engine oil, and corrosion of exhaust system parts. Limits on sulfur
concentration in a fuel can be required for special uses in connection with heat treat-
ment, nonferrous metal, glass, and ceramic furnaces or to meet regulatory legislation
or regulations. The effect of sulfur content on engine wear and deposits appears to vary
considerably in importance and depends largely on operating conditions. Fuel sulfur
can affect engine wear, deterioration of engine oil, corrosion of exhaust system parts,
exhaust catalyst deactivation, and emission control system performance. To ensure the
maximum availability of fuels, the permissible sulfur content should be specified as
high as practical, consistent with maintenance considerations.
The U.S. Environmental Protection Agency (EPA)’s Federal Tier 2 Motor Vehicle
and Emission Standards and Gasoline Sulfur Control Requirements establish sul-
fur standards for refineries and importers producing reformulated gasoline (RFG),
reformulated blendstock for oxygenate blending, and conventional gasoline. EPA has
established gasoline sulfur controls to support vehicle emission standards. Sulfur con-
taminates the catalytic converter necessary for reducing emissions of hydrocarbons
(HCs), carbon monoxide (CO), and oxides of nitrogen (NOx).
California specifies that compliance with the California sulfur standard for dena-
tured ethanol should be determined using Test Method D5453-93. EPA allows Test
Methods D3120-06e1, D5453-08a, or D7039-07 for measuring sulfur in gasoline as long
as these alternative test method results are correlated to the EPA designated Test
Method D2622-05 when determining compliance with federal EPA sulfur standards.
Table 8.1 shows the referee and alternative test methods for sulfur, the range over which
each test method applies, and the corresponding fuel grades of diesel fuel oils. Table 8.2
lists the available ASTM Test Methods for the determination of sulfur in liquid fuels.

Table 8.1 Sulfur Limits in Biofuels Specifications
ASTM Biofuel Specification ASTM Test Method Total Sulfur, mg/kg Sulfate, mg/kg
D4806 Denatured Fuel Ethanol D2622, D5453, or D7039 30 max

D7319 or D7328 4 max
D4814 Gasoline D2622, D5453, or D7039 350 max for unleaded;
1500 max for leaded
D5798 Ethanol Ed75-85 D2622, D5453, or D7039 210–300
D6751 B100 Biodiesel Fuel Blend D2622, D5453, or D7039 15–500 max
D7467 Biodiesel Blend Diesel D2622, D5453, or D7039 15 max
Fuel Oil
D7544 Pyrolysis Liquid Biofuel D4294 500 max
D7566 Aviation Turbine Fuel D1266, D2622, D4294, or 3000 max
Containing Synthesized D5453
Hydrocarbons
Table 8.2 Sulfur ASTM Test Methods Applicable to Liquid Fuels
ASTM Test
Method Technique Applicability Scope Range Interferences
D129 Bomb Combustion + Petroleum products, >0.1 mass % Some metals

Gravimetry lube oils, additives,
greases
D1266 Lamp Combustion + Gasoline, kerosine, 0.01–0.04
Gravimetry or naphtha mass %
Titrimetry or
Turbidimetry
D1552 High-Temperature Petroleum products, 0.6–8 mass % Chlorine and nitrogen
Combustion + Iodate coke in iodate titration
Titration or IR
D2622 WD–XRF Gasoline, diesel, M85 3 mg/kg to Oxygenates
and M100 Fuels 5.3 mass %
D3120 Microcoulometry Light liquid HCs, 3–100 mg/kg Chlorine, nitrogen,
ethanol fuels and heavy metals
D4294 ED–XRF Gasoline, diesel, M85 150 mg/kg to >100 mg/kg
and M100 fuels 5 mass % halogens
D5453 UV-Fluorescence Gasoline, diesel, biofuels 1–8000 mg/kg >0.35 % halogens
D6445 ED–XRF Gasoline 48–1000 mg/ >100 mg/kg
kg halogens
D6920 Combustion– Gasoline, diesel 0.05–100 mg/ Moisture
Electrochemical kg
D7039 MWD–XRF Gasoline, diesel 2–500 mg/kg Oxygenates
D7212 ED–XRF Gasoline, diesel 7–50 mg/kg Oxygenates, chloride
D7220 Polarization ED-XRF Gasoline, diesel 6–50 mg/kg Oxygenates
IR: infrared; WD-XRF: wavelength-dispersive X-ray fluorescence; UV: ultraviolet; ED-XRF: energy-dispersive
X-ray fluorescence; HCs: hydrocarbons; MWD-XRF: monochromatic wavelength-dispersive X-ray fluorescence.

Analysis of Biofuels 197
Many test methods, including those for sulfur determination, have been simply
picked from a slate for petroleum analysis and included in the biofuels applications.
Most of such petroleum test methods do not include biofuels in their scopes. Most of
the test methods for sulfur determination fall in this second category. It is not clear
that biofuels behave the same way toward petroleum test methods regarding their pre-
cision and accuracy. See Nadkarni for an evaluation and status of the challenges facing
analysis of biofuels at present [1]. The technical discussion of all sulfur test methods
included in this chapter can be found in Chapter 2 and others in this book. Some test
methods quoted in some biofuel specifications for the determination of sulfur do not
include biofuels in their applicability scope: D129, D1266, and D1552.
The three test methods for sulfur included in the biofuel specifications are ASTM
D129, D2622, and D5453. Of these, the first test method is antiquated and rarely used in
modern laboratories. Moreover, it is limited to samples of low volatility and containing
at least 0.1 mass % sulfur. Thus, it is the wrong choice for biofuels with specifica-
tion limits of less than 0.05 mass % sulfur. ASTM D2622 or D4294 are wavelength-
and energy-dispersive X-ray fluorescence methods, respectively. They are widely used
in the oil industry for sulfur determination in diverse petroleum product matrices.
However, one major drawback of these methods for use in biofuel analysis is their
oxygen content, which can seriously affect the sulfur results. ASTM D7039 is an X-ray
fluorescence (XRF) method based on monochromatic wavelength-dispersive tech-
nique. It has not been extensively studied for application to biofuels, but preliminary
data show no doubt that it will be useful for such analysis. On the basis of an extremely
limited study conducted by the Alberta Research Council, the following precision esti-
mates were obtained for biofuels. However, these data should be treated with caution
because they are based on no more than one or two samples of each type [2].
Samples Number of Samples Range, mg/kg Repeatability Reproducibility
Biodiesel blends 2 4—17 0.53X 0.5

0.77X0.5
Ethanol 1 1.7—3.1 0.47 1.4
Note: Where X is the average of individual results.
Likewise, agreement between D5453 and D7039 results for sulfur in ASTM ethanol fuel
Interlaboratory Crosscheck Program (ILCP) crosschecks is also excellent. All results
are in milligrams per kilogram.
Samples D5453 D7039
ASTM ILCP EtOH 1008 1.31 ± 0.36 (41) 1.08 ± 0.23 (10)
ASTM ILCP EtOH 1012 3.61 ± 0.91 (43) 3.31 ± 0.34 (9)
Note: Mean ± standard deviation (number of results).
In other major biodiesel producing regions, sulfur methods equivalent to ASTM

D5453 and D4294 are included in their specifications.
• Brazil: D5453 (ANP 42)
• European Union: ISO 20884 and ISO 20846 (EN 14214)

The main problem in using the XRF test methods for sulfur determination in
biofuels is the presence of oxygenates. Differences in the carbon-to-hydrogen ratio of
the sample and the calibration standard (usually a pure organic sulfur compound)
introduce errors in the sulfur determination. It is estimated that in the D2622 wave-
length-dispersive X-ray fluorescence (WD-XRF) test method, up to 2.8 mass % oxy-
gen, 25 mass % fatty acid methyl ester (FAME), 8.6 mass % ethanol, and 6 mass %
methanol can be tolerated. Fuels containing large amounts of ethanol or methanol
have a high oxygen content leading to significant absorption of sulfur K alpha radia-
tion resulting in low sulfur results. However, such fuels can be analyzed using this test
method provided that correction factors are applied to the results (when calibrating
with white oil) or that the calibration standards are prepared to match the matrix
of the samples.
In a recent interlaboratory study (ILS), among other petroleum samples, one sam-
ple each of B5, B100 biodiesels, E85 gasohol, gasolines with 13 % ethyl tert butyl ether
(ETBE), and gasoline with 5 % ethanol were analyzed with satisfactory results using
Test Method D2622. These samples contained sulfur levels between 18 and 232 mg/kg
[3,4]. In an earlier ILS conducted in 2002, among many gasoline and diesel samples,
two biodiesels and one soy biodiesel were analyzed by various test methods for sulfur
[5]. Both of these studies clearly show that with proper interference calibration, Test
Method D2622 is capable of determining trace amounts of sulfur in biofuels.
For white-oil-based standards, in the energy-dispersive X-ray fluorescence
(ED-XRF) D4294 Test Method, the following corrections are required:
• Sulfur (in M85), mass % = sulfur, mass %/0.59
• Sulfur (in M100), mass % = sulfur, mass %/0.55
In the monochromatic wavelength-dispersive X-ray fluorescence (MWD-XRF)
D7039 Test Method, a matrix correction factor can be used to correct for bias result-
ing from differences in matrices of calibrants and test samples due to hydrogen,
carbon, and oxygen. For general analytical purposes, the matrices of test sample and
calibrant are considered to be matched when the calculated correction factor is
within the range of 0.98–1.04. No matrix correction is required in this range. For
most testing, matrix correction can be avoided with a proper choice of calibrants.
Gasoline samples containing oxygenates may be analyzed with this test method if
the matrix of the calibration standards is matched to the sample matrices or the
matrix correction given in the method is applied to the results. For gasolines with
oxygenates, up to 2.3 mass % oxygen (i.e., 12 mass % methyl tert butyl ether
[MTBE]) can be tolerated for the test samples with the same carbon-to-hydrogen
ratio as the calibrants.
In a limited study conducted at the Alberta Research Council, a sample of fuel
ethanol was analyzed by 31 laboratories to obtain a value of 1.6879 ± 0.4837 mg/kg to
demonstrate the ability of this test method to analyze ethanol samples with extremely
low sulfur values [2]. In the 2007 ASTM ILS for establishing the precisions of Test

Table 8.3 Replicate Analysis of Sulfur in Biofuels by XRF Methods
Product D2622 D4294
B100 Biodiesel 12.99 ± 1.53 (28) 18.41 ± 5.81 (23)

B20 Biodiesel 65.46 ± 2.75 (28) 75.90 ± 8.45 (23)
E85 Gasohol 6482.0 ± 152.4 (27) 6634.8 ± 257.9 (24)
E5 Gasohol 22,217 ± 521.8 (26) 22,415 ± 348 (21)
Note: All results are in mg/kg. The results are expressed as mean ± standard deviation (number of
results).
Table 8.4 Precision of XRF Test Methods for Biofuels
Sample Types D2622 Repeatability D2622 Reproducibility D4294 Repeatability D4294 Reproducibility
All samples 0.1462X 0.8015

0.4273X 0.8015
0.4347X 0.6446
1.9182X0.6446
Gasoline 0.5006X0.4377 1.4533X0.4377 1.4477X0.3661 7.1295X0.3661
Diesel 0.1037X 0.8000
0.3586X 0.8000
1.6658X 0.3300
8.9798X0.3300
Note: Where X is the mean of duplicate determinations.
Methods D2622 and D4294, 27 samples were analyzed among 15 and 25 laboratories,
respectively. Of these, four samples were biodiesels and ethanol fuels. Each sample was
analyzed in duplicate by each laboratory. Most laboratories produced consistent results
(Table 8.3).
On the basis of the above study, the precision estimates presented in Table 8.4
have been calculated for all samples and for biofuels.
D5453: Determination of Sulfur Using Combustion UV Fluorescence

Detection
Test Method D5453 is a combustion UV-fluorescence test method that is widely used
in the industry for the determination of low amounts of sulfur in diverse petroleum
products. Specifically, its scope includes application to liquid petroleum products;
FAME; oxygen-enriched gasolines; ethanol blends (E85, M85, and RFG); biodiesel;
and diesel/biodiesel blends. To demonstrate its applicability to biofuels, several exper-
iments were performed [6].
In one study, data from a round robin conducted by the Western States Petroleum
Association in 2000 were analyzed. Nine industry laboratories plus the California Air
Resources Board (CARB) laboratory participated in this round robin. Thirteen sam-
ples were used, each analyzed in triplicate by each laboratory. Ten of the materials were
denatured fuel ethanol for blending with gasoline for use as automotive spark-ignition
engine fuel conforming to D4806 specifications containing from 1.5 to 42 mg/kg sul-
fur. Two samples were isooctane-based materials with controlled amounts of sulfur
(two at 20 mg/kg and one blank). Overall, the repeatability and reproducibility found
in this round robin were worse than those given in Test Method D5453 for sulfur

concentrations less than 17 mg/kg. At 1.5 mg/kg, it is more than twice the published
repeatability, but it is 26 % less at 40 mg/kg. The estimated reproducibility is also worse
than the published reproducibility for concentrations less than 10 mg/kg sulfur. It is
not quite twice the published reproducibility at 1.5 mg/kg, but it is 38 % less at 40 mg/
kg sulfur [6].
In another study, an ASTM RFG 0607 sample was blended with 0–90 % varying
amounts of ethanol. The data presented in Table 8.5 show close agreement between the
averages measured and the expected sulfur values. The ethanol diluent was found to
contain approximately 3 mg/kg total sulfur [6].
In a separate study, several organic compounds containing sulfur-oxygen bonds
were analyzed at sulfur concentrations of approximately 100 mg/kg in aqueous solution
and analyzed in five replicates. Results and recoveries are reported in Table 8.6 [6].
Table 8.5 Sulfur Determination in Gasoline/Ethanol Mixtures Using Test Method D5453
Expected Sulfur Concentration, mg/

Percentage Ethanol Average Measured Sulfur, mg/kg kg
0 33.7
2 33.4 33.0
5 32.5 32.0
10 30.6 30.3
20 27.9 27.0
30 24.7 23.6
40 21.4 20.2
50 18.3 16.9
60 15.2 13.5
70 11.5 10.1
80 9.1 6.7
90 5.7 3.4
100 3.4 0.0
Table 8.6 Recovery of S–O Compounds
Expected Concentration, Observed Concentration,

Compound ppm ppm Recovery, %
2-Thiophene carboxylic acid 125 110 88

Sodium sulfate 105 99 94
Benzene sulfinic acid 124 110 89
2-Methyl-2-propene-1-sulfonic acid 115 113 98
Benzene sulfonic acid 108 86 80

Table 8.7 Sulfonate Recovery Using Test Method D5453
Expected Observed
Compound Concentration, ppm Concentration, ppm Recovery, %
Dodecylbenzenesulfonate 10.1 7.9 78

Table 8.8 Reproducibility of D5453 Test Method in ASTM ILCP Crosschecks
Mean ± Standard Reproducibility of

Biodiesel ILCP Deviation (valid results) D5453 Reproducibility These Data
BIOD 0511 1.3 ± 0.7 (11) 0.7 1.8

BIOD 0604 1.2 ± 0.4 (17) 0.7 1.1
BIOD 0608 6.1 ± 1.5 (21) 2.2 3.8
BIOD 0611 1.5 ± 0.5 (21) 0.7 1.3
BIOD 0704 7.5 ± 1.6 (44) 2.6 4.5
BIOD 0711 3.49 ± 0.76 (23)
Sulfonate compounds were separately studied for their recovery in a HC solution

prepared in isopropyl alcohol and isooctane using dibenzothiophene in isooctane as a
standard. The results in Table 8.7 are essentially identical to the results obtained in
aqueous solutions in that approximately 80 % of the sulfur is recovered [6].
Another study involved analysis of an ASTM biodiesel sample BIOD 0704 in the
ILCP crosscheck. Forty-four laboratories analyzed this sample using Test Method
D5453. Only four laboratories had results outside of the 3σ range of the stated D5453
reproducibility. The “recalculated” reproducibility is less than 2 mg/kg from repro-
ducibility in D5453 at the 7.5-mg/kg level [6]. Some crosscheck results indicate that
further improvement in D5453 operation is necessary when analyzing biodiesels to
improve the precision. Table 8.8 shows several examples of the applicability of Test
Method D5453 to the analysis of biodiesels in ASTM proficiency testing programs.
Thus, on the basis of these multiple studies, it appears clear that Test Method
D5453 is capable of accurately determining sulfur in biofuels at low levels of sulfur.
The major benchmark ILS mentioned earlier in the chapter on petroleum prod-
ucts included a few biodiesel samples. The data in Table 8.9 show that all three test
methods produce reproducible sulfur results for the biodiesel matrix.
Test Method D3120, which is included in some petroleum product specifica-
tions, has also been shown to be applicable to ethanol fuels such as denatured fuel
ethanol (ASTM D4806), automatic spark-ignition engine fuel (ASTM D4814), Ed75–
Ed85 (ASTM D5798), or gasoline-oxygenate fuel blends with greater than 10 vol %
ethanol. A ruggedness study in which one laboratory sample each of gasoline, gasoline
with 10 % ethanol, pure ethanol, and ethanol spiked with sulfur at two levels were

Table 8.9 Sulfur in Biodiesels by Alternative Test Methods
Sample D2622 D3120 D5453 D6920
D11 biodiesel NA 11.9 ± 3.3 11.0 ± 2.3 9.18 ± 2.92

D12 biodiesel NA 27.5 ± 4.3 29.0 ± 4.4 26.1 ± 6.9
D14 soy biodiesel NA NA 0.82 ± 0.82 1.06 ± 0.84
NA: data not available.

Note: All results are in mg/kg of sulfur. Mean value ± standard deviation.
Table 8.10 Ruggedness Study for Analysis of Ethanol Fuels Using Test Method D3120
Sulfur Found, Standard

Sample n mg/kg Deviation % RSD Repeatability
Gasoline EM87 18 17.75 0.358 2.02 0.991

Gasoline EM 87 + 10 % Ethanol 18 15.40 0.176 1.014 0.487
Ethanol 20 0.192 0.156 81.3 0.433
Ethanol + spike 1.42 10 1.37 0.06 4.39 0.167
Ethanol + spike 2.25 15 2.18 0.09 4.13 0.248
RSD: relative standard deviation.
analyzed multiple times using a Mitsubishi TOX-100 instrument was conducted.

These results are presented in Table 8.10 [7]. Precision of major ASTM Test Methods
for sulfur determination in biofuels is shown in Table 8.11.
Sulfate Species in Fuel Ethanol

Ethanol is used as a blending agent added to gasoline. The presence of small amounts
of inorganic sulfates in denatured ethanol under the right conditions can contribute to
turbine meter deposits and the premature plugging of fuel-dispensing pump filters in
the fuel distribution system. The sulfates have also been shown to cause fuel injector
sticking, resulting in engine misfiring and poor drivability in automobiles.
Sulfates are indicated in filter-plugging deposits and fuel injector deposits.
When fuel ethanol is burned, sulfates may contribute to sulfuric acid emissions.
Ethanol acceptability for use depends on the sulfate content. In addition to total
sulfur, fuel ethanol specification D4806 also requires the determination of total sul-
fate, existent inorganic sulfate, and potential sulfate in the samples. These terms are
defined as follows in these test methods:
• Existent inorganic sulfate: Sulfate species present as sulfuric acid, ionic salts of this
acid, or mixtures of these (D7318); inorganic sulfate species present in the sample
at the time of the analysis with no oxidation treatment (D7319; D7328).
• Inorganic sulfate: Sulfate species present as sulfuric acid, ionic salts of this acid, or
a mixture of these (D7319; D7328).

• Potential sulfate: Inorganic sulfate species present after the sample reacted with an
oxidizing agent (D7319); total sulfur species present in the sample that can be oxi-
dized to inorganic sulfate in the presence of an oxidizing agent (D7328).
Three ASTM test methods—D7318, D7319 and D7328—can be used for this analy-
sis. The first one is based on potentiometric titration, and the last two are based on
ion chromatographic determination. Of the latter two, D7319 is based on direct
injection suppressed ion chromatography and D7328 uses aqueous sample injection.
The Test Method D7319 is intended for ethanol samples that contain between 1 and 20
mg/kg of total or potential inorganic sulfate. The D7328 method can measure between
0.5 and 20 mg/kg of total inorganic sulfate and 4–20 mg of potential inorganic sulfate.
Technical details of both of these test methods can be found in Chapter 2 of this mono-
graph. The precision of these two test methods is given in Table 8.12 below. Some
examples of its application to fuel ethanol crosschecks are given in Table 8.13 [8]. Test
performance indices (TPIs) for biofuel sulfur determination are given in Table 8.14.
The TPI concept is explained in the next chapter in this book.
Therefore, what is the status for sulfur test methods for applying to biofuels?
Table 8.15 makes an attempt to summarize the current status of these developments.
Although some test methods have been validated for application to biofuels, many
more have not yet been validated or some of them are not suitable for analyzing such
low levels of sulfur in biofuels. This issue is larger than just for sulfur analysis and has
been discussed at greater length for other analyses [1]. It is hoped that the product
Table 8.11 Precision of Sulfur Test Methods for Biofuels
ASTM Test Method Sulfur Concentration Repeatability Reproducibility
D2622 (WD-XRF) 3 mg/kg to 4.6 mass % 0.1462X0.8015 0.4273X0.8015

D5453 (UV-Fluorescence) <400 mg/kg 0.1788X0.75 0.5797X0.75
>400 mg/kg 0.02902X 0.1267X
D7039 (MWD-XRF) 4–17 mg/kg 0.23X0.5 0.5X0.5
Note: Where X is the average of two results.
Table 8.12 Precision of Ion Chromatographic Test Methods for Sulfur Species [9]
Test
Sulfur Species Method Repeatability Reproducibility
Total sulfate D7318 0.1711(X + 0.1301) 0.2678

0.5807(X + 0.1301)0.2678
D7319 8.604 × (X + 1.00 )
-2 –4 0.6175
1.2160(X + 1.00–4 )0.6175
D7328 0.2319(X + 1.00 ) –4 0.500
1.0963(X + 1.00–4 )0.500
Potential sulfate D7319 0.1266X 0.6940
1.4334X0.6890
D7328 0.1763X0.400 1.0505X0.400
Note: Where X is the average of two determinations.

Table 8.13 Sulfur Determination in Biofuels in ASTM ILCP Crosschecks
Potential Sulfate,
Total Sulfur, Total Sulfate, mg/kg mg/kg
Analysis mg/kg (D5453) (D7319) (D7328) (D7319) (D7328)
BIOD 0804 2.97 ± 1.01 (50)

BIOD 0808 5.31 ± 0.77 (56)
BIOD 0811 3.44 ± 0.69 (62)
BIOD 1104 0.58 ± 0.42 (58)
BIOD 1108 0.70 ± 0.35 (60)
BIOD 1111 1.10 ± 0.38 (62)
ETOH 0804 2.75 ± 0.63 (33) 0.06±0.06(10) 0.055±0.047(6)
ETOH 0808 2.62 ± 0.71 (29) 0.47±0.5(10) 0.125± 0.124(9)
ETOH 0812 1.64 ± 0.36 (28) 0.48±0.16(9) 0.454±0.192(10) 0.48± 0.16(9)
ETOH 1012 3.61 ± 0.91 (43) 5.88±2.34(25) 4.65±2.29(21)
ETOH 1104 1.29 ± 0.32 (46) 0.11±0.1(31) 0.222±0.251(24)
Note: All results are expressed as robust mean ± robust standard deviation (number of valid results).
Table 8.14 TPIs for Analysis of Biofuels for Sulfur
Material Sulfur D5453 TPI Sulfate D7328 TPI
BIOD 0804 0.47

BIOD 0808 0.95
BIOD 0811 0.76
BIOD 0911 0.40
BIOD 1004 0.89
BIOD 1008 1.18
BIOD 1011 0.84
BIOD 1104 0.34
ETOH 0804 0.71 1.98
ETOH 0808 0.60 1.13
ETOH 0812 0.84 1.29
ETOH 0904 0.68 2.44
ETOH 0912 0.65 1.08
ETOH 1004 0.60 0.91
ETOH 1008 0.71 1.05
ETOH 1012 0.60 0.37
ETOH 1104 0.79 0.74

Table 8.15 Sulfur Test Method Status for Biofuels
Applicability and Applicability and Precision Not Applicable to

Analysis Precision Available Need to Be Checked Biofuels
Sulfate in ethanol D7318; D7319; D7328
Sulfur D2622; D5453 D3120; D4294; D6445; D6920; D129; D1266; D1552
D7039; D7212; D7220
specification writers will take this view in consideration when writing the biofuel
product specifications. Further detailed discussion of the test method capabilities for
elements in addition to sulfur can be found in references [10] and [11].
References
[1] Nadkarni, R. A., “Challenge of Analytical Characterization of Biofuels,” J. ASTM Int., Vol. 7,
2010, 102445.
[2] Wispinski, D., Statistical Comparison of Sulfur in Motor Gasoline, Aviation Gasoline &
Diesel Using ASTM D5453 and D7039 Test Methods, GO-2005-1026, Alberta Research
Council, Calgary, Canada, 2010.
[3] Dahnke, K., Interlaboratory Study to Establish Precision Statements for D4294-07
Standard Test Method for Sulfur in Petroleum Products by Wavelength Dispersive X-Ray
Fluorescence, ASTM RR-D02-1622, ASTM International, West Conshohocken, PA, 2007.
[4] Pohl, M., Interlaboratory Study to Establish Precision Statements for D2622-07
Standard Test Method for Sulfur in Petroleum products by Energy Dispersive X-Ray
Fluorescence, ASTM RR-D02-1635, ASTM International, West Conshohocken, PA, 2007.
[5] Nadkarni, R. A. and Bly, K. J., Interlaboratory Study for the Evaluation of Test Method
Capabilities for the Determination of Low Levels of Sulfur in Gasoline and Diesel, ASTM
RR-D02-1547, ASTM International, West Conshohocken, PA, 2003.
[6] Nadkarni, R. A. and Crnko, J., Research Report in Support of 2007 Revisions to
D5453-06, ASTM RR-D02-1633, ASTM International, West Conshohocken, PA, 2007.
[7] Manahan, M., Note 3 in ASTM D3120-08.
[8] Nadkarni, R. A. and McKlindon, A., “ASTM Proficiency Testing Programs for Biofuels,”
J. ASTM Int., Vol. 6, 2009, 102469.
[9] Dahnke, K., Interlaboratory Studies for the Determination of Chloride and Sulfate in Ethanol
Fuel Blends, ASTM RR-D02-1611, -1614, and -1615, ASTM International, West Conshohocken,
PA, 2007.
[10] Nadkarni, R. A., “Spectroscopic Analysis of Biofuels and Biolubes,” Spectroscopic Analysis
[11] Nadkarni, R. A., “Elemental Analysis of Biofuels,” Elemental Analysis of Fossil Fuels
and Related Materials, MONO10, ASTM International, West Conshohocken, PA, 2014,
pp. 733–775.

Chapter 9 | Proficiency Testing
Programs for Sulfur in Petroleum
Products and Lubricants
INTRODUCTION
Quality management systems such as ASTM D6792 or International Organization of
Standardization (ISO) 17025 require the laboratories to use processes to manage
the precision and bias of their laboratory testing operations. One aspect of overall
laboratory performance includes comparison of precision and bias of one laboratory
relative to others in the industry. One tool for such an endeavor is proficiency testing.
ASTM Proficiency Testing Programs (PTPs) give the participating laboratories a com-
petitive edge, p roviding them with a statistical quality assurance (SQA) tool, enabling
them to compare their performance in the use of ASTM petroleum and lubricant test
methods against other laboratories worldwide and to monitor the laboratory’s
strengths and weaknesses, and helping to improve their skills. Many accreditation
systems (e.g., American Association for Laboratory Accreditation [A2LA]) require
participation in such programs. The American Chemistry Council requires participa-
tion in the lube oil program to give license for using the oils in commerce. A second
reason for conducting such PTPs is to validate if the field laboratories are able to repro-
duce the precision given in the standard test methods. For intercompany commerce
and regulatory compliance, reproducibility of the data is a key parameter in deciding
the validity of certificates of analysis (COA) sent by the suppliers to the customers. The
residual crosscheck sample becomes a useful reference material for later quality-assur-
ance use in the laboratory.
Several articles have been published describing the ASTM D02 Committee’s PTP
crosschecks [1–8]. In addition, talks have been given about this project in non-ASTM
forums [9– 11]. Specific reviews of analytical performance of data have been published
for base oil [12], ultralow-sulfur diesel (ULSD) [13], biofuels [14], and overall D02 PTPs
[15]. At least two ASTM guides provide information on how to interpret the profi-
ciency testing results. These are E1301 Standard Guide for Proficiency Testing by
Interlaboratory Comparisons and D7372 Standard Guide for Analysis and
Interpretation of Proficiency Test Program Results. The latter guide is specifically
aimed at the petroleum product and lubricant PTP conducted under the jurisdiction
of the ASTM Committee D02 on petroleum products and lubricants. Bover has illus-
trated the evaluation of such results in reference [15].

Some relevant terminology in the proficiency testing discussion is summarized in

Table 9.1. Most of these definitions are given in various ASTM standards, which are
cited in the table.
Table 9.1 Terminology Used in Proficiency Testing
Term Definition ASTM Source
Accepted A value that serves as an agreed-upon reference for comparison D6299

reference value and that is derived as (1) a theoretical or established value based
(ARV) on scientific principles; (2) an assigned value based on
experimental work of some national or international organization,
such as the U.S. National Institute of Standards and Technology;
or (3) a consensus value based on collaborative experimental
work under the auspices of a scientific or engineering group.
Accuracy The closeness of agreement between a test result and an D6299
accepted reference value.
Assignable cause A factor that contributes to variation and that is feasible to detect D6299
and identify.
Assigned test The average of all results obtained in the several laboratories that D3244
value (ATV) are considered acceptable on the basis of the reproducibility of
the test method.
Bias A systematic error that contributes to the difference between a D6299,
population mean of the measurements or test results and the E456
accepted reference or true value.
Common cause One of the generally numerous factors, individually of relatively D6299
small importance, that contributes to variation and that is not
feasible to detect or control.
Degrees of The divisor used in the calculation of variance. Usually, it is n – 1, D6300
freedom where n is the number of results.
Interlaboratory ASTM International PTP sponsored by Committee D02 on
Crosscheck petroleum products and lubricants.
Program (ILCP)
Outlier A result far enough in magnitude from other results to be D6300
considered not a part of the set.
Population mean The value toward which the mean of results would converge were
an ever-larger number of results to be obtained under the same
sampling conditions.
Precision The closeness of agreement between the test results obtained D6299,
under prescribed conditions; the degree of agreement between D6300
two or more results on the same property of identical test
material. Precision statements are quoted as repeatability (r) or
reproducibility (R).
Precision ratio An estimate of the relative magnitude of repeatability and D6792
(PR) reproducibility. The PR for a given standard test method can
provide information on the relative significance between
variations caused by different operators and laboratories
compared with a single operator in a single laboratory performing
the standard test method. Essentially, it is the ratio of the
reproducibility to the repeatability of a test.

Proficiency Testing Programs for Sulfur in Petroleum Products and Lubricants 209
Table 9.1 Terminology Used in Proficiency Testing (Continued)
Term Definition ASTM Source
Proficiency testing Determination of a laboratory’s testing performance or capability D6299,

by evaluating its test results by means of interlaboratory exchange D6792,
testing or crosscheck programs. E1301
Relative bias The difference between the population mean of the test results D6300
and an accepted reference value, which is the agreed-upon value
obtained using an accepted reference method for measuring the
same property.
Repeatability (r) The quantitative expression of the random error associated with a D6300
single operator in a given laboratory obtaining repetitive results
by applying the same test method with the same apparatus under
constant operating conditions on identical test material within a
short interval of time on the same day. It is defined as the
difference between two such results at the 95 % confidence level.
Reproducibility (R) A quantitative expression of the random error associated with D6300
different operators from different laboratories using different
apparatuses each obtaining a single result by applying the same
test method on an identical test material. It is defined as the 95 %
confidence limit for the difference between two such single and
independent results.
Site precision (R’) The value below which the absolute difference between two D6792
individual test results obtained under site precision conditions
may be expected to occur with a probability of approximately
95 %. It is defined as 2.77 times the standard deviation of the
results obtained under site precision conditions.
Standard deviation The most common measure of the dispersion of observed results D6300
expressed as the positive square root of the variance.
Test performance An approximate measure of a laboratory’s testing capability, D6792
index (TPI) defined as the ratio of the test method reproducibility to site
precision.
True value The value toward which the average of single results obtained by D3244
n laboratories tends when n becomes very large. Consequently,
such a true value is associated with the particular test method
used. It is recognized that sometimes a true value may not be
equal to the method average if the method has a bias.
Uncertainty An indication of the magnitude of error associated with a value E2655
that takes into account systematic errors and random errors
associated with the measurement or test process.
Variance A measure of the dispersion of a series of accepted results about D6300
the average. It is equal to the sum of the squares of the deviation
of each result from the average divided by the number of degrees
of freedom.
Z score A standardized and dimensionless measure of the difference D7372
between an individual result in a dataset and the arithmetic mean
of the dataset. The Z score is the difference of an individual result
minus the mean divided by the standard deviation for the dataset.

How Do PTPs Work?

A central organizer distributes identical aliquots of a material to the participat-
ing laboratories. If possible, the material should be representative of the com-
mercial production. The laboratories analyze the sample(s) using suggested
standard test methods and return the results to the issuing body. There, the
results are statistically analyzed and the conclusions reported back to all partic-
ipating laboratories.
Benefits of PTPs
The benefits of PTPs are as follows [15]:
• Help satisfy laboratory accreditation requirements
• Provide a statistical quality control (SQC) tool to compare individual performance
against that of other laboratories
• Provide data for monitoring strengths and weaknesses regarding the test
method capability of a laboratory
• Offer ability to compare results among several test methods measuring the
same property of a material
• Demonstrate testing capability to the customers
• Help ASTM workgroups validate test method performance under real-world
conditions
• Provide opportunity for continuous improvement for the individual laboratories
and for ASTM working groups to improve on the test method protocol based on
the learnings from the PTP data
• Help a bulk sample supplier evaluate the material analyzed by a worldwide
laboratory population versus the manufacturing specifications
• Provide residual PTP materials that, along with the published statistical data, can
serve as quasi-standards for internal quality-control work
• Provide opportunity to establish analyst proficiency (i.e., consistency and
comparability of data) when coupled with other tools or mechanisms.
ASTM COMMITTEE D02’s PTP

Participation in the ASTM PTP program is open to all laboratories worldwide on
an annual-fee basis. There are 24 programs in the petroleum products and lubri-
cants area. Of these, 16 programs include determination of sulfur. In 2012, there
were a total of 2400 laboratory units participating in the ASTM PTP crosschecks,
spanning approximately 35 countries from Argentina to Zimbabwe. Approximately
50 % are laboratories not based in the United States. Table 9.2 lists the PTPs that use
sulfur test methods. The most frequently cited ASTM sulfur test methods are D1552,
D2622 , D4294, D4927, D4951, D5185, D5453, D7039, etc. Table 9.3 gives the list of all
sulfur test methods used in individual product Interlaboratory Crosscheck
Programs (ILCPs).

Table 9.2 ASTM D02 PTPs for Sulfur Determination
Material Acronym Sulfur Test Method(s) Used Frequency
No. 2 Diesel Fuel #2DF D129, D2622, D4294, D5453, February, June, October
D7039
No. 6 Fuel Oil #6FO D1552, D2622, D4294 January, May, September
Hydraulic Fuel Oil HFO D4951, D5185
Automotive Lubricant ALA D1552, D4927, D4951, D5185 February, June, October
Additive
Aviation Turbine Fuel JF D1266, D1275, D1552, D2622, March, July, November
D4294, D5453
Base Oil BO D2622, D3120, D4294 April, August, December
Biodiesel BIOD D1266, D5453, D6428 April, August, November
Crude Oil CO D2622, D4294 March, July, November
Fuel Ethanol EtOH D5453, D7039 April, August, December
Gear Oil GO D4294 April, August, December
General Gas Oil GGO D1552, D2622, D4294 March, July, November
Lubricating Oil LU D129, D1552, D4927, D4951, January, May, September
D5185, D5453, D6481
Used Lubricating Oil ISDO D5185, D6595
Motor Gasoline MG D1266, D3120, D2622, D4294, April, August, December
D5453, D7039
Reformulated Gasoline RFG D2622, D4294, D5453 Monthly
Ultralow Sulfur Diesel ULSD D2622, D5453, D7039 Monthly
Petroleum Naphtha PN D2622, D4294, D5453, D7039
Petroleum Coke PC D1552, D6376 April, July, October
Each participating laboratory receives a different sample that is representative of

the product line usually three times a year for most programs, but monthly for refor-
mulated gasoline (RFG) and ULSD programs. The laboratory performs the tests they
normally perform in their laboratory among the specified ASTM Test Method set
cited in each product program. Single determinations by each laboratory are required.
The data are electronically submitted by the laboratory to the ASTM PTP office using
a form provided by ASTM. The results are usually due in the ASTM office within a
month of sample receipt. All data are statistically evaluated by the D2PP software
program (based on ASTM D6300 statistical standard), and the report is distributed
to all participating laboratories. The laboratory identification is held strictly confiden-
tial. Each laboratory is identified numerically, and only the specific laboratory is noti-
fied as to what its identification number is in a particular crosscheck.
Each report contains for each test method alphanumerically arranged results
from each laboratory, its deviation from the average result, its Z score, its historic

Table 9.3 Sulfur Test Methods Used in D02 PTP Programs
Test Method Analysis Producta
D129 Sulfur in Petroleum Products (General Bomb Method) #2DF, LU

D1266 Sulfur in Petroleum Products (Lamp Method) JF, BIOD, MG
D1552 Sulfur in Petroleum Products (High-Temperature #6FO, ALA, JF , GGO, LU, PC
Method)
D2622 Sulfur in Petroleum Products by WD-XRF Spectrometry #2DF, #6FO, JF, BO, CO, GGO,
MG, RFG, ULSD, PN
D3120 Trace Quantities of Sulfur in Light Liquid Petroleum BO, MG
Hydrocarbons by Oxidative Microcoulometry
D4294 Sulfur in Petroleum Products by ED-XRF Spectrometry #2DF, #6FO, JF, BO, CO, GO,
RFG, MG, GGO, PN
D4927 Elemental Analysis of Lubricant and Additive ALA, LU
Components by WD-XRF Spectroscopy
D4951 Additive Elements in Lubricating Oils by ICP-AES HFO, ALA, LU
D5185 Additive Elements, Wear Metals, and Contaminants in HFO, ALA, LU, ISDO
Used Lubricating Oils and Selected Elements in Base
Oils by ICP-AES
D5453 Total Sulfur in Light Hydrocarbons, Spark-Ignition #2DF, JF, BIOD, LU, EtOH,
Engine Fuel, Diesel Engine Fuel, and Engine Oil by MG, RFG, ULSD, PN
UV-Fluorescence
D6376 Trace Elements in Petroleum Coke by WD-XRF PC
Spectroscopy
D6481 Elements in Lubricating Oils by ED-XRF LU
D6595 Wear Metals and Contaminants in Used Lubricating Oils ISDO
or Used Hydraulic Fluids by Rotating Disc Electrode AES
D7039 Sulfur in Gasoline and Diesel Fuels by MWD-XRF #2DF, MG, EtOH, PN, ULSD
Spectrometry
WD-XRF: wavelength-dispersive X-ray fluorescence; ED-XRF: energy-dispersive X-ray fluorescence;
MWD-XRF: monochromatic wavelength-dispersive X-ray fluorescence; ICP-AES: inductively coupled
plasma-atomic emission spectrometry; AES: atomic emission spectrometry; UV: ultraviolet.
a
See Table 9.2 for definition of acronyms.
Z scores, its mean Z score ± standard deviation of the Z score, the precision indi-
cator, and the significant difference. The report also contains a summary of the
results that includes the number of valid results, the robust mean ± robust stan-
dard deviation, the reproducibilities of the ASTM standard used and of the test
data, the Anderson-Darling (AD) statistic, and the test performance index (TPI).
See Fig. 9.1 for an illustration of a page from the report. The data from all laborato-
ries for each test are also plotted as a S-curve arranged by increasing magnitude of
results and identified only by a laboratory identification number. For very precise
results, this curve should be a nearly horizontal line. For tests with varying preci-
sions, the curve exhibits an S-curve as the values increase and then plateau out. See
Fig. 9.2 for an example of the sulfur analysis of ULSD using Test Method D2622 .

Fig. 9.1 Report Page of Sulfur Analysis Using Test Method D7039 for ILCP Ethanol
Fuel 1208.
In addition, each report contains, where possible, histograms and box and whis-
ker plots. The ILCP program plots histograms for all datasets in which there are at least
20 data points. A histogram is a useful graphical tool for viewing data distribution and
variability. See Fig. 9.3 for a histogram of sulfur analysis in crude oil by Test Method
D2622. In this particular figure, a good Gaussian curve is obtained; however, the histo-
grams often show biased patterns. For example, see Fig. 9.4 for sulfur in Diesel Fuel
No. 2 using Test Method D4294 showing an extremely biased analysis.
Box and whisker plots are available when the data are generated for a property by
two or more different test methods. The size (length) of the box and whisker is a
measure of the precision of the proficiency test results. Box and whisker plots readily
visualize the precision of alternative test methods for the determination of the same

Fig. 9.2 S-Curve of Sulfur Analysis of ULSD 1301 Sample Using Test Method D2622.
Fig. 9.3 Histogram of Sulfur Determination in Crude OilI LCP 1211 Using Test Method
D2622.

Fig. 9.4 Sulfur in Diesel Fuel #2 ILCP 1206 Using Test Method D4294.
parameter. See Fig. 9.5 for a box and whisker plot of the sulfur analysis in ULSD sam-
ple 1301 by Test Methods D2622, D5453, and D7039. Another example is shown in
Fig. 9.6 for the sulfur analysis of Diesel Fuel No. 2 sample 1206. Among the four test
methods used here, Test Method D4294 has extreme variation whereas the three
other test methods show minimal dispersion of results.
Statistical Data Analysis

Conclusions of the data are only as good as the logic behind the data treatment.
Considerable effort from statisticians has been devoted in supplying sound statisti-
cal conclusions on the basis of the many data that this program generates. The
statistics are performed on data tables containing six or more test results. Means
and standard deviations are computed using a two-stage robust procedure that is
designed to limit the influence of unusually large or small results while eliminating
only the most egregious among them. The computations and philosophy are
explained more fully in reference [16]. In this protocol, data are subjected to these
robust computations twice. At the first stage, a robust mean estimate and a robust
standard deviation estimate are computed using all results. Results that differ from
this first stage robust mean by more than three times the first stage robust standard
deviation are noted as outliers and are excluded from the second stage robust com-
putation. The second stage estimates are determined by applying the robust mean

Fig. 9.5 Box and Whisker Plot of Sulfur Determination in ULSD 1301 Sample.
and the standard deviation procedure to those nonoutlying results. There is no

second stage exclusion.
Z Scores
The Z score reports each laboratory’s deviation in units of standard deviations. The
Z score is the ratio of the deviation to the standard deviation. Per the D6299 Standard
Guide, a Z score is defined as a standardized and dimensionless measure of the differ-
ence between an individual result in a dataset and the robust mean of the dataset re-
expressed in units of standard deviation of the dataset (by dividing the actual difference
from the robust mean by the standard deviation for the dataset).

Fig. 9.6 Box and Whisker Plot of Sulfur Determination in Diesel Fuel #2 in ILCP 1206
Sample.
X(Individual Lab Result) – Robust Mean (These Data)

Z score = (9.1)
Robust Standard Deviation (These Data)
The sign (+ or –) and the magnitude of the Z score reflect the relative bias of the
individual result versus the mean of the sample group. The significance of the bias
increases as Z Average moves further from zero. Z scores for the current and past six
test cycles are provided for each laboratory by test parameter. The purpose of this is

to provide a chronological approach to monitoring Z scores as a means of evaluat-

ing the laboratory precision over time to ascertain the in-statistical-control status
of the laboratory performance and the measurement system being used.
A Z score greater than 2 or less than negative 2 should cause a laboratory to review
their test data for any possible systematic error. Z scores outside of this range should
occur only approximately 1 time in 20 if a laboratory has average capability running the
method. Laboratories should strive to obtain Z score values close to zero.
The Z score for the current and past six test cycles are provided for each laboratory
by test parameter, in which the robust statistical routine is used to generate statistics in
the statistical summary report. The purpose of reporting the current and past Z score
is to provide a chronological approach to monitoring Z score as a means of evaluating
laboratory precision over time to ascertain the in-statistical-control status of labora-
tory performance and the measurement system being used. By use of the precision
indicator for each test in each statistical summary report, a laboratory can immedi-
ately confirm their performance precision over the current trial and past six test cycles
depending on the availability of the historical Z score in the ILCP database.
Test Performance Index

Although ASTM Standard Practice D6792 defines TPI as test method reproducibility
divided by site precision, in these proficiency testing reports it is defined using the
formula TPIIndustry = R ASTM/Robust RThese Data. Thus, TPI is a measure of the laboratory
capability to meet the published precision of the test method. The equation for calcu-
lating TPI is basically as follows:
Reproducibility of ASTM Standard

TPI = (9.2)
Reproducibility of ILCP Dataset
Extending the concept further using the ILCP data, TPIIndustry can be calculated
using reproducibility obtained in a particular crosscheck. Table 9.4 gives the
guidelines for interpreting the TPIs and what actions should be followed up on.
Further guidance on interpreting the results can be found in ASTM Standard
Guide D7372 . TPI values in the less than 0.8 and 0.8–1.2 ranges should inspire all
laboratories to consider their own contribution to the relatively poor performance
by the industry group. In particular, a TPI value of less than 0.8 coupled with a
Z score of greater than 3 (or > –3) implies that the laboratory is likely to be a signifi-
cant contributor to the group’s poor performance. When the TPI value is less than
0.8 and the Z score is between 2 and 3 (or between –2 and –3), the laboratory
should consider the situation as a warning and consider an investigation to find
the root cause [15].
Table 9.27 toward the end of this chapter provides a summary of the TPIs obtained
for sulfur determination by the most commonly used test methods for various

Table 9.4 Implication of TPI Results from PTP Crosscheck
TPI Value Implications
>1.2 The performance of the group providing the data is probably satisfactory relative to
the corresponding ASTM published precision for that test method. In general, the
greater the TPI value above 1.2, the more significant the difference in reproducibility
precisions.
0.8–1.2 The performance of the group providing the data may be marginal, and each laboratory
should consider reviewing the test method procedures to identify opportunities for
improvement.
<0.8 The performance of the test method as practiced by the group is not consistent with the
ASTM published precision, and all laboratories should investigate the laboratory method
performance improvements.
products used in the PTP for 2012 crosschecks. Many do not show satisfactory TPI
values, indicating noncompliance or inadequacy of good laboratory practices in these
analyses.
For situations in which the TPI is less than 0.8 and a laboratory Z score is very
high (>2 or >3) or very low (< –2 or < –3), the laboratory needs to consider their contri-
bution to the relatively poor performance by the industry group. Although influencing
a large group of participants to improve overall performance is beyond the capability
of a single laboratory, each laboratory should consider taking action as appropriate on
the basis of the guidance given here [15].
TPI Z Score Implication
<0.8 >3.0 or < –3.0 The laboratory is likely a significant contributor

to the group’s poor reproducibility. The laboratory
should investigate the root causes of the
problem.
<0.8 2–3 or –2 to –3 There are more laboratories in this group, and

each should consider actions to improve precision.
Anderson Darling Statistic

The AD statistical test is used to test if a sample of data came from a population with
a specific distribution; namely, it performs a “goodness-of-fit” test to determine if the
data are from a normal distribution. ILCP test data are tested against normal
behavior and measurement resolution adequacy using the AD statistic [16]. The PTP
uses the AD test as the primary tool for testing for normal distribution. ASTM
Standard Practice D6299 recommends the following criteria to evaluate the AD
statistic, and these also should apply to the PTP data. Gross violations (AD > 1.0) are
flagged, and a comment is systematically added to the data tables stating that the
data should be interpreted using conventional normal-distribution-based
probabilities.

AD < 1.0 Data are likely to be normally distributed and the participants should take action to
address all data flags.
AD > 1.0 Data may not represent a normal distribution, and participants should exercise caution in
planning actions for flagged data.
AD >>> 1 There is strong evidence of inadequate variation in the dataset because of inadequate
numerical resolution. It may also arise from the unremoved outliers or a perversely
non-normal data distribution.
Graphs
Graphs are provided for test methods in which there are at least six test results. Each
laboratory’s data are plotted excluding outliers. Horizontal lines are provided at the
mean and mean ± two sets of 3σ control limits. The two sets of control limits are repro-
ducibility of these test data calculated by multiplying the robust standard deviation by
2.77 and the reproducibility of the ASTM standard precision statement calculated by
multiplying 1.083 times the ASTM reproducibility (Fig. 9.2).
Histograms
Histograms are provided for test methods in which at least 20 test results are available.
This is a useful graphical tool for viewing data distribution and variability. If the data
are considered to be a normal distribution as determined by the AD statistic of a factor
of not greater than 1.0, then the determination of the 1 % and 99 % confidence fences
and medians in histograms with 30 or more data points are calculated using the
formula
Robust Mean ± 2.33 × Robust Standard Deviation (9.3)
If the AD statistic indicates a non-normal distribution of data (AD > 1.0), then
the resulting histogram will display the median and 1 and 99 % confidence fences
that are produced using an algorithm to determine what intervals contain a fixed
percentage of the population values (Figs. 9.3 and 9.4). A comment appears on the
data summary table stating that the test data are non-normal.
Box and Whiskers Graphs

Box and whisker graphs provide a cross-reference of test data generated from differ-
ent procedures and methods that determine the same test parameter (e.g., sulfur
determination by X-ray fluorescence [XRF] methods D2622, D4294, or D7039;
inductively coupled plasma–atomic emission spectrometry [ICP-AES] methods
D4951 and D5185, or other microchemical methods [D3230, D5453, etc.]). The box
and whiskers graphs separate the test data by standard, with the box representing
the middle 50 % of test data centered around the median. The horizontal line within
the box represents the median of the reported data. The whisker length is adjusted
to the last data point that falls within 1.5 times the difference between the upper
and lower values of the shaded box. Data points above and below the whiskers are
included. Outlier data are not included in this graph (Figs. 9.5 and 9.6).

Proof of the Pudding

Results of the 2011–2012 ASTM D02 ILCP crosscheck results for sulfur determination
in petroleum products and lubricants are given in Tables 9.5–9.26. In all tables the
results are expressed as robust average ± robust standard deviation (number of valid
results). In cases in which there are less than six results, no statistics are calculated
(shown as NA).
With some exceptions, most laboratories appear to be performing well in the
determination of sulfur whether at mass percentage or milligram per kilogram
levels in different products. Where within the scope, the alternative sulfur test
methods produce equivalent results within the test method reproducibility lim-
its. Often the reproducibility found in the crosschecks is inferior to that given in
the standard test method. As a result, most TPIs obtained in the crosschecks fall
in the “unsatisfactory” category as defined by ASTM Guide D7372 .
Table 9.5 2011–2012 ILCP Results for Sulfur in Motor Gasoline (mg/kg)
Test Method MG 1112 MG 1204 MG 1208 MG 1212
D2622 38.25 ± 2.57 (49) 0.01 ± 0.0 (42) 0.67 ± 0.80 (19) 6.69± 1.00 (33)
D4294 40.55 ± 7.72 (29) 0.01 ± 0.00 (29) 5.79 ± 6.05 (19) 5.90± 5.40 (13)
D5453 36.3 ± 3.3 (99) 51.7 ± 4.0 (95) 0.4 ± 0.3 (67) 6.2 ± 0.7 (74)
D7039 37.31 ± 1.66 (16) 54.02 ± 2.97 (23) 0.74 ± 0.48 (18) 6.42 ± 0.50 (17)
Table 9.6 2011–2012 ILCP Results for Sulfur in No. 2 Diesel Fuel (mg/kg)
Test Method #2DF 1110 #2DF 1202 #2DF 1206 #2DF 1210
D2622 7.32 ± 1.22 (67) 7.08± 0.94 (54) 7.85 ± 1.14 (70) 7.75 ± 1.14 (65)
D4294 8.0 ± 8.2 (82) 10.6± 10.8 (66) 17.03 ± 13.52 (92) 12.97 ± 9.25 (77)
D5453 7.37 ± 0.69 (182) 7.36±0.68 (170) 7.64 ± 0.71 (184) 7.69 ± 0.71 (199)
D7039 7.31 ± 0.58 (47) 7.15± 0.55 (48) 7.77 ± 0.47 (62) 7.54 ± 0.58 (67)
Table 9.7 2012 ILCP Results for Sulfur in Aviation Turbine Fuel (mass %)
Test Method JF 1203 JF 1207 JF 1211
D2622 0.0475 ± 0.0013 (61) 0.1837 ± 0.0042 (54) 0.1776 ± 0.0040 (62)
D4294 0.0486 ± 0.0025 (141) 0.1847± 0.0050 (140) 0.1797± 0.0049 (163)
D5453 0.04741 ± 0.00236 (86) 0.1792 ± 0.00665(51) 0.1746 ± 0.00746(61)
D7039 0.046584 ± 21.82 (16) 0.1800± 0.00647 (13) 0.1748 ± 0.0056 (12)

Table 9.8 2011–2012 ILCP Results for Sulfur in No. 6 Fuel Oil (mass %)
Test Method #6FO 1109 #6FO 1201 #6FO 1205 #6FO 1209
D1552 2.03 ± 0.071 (6) NA NA NA

D2622 1.96 ± 0.05 (27) 1.97 ± 0.06 (20) 2.81 ± 0.10 (21) 0.83 ± 0.03 (21)
D4294 2.01 ± 0.05 (210) 2.094 ± 0.070 (183) 2.89 ±0.076 (212) 0.862 ±0.031(209)
Table 9.9 2012 ILCP Results for Sulfur in Automotive Lubricant Additives (mass %)
Test Method ALA 1202 ALA 1206 ALA 1210
D1552 2.57 ± 0.073 (8) 2.280 ± 0.038 (6) 2.316 ± 0.110 (6)
D4927a 2.51 ± 0.01 (3) – –
D4927b 2.60 ± 0.05 (4) – –
D4951 2.57 ± 0.1092 (17) 2.272 ± 0.123 (24) 2.248 ± 0.075 (26)
D5185 2.61 ± 0.14 (10) 2.2568 ± 0.1353 (10) 2.248 ± 0.0704 (12)
Table 9.10 2012 ILCP Results for Sulfur in Lubricating Oils (mass %)
Test Method LU 1201 LU 1205 LU 1209
D129 0.259 ± 0.009(5) NA 0.30 ± 0.05 (5)

D4927A 0.2526 ± 0.0184 (7) 0.4955 ± 0.0293 (14) 0.2697 ±0.0226 (11)
D4951 0.2548 ± 0.0142 (34) 0.5052 ± 0.0365 (39) 0.2839 ± 0.0182 (30)
D5185 0.2458 ± 0.0203 (26) 0.5046 ± 0.0389 (39) 0.2778 ± 0.0359 (39)
D5453 0.2166 ± 0.0306 (11) 0.3860 ± 0.0579 (15) 0.2480 ± 0.0268 (14)
D6443 0.2543 ± 0.0086 (10) 0.4914 ± 0.0245 (13) 0.2782 ± 0.0089 (8)
D6481 0.2727 ± 0.0313 (11) 0.4845 ± 0.0441 (16) 0.2829 ± 0.0415 (15)
Table 9.11 2011–2012 ILCP Results for Sulfur in Transmission Fluids (mg/kg)
Test
Method ATF 1103 ATF 1107 ATF 1111 ATF 1203 ATF 1207 ATF 1211
D4951 861 ± 240 (9) 1165 ± 51 (8) 1136 ± 105 (11) 2089 ± 159 (9) 1047 ± 76 (12) 701 ± 103 (5)
D5185 811 ± 65 (9) 1159 ± 101 (10) 1071 ± 66 (10) 2172 ± 248 (10) 1076 ± 120 (10) 763 ± 76 (8)
D1552 750 ± 20 (5) 1200 ± 100 (5) 1112 ± 20 (4) 1900 ± 80 (4) 1000 ± 30 (3) NA

Table 9.12 2011–2012 ILCP Results for Sulfur in Hydraulic Fluid Oils (mass %)
Sample D4951 D5185
HFO 1101 0.057 ± 0.009 (13) NA

HFO 1105 0.1604 ± 0.0177 (10) 0.1682 ± 0.0169 (9)
HFO 1201 0.092 ± 0.02 (8) NA
HFO 1205 0.1629 ± 0.0162 (12) 0.15683 ± 0.01865 (8)
HFO 1210 NA 0.0568 ± 0.00568 (7)
Table 9.13 2011–2012 ILCP Results for Sulfur in Base Oils (mg/kg)
Test Method BO 1104 BO 1112 BO 1204 BO 1208 BO 1212
D2622 9.94±1.39(14) 141.2±7.5(19) 0.00±0.00(21) 11.5± 1.6 (19) 148.9±6.4 (20)

D4294 6.52±5.97(15) 138.3±24.9(19) 0.00±0.00(15) 12.4±6.62(11) 147.3±11.4(24)
Table 9.14 2011–2012 ILCP Results for Sulfur in Biodiesels (mg/kg)
Sample D5453 Sample D5453 D7039
BIOD 1104 0.58 ± 0.41 (54) BIOD 1204 0.56 ± 0.32 (62) NA
BIOD 1108 NA BIOD 1208 0.51 ± 0.35 (52) 0.268±0.247 (6)
BIOD 1111 1.06 ± 0.37 (59) BIOD 1211 1.26 ± 0.37 (57) 1.286 ± 0.598 (7)
Table 9.15 2011–2012 ILCP Results for Sulfur in Fuel Ethanol (mg/kg)
Sample D5453 D7039 Sample D5453 D7039
EtOH 1104 1.29 ±0.32(46) 0.75±0.46(16) EtOH 1204 1.51±0.40(49) 1.19±0.43 (20)
EtOH 1108 NA EtOH 1208 1.91±0.57(46) 1.38±0.44(17)
EtOH 1112 NA EtOH 1212 1.79±0.54(50) 1.34±0.46(19)

Table 9.16 2011–2012 ILCP Results for Sulfur in General Gas Oils (mass %)
Sample D2622 D4294
GGO 1103 0.0466 ± 0.0024 (20) 0.0466 ± 0.0043 (34)

GGO 1107 0.3977 ± 0.0181 (19) 0.4086 ± 0.0133 (36)
GGO 1111 0.6195 ± 0.0160 (18) 0.6298 ± 0.0124 (28)
GGO 1203 0.0435 ± 0.0012 (21) 0.0447 ± 0.0026 (32)
GGO 1207 1.8687 ± 0.062 (16) 1.9144 ± 0.040 (42)
GGO 1211 2.1134 ± 0.0879 (18) 2.1863 ± 0.0654 (38)
Table 9.17 2012 ILCP Results for Sulfur in Crude Oil (mass %)
Test Method CO 1203 CO 1207 CO 1211
D2622 2.899 ± 0.125 (23) 1.093 ± 0.050 (26) 3.397 ± 0.175 (25)
D4294 3.007 ± 0.092 (103) 1.118 ± 0.033 (101) 3.501 ± 0.104 (106)
Table 9.18 2011–2012 ILCP Results for Sulfur in Gear Oil (mass %)
Test Method GO 1108 GO 1208 GO 1212
D4294 NA 1.8174 ± 0.1502 (4) 1.874±0.25 (7)

D4951 0.8284 ± 0.1135 (9) 1.74880 ±0.1362(8) 1.737±0.11(8)
D5185 0.7716 ± 0.0597 (7) 1.8318 ± 0.0736 (6) 1.826±0.0427(6)
Table 9.19 2012 ILCP Results for Sulfur in Used Lubricating Oil (mass %)
Test Method ISDO 1111 ISDO 1203 ISDO 1207 ISDO 1211
D5185 0.3064 ± 0.0423 (16) 0.3307 ± 0.0373 (15) 0.3923 ± 0.0398 (17) 0.3162 ± 0.0364 (16)
Table 9.20 2011-2012 ILCP Results for Sulfur in Hydraulic Fluid Oils (mg/kg)
Test Method HFO 1101 HFO 1105 HFO 1201 HFO 1205
D4951 570 ± 90 (8) 1604 ± 177 (10) 920 ± 200 (8) 1613 ± 168 (13)
D5185 NA 1682 ± 169 (9) NA 1511.6 ± 145.8 (8)

Table 9.21 2012 ILCP Results for Sulfur in Petroleum Coke (mass %)
ASTM Sample D1552 (IR) D6376 (WD-XRF)
PC 1207 3.458 ± 0.053 (10) 3.470 ± 0.073 (71)

PC 1210 7.404 ± 0.305 (9) 7.4 ± 0.9 (6)
PC 121x
Table 9.22 2012 ILCP Results for Sulfur in RFG Samples (mg/kg)
ASTM Sample Number D2622 D4294 D5453 D7039
RFG 1201 66.29 ± 4.46(44) NA 61.16 ± 5.03 (73) 64.44 ±3.61 (35)
RFG 1202 8.18 ± 1.47 (41) 31.8 ± 30 (6) 7.53 ± 0.69 (80) 7.75 ± 0.81 (37)
RFG 1204 6.22 ± 1.29 (43) NA 6.07 ± 0.67 (88) 6.10 ± 0.71 (38)
RFG 1205 7.75±1.37 (52) NA 8.005±0.915 (98) 7.86 ± 0.77 (45)
RFG 1206 9.17±1.52 (53) NA 8.748±0.906 (96) 8.79 ± 0.61 (36)
RFG 1207 17.98 ±1.88 (59) 28.71±13.39 (7) 18.05 ± 1.59 (98) 18.06±0.91 (41)
RFG 1208 25.1 ± 1.86 (53) NA 25.65 ± 1.80 (88) 25.13± 1.37 (40)
RFG 1209 65.43 ±2.80 (59) NA 64.17± 4.59 (94) 64.92 ±3.40 (39)
RFG 1210 25.18 ±1.76 (45) NA 25.54± 2.08 (80) 25.28± 1.36 (29)
RFG 1211 25.27 ±1.37 (45) NA 25.00± 2.38 (89) 24.97± 1.28 (38)
RFG 1212 18.25 ±1.26 (48) NA 16.44 ±1.66 (83) 17.24 ±1.23 (38)
Table 9.23 Analysis of NIST SRM 2723a in ASTM ULSD Crosschecks
ULSD Cycle D2622, mg/kg D5453, mg/kg
0404 10.5 10.95

0405 10.8 10.8
0406 10.0 10.2
0407 11.0 10.5
0408 11.0 11.7
0409 11.1 11.2
0410 10.8 11.2
0411 10.8 11.2
0412 11.0 11.1
0501 11.1 10.6
(Continued)

Table 9.23 Analysis of NIST SRM 2723a in ASTM ULSD Crosschecks (Continued)
ULSD Cycle D2622, mg/kg D5453, mg/kg
0502 11.0 10.99

0503 11.1 10.7
0504 10.7 10.9
0505 10.9 10.7
0506 10.8 10.69
0507 10.6 10.5
0508 10.5 11.4
0509 10.6 10.8
0510 10.7 10.66
0511 10.2 11.8
0512 10.5 10.9
0601 10.6 10.9
0602 10.5 10.75
0603 10.8
0604 10.4
0605 10.8 10.8
Note: Sulfur certified for NIST SRM 2723a is 11.0 ± 1.1 mg/kg sulfur.
Table 9.24 2012 Results of ASTM ULSD PTP Analyses (mg/kg)
ASTM Sample D2622 D5453 D7039
ULSD 1201 9.82 ± 0.75 (88) 9.95 ± 0.55 (178) 9.97 ± 0.42 (96)
ULSD 1202 9.87 ± 0.77 (93) 9.85 ± 0.65 (204) 9.94 ± 0.64 (113)
ULSD 1203 9.91 ± 0.69 (94) 9.96 ± 0.69 (221) 10.07 ± 0.48 (122)
ULSD 1204 9.91 ± 0.89 (110) 9.90 ± 0.62 (242) 9.90 ± 0.62 (131)
ULSD 1205 3.10 ± 0.62 (90) 2.94 ± 0.30 (218) 3.27 ± 0.45 (134)
ULSD 1206 3.10 ± 0.52 (106) 2.93 ± 0.32 (218) 3.23 ± 0.40 (118)
ULSD 1207 3.03 ± 0.58 (100) 2.91 ± 0.33 (216) 3.30 ± 0.41 (132)
ULSD 1208 3.16 ± 0.49 (93) 2.97 ± 0.31 (225) 3.29 ± 0.37 (125)
ULSD 1209 7.84 ± 0.48 (92) 8.51 ± 0.70 (231) 7.97 ± 0.48 (126)
ULSD 1210 9.93 ± 1.01 (99) 9.98 ± 0.75 (220) 10.00 ± 0.61 (113)
ULSD 1211 3.17 ± 0.63 (84) 2.97 ± 0.33 (221) 3.25 ± 0.44 (127)
ULSD 1212 1.40 ± 0.68 (65) 1.79 ± 0.30 (187) 1.41 ± 0.42 (95)

Table 9.25 Performance of EPA and CARB Laboratories in ULSD Crosschecks
Sample Test Method Mean Result EPA Result CARB Result
ULSD 1201 D2622 9.82 ± 0.75 9.7 –

D5453 9.95 ± 0.55 10.1 10.2
D7039 9.97 ± 0.42 9.6 –
ULSD 1202 D2622 9.87 ± 0.77 9.7 –
D5453 9.85 ± 0.65 – 9.9
D7039 9.94 ± 0.64 9.7 –
ULSD 1203 D2622 9.91 ± 0.69 11.2 –
D5453 9.96 ± 0.69 – 10.5
D7039 10.07 ± 0.48 9.5 –
ULSD 1204 D2622 9.91 ± 0.89 9.4 –
D5453 9.90 ± 0.62 9.7 10.5
D7039 9.90 ± 0.62 9.3 –
ULSD 1206 D2622 3.15 ± 0.50 3.2 –
D5453 2.91 ± 0.29 3.3 3.0
D7039 3.22 ± 0.38 2.8 –
ULSD 1207 D2622 3.03 ± 0.58 4.1 –
D5453 2.90 ± 0.33 3.3 3.0
D7039 3.39 ± 0.40 2.8 –
ULSD 1208 D2622 3.14 ± 0.50 3.7 –
D5453 2.96 ± 0.31 3.3 3.1
D7039 3.31 ± 0.38 2.9 –
ULSD 1209 D2622 7.85 ± 0.48 8.2
D5453 8.50 ± 0.71 8.7
D7039 7.98 ± 0.48 7.2
ULSD 1211 D2622 3.18 ± 0.64 3.1
D5453 2.97 ± 0.32 3.2 3.1
D7039 3.25 ± 0.44 2.9
ULSD 1212 D2622 1.40 ± 0.68 1.75
D5453 1.79 ± 0.39 1.80 1.85
D7039 1.41 ± 0.42 0.85
ASTM ULSD ILCP PROGRAM

In 2004, ASTM D02.CS 92 started a new PTP for determination of sulfur in ULSD
fuels. EPA and CARB had particular interest in this program to evaluate the capability
of industry laboratories for measuring the sulfur levels at or below 15-mg/kg levels
in diesel fuels. The test methods allowed in this program are the ones approved by
EPA for use for certifying diesels leaving the refinery, terminals, and blending
plants. This is a monthly program, and only four test methods are allowed to be

Table 9.26 Performance of EPA and CARB Laboratories in RFG Crosschecks
Sample Test Method Mean Result EPA Result CARB Result
RFG 1201 D2622 66.6 ± 4.35 65.2 –

D5453 61.16 ± 5.02 – 65, 63
RFG 1202 D2622 8.18 ± 1.47 6.9 –
D5453 7.53 ± 0.69 – 8.0, 7.2
RFG 1204 D2622 6.22 ± 1.29 5.4 –
D5453 6.07 ± 0.67 6.2 5.8, 6.7
RFG 1205 D2622 7.77 ± 1.26 8 –
D5453 8.03 ± 0.94 8.6 8.1, 7.9
RFG 1206 D2622 9.26 ± 1.51 7.7 –
D5453 8.75 ± 0.87 9.6 8.7, 8.7
RFG 1207 D2622 18.09 ± 1.75 17.2 –
D5453 18.03 ± 1.66 18.4 19, 18.1
RFG 1208 D2622 25.07 ± 0.78 28.7
D5453 25.62 ± 1.85 27.0, 25.0
RFG 1209 D2622 65.4 ± 2.80 63.8
D5453 64.2 ±4.6 66.3 66.0, 64.0
RFG 1210 D2622 25.2 ± 1.76 24.5
D5453 25.2 ± 2.1 23.9 27.0, 27.0
RFG 1211 D2622 25.3 ± 1.37
D5453 25.0 ± 2.38 26.6 27.0, 27.0
RFG 1212 D2622 18.25 ± 1.26 17
D5453 16.44 ± 1.66 16.5 17, 17
used: D2622, D3120, D5453, and D7039. In the beginning, a few other test methods
were allowed, including D3120, D6920, D7212, and D7220; however, with time, these
were deleted because very few laboratories performed these tests.
In the beginning of this program, ASTM had recommended the use of NIST SRM
2723, a diesel fuel with a certified sulfur value of 11.0 ± 1.1 mg/kg, to be analyzed
along with each month’s crosscheck sample. These data were to be used by EPA to
evaluate the industry capability for low-level sulfur analysis. After a few years of expe-
rience, ASTM dropped this requirement because most participating laboratories
appear to have good control of analysis of SRM 2723a. Analysis of approximately 3
years worth of data is summarized in Table 9.23. Results by D2622 and D5453 appear
to be well in compliance with the expected value for this SRM.
This program proved quite successful with over 170 laboratories participating.
Some typical results obtained in these crosschecks are shown in Table 9.24. Some con-
clusions from these data are as follows:

Table 9.27 Sulfur TPI Comparison of Test Methods in PTP Crosschecks
Producta D2622 D4294 D5453 D7039 Other Test Methods
BIOD 1104 0.34

BIOD 1111 0.60
BIOD 1204 0.43 NA
BIOD 1208 0.36 NA
BIOD 1211 0.68 NA
BO 1208 0.70 0.53
BO 1212 1.32 1.52
CO 1203 0.47 0.58
CO 1207 0.53 0.86
CO 1211 0.38 0.57
EtOH 1204 0.71 NA
EtOH 1208 0.49 NA
EtOH 1212 0.60 NA
#2DF 1202 0.79 0.29 1.38 0.88
#2 DF 1206 0.71 0.32 1.35 1.07
#2DF 1210 0.70 0.39 1.36 0.85
EtOH 1208 0.59 NA
#6FO 1109 0.86 0.81 1.93 (D1552)
#6 FO 1201 0.71 0.59
#6 FO 1205 0.57 0.68
#6 FO 1209 0.75 0.77
HFO 1101 0.82 (D4951)
HFO 1105 0.67 (D5185)
HFO 1205 0.58 (D5185)
MG 1204 1.01 0.45
MG 1208 0.14 0.36 0.38 0.32
MG 1212 0.71 0.40 1.21 0.91
RFG 1201 1.00 0.91 NA
RFG 1202 0.57 0.21 1.38 NA
RFG 1204 0.52 NA 1.21 NA
RFG 1205 0.58 1.09 1.29
RFG 1206 0.60 NA 1.17 NA
RFG 1207 0.83 0.42 1.16 NA
RFG 1208 1.10 NA 1.32 NA
(Continued)

Table 9.27 Sulfur TPI Comparison of Test Methods in PTP Crosschecks (Continued)
RFG 1209 1.57 1.03 NA
RFG 1210 1.16 NA 1.14 NA

RFG 1211 1.50 NA 0.99 NA
RFG 1212 1.26 NA 1.03 NA
JF 1203 10.33 39.58 0.92
JF 1207 9.47 46.45 1.23
JF 1211 1.55 1.76 1.07 NA
ULSD 1201 1.28 NA 2.12 1.35
ULSD 1202 1.25 NA 1.78 0.89
ULSD 1203 1.40 NA 1.69 1.19
ULSD 1204 1.08 NA 1.88 0.91
ULSD 1205 0.61 1.57 0.72
ULSD 1206 0.73 1.46 0.81
ULSD 1207 0.64 1.40 0.80
ULSD 1208 0.78 3.01 0.88
ULSD 1209 1.66 1.49 1.05
ULSD 1210 0.96 1.57 0.93
ULSD 1211 0.61 NA 1.42 0.74
ULSD 1212 0.29 NA 0.83 0.50
ATF 1207 0.68 (D5185)
LU 1201 0.32 2.00 (D129), 1.04
(D4927)
0.74 (D5185), 1.99
(6443)
LU 1205 0.30 1.28 (D4927), 1.60
(D4951)
0.67 (D5185), 0.48
(D6481)
LU 1209 0.42 0.90 (D4927A), 0.46
(D5185)
2.08 (D6443), 0.34
(D6481)
ALA 1206 3.62 (D1552)
ALA 1210 1.25 (D1552)
GGO 1103 0.89 0.85
GGO 1107 0.65 1.11
GGO 1111 0.17

Table 9.27 Sulfur TPI Comparison of Test Methods in PTP Crosschecks (Continued)
GGO 1203 0.26 1.36

GGO 1207 0.66 0.99
GGO 1211 0.51 0.66
ISDO 1207 0.54 (D5185)
ISDO 1211 0.50 (D5185)
PC 1207 2.99 (D1552),
1.09(D6376)
PC 1220 – 0.08
(D6376)
Note: NA. The TPIs cannot be calculated because the sulfur level is outside of the scope range of the
standard test method or the reproducibility of the standard test method is not available.
a
• Most laboratories use D2622, D5453, and D7039 Test Methods. Very few, if any,
laboratories use the D3120, D6920, D7212, or D7220 Test Methods.
• Generally, the results by D2622, D3120, D5453, and D7039 Test Methods are
comparable. Some typical results are summarized in Table 9.24.
• The reproducibilities obtained in these crosschecks are similar to those given in
the standard test methods.
• U.S. Environmental Protection Agency (EPA) and California Air Resources Board
(CARB) laboratories that take part in these crosschecks have reported results that
are consistent with the oil industry laboratories (Tables 9.25 and 9.26).
• For diesel samples with less than 1 mg/kg sulfur content, most laboratories and
ASTM Test Methods are incapable of producing precise or accurate results.
However, because the mean values of these samples are well below the regulatory
compliance limits, the high precision uncertainty should not be a limiting factor
at sulfur at these low levels. Since 2005, the ULSD program has been limited to
using diesels with sulfur content between 5 and 15 mg/kg because there is little
point in conducting crosschecks at a level well known as not capable of being
determined at present.
Stanley and Schaefer thoroughly investigated the dataset of the 2004 ULSD
ILCP on the basis of the statistical performance of alternative test methods used for
this analysis [13]. The performances of individual laboratories over the entire year as
well as long-term single laboratory performance (site precision) were evaluated. The
latter was found to be the largest contributor to reproducibility for the two most
popular methods (D2622 and D5453). Persistent relative biases among laboratories
also contributed significantly. Although overall performance was better than antic-
ipated from published precisions, some laboratories performed consistently better
than others in their outlier rate, repeatability performance, and reproducibility

performance. Precision performance in the crosscheck program was consistently

better than as published in the individual test methods. The most popular test
methods have small, manageable biases relative to each other. Performance is
not consistent from laboratory to laboratory. In all measures of performance—
outlier rate, repeatability performance, and reproducibility performance—some
laboratories perform better than others. However, the laboratories that performed
best during the first three quarters of 2004 continued to perform better in the
fourth quarter. Past performance is predictive of future results.
Continuous Improvement
The main reason for a laboratory to participate in a PTP is to check how one’s labo-
ratory compares with the rest of the industry laboratories. If the crosscheck shows
poor results for a particular test reported by a laboratory, then it is incumbent upon
that laboratory to investigate why its results are not consistent with those of other
industry laboratories. To that effect, some of the questions that one should look into
are given below. These should be looked into by a laboratory in the spirit of contin-
uous quality improvement. Laboratories, particularly those that show poor Z scores
or TPIs, need to be more vigilant in conducting the tests using appropriate calibra-
tion, quality control, and adherence to the details in the test methods.
A checklist for investigating the root cause of unsatisfactory analytical perfor-
mance in such ILCPs would include the following:
• Check the results for typos, calculation errors, and transcription errors.
• Reanalyze the sample; check for repeatability.
• Check the sample for homogeneity or contamination and that a representative
specimen has been analyzed.
• Review the test method and ensure that the latest version of the ASTM Test
Method is being used. Check the procedure step by step with the analyst.
• Check the instrument calibration.
• Check the statistical quality control chart to see if the problem was developing
earlier.
• Check the quality of the reagents and standards used and whether they have
expired or been contaminated.
• Check the equipment for proper operation against instrument manufacturer’s
operating manual.
• Call the vendor for maintenance or repairs.
• After the problem has been resolved, analyze a certified reference material, if
one is available, or the laboratory quality-control sample to ascertain that the
analytical operation is under control.
• Provide training to new analysts and, if necessary, refresher training to the
experienced analysts.
• Document the incident and the lessons learned for use in future similar problems.

SULFUR TEST METHODS FOR LIQUID FUELS: WHAT NEXT? [17]

We have seen through the discussion in this monograph that there really is not a prob-
lem when it comes to determining major or minor amounts of sulfur in crude oils,
additives, lubricating oils, grease, and other similar petroleum products. The most
commonly used sulfur test methods for fuels are D2622, D4294, D5453, or D7039. For
lubricants, these are D4927, D4951, or D5185. The problem comes with determining
trace levels of sulfur in some new products such as ULSD, biofuels, ethanol fuel, etc.
Approximately 25 test methods for sulfur are available that are based on various chem-
ical techniques. Many of these are in widespread use throughout the industry
(Table 9.28).
At the low level of sulfur concentration that this discussion is about, the
following analytical parameters are given for the test methods of interest.
Precision—repeatability and reproducibility—are calculated at a nominal sulfur
level of 5 mg/kg (Table 9.29).
There is no doubt that several ASTM Test Methods using diverse technology
do give sulfur results within acceptable precision when the sulfur levels are high
enough. See Table 9.30 for some examples from ILCPs in which many laboratories
worldwide often participate.
Alternative test methods can adequately determine sulfur in NIST Standard
Reference Materials (SRMs) when the sulfur concentration within them is in apprecia-
ble amounts (Table 9.31).
As is true in analysis sequence, the quality of precision is related to the sulfur
concentration: The higher the sulfur level, the easier it is to obtain good precision if the
appropriate test method is used (Table 9.32).
Particularly at low levels of sulfur, the energy-dispersive X-ray fluorescence Test
Method D4294 gives false-positive results. This fact has been noted for a long time;
Table 9.28 Sulfur Test Methods for Liquid Fuels
Analytical Technique ASTM Test Methods
Wavelength-Dispersive X-Ray Fluorescence D2622, D4927, D6334, D6443

Energy-Dispersive X-Ray Fluorescence D4294, D6445, D7212, D7220
Monochromatic Wavelength-Dispersive X-Ray Fluorescence D7039
Inductively Coupled Plasma–Atomic Emission Spectrometry D4951, D5185, D7691
Coulometry D3120, D3246
Combustion UV-Fluorescence D5453, D6667
Hydrogeneolysis D4045
Combustion Electrochemical Detection D6428, D6920
Wet Chemistry D129, D1266, D1552, D2784
Note: Test methods appearing in bold are arguably more widely used in the industry.

Table 9.29 Analytical Parameters for Sulfur Test Methods
Test Method Scope PLOQ at 5 mg/kg Sulfur at 5 mg/kg Sulfur
D2622 Wavelength-Dispersive 3 ppm to 4.6 3 ppm 0.5 1.6

X-Ray Fluorescence mass %
D3120 Coulometry 3–1000 ppm 3–5 ppm 1.0 2.07
D4294 Energy-Dispersive X-Ray 17 ppm to 4.6 16 ppm 1.2 5.4
Fluorescence mass %
D5453 UV-Fluorescence 1–8000 ppm 1 ppm 0.6 1.9
D7039 Monochromatic 2–500 ppm 1.9 ppm 1.0 1.3
Wavelength-Dispersive X-Ray
Fluorescence
D7212 Energy-Dispersive X-Ray 7–50 ppm 1.9 ppm 1.9 4.4
Fluorescence
D7220 Energy-Dispersive X-Ray 3–942 ppm 1.4 ppm 1.4 2.5
Fluorescence
PLOQ: pooled limit of quantitation.
Table 9.30 Several Sulfur Test Methods Give Equivalent Results
Producta D2622 D4294 D5453 D7039
MG 9904 ppm 96 ± 87 (30) 105 ± 34 (49) 78.7 ±14.2 (15)

MG 1112 ppm 38.3 ± 2.57 (49) 40.6 ± 7.7 (29) 36.3 ± 3.3 (99) 37.3 ± 1.7 (16)
RFG 9906 ppm 16.7 ± 6.0 (66) 29 ± 21 (31) 13.9 ± 1.6 (22)
DL 9902 ppm 466 ± 19 (64) 487 ± 27 (142) 471 ± 55 (20)
JF 1203 ppm 475 ± 13 (61) 486 ± 25 (141) 474.1± 23.6 (86) 465.8 ± 21.8 (16)
JF 1207 ppm 1837 ± 42 (54) 1847 ± 50 (192) 1792 ± 66.5 (51) 1800 ± 64.7 (13)
JF 1211 ppm 1776 ± 40 (62) 1797 ± 49 (163) 1746 ± 75 (61) 1748 ± 56 (12)
#6 FO 1201 mass % 1.97 ± 0.06 (20) 2.05 ± 0.07 (183)
#6 FO 1205 mass % 2.81 ± 0.10 (21) 2.89 ± 0.08(212)
GGO 1202 mass % 1.87 ± 0.06 (16) 1.91 ± 0.04 (42)
GGO 1211 mass % 2.1134 ± 0.0879 (18) 2.1863 ± 0.0654 (40)
CO 1207 mass % 1.09 ± 0.05 (24) 1.12 ± 0.03 (101)
D4951 D5185 Others
HFO 1205 mass % 0.161 ± 0.017 (13) 0.151 ± 0.015 (8)
GO 1208 mass % 1.75 ± 0.14 (8) 1.83 ± 0.074 (6)
ALA 1206 mass % 2.27 ± 0.123 (24) 2.26 ± 0.135 (10) 2.28 ± 0.04
(D1552)
LU 1205 mass % 0.505 ± 0.037 0.505 ± 0.039 (39) 0.496 ± 0.03 (14)
(39) (D4927A)
ATF 1111 mass % 0.114 ± 0.011 (11) 0.107 ± 0.007 (10)
Note: All results are expressed as mean value ± robust standard deviation (number of valid results).
a

Table 9.31 Analysis of NIST SRMs for Sulfur
Analysis, mass % SRM 1848 Adpack SRM 2721 Crude Oil SRM 2722 Crude Oil
D5185 (ICP-AES) 2.30

D6443 (WD-XRF) 2.88
D2622 (WD-XRF) 1.5884 0.2105
D4294 (ED-XRF) 1.6118 0.2082
NIST Certified 2.327 ± 0.0043 1.5833 0.2104
WD-XRF: wavelength-dispersive X-ray fluorescence; ED-XRF: energy-dispersive X-ray fluorescence.
Table 9.32 Sulfur Concentration Versus Analysis Precision
D5453 D2622
Samplea Mean, ppm % RSD Mean, ppm % RSD
Below 10 ppm Sulfur

RFG 9810 2.5 ± 1 40 6.5 ± 5.5 85
RFG 9907 2.2 ± 0.9 40 6.0 ± 5.7 95
JF 9711 3.5 ± 1.8 51 13.9 ± 13.3 96
Between 10–30 ppm Sulfur
MG 9612 10 ± 2 20 14 ± 10 71
RFG 9609 14 ± 3 21 15 ± 6 40
RFG 9904 29 ± 7 24 30 ± 19 63
RFG 9906 14 ± 4 29 17 ± 17 100
RSD: relative standard deviation.

a
See Table 9.2 for definitions of acronyms.
however, industry laboratories continue using these analyzers because of the low cost
and ease of operation. See comparable data for such low-level sulfur matrices in
Table 9.33. Not only are the D4294 results artificially high, but the precision is also on
the order of 100 % or more.
Samples of RFG and ULSD analyzed in 2012 also echo similar trends in test
method capabilities for sulfur determination (Table 9.34). Given the known propen-
sity of Test Method D4294 for erroneously high sulfur results, that test method is not
allowed in ULSD sample analysis.
Biofuels that have sulfur levels even below ULSD samples do not fare as well in the
imprecision of the analysis (Table 9.35).
Low pooled limit of quantitation does not necessarily mean good precision (in
terms of % relative standard deviation). For several matrices with low sulfur levels, the
following percent relative standard deviations are generally observed:

Table 9.33 Low Level Sulfur Analysis by Alternative Methods
Sample, ppma D2622 D5453 D4294 D7039
JF 9811 6.1 ± 15.8 (259%) 2.85 ± 1.8 (63%) 34 ± 83 (244%)

RFG 9904 30 ± 19 (63%) 29 ± 7 (24%) 42 ± 69 (164%)
RFG 9906 17 ± 17 (100%) 14 ± 4 (29%) 29 ± 58 (200%)
#2DF 1110 7.32 ± 1.22 (16.7%) 7.37 ± 0.69 (9.4%) 8.0 ± 8.2 (103%) 7.31 ± 0.58 (8 %)
#2DF 1202 7.08 ± 0.94 (13.3%) 7.36 ± 0.68 (9.3%) 10.6 ± 10.8 (102%) 7.15 ± 0.55 (7.7 %)
#2DF 1206 7.85 ± 1.14 (14.5%) 7.64 ± 0.71 (9.3%) 17.0 ± 13.5 (79.4 %) 7.77 ± 0.47 (6.1 %)
Note: Values in parentheses are percent relative standard deviation of analysis.

a
Table 9.34 Sulfur Determination in RFG and ULSD Samples
Samplea D2622 D4294 D5453 D7039
RFG 1201 66.55 ± 4.35 (41) 6.5% 61.16 ± 5.02 (73) 8.2% 64.44 ± 3.61 (35) 5.6%
RFG 1202 8.18 ± 1.47 (41) 18% 31.8 ± 30 (6) 94% 7.53 ± 0.69 (80) 9% 7.75 ± 0.81 (37) 10%
RFG 1205 7.75 ± 1.37 (52) 18% 8.01 ± 0.92 (98) 12% 7.86 ± 0.77 (45) 10%
RFG 1206 9.17 ± 1.52 (53) 17% 8.75 ± 0.91 (96) 10% 8.79 ± 0.61 (36) 7%
RFG 1207 17.98 ± 1.88 (59) 11% 28.7 ± 14.4 (7) 18.05 ± 1.59 (98) 9% 18.06 ± 0.91 (41) 5%
50%
RFG 1208 25.1 ± 1.86 (53) 7% 25.7 ± 1.8 (88) 7% 25.13 ± 1.37 (40) 6%
RFG 1209 65.4 ± 2.8 (59) 4% 64.17 ± 4.59 (94) 7% 64.92 ± 3.4 (39) 5%
RFG 1210 28.18 ± 1.76 (45) 7% 25.54 ± 2.08 (80) 8.1% 25.28 ± 1.36 (29) 5.4%
RFG 1211 25.27 ± 1.37 (45) 5.4% 25.00 ± 2.38 (89) 9.5% 25.05 ± 1.26 (32) 5%
RFG 1212 18.25 ± 1.36 (48) 7.5% 16.44 ± 1.66 (83) 10.1% 17.24 ± 1.23 (38) 7.5%
ULSD 1204 9.91 ± 0.89 (10) 9% 9.90 ± 0.62 (242) 6% 9.90 ± 0.62 (131) 6%
ULSD 1205 3.10 ± 0.60 (90) 20% 2.94 ± 0.30 (218) 10% 3.27 ± 0.45 (134) 14%
ULSD 1206 3.10 ± 0.52 (106) 17% 2.93 ± 0.32 (218) 11% 3.23 ± 0.40 (118) 12%
ULSD 1207 3.08 ± 0.58 (100) 19% 2.91 ± 0.33 (216) 11% 3.30 ± 0.41 (132) 12%
ULSD 1208 3.16 ± 0.49 (89) 16% 2.97 ± 0.31 (219) 10% 3.29 ± 0.37 (121) 11%
ULSD 7.84 ± 0.48 (92) 6% 8.51 ± 0.70 (231) 8% 7.97 ± 0.48 (126) 6%
1209
ULSD 1210 9.97 ± 0.96 (97) 10% 10.01 ± 0.69 (210) 7% 10.00 ± 0.61 (113) 6%
ULSD 1211 3.18 ± 0.64 (82) 20.1% 2.97 ± 0.32 (222) 10.8% 3.25 ± 0.44 (131) 13.5%
ULSD 1.40 ± 0.68 (65) 48.6% 1.79 ± 0.39 (187) 21.8% 1.41 ± 0.42 (95) 29.8%
1212
Note: Results are expressed as mean value in ppm ± standard deviation (number of valid results) and %
relative standard deviation.
a

Table 9.35 Determination of Sulfur in Biofuels
Biofuel Samplea D5453, ppm (#) % RSD D7039, ppm (#) % RSD
BIOD 1104 0.58 ± 0.41 (54) 82 NA

BIOD 1108 0.70 ± 0.35 (60) 50 NA
BIOD 1111 1.10 ± 0.38 (62) 34.5 NA
BIOD 1204 0.56 ±0.32 (62) 57 NA
BIOD 1208 0.51 ± 0.35 (52) 69 0.268 ± 0.247 (6) 92.1
BIOD 1211 1.26 ± 0.37 (57) 29.4 1.286 ± 0.598 (7) 46.5
EtOH 1012 3.61 ±0.91 (43) 25 3.31 ± 0.34 (9) 10
EtOH 1104 1.29 ± 0.32 (46) 27 0.75 ± 0.46 (16) 61
EtOH 1108 2.17 ± 0.53 (52) 24 1.57 ± 0.28 (19) 18
EtOH 1204 1.51 ± 0.40 (49) 27 1.19 ± 0.43 (20) 39
EtOH 1208 1.91 ± 0.57 (46) 30 1.38 ± 0.44 (17) 32
EtOH 1212 1.79 ± 0.54 (50) 30 1.34 ± 0.46 (19) 34
NA: not applicable; RSD: relative standard deviation.

a
Earlier in this chapter the concept of TPI was discussed. The TPI is essentially an
indication of how well a laboratory or a group of laboratories perform a standard anal-
ysis. TPIs for low-level sulfur analysis by established ASTM Test Methods in the
recent biodiesel, ethanol fuel, reformulated gasoline, and ULSD samples are summa-
rized in Table 9.36 for use of Test Method D5453 and in Table 9.37 for the use in Test
Method D2622. As discussed earlier, TPIs greater than 1.2 are desirable as an indi-
cator of a well-performing laboratory. Most of the TPI values for the materials stud-
ied here do not appear to be ideal.
Table 9.36 TPIs for Low-Level Sulfur Determination Using Test Method D5453
BIOD D5453 EtOH D5453 RFG D5453 ULSD D5453

Sample TPI Sample TPI Sample TPI Sample TPI
1004 0.89 1004 0.60 1204 0.15 1205 1.57

1008 1.18 1008 0.71 1205 1.09 1206 0.46
1011 0.84 1012 0.60 1206 1.17 1207 1.40
1104 0.34 1104 0.79 1207 1.16 1208 1.52
1111 0.59 1108 0.71 1208 0.17 1209 1.49
1204 0.43 1112 0.60 1209 1.03 1210 1.70
1204 0.71 1210 1.14 1112 1.71
1211 0.68 1208 0.71 1211 0.99 1211 1.47
1212 0.60 1212 1.03 1212 0.83
Note: See Table 9.2 for definitions of acronyms.

RFG Sample D2622 TPI ULSD Sample D2622 TPI
1204 0.52 1205 0.61

1205 0.58 1206 0.73
1206 0.60 1207 0.64
1207 0.83 1208 0.78
1208 1.10 1209 1.66
1209 1.57 1210 1.01
1210 1.16 1112 1.06
1211 1.50 1211 0.61
1212 1.26 1212 0.29
Test Method D7039, a competing technology for low-level sulfur determination,

does not yet have an assigned reproducibility estimate although the test method is in
wide use throughout the industry. Pending the D02 ballot, the following precision
estimates are proposed:
On the basis of this estimate, TPIs are calculated in Table 9.38 for several recent
ILCP crosschecks; once again, most are less than ideal.
Whatever the reason for the sub-par performance of the test methods, it is not
lack of statistics. Many laboratories usually take part in these crosschecks, and only a
few statistical outliers are detected in each cycle (Table 9.39).
ILCP Mean ± SD TPI ILCP Mean ± SD TPI
ULSD 1206 3.23 ± 0.40 0.88 ULSD 1207 3.30 ± 0.41 0.80
ULSD 1208 3.29 ± 0.37 0.91 ULSD 1209 7.97 ± 0.48 1.05
ULSD 1210 10.00 ± 0.61 0.93 ULSD1211 3.25±0.44 0.74
JF 1203 465.8 ± 21.8 0.35 JF 1207 1800 ± 64.7 0.27
MG 1112 37.31 ± 1.66 0.66 MG 1204 54.02 ± 2.97 0.45
2DF 1110 7.31 ± 0.58 0.38 2DF 1202 7.15 ± 0.55 0.34
2DF 1206 7.77 ± 0.47 1.07
RFG 1201 64.44 ± 3.61 1.30 RFG 1202 7.75 ± 0.81 0.48
RFG 1205 7.86 ± 0.77 0.81 RFG 1206 8.79 ± 0.61 1.09
RFG 1207 18.06 ± 0.91 1.14 RFG 1208 25.13 ± 1.37 0.39

Table 9.38 TPIs for Low-Level Sulfur Determination Using Test Method D7039 (Continued)
ILCP Mean ± SD TPI ILCP Mean ± SD TPI
RFG 1209 64.92 ± 3.4 0.67

EtOH 1012 3.31 ± 0.34 0.34 EtOH 1104 0.75 ± 0.46 1.14
EtOH 1108 1.57 ± 0.28 0.82 EtOH 1204 1.19 ± 0.43 0.24
EtOH 1208 1.38 ± 0.44 0.48 EtOH 1212 1.34 ± 0.46 0.32
SD: standard deviation.

Table 9.39 Statistical Outliers in Low-Sulfur Crosschecks
Test Methoda D2622 D4294 D5453 D7039
#6FO 1205 1/22 8/220

EtOH 1204 3/52 3/22
EtOH 1212 2/52 5/24
CO 1207 2/26 11/112
CO 1211 0/25 5/106
BO 1208 2/21 4/18
BO 1212 1/21 4/28
MG 1204 3/42 3/9 5/95 2/23
MG 1208 2/31 2/27 4/71 0/18
ULSD 1204 1/111 4/242 1/131
ULSD 1206 2/98 6/199 3/125
ULSD 1208 4/93 6/225 4/125
RFG 1207 4/63 2/9 4/102 3/44
RFG 1208 3/56 2/90 2/42
RFG 1209 1/50 3/85 4/33
RFG 1210 1/45 1/81 0/29
RFG 1211 2/45 2/93 1/33
RFG 1212 3/51 3/86 3/41
BIOD 1204 6/68 0/5
BIOD 1208 2/52 0/6
BIOD 1211 6/63 0/7
JF 1205 4/65 19/160 9/95 0/16
JF 1211 6/62 8/163 4/61 0/12
#2DF 1204 7/77 23/115 13/197 1/63
ULSD 1211 4/88 7/228 6/133
ULSD 1212 6/71 3/190 6/101
a
See Table 9.2 for definitions of acronyms.

The above discussed (im)precision is reflected in the unsatisfactory TPIs found

in the above tables. In general, for Test Method D5453, TPIs are less than 0.8 in bio-
diesels and ethanol fuels and less than 1 for reformulated gasoline. For Test Method
D2622, TPIs are less than 0.8. For Test Method D7039, most TPIs are less than 1 at low
sulfur levels in several products. There could be multiple reasons for this lack of
accuracy:
• The laboratories may not be correctly following the test method instructions.
• The laboratories may not be using adequate calibration and quality-control
practices.
• Interferences in some methods may not be adequately compensated for,
particularly for XRF methods in which there is strong interference from
oxygenated matrices.
• The precision given in the STM may not represent the real-world situation. The
interlaboratory studies undertaken to establish precision in the test methods often
use the fewest laboratories and samples as possible. These are usually the
laboratories that take part in ASTM meetings, etc. However, when the test method
is practiced by many real-world laboratories, the resultant precision is quite
different and usually worse than that found in the original interlaboratory study.
It has to be recognized that every test method has some limitations. Many cur-
rent sulfur test methods are not sensitive enough or precise enough for a changing
paradigm of decreasing sulfur levels in fuel products. Despite the “irrational exu-
berance” on the part of some instrument vendors, their claims are not provable in
the field.
References
[1] Bover, W. J., “ASTM, the Petroleum Industry, and Quality Assurance—Good Partners Years
Ago… Still Good Today,” ASTM Standardization News, Vol. 26, 1988, pp. 29–33.
[2] Bover, W. J., “Tackling Interlaboratory Variability for the Global Marketplace,” ASTM
Standardization News, Vol. 22, 1994, pp. 56–63.
[3] Nadkarni, R. A., “Does Your Laboratory Measure Up? ASTM Program Helps Build
Proficiency,” Lubes’N’Greases, April 2001, pp. 28–34.
[4] Tanguay, W., “Confirm Lab Quality With the Cross-Check Program,” Practicing Oil Analyst,
July–August 2002, pp. 54–58.
[5] McKlindon, A., “Two New ASTM Proficiency Programs to be Launched in the Coming
Months,” ASTM Standardization News, October 2003, pp. 18–19.
[6] Bradley, D., “ASTM Proficiency Testing Programs: Statistical Quality Assurance Tool for
Laboratories,” ASTM Standardization News, Vol. 32, 2004, pp. 26–29.

[7] Nadkarni, R. A. and Bover, W. J., “Bias Management and Continuous Improvements
through Committee D02’s Proficiency Testing,” ASTM Standardization News, Vol. 32,
2004, pp. 36–39.
[8] Bradley, D. and McKlindon, A., “Assessing Laboratory Performance,” ASTM

Standardization News, February 2007, pp. 23–25.
[9] Nadkarni, R. A., “Interlaboratory Proficiency Testing Programs for Petroleum Products and
Lubricants: A Cutting Edge for Quality,” Paper presented at the STLE Meeting,
Philadelphia, PA, March 2003.
[10] Bover, W. J., “Relevant Global Standards: A Petroleum Industry Perspective—Continuous

Improvement Through Proficiency Testing and Training Programs,” Paper presented at
the International Forum on Process Analytical Technology, Arlington, VA, February 2006.
[11] Nadkarni, R. A., Bover, W. J., and Bradley, D., “Proficiency Test Programs—Impact on
Analytical Test Methods Used by the Petroleum Industry,” Paper presented at the Eastern
Analytical Symposium, Somerset, NJ, 2006.
[12] Nadkarni, R. A. and Mason, K. J., “New Program Puts Base Oils to the Test,” Lubricants
World, Vol. 11, October 2001, pp. 30–33.
[13] Stanley, R. M. and Schaefer, R., “Statistical Performance of Methods for Measuring Sulfur
Concentrations in Ultra Low Sulfur Diesel,” J. ASTM Int., Vol. 3, 2006, 100294.
[14] Nadkarni, R. A. and McKlindon, A., “ASTM Proficiency Testing Programs for Biofuels,” J.
ASTM Int., Vol. 6, 2009, 102469.
[15] Bover, W. J., “Analyzing and Interpreting Proficiency Test Program Data for Spectroscopic
Analysis of Petroleum Products and Lubricants,” Spectroscopic Analysis of Petroleum
Products and Lubricants, MONO9, R. A. Nadkarni, Ed., ASTM International, West
Conshohocken, PA, 2011, pp. 74–111.
[16] Shapiro, S. S., “How to Test Normality and Other Distribution Assumptions,” American
Society for Quality, Milwaukee, WI.
[17] Nadkarni, R. A., “Sulfur Test Methods for Fuels: What Next?” ASTM D02.SC 3 Committee
Meeting Presentation, Norfolk, VA, December 4, 2012.

Appendix 1 | ASTM Standards Cited
ASTM Standard Analysis Matrix ASTM Research Report Number
D1552 Total Sulfur Petroleum products RR-D02-1231

D2622 Total Sulfur Petroleum products RR-D02-1428, -1547, -1622
D2784 Total Sulfur LPG NA
D3120 Trace Quantities Light liquid petroleum RR-D02-1036, -1546, -1547
Sulfur hydrocarbons
D3227 Thiol Mercaptan Liquid petroleum products NA
Sulfur
D3246 Total Sulfur Petroleum gas NA
D4927 Total Sulfur Lubricants and additives RR-D02-1259
D4951 Total Sulfur Lubricating oils RR-D02-1349
D4952 Active Sulfur Species Fuels and solvents NA
D5185 Total Sulfur Used lubricating oils and RR-D02-1282
base oils
D5453 Total Sulfur Liquid petroleum products RR-D02-1307, -1456, -1465,
-1475, -1547, -1633
D5623 Sulfur Compounds by Light petroleum liquids RR-D02-1335
Gas Chromatography
D6334 Total Sulfur Gasolines NA
D6443 Total Sulfur Lubricating oils and additives RR-D02-1450
D6445 Total Sulfur Gasoline NA
D6481 Total Sulfur Lubricating oils NA
D6667 Total Volatile Sulfur Gaseous hydrocarbons RR-D02-1506
and LPG
D6920 Total Sulfur Liquid petroleum products RR-D02-1547
BK-AST-MONO11-140027-Appendix 1.indd 243 5/22/2014 12:14:24 PM

ASTM Standard Analysis Matrix ASTM Research Report Number
D7039 Total Sulfur Gasoline and diesel fuels RR-D02-1552

D7041 Total Sulfur Liquid petroleum products RR-D02-1558
D7183 Total Sulfur Aromatic hydrocarbons RR-D16-1035
D7212 Total Sulfur Automotive fuels RR-D02-1587
D7220 Total Sulfur Automotive fuels RR-D02-1592, -1736
D7318 Existent Inorganic Ethanol RR-D02-1615
Sulfate
D7319 Existent and Fuel ethanol RR-D02-1614
Potential Sulfate
D7328 Existent and Fuel ethanol RR-D02-1611
Potential Inorganic
Sulfate
D7620 Total Sulfur Liquid petroleum fuels RR-D02-1701
D7691 Total Sulfur Crude oils RR-D02-1716
D7751 Total Sulfur Lubricating oils RR-D02-1732
D1072 Total Sulfur Fuel gases NA
D1988 Mercaptans Natural gas NA
D4084 Hydrogen Sulfide Gaseous fuels NA
D4468 Total Sulfur Gaseous fuels NA
D4810 Hydrogen Sulfide Natural gas NA
D5504 Sulfur Compounds Natural gas and gaseous fuels NA
D7165 Sulfur Compounds Gaseous fuels NA
D7166 Total Sulfur Gaseous fuels NA
D7551 Total Volatile Sulfur Gaseous hydrocarbons, NA
liquefied petroleum gas, and
natural gas
D7652 Sulfur Compounds Hydrogen fuel NA
D1757 Sulfate Sulfur Ash from coal and coke NA
D2492 Forms of Sulfur Coal RR-D05-1009
D3176 Ultimate Analysis Coal and coke NA
D3177 Total Sulfur Coal and coke NA
D4239 Total Sulfur Coal and coke RR-D05-1039, -1041
D5016 Total Sulfur Coal and coke Combustion RR-D05-1033
residues
NA, not available.

Appendix 2 | Index of Description
of ASTM Test Methods
Test Method Analysis Matrix Main Pages
D129 Sulfur Using Bomb Combustion Petroleum products

D1072 Sulfur Using Combustion/Titration Fuel gases
D1266 Sulfur Using Lamp Combustion Petroleum products
D1552 Sulfur Using High-Temperature Petroleum products
Combustion
D1757 Sulfate Sulfur Ash from coal and coke
D1988 Mercaptans Using Length-of-Stain Natural gas
Detector
D2420 H2S Using Lead Acetate Paper LPG
D2622 Sulfur Using WD-XRF Gasoline and diesel
D2784 Sulfur Using Oxy-Hydrogen Burner or LPG
Lamp
D3120 Sulfur Using Oxidative Microcoulometry Petroleum products
D3177 Sulfur Using Gravimetry Coal and coke
D3227 Thiomercaptans Using Potentiometric Gasoline
Titration
D3246 Sulfur Using Oxidative Microcoulometry Petroleum gases
D3712 Sulfonates Using Liquid Chromatography Petroleum liquids
D4045 Sulfur Using Combustion–Hydrogeneolysis Petroleum products
and Rateometric Colorimetry
D4084 H2S Using Lead Acetate Reaction Rate Gaseous fuels
D4239 Sulfur Using High Temperature Tube Coal and coke
Furnace Combustion

D4294 Sulfur Using ED-XRF Gasoline and diesel

D4468 Sulfur Using Hydrogeneolysis and Gaseous fuels
D4810 H2S using Length of Stain Detector Tubes Natural gas
D4927 Additive Elements Using WD-XRF Lubricants
D4951 Additive Elements Using ICP-AES Lubricants
D5016 Sulfur Using High-Temperature Tube Coal and coke
Furnace Combustion and IR Detection
D5185 Additive and Wear Elements Using Lube and base oils
ICP-AES
D5303 Carbonyl Sulfide Using Gas Propylene
Chromatography
D5305 Ethyl Mercaptan LPG vapors
D5453 Sulfur Using Combustion UV-Fluorescence Petroleum products
D5504 Sulfur Compounds Using GC and Natural gas
Chemiluminescence
D5623 Sulfur Using GC and Sulfur Selective Petroleum products
Detection
D5705 H2S in Vapor Phase Residual fuel oils
D6021 H2S Using Multiple Headspace Extraction Residual fuels
and Specific Detection
D6228 Sulfur Compounds Using GC-Flame Natural gas
Photometry
D6334 Sulfur Using WD-XRF Gasoline
D6376 Sulfur Using WD-XRF Petroleum coke
D6428 Sulfur Using Combustion-Electrochemical Aromatic hydrocarbons
Detection
D6443 Additive Elements Using WD-XRF Lube oils and additives
D6444 Sulfur Using WD-XRF Gasoline
D6445 Sulfur Using ED-XRF Gasoline
D6481 Additive Elements Using ED-XRF Lube oils
D6667 Sulfur Using Combustion UV-Fluorescence LPG
D6920 Sulfur Using Combustion Electrochemical Gasoline and diesel
Detection
D6968 Sulfur Compounds Using GC-AED Natural gas
D7039 Sulfur Using MWD-XRF Gasoline; diesel
D7041 Sulfur Using GC-FPD Online Petroleum products
D7111 Elements Using ICP-AES Middle distillate fuels
D7165 Sulfur Using Online Analyzer Gaseous fuels
D7166 Sulfur Using Online Analyzer Natural gas

Index of Description of ASTM Test Methods 247
D7183 Sulfur Using UV-Fluorescence Aromatics hydrocarbons

D7212 Sulfur Using ED-XRF Gasoline and diesel
D7220 Sulfur Using Polarization ED-XRF Gasoline and diesel
D7318 Sulfate Using Potentiometric Titration Fuel ethanol
D7319 Sulfate Using Ion Chromatography Fuel ethanol
D7328 Inorganic Sulfate Using Ion Fuel ethanol
Chromatography
D7359 Sulfur Using Oxidative Pyrohydraulic Aromatic hydrocarbons
Combustion and Ion Chromatography
D7493 Sulfur Compounds Using Online GC Natural gas
D7551 Sulfur Using UV-Fluorescence Natural gas
D7620 Sulfur Using Oxidation and Liquid hydrocarbons
UV-Fluorescence
D7621 H2S Using Rapid Liquid-Phase Extraction Fuel oil
D7652 Sulfur Compounds Using GC Hydrogen fuel
Chemiluminescence Detection
D7691 Elements Using ICP-AES Crude oil
D7751 Additive Elements Using ED-XRF Lube oils
E775 Sulfur Using Gravimetry Refuse-derived fuel
Test method standards in italics have been withdrawn by ASTM International.

Index
A alternative test methods, 4

Abu Dhabi crude oil, 66 (table) for low level sulfur analysis,
accepted reference value (ARV), 208 236 (table)
(table) for sulfur determination in
accuracy, 208 (table) additives, 159 (table), 161
acid rain, 4, 14–15 for sulfur determination in gasoline,
active sulfur, 128–129 195, 196 (table), 202 (table)
additive concentrates, test methods, for sulfur determination in
82, 85 lubricants, 159 (table), 161
additives See also ASTM test methods
alternative test methods, 159 American Chemistry Council, 207
(table), 161 amino acids, 5
energy dispersive-X-ray analytical techniques, 9–10, 10 (table),
fluorescence and, 158–159 11, 24–25
inductively coupled plasma- for lubricants, 11
atomic emission spectroscopy for petroleum products, 11, 65 (table)
and, 156–158, 158–159 See also additives; biofuels; coal;
proficiency testing and, 160–161 gaseous fuels; lubricants; oil
standard reference materials shale; petroleum products;
(SRMs) for, 32 (table) specific techniques; total sulfur
test methods, 110, 154 (table), 159 analyzers, 26–27
(table), 161 Anderson Darling statistic, 219–220
See also additives, specific anions, 145 (figure), 147
analytical techniques; Antek nitrogen analyzer, 27
wavelength dispersive-X-ray Antek sulfur analyzer, 27
fluorescence and, 153–155, 158 antiknock effect, 71
Africa crude oil, 65 (table), 66 (table) antioxidants, 6
air oxidation, 105–106 aqua regia, 42
Alaska crude oil, 66 (table) aqueous acid, 42, 43
Alberta Research Council study, 104, aqueous analysis technique. See ion
117, 197, 198–199 chromatography
alcohol, test methods, 92 Argentina crude oil, 68 (table)
BK-AST-MONO11-140027-Index.indd 249 5/22/2014 12:22:13 PM

argon (Ar), 17–18 ASTM D2784, 83, 165–168, 168

aromatic hydrocarbons, 89–90, 104, (figure), 169 (figure)
105 (table) ASTM D3120, 16, 72, 79 (table), 81,
Asia crude oil, 68 (table) 90–92, 91 (figure), 92 (table)
assignable cause, 208 (table) biofuel and, 201, 202 (table)
assigned test value (ATV), 208 (table) Interlaboratory Crosscheck
ASTM C816, 63 Program (ILCP) and,
ASTM Committee D02 Proficiency 228, 231
Testing Program (PTP). See ASTM D3172, 41
Proficiency Testing Program (PTP) ASTM D3173, 44, 45
ASTM D02 Committee crosscheck ASTM D3177, 44
program, 27 ASTM D3227, 70, 129–130, 130
ASTM D1072, 165, 166 (figure), 167 (figure)
(figure) ASTM D3230, 92 (figure)
ASTM D1266, 16, 81, 83–85, 84 ASTM D3246, 16, 92–93
(figure), 84 (figure) ASTM D346, 44
ASTM D1275, 127–128 ASTM D3712, 130–131
ASTM D129, 16, 82–83, 161, 197 ASTM D396, 61 (table)
ASTM D1552, 16, 63, 82, 83, 85–86, 86 ASTM D4045, 16, 93 (figure), 93–95,
(figure), 87 (figure), 161 94 (figure)
ASTM D1662, 128–129 ASTM D4084, 179, 180 (figure), 181
ASTM D1757, 37–43 (figure)
ASTM D1988, 175–177, 177 (figure) ASTM D4239, 45–46, 46 (figure)
ASTM D2013, 41, 44 ASTM D4294, 4, 16, 21, 81, 100,
ASTM D2492, 38–43, 39 (table), 53–55 118–124, 234 (table)
ASTM D2622, 4, 16, 21 biofuel and, 197, 198
biofuel analysis and, 197, 198 false positive results and,
crosschecks and, 122, 123 233–235
crude oil analysis and, 68 interference and, 109 (table)
gasoline and diesel analysis and, lubricant analysis and, 161
72, 75, 79 (table), 80, 81–82 ASTM D4468, 168–169, 170 (figure),
interference and, 109 (table) 170 (table)
Interlaboratory Crosscheck ASTM D4810, 179–181
Program (ILCP) and, 228, 231, ASTM D4927, 16, 21, 153–155, 161
234 (table), 240 ASTM D4951, 16, 19, 155–156
low level sulfur determination ASTM D4952, 131–132
and, 238 (table) ASTM D5016, 46–47
lubricant analysis and, 161 ASTM D5185, 16, 19, 67–68,
petroleum product analysis and, 156–157, 161
109–112 ASTM D5303, 131, 135 (figure)
research studies and, 100, 101 ASTM D5305, 177–178

Index 251
ASTM D5453, 4, 16, 72, 73, 79 (table), ASTM D7220, 16, 21, 125–126, 228, 231
80, 81–82, 96–104, 97 (figure), 98 ASTM D7260, 19
(figure), 100 (table), 122, 123, 161 ASTM D7318, 142–143, 144 (figure),
biofuel analysis and, 197 145 (figure), 148 (figure)
Interlaboratory Crosscheck ASTM D7319, 25, 144–146, 145
Program (ILCP) and, 228, 231, (figure), 146 (figure), 148, 148
234 (table), 240 (table)
low level sulfur determination ASTM D7328, 25, 146–148, 147
and, 237 (table) (figure), 148 (table)
ASTM D5623, 134–136, 136 (figure) ASTM D7343, 21
ASTM D5705, 136–138, 140 ASTM D7359, 89–90
ASTM D5987, 25 ASTM D7372, 207
ASTM D6012, 138–140, 139 (figure) ASTM D7493, 186–188, 188 (figure),
ASTM D6228, 183–184, 184 (figure), 189 (figure)
185 (figure) ASTM D7551, 173–174, 174 (figure),
ASTM D6299, 216, 219 175 (figure)
ASTM D6300, 73, 116 ASTM D7582, 45
ASTM D6334, 16, 21, 112, 113 (table) ASTM D7621, 140–142, 141 (figure),
ASTM D6376, 63, 127 142 (figure)
ASTM D6428, 4, 72, 73–79 ASTM D7652, 189–192, 193 (table)
ASTM D6443, 16, 21, 158, 161 ASTM D7691, 67
ASTM D6444, 21 ASTM D7751, 159 (table), 159–161
ASTM D6445, 16, 21, 124 ASTM E1301, 207
ASTM D6481, 21, 158–159 ASTM E775, 49–50
ASTM D6708, 73 ASTM ILCP 0807, 68 (table)
ASTM D6920, 16, 78, 79 (table), ASTM ILCP 0811, 68 (table)
87–89, 228, 231 ASTM ILCP 0903, 68 (table)
ASTM D6966, 186 (table) ASTM ILCP crosschecks, 118 (table),
ASTM D6968, 184–185, 187 (figure) 201, 204 (table)
ASTM D7039, 4, 21, 16, 80, 104, 113– ASTM ILCP crude oil, 124 (table)
118, 114 (figure), 161 ASTM ILCP CS92, 117
biofuel and, 197, 198 ASTM Proficiency Testing Programs.
Interlaboratory Crosscheck See Proficiency Testing Program
Program (ILCP), 228, 231, 234 (PTP)
(table), 240 ASTM research reports, ultraviolet-
low level sulfur determination fluorescence and, 99
and, 238, 238–239 (table) ASTM Test Methods
ASTM D7041, 16, 95–96 comparison of, 121 (table), 229–
ASTM D7165, 171–172 231 (table)
ASTM D7166, 172–173 interlaboratory study (ILS) and, 78
ASTM D7183, 104–105 (table). See also interlaboratory
ASTM D7212, 16, 21, 124, 228, 231 study (ILS)

precision in sulfur determination at-line fuel monitor system, 171

and, 28–30 (table) atomic absorption spectrometry (AAS)
qualification criteria, 79–80 coal analysis and, 38, 39, 40–41
sulfate sulfur in coal and coke oil shale analysis and, 53
and, 37 (table), 37–43 atomic emission detection, 184–185. See
for sulfur compound also inductively coupled plasma-atomic
determination in gaseous fuels, emission spectrometry (ICP-AES)
174–178, 181–193 Australian oil shale, 55 (table), 57
for sulfur compound automatic spark engine fuel, test
determination in petroleum methods, 201
products, 66 (table), 127–148 automatic transmission fluids, 16, 59
for sulfur determination in automotive fuel. See diesel; gasoline
biofuel, 196 (table) automotive lubricant additives, 16, 211
for sulfur determination in (table), 222 (table)
gasoline and diesel, 107 (table) aviation certification turbine fuel, 61
for sulfur determination in fuel (table)
oil, 61 (table), 62 (table) aviation fuel, 12–13, 14
for sulfur determination in liquid test methods, 59, 60 (table), 92,
fuels, 233 (table), 233–240, 234 109, 113, 119, 125
(table), 235 (table), 236 (table), total sulfur content of, 71
237 (table), 238–239 (table) aviation turbine fuel, 60 (table), 61
for sulfur determination in (table), 211 (table), 221 (table)
lubricants and additives, 153–
161, 154 (table), 159 (table) B
for sulfur determination in barium, interference, 37
petroleum products, 59–127, barium perchlorate titration, 53, 167
63–64 (table) barium sulfate (BaSO4), 39, 44, 50
for total sulfur in coal and coke base oil, 14, 62, 156–157
and, 37 (table), 43–50 proficiency testing and, 211
for total sulfur in gaseous fuels, (table), 223 (table)
165–174 standard reference materials
See also alternative test methods; (SRMs) for, 31 (table)
specific analytical techniques test methods, 59
ASTM ULSD ILCP Program, 227–228, Beckman burner-type apparatus, 167,
231–232 169 (figure)
ASTM ULSD ILCP samples, 103 benzene, test methods, 93
(figure) bias, 207, 208 (table), 217
ASTM ULSD Proficiency Testing in coal analysis, 38, 44, 45
Program (PTP) analysis, 226 (table). in combustion-chemical analytical
See also Proficiency Testing Program methods, 88, 89
(PTP) in gasoline and diesel analysis,
at-line analyzer, 102 73, 78

Index 253
laboratory-specific, 80 Boscan crude oil, 66

X-ray fluorescence spectrometry box and whisker graphs, 213, 215, 216
and, 114, 115 (figure), 125 (figure), 217 (figure), 220
See also relative bias Brazil, biofuel test methods, 197
BIOD 0704 sample, 201 Brazil crude oil, 68 (table)
biodiesel blend (B6-B20) diesel fuel oil, Brazilian oil shale, 57
61 (table) butane, 168–169
biodiesel fuel blend stock B100, 60
(table) C
biodiesel calcinated petroleum coke, standard
blends, 60–61 reference materials (SRMs) for, 31
interlaboratory study (ILS) (table). See also coke, petroleum
and, 72 calibration curve, 108
proficiency testing, 211 (table), calibration standards, 156, 192
223 (table) calibration, in X-ray fluorescence
test methods, 88, 96, 109, 113, analysis, 108–109, 155, 158, 159
119, 237 (table) California crude oil, 65 (table), 66
See also biofuel (table), 68 (table)
biofuel, 195–199, 237 (table) California sulfur regulations, 71, 195
ASTM ILCP crosschecks and, 204 Canada crude oil, 66 (table)
(table) CARB diesel, interlaboratory study
combustion-ultraviolet (ILS) and, 72
fluorescence detection analysis CARB Laboratory performance, 227
of, 199–202 (table), 228 (table), 231
precision of test methods for, 203 CARB Phase 2 gasoline,
(table) interlaboratory study (ILS) and, 72
sulfate species in, 202–205 carbon dioxide (CO2), 84 (figure), 102
sulfur limits in, 196 (table) carbon-forming tendency, 12
test methods, 195–199, 196 carbonyl sulfide (COS), 133, 134
(table), 202 (table), 205 (table) (figure), 135 (figure), 174
test performance index (TPIs) Carlo Erba 1106 analyzer, 26
and, 204 (table) carrier gas, 171, 172, 173
See also biodiesel catalytic converters, 14
biotin, 5 CEN TC19 WG27, 126
bitumens, 67 (table) ceramic tubes, 94
bituminous coal, standard reference certificates of analysis (COA), 207
materials (SRMs) for, 31 (table), 36 certified reference materials (CRMs),
Blanco, F., 54 27, 69. See also standard reference
boat inlet system, 98 (figure) materials (SRMs)
boiling point, 93, 95, 105, 134 certified value, 30
bomb method, 11 (table) chemiluminescence detection, gaseous
bomb-washing method, 44, 50 fuel analysis and, 182, 189–192

chemiluminiscence detector, 136, 182, combustion and absorption apparatus,

189, 191 166 (figure)
China crude oil, 68 (table) combustion and barium chloride
chlorine (Cl), interference, 26, 40, titration, 165
48, 102 combustion tubes, 89, 96, 97 (figure),
chromic acid chemistry, 186 106 (figure)
Chromosorb W column, 186 combustion
Claus process, 2, 4–5 oils shale analysis and, 53, 55
coal fly ash, standard reference petroleum product analysis and,
materials (SRMs) for, 31 82–106
(table), 36 See also specific analytical
coal, 12 techniques; sulfur oxides
samples, 48 (table), 49 (table) combustion-chemical analysis, 10
standard reference materials (table), 65 (table), 82–89, 233 (table)
(SRMs) and, 36 combustion-detection devices, 63. See
sulfate sulfur determination in, also specific techniques
37 (table), 37–43, 40 (table), 42 combustion-infrared, 10 (table), 65
(table), 43 (table) (table)
sulfide minerals in, 35–36 combustion-ion chromatographic
test method precision and, 28 methods, 89–90
(table) combustion-microcoulometry,
test methods, 17 (table) 10 (table), 65 (table) , 90–106.
total sulfur determination in, See also combustion-oxidative
43–50 microcoulometry methods
cobalt, 156 combustion-ultraviolet fluorescence, 10
coke, petroleum, 12, 62–63 (table), 65 (table), 169–171, 233 (table)
proficiency testing, 211 (table), commercial boiler fuels, 61 (table)
225 (table) common cause, 208 (table)
test method precision and, 28 compound determination. See sulfur
(table) compound determination
test methods, 17 (table), 85, 127 contaminants, 156–157, 191 (table)
Colorado kerogen, 56 (table) continuous fuel monitor system
Colorado oil shale, 54, 54 (table), 55 (CFMS), 171
(table), 56 (table), 57 (table) continuous injection, 105–106
Columbia crude oil, 65 (table) copper strip classification, 128 (table)
columns, 191–192. See also specific copper strip tarnish level classification,
column types 129 (table)
combustion-electrochemical detection, corrosion, 12–13
233 (table) crude oil and, 14
combusion-hydrogeneolysis- diesel engines and, 13
rateometric colorimetry, 93 (table), gasoline and, 71
93–95, 94 (figure) internal combustion engines and, 14

Index 255
corrosive sulfur, 127 test method accuracy, 231

coulometric method, 92 (figure) test methods, 72–82, 88, 95–96,
coulometry, test methods, 233 (table). 109, 113, 119
See also microcoulometry X-ray fluorescence spectrometry
crosscheck programs, 27. See also and, 118 (table), 124
Proficiency Testing Program (PTP) diesel-biodiesel blends, test methods,
Crude Oil LCP 1211, 214 (figure) 96, 125
crude oil, 14 diesel engine sulfur tolerance, 13
gasoline and diesel, 70–82, 73 (figure), Diesel Fuel #2 ILCR 1206, 215 (figure)
74 (figure), 75 (figure). See also diesel fuel oil, 31 (table), 60 (table)
diesel; gasoline Di-n-butyl sulfide, standard reference
inductively coupled plasma-atomic materials (SRMs) for, 31 (table)
emission spectrometry and, 19 direct-injection inlet system, 96, 97
(table), 19–20 (figure)
mercaptans in, 69–70 distillate fuels. See distillates
proficiency testing and, 211 (table), distillates, 15, 88, 90, 96, 109, 119,
224 (table) 134, 139
sampling for X-ray fluorescence, 107 distillation, 12
standard reference materials (SRMs) doctor test, 11 (table), 15, 131–132
for, 31 (table), 69 doubly curved crystal (DCC) optics, 113
sulfur content of, 3, 65–69, 68 (table) downstream quality assurance, 79, 80
test methods, 109, 119
cutting oils, 128–129 E
cysteine, 5 Egypt crude oil, 66 (table)
electrical insulating oils, 127–128
D electrochemical detection
damaging effects of sulfur, 3–4, 12–16 in gaseous fuel analysis, 186–188
biofuel and, 195 in petroleum product analysis, 87–89
gasoline and, 71 emission levels, sulfur, 4, 16
death, 4 emissions, 14–15
degrees of freedom, 208 (table) energy dispersive X-ray fluorescence
demineralization, 55 analyzer, 22 (figure)
denatured fuel ethanol, 60 (table), 201 energy dispersive-X-ray fluorescence
deposits, 1–2, 2 (table), 12 (ED-XRF), 10 (table), 11 (table), 21
detector tubes, 175–177 gasoline and diesel analysis and, 81,
determination of sulfur compounds. 118–124
See sulfur compound determination monochromatic, 125–126
diesel, 12, 71–72 petroleum product analysis
interlaboratory study (ILS) and, and, 120
72–82 test methods, 65 (table)
standard reference materials engine fuel. See motor fuel
(SRMs) for, 31 (table), 72, 78 engine oil. See motor oil

engine wear, 71 fossil fuels

environmental laws. See government analytical techniques and, 9–10,
regulations 10 (table), 11, 24–25
Environmental Protection Agency importance of sulfur in products
(EPA), 4, 16, 195 of, 12–16
enzymes, 5 See also specific analytical
Environmental Protection Agency EPA techniques; specific fuels
laboratory performance, 227 (table), foundry coke, standard reference
228 (table), 231 materials (SRMs) for, 31 (table)
Eschka method, 44, 50, 54 Frasch process, 4
ethane, 168–169 fuel ethanol
ethanol denatured, 60 (table)
biofuel analysis and, 200 proficiency testing, 211 (table),
fuel blends, 60 (table) 223 (table)
sulfate determination in, sulfates in, 142–148, 142–148
142–148 test methods, 90
test methods, 96, 113, 201, 237 fuel gas, test methods, 179
(table) fuel methanol, 60 (table)
See also biofuel fuel oil, 59, 60 (table)
ethylene, 168–169 fuel oil distillate, standard reference
European Union, biofuel test materials (SRMs) for, 31 (table)
methods, 197 fuel sulfur tolerance, 71
existent inorganic sulfate, 142, 145 furnace, 25–26, 86 (figure), 87 (figure),
(figure), 148 (table), 202 91. See also specific furnaces
extraction. See ground extraction
eye irritation, 4 G
galena (PbS), 35
F gas burner, 166 (figure)
false-positive results, 122 gas chromatography (GC), 10 (table),
fatty acid methyl ester (FAME), test 133–136, 171–172
methods, 96, 198 gaseous fuel analysis and,
Federal Tier 2 Motor Vehicle and 182, 183 (figure), 183–193,
Emission Standards and Gasoline 188 (table), 190 (table),
Sulfur Control Requirements, 195 193 (table)
Fischer assay water, 57 (table) isothermal, 186
flame photometric detection, 95–96, test methods, 65 (table)
183–184, 184 (figure) gas chromatography-based online/
flame photometric detector at-line analysis, 171–172
(FPD), 183 gas oil, 32 (table), 59
flare gas, test methods, 179 gas turbine fuel oil, 60 (table)
flow system, 180 (figure) gas turbines, 12

Index 257
gaseous fuels, 17 (table), 163–164 gasoline and, 71–72, 195

hydrogen sulfide (H2S) sulfur emission levels and, 4
determination in, 178–181 grade 94 unleaded aviation gasoline
sampling of, 164–165 certification, 61 (table)
sulfur compound determination graphs, 220
in, 174–178, 181–193 green petroleum coke, standard reference
test method precision and, 28 materials (SRMs) for, 31 (table)
(table) Green River oil shale, 54, 54 (table), 55
total sulfur determination in, (table)
165–174 ground extraction, 4
gasohol, test methods, 109, 119
gasoline, 70–71 H
energy dispersive-X-ray hand-operated pump, 137
fluorescence analysis and, health hazards, 136–137
118–124 high-boiling-range fractions, 12
interlaboratory study (ILS) and, high concentration sulfur
72–79, 80–82 determinations, 122 (table)
with methyl tert-butyl ether high-level sulfur determination.
(MTBE), 72 See X-ray fluorescence (XRF)
monochromatic wavelength spectrometry
dispersive-X-ray fluorescence high-octane gasoline, standard
analysis and, 113–118 reference materials (SRMs) for, 32
test methods, 34, 72–82, 88, (table)
95–96, 109, 112–124 high-octane unleaded test fuel, 61
wavelength dispersive-X-ray (table)
fluorescence analysis and, high-pressure decomposition, 82–83
112–113 high-speed engines, 13
gasoline-ethanol blends, test methods, high-temperature combustion, 11
71, 113, 200 (table) (table), 45–46, 46–47
gasoline-oxygenate fuel blends, test high-temperature method, 85–86
methods, 90, 96 histograms, 220
gasoline-reformulated gasoline, history, 1
standard reference materials (SRMs) hydraulic fuel oil, 211 (table), 223
for, 32 (table) (table), 224 (table)
gear oils, 16, 59, 211 (table), 224 (table) hydraulic oil, test methods, 109, 119
general gas oil, proficiency testing, 211 hydrocarbons, 70–71
(table), 224 (table) aromatic, 89–90, 104–105
glutathione, 6 in gaseous fuels, 184–186
“goodness-of-fit” test, 219 liquid, 90–92, 95–104
government regulation, Europe, 15, 16 total sulfur in, 87–89
government regulation, United test methods, 173
States, 13 See also gasoline

hydrochloric acid (HCl) industrial burner fuel, 60 (table)

in coal, 37, 38–39, 41 information value, 30
in oil shale, 53, 54 injection profile, 172 (figure)
hydrodesulphurization, 2, 3–4. See also inline fuel monitor system, 171
specific methods inorganic sulfate, 142, 143, 146–147,
hydrogen (H), 3 148 (table), 202
hydrogen fluoride (HF), 55 instrumentation, 25–27
hydrogen gas, 190, 191 (figure) coal analysis and, 46 (figure)
hydrogen iodide (HI), 55 detectors, 137, 175–177, 179–181,
hydrogen sulfide (H2S), 2, 12 182–183, 189, 191
compressed gas standard and, 174 furnaces, 25–26, 86 (figure), 87
in crude oil, 14, 67 (figure0, 91
in fuel oil, 11 (table), 140–142 inert or passivated, 175, 181
in gaseous fuels, 178–181, 181 injection apparatuses, 96, 97
(figure) (figure)
in liquid petroleum gas, 11 (table) monitoring apparatuses, 163, 171
hydrogeneolysis, 93 (figure), 168–169, tubes, 89, 90, 91 (figure), 96, 97
233 (table) (figure), 106 (figure), 175–177,
178, 191
I See also specific analytical
Illinois coals, 35, 42–43 techniques; specific instruments
ILS RR-D01-1335, 136 interference
ILS RR-D02-1282, 157 in coal analysis, 37, 47
ILS RR-D02-1358, 137 in combustion-chemical analysis
ILS RR-D02-1450, 158 and, 82, 85
ILS RR-D02-1614, 146 combustion-ion chromatographic
ILS RR-D02-1615, 143 methods and, 89
ILS RR-D02-1635, 120 in combustion-oxidative
ILS RR-D02-1732, 161 microcoulometry methods, 101,
Indonesia crude oil, 65 (table) 102–104, 106–107, 109 (table),
induction furnace, 25–26, 86 (figure) 110, 112
inductively coupled plasma-atomic detector tubes and, 178
emission spectroscopy (ICP-AES), in gasoline and diesel analysis,
10 (table), 16–20, 18 (figure) 73, 75
additive analysis and, 156–158 in X-ray fluorescence
coal analysis and, 38, 39, 40–41 spectrometry, 125
crude oil analysis and, 19 (table), ion chromatography, 89, 146
67–68, 68 (figure) mercaptan determination in
lubricant analysis and, 155–158 natural gas and, 176
oil shale analysis and, 53 in X-ray transmission online
test methods, 65 (table), 233 (table) determination, 126–127

Index 259
Interlaboratory Crosscheck Program K

(ILCP), 208 (table), 210–215. See K alpha radiation, 125
also Proficiency Testing Program kerogen, 57 (table)
(PTP) kerosene, standard reference materials
interlaboratory study (ILS) (SRMs) for, 32 (table)
bifuel analysis and, 198–199 kerosine, 94, 156
crude oil analysis and, 68–69 mercaptans in, 132
gasoline and diesel and, 72–82 test methods, 60 (table), 92, 113, 119
low-cost, 121 Kuwait crude oil, 66 (table)
ion chromatography (IC), 10 (table),
23–25, 24 (figure) L
biofuel analysis and, 203 laboratory precision improvement,
coal analysis and, 40, 42 232. See also Proficiency Testing
fuel-ethanol analysis and, Program (PTP)
144–146, 145 (figure) laboratory-specific bias, 80
interferences, 146 lamp method, 11 (table), 83
monochromatic wavelength lamp unit, 84 (figure)
dispersive-X-ray fluorescence landfill gas, test methods, 179
and, 115 (figure), 117 lead, interference, 158
oil shale analysis and, 56 (figure), lead-acetate-impregnated paper, 179
56 (table), 57 (table) lead acetate method, 178–181
petroleum product analysis and, lead acetate reaction rate method, 179,
89–90 180 (figure), 181 (figure)
test methods, 65 (table) lead acetate tape test, 102
wavelength dispersive-X-ray Leco induction furnace, 25–26
fluorescence and, 110–112, 111 Leco SC 32 analyzer, 26
(table) Leco SC 32 combustion-IR detection,
X-ray fluorescence spectrometry 49
and, 119–120 length-of-stain detector, 137, 175–177,
IP 342, 70 177 (figure), 179–181
IR absorption detector, 45, 47 light petroleum liquids, 134–136
IR absorption method, 46–47 liquid chromatography, 130–131
Iran crude oil, 66 (table) liquid fuel, test methods, 233 (table),
iron (Fe), 37, 41 233–240, 234 (table), 235 (table),
iron sulfide, interference, 63–64, 112 236 (table), 237 (table), 28–239
isooctane, 110, 120 (table). See also specific fuels
isothermal gas chromatography, 186 liquid hydrocarbons
total sulfur determination in, 95–96
J trace amount of sulfur determination
jet fuel. See aviation fuel in, 96–104
jet-B wide-cut aviation turbine fuel, 60 liquid natural gas (LNG), test
(table) methods, 173

liquid petroleum gasoline (LPG), lubricating oil additive, standard

13–14 reference materials (SRMs) for, 32
hydrogen sulfide (H2S) in, 11, (table)
178–179 lubricating oils. See lubricants
test methods, 60 (table), 173, 179
total sulfur determination in, M
165–168, 169–171, 171 (figure), manufactured gas, test methods, 165
172 (figure) marcasite (FeS2), 35
vapor, 177–178 marine fuels, 16
liquid petroleum hydrocarbons, 90–92 mathematical correction
lithium aluminum hydride procedure, 158
(LiAlH4), 54 matrix correction, biofuel analysis
Louisiana crude oil, 65 (table) and, 198
low concentration sulfur levels, 123 matrix effects, X-ray fluorescence
(table), 124, 233 (table), 233–240, spectrometry, 107, 109, 114, 119
236 (table), 237 (table), 238–239 mercaptans, 11 (table), 15, 129–130,
(table) 130 (figure)
low thermal mass gas chromatography in crude oil, 15, 69–70
(LTMGC), 136 in distillate fuel, 131–132
low-background proportional methyl, 174
counter, 124 test methods, 186–188
low-speed engines, 13 mercuric chloride, interference, 176
lubricants metal sulfonates, 16, 156
alternative test methods, 159 metallic sulfides, 1
(table), 161 metals, determination in lubricants,
analytical techniques for, 11 158–159
energy dispersive-X-ray methionine, 5
fluorescence and, 155–158 methyl mercaptan, 174, 177–178
inductively coupled plasma- Mexico crude oil, 68 (table)
atomic emission spectroscopy microchemical techniques, 57. See also
and, 155–158 specific analytical techniques
proficiency testing, 211 (table), microcoulometry, 10 (table), 11 (table),
222 (table), 224 (table) 65 (table), 79 (table), 81, 90–106
sulfur content in, 16 microelemental techniques, 9. See also
test methods, 17 (table), 82, 85, specific techniques
110, 119,154 (table), microwave oven dissolution, 54–55
159 (table), 161 Mid-East crude oil, 65 (table), 66
wavelength dispersive-X-ray (table)
fluorescence and, 153–155, 158 mixed gas, test methods, 165
See also lubricants, specific molybdenum, interference, 158
analytical techniques monitoring systems, test methods and,
lubricating greases, test methods, 82 171–172

Index 261
monochromatic wavelength dispersive near-real-time monitoring systems,

X-ray fluorescence analyzer, 22 163, 171
(figure) Nigeria crude oil, 66 (table)
monochromatic wavelength dispersive- NIST fossil fuel SRMs, 49 (table)
X-ray fluorescence (MWD-XRF), NIST gasoline, interlaboratory study
22–23 (ILS), 72
biofuel analysis and, 198 NIST SRM 2721 Light Sour Texas, 68
crude oil analysis and, 68 (table)
gasoline and diesel analysis and, NIST SRM 2722 Heavy Sweet Texas,
72, 75, 79 (table), 80, 81–82 68 (table)
test methods, 233 (table) NIST SRM 2723a, 115–116, 116
monosulfides, 38, 41 (table), 225–226 (table)
Moroccan oil shale, 55 (table) NIST SRM 8505 Venezuela, 68 (table)
motor fuel NIST SRMs, 111 (table), 120 (table)
of the future, 78 (table) analysis, 235 (table)
mercaptans and, 132 crude oil, 123 (table)
proficiency testing and, 211 (table), samples, 68 (table), 115–116, 116
221 (table) (table), 225–226 (table)
test methods, 88, 90, 96, 134 See also specific samples
motor oil, test methods, 96 nitrate, interference, 40
MTBE for blending, 60 (table) nitrogen, interference, 26, 73, 75,
multiple headspace extraction (MHE), 85, 102
138–140, 139 (figure) No. 2 diesel fuel, 211 (table), 221
(table)
N No. 2 heating fuel, test methods, 125
naphthas No. 6 diesel fuel, 211 (table), 222
proficiency testing and, 211 (table)
(table) No. 6 fuel oil, test methods, 59
test methods, 88, 93, 96, 109, 113, No. 60 sieve, 44, 45
119 nondestructive analysis. See inductively
National Institute of Standards and coupled plasma-atomic emission
Technology (NIST), 27, 30. spectrometry (ICP-AES); X-ray
See also standard reference fluorescence (XRF)
materials (SRMs) nonreactive containers, 175
natural gas, 2, 4 nonuniform distribution of pyrite
hydrogen sulfide (H2S), particles in coal, 43–44
determination in, 179–181
mercaptan determination in, O
175–177, 177 (figure) Occupational Safety and Health
sulfur compound determination Administration (OSHA),
in, 182–188 136–137, 138
test methods, 163, 164 (table), 165 odorants, 175, 177, 182, 186

oil shale, 32, 53–57 petroleum products, 2–3, 3 (table),

oil-soluble sulfonate products, 59–65
130–131 analytical techniques for sulfur
Oklahoma crude oil, 66 (table) determination in, 11,
online determination, 126, 186 65 (table)
online diesel analysis, 118 (table) combustion-chemical analysis
online fuel monitor system, 171 and, 82–89
online gas chromatography, combustion-ion chromatographic
95–96 analysis and, 89–90
on-line gasoline-oxygenate fuel blends, combustion-oxidative
test methods, 201 microcoulometry analysis and,
organic sulfur, 35–36 90–106
organo-sulfur compounds, 3 crude oil, 65–70, 126–127
outlier, 208 (table), 239 (table) gasoline and diesel, 71–82
oxidative combustion, 87–89 specifications for, 60–61 (table)
oxidative microcoulometry, 11 (table), sulfur species determination in,
92–93 127–148
oxidative pyrophydrolic combustion, test methods, 17 (table), 61
89–90 (table), 62 (table), 63–64 (table)
oxygen bomb, 47–48 test method precision, 28–30
oxygen bomb combustion-ion (table)
chromatography, 49 X-ray fluorescence (XRF)
oxygen interference, 115 (figure) spectrometry, 106–126
oxygenates, 124 X-ray transmission online
oxygen-hydrogen burner, 165 detection, 126–127
oxy-hydrogen combustion apparatus, See also additives; crude oil; diesel;
167, 168 (figure) gasoline; lubricants
o-xylene. See xylene petroleum refining, 2
phosphorus, 48
P photorateometric H2S readout, 93, 94
Paraho shale oil, 56 (table) (figure)
Parr bomb combustion, 55 physicochemical properties, 5 (table)
Parr oxygen bomb, 47–48. See also Parr pipelines, 102, 179–181
bomb combustion plysulfide oil concentrates, 108
particulates, 157 pollution, 15. See also acid rain;
passivation, 190 emissions
performance-based measurement population mean, 208 (table)
system (PBMS), 11, 79 potassium iodate (KIO3), 25
peroxides, 132 potassium iodide (KI), 25
petroleum coke. See coke, petroleum potential sulfate, 143, 203
petroleum gas, 92–93 potentiometric method, 129–130, 203

Index 263
potentiometric titration curve, 131 sulfur test methods for liquid fuels
(figure), 145 (figure) and, 233 (table), 233–240,
precision, 11, 207, 208 (table) 234 (table)
for active sulfur, 129 (table) test method comparisons, 229–231
in biofuel analysis, 203 (table) (table)
in coal analysis, 38, 39 (table), 44, See also proficiency testing
45, 47–49, 48 (table) proficiency testing, 160–161 (table),
in combustion-chemical analysis 207, 208–209 (table). See also
methods, 86, 87 (figure), 88 Proficiency Testing Program (PTP)
in combustion-oxidative propane, test methods, 168–169
microcoulometry methods, 94, propylene (C3H6), 133, 178
102, 105 (table), 106 proteins, 5–6
crosscheck programs and, 232 pulsed flame photometric detector
gas chromatography and, 136 (PFPD), 183
in gasoline and diesel analysis and, purified air system, 167 (figure)
72, 75, 78, 78 (table), 81 (table) pyrite sulfur (FeS2)
interlaboratory study test methods in coal, 35–36, 38–39, 40, 41
and, 78 (table) in oil shale, 53, 54, 55 (table), 54
X-ray fluorescence spectrometry See also ASTM D2492
and, 111 (table), 113 (table), pyrolysis liquid biofuel, 61 (table)
114–115, 123 (table), pyrolysis tube, 90, 91 (figure)
125 (table)
See also repeatability;
Q
reproducibility
qualification criteria, ASTM test
precision ratio (PR), 208 (table)
method, 79–80
Proficiency Testing Program (PTP), 27,
quality assurance (QA)
207, 210
downstream, 79, 80
ASTM Committee D02’s, 210–215,
statistical, 207
211 (table), 212 (table), 221,
in sulfur analysis of materials,
227. See also Proficiency Testing
30–33
Program (PTP), crosscheck
quality control (QC) chart, 33
findings
quality control criterion, 79
ASTM ULSD ILCP program,
quick turnaround analysis, 15, 45
227–232
crosscheck findings, 219 (table),
221, 222 (table), 223 (table), 224 R
(table), 225 (table), 226 (table), radiofrequency (RF), 17–18
227 (table), 228 (table) rapid-liquid phase extraction, 140–142
laboratory proficiency rateometric colorimetry, 168–169
improvement and, 232 recycle gas, test methods, 179
statistical data analysis, 315–220 reference value, 30

reformulated gasoline (RFG) in diesel analysis, 73, 75, 77

California specifications for, 71 (figure), 78–79, 82 (table)
interlaboratory study (ILS) in gasoline analysis, 73, 75, 74
and, 72 (table), 75 (table), 81–82, 82
proficiency testing and, 211 (table)
(table), 225 (table) for hydrogen sulfide (H2S)
test methods, 88, 96, 125, 236 concentrations, 143 (table)
(table), 237, 237 (table) in X-ray fluorescence
refuse derived fuel, 49 spectrometry, 115, 116, 117,
relative bias, 76 (figure), 209 (table), 120, 126
217, 231–232 See also precision; test
removal, of sulfur, 3–4. See also performance index (TPI)
hydrodesulphurization; specific residual fuel oil, 12; standard reference
methods materials (SRMs) for, 31 (table), 32
repeatability, 209 (table) (table)
in biofuel analysis, 200 test methods, 109, 119, 139, 136–142
in combustion-chemical analytical vapor phase above, 136–142, 139
methods, 88 (figure)
in combustion-oxidative resistance furnace, 87 (figure)
microcoulometry methods, 94, respiratory illness, 4
96, 110–111 retention times, of sulfur compounds,
crosscheck programs and, 185 (table), 187, 188, 190 (table)
231–232 Riley, J. T., 43 in coal and coke and, 37
in gasoline and diesel analysis, 73 (table), 43–5044
(figure), 74 (figure), 75, 78–79) round robin testing
for hydrogen sulfide (H2S) of coal samples, 41–42
concentrations, 143 (table) precision of gasoline and diesel
sulfur concentrations in nitrogen testing in, 81 (table)
(N) and, 190 (table) ultraviolet fluorescence and, 99
in X-ray fluorescence X-ray fluorescence spectrometry
spectrometry, 115, 116, 117, and, 117
120, 121, 122, 126 Rundle oil shale, 56 (table)
See also precision rusting, 12
reproducibility, 207, 209 (table), 218
in biofuel analysis, 200, 201 (table) S
in combustion-chemical analytical sample, relationship with sulfur, 133
methods, 88 sampling
in combustion-oxidative crude oil, 107
microcoulometry methods, 94, gaseous fuels, 164–165
96, 110–111 pyrite, 44
crosscheck programs and, vapor above residual fuel oil, 140
231–232 See also specific fossil fuels

Index 265
Schaefer, R., 231 subbituminous coal, standard reference

Schoniger methods, 47–48 materials (SRMs) for, 31 (table), 36
S-curve, 214 (figure) substitute natural gas, test
shale oil. See oil shale methods, 179
Silcosteel-lined vessels, 175, 181 suction system, 167 (figure)
silica, 48 sulfates, 1, 38–43
site precision (R’), 209 (table) in ash from coal and coke,
Smith, J. W., 54 37–43
sodium hydroxide (NaOH), 53, 55 in fuel-ethanol, 142–148,
solvents, 15, 131–132. See also 202–205
kerosine; o-xylene in oil shale, 53
sour crude oil, 67 recovery failure, 44
Southwest Research Institute (SWRI), See also specific sulfates
80, 100, 117 sulfide minerals, 35, 38. See also
spark-ignition engine fuel, 60 (table) specific minerals
spectral interference, 119 sulfides, 35, 53, 186–188. See also
spent shale leachate, 57 (table) metallic sulfides; specific sulfides
sphalerite (ZnS), 35 sulfonate recovery, 100 (table), 201
spiked gasoline, 103 (table) (table)
standard deviation, 100 (figure), 101 sulfur compounds, 129–130, 131–132,
(figure), 209 (table), 216, 235, 236 174–178, 181–193
(table), 237 (table). See also Z score as additives, 154 (table)
Standard Guide for Analysis and in cutting oils, 128–129
Interpretation of Proficiency Test in electrical insulating oils,
Program Results, 207 127–128
standard reference materials (SRMs), in fuel-ethanol, 142–148
27–30, 31–32 (table) in gaseous fuels, 181–193
inductively coupled plasma- in light petroleum liquids,
atomic emission spectrometry 134–136
and, 156 in oil-soluble sulfonate products,
sulfur determination in coal and, 130–131
31 (table), 36 physical properties of, 183 (table)
sulfur determination in crude oil in propylene, 133
and, 31 (table), 69 in residual fuel oils, 136–142
sulfur determination in diesel and, retention times and, 185 (table),
31 (table), 72, 78 190 (table)
See also specific fossil fuels volatile, 172
Stanley, R. M., 231 sulfur dioxide (SO2), 4, 25–26, 27
statistical data analysis, 215–220. See coal analysis and, 45
also specific aspects coal ashing and, 35–36
statistical quality assurance (SQA), 207 ultraviolet-fluorescence detection
steam condensate, test methods, 93 and, 96

sulfur oxides Texas crude oil, 65 (table)

damaging effects of, 13 TFE-fluorocarbon tube, 191
engine damage and, 3 thiamine, 5
recovery of compounds, 200 thiol mercaptan sulfur, 15, 129–130.
(table) See also mercaptans
See also sulfur dioxide (SO2) thioredoxin, 6
sulfur-oxygen compound recovery, 99 titration, 25–26; coal analysis and, 48
(table) toluene, 93, 110, 120
sulfur-selective detection, 134–136 total sulfur analyzer-based online/
sulfur specific detection, 138–140. at-line, 172–173
See also specific analytical techniques; total sulfur
specific fossil fuels in aromatic hydrocarbons, 104–105
sulfur trioxide (SO3), 25–26, 37 in coal and coke and, 37 (table),
sulfuric acid (H2SO4) 43–50
in distillate fuels, 131–132 in liquid hydrocarbons, 87–89, 95,
emissions, 202 105–106
in oil shale, 54 trace sulfur determination, 90–92,
toxicity of, 4 96–104, 113, 189–192
use of, 5 Tracor Atlas analyzer, 26
in vapor phase above residual fuel transmission fluids, 16, 59, 222 (table)
oil, 136–142, 139 (figure) transportation, fuel, 102. See also
suspended water, 120 specific fuels
sweet crude oil, 67 treatment offgasses, test methods, 179
syringe drive mechanism, 76–78 true value, 209 (table)
tubes, 85, 86 (figure), 89, 90, 91
T (figure), 96, 97 (figure), 106 (figure),
tank atmosphere, residual fuel oil, 175–177, 178
137–142 turbidimetric testing, 167
tar sand bitumens, 67 (table)
tar sands, 66 U
Tedlar bags, 175, 181 ULSD 1301, 214 (figure)
Tennessee oil shale, 57 ULSD samples, 115–116, 116 (table),
test methods. See ASTM test methods; 118, 237 (table)
specific test methods ULSD1301, 216 (figure)
test performance index (TPIs), 204 ultralow sulfur fuels, 79 (table), 211 (table)
(table), 209 (table), 218–219, 219 ultraviolet-fluorescence
(table), 237, 240 (UV-fluorescence), 11 (table), 72, 79
for low level sulfur determination, (table), 80, 81–82
237 (table), 238 (table), 239 (table) aromatic hydrocarbon analysis
test method comparison in and, 104, 105 (table)
precision testing crosscheck gaseous fuel analysis and,
programs, 229–231 (table) 169–171, 173–174

Index 267
petroleum product analysis and, gasoline and diesel analysis and,

96–104, 97 (figure), 98 (figure), 112–113
100 (table) petroleum product analysis and,
spiked gasoline analysis and, 103 109–112, 127
(table) test methods, 233 (table)
total sulfur analysis in liquid wear metals, in lubricants, 156–157
hydrocarbons, 105–106 West African crude oil, 68 (table)
uncertainty, 209 (table) Western States Petroleum Association, 112
United States crude oil, 65 (table), 66 wet chemical techniques, 9, 233 (table)
(table), 68 (figure) wick lamp, 83
unleaded aviation gasoline, 60 (table), Wickbold combustion, 11 (table), 81,
61 (table) 167, 168 (figure)
unleaded fuel, test methods, 60 (table), Wyoming crude oil, 66 (table)
61 (table), 109. See also specific fuels
used oils, standard reference materials X
(SRMs) for, 32 (table) X-ray fluorescence analyzer, 20, 21
USGS SCO-1, 56 (table) (figure), 22 (figure)
USGS SGR-1, 56 (table) X-ray fluorescence (XRF)
UV-fluorescence. See ultraviolet- spectrometry, 20–23, 104, 106–107
fluorescence (UV-fluorescence) biofuel analysis and, 197–198,
199 (table)
V calibration in, 108–109
vacuum spectrometer, 18 coal analysis and, 48, 49
vapor phase above residual fuel oil, gasoline and diesel analysis and,
136–142, 139 (figure) 112–124, 107 (table)
variability, across sulfur concentration, interference in, 106–107, 109
101 (table) (table), 110
variance, 209 (table) oil shale analysis and, 53, 57
Venezuela crude oil, 65 (table), 68 (table) petroleum product analysis and,
volatile samples, 109, 113, 119 63, 109–112, 125–126
volatile sulfur, in gaseous fuel, 169 test methods, 65 (table)
volatile sulfur compounds, 172–173, 184 See also ultraviolet-fluorescence
voluntary consensus standardization (UV-fluorescence); X-ray
body (VCSB), 79 fluorescence analyzer
X-ray transmission online
W determination, 126–127
wavelength dispersive X-ray xylene, 156, 157
fluorescence analyzer, 21 (figure)
wavelength dispersive-X-ray Z
fluorescence (WD-XRF), 10 (table), Z score, 209 (table), 216–218
11 (table), 20–21
biofuel analysis and, 198

Nadkarni
Sulfur
Dr. R.A. Kishore Nadkarni received his
Analysis of Fossil Fuel Products

Sulfur: Chemistry and
Ph.D. in analytical chemistry at the University of Bombay.
Since then he has worked as a research associate at
the University of Kentucky, manager of the Materials
Science Center Analytical Facility at Cornell University,
and analytical leader in the ExxonMobil Company.
In his last position he was responsible for technical
quality management of the Paramins Division’s global
plant laboratories.
Chemistry and Analysis of
Fossil Fuel Products
He has authored more than 140 technical publications
including 21 new ASTM standards in the area of
analytical chemistry and quality management. He is a member of the American
Chemical Society and ASTM International. He is very active in ASTM and ISO in
the petroleum products and lubricant field, holding the position of immediate past
chairman of ISO/TC28, chairman of ASTM’s D02.03 on Elemental Analysis, vice-
chairman of D02.92 on Proficiency Test Programs, D02.94 on Quality Assurance and R.A. Kishore Nadkarni
Statistics.
Dr. Nadkarni has received the Award of Appreciation (1991) and Awards for Excellence
(1998, 1999, and 2013) from ASTM’s D02 Committee for his contribution to the oil
industry, the Award of Merit (2005) and the George Dyroff Award of Honorary D02
membership (2006), and the Sydney Andrews D02 Scroll of Achievement Award (2005).
He is the author or editor of STP 1109, Modern Instrumental Methods of Elemental

Analysis of Petroleum Products and Lubricants (1991); STP 1468, Elemental Analysis of
Fuels and Lubricants (2005); Manual 44, Guide to ASTM Test Methods for the Analysis
of Petroleum Products and Lubricants (2007); Manual 61, Guide to ASTM Test Methods
for the Analysis of Coal and Coke (2008); Monograph 9, Spectroscopic Analysis of
Petroleum Products and Lubricants (2011); and Monograph 10, “Elemental Analysis of
Fossil Fuels and Related Materials” (2014).
www.astm.org
ISBN: 978-0-8031-7052-0
Stock #: MONO11

Mono11 2014

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Mono11 2014

Uploaded by

Copyright:

Available Formats

Nadkarni

Analysis of Fossil Fuel Products

He is the author or editor of STP 1109, Modern Instrumental Methods of Elemental

Sulfur: Chemistry and Analysis

Printed in the U.S.A.

BK-AST-MONO11-140027-FM.indd 1 5/23/2014 6:43:37 PM

ASTM Photocopy Rights

Printed in City, State

BK-AST-MONO11-140027-FM.indd 2 5/23/2014 6:43:37 PM

BK-AST-MONO11-140027-FM.indd 3 5/23/2014 6:43:37 PM

BK-AST-MONO11-140027-FM.indd 4 5/23/2014 6:43:37 PM

2. Analytical Techniques for Sulfur Determination9

3. Analysis of Coal and Coke Products35

4. Analysis of Oil Shales53

5. Analysis of Petroleum Products59

6. Analysis of Lubricants and Additives153

7. Analysis of Gaseous Fuels163

9. Proficiency Testing Programs for Sulfur in Petroleum Products and Lubricants207

Appendix 1 ASTM Standards Cited243

Appendix 2 Index of Description of ASTM Test Methods245

BK-AST-MONO11-140027-FM.indd 5 5/23/2014 6:43:37 PM

BK-AST-MONO11-140027-Chp01.indd 1 5/22/2014 12:16:45 PM

Table 1.1 Typical Sulfur Content of Some Important Oil Fields

Country Sulfur, mass % Country Sulfur, mass %

Abu Dhabi 0.62–0.77 Nigeria 0.10–0.26

Texas, Colorado, Nevada, Wyoming, and California. It exists in several ­allotropic

R-S-R + 2 H2  2 RH + H2S (1.1)

where R is an organic ligand.

3 O2 + 2 H2S  2 SO2 + 2 H2O (1.2)

SO2 + 2 H2S  3 S + 2 H2O (1.3)

BK-AST-MONO11-140027-Chp01.indd 2 5/22/2014 12:16:45 PM

Table 1.2 Typical Sulfur Content of Petroleum Products

Product Sulfur, mass % Product Sulfur, mass %

Compound Types Range

Sulfur compounds CnH2n+2S to CnH2n-42S 23

Sulfur-oxygen CnH2n-10SO to CnH2n-30SO 11

BK-AST-MONO11-140027-Chp01.indd 3 5/22/2014 12:16:45 PM

BK-AST-MONO11-140027-Chp01.indd 4 5/22/2014 12:16:46 PM

a catalytic oxidation using porous catalysts such as aluminum oxide (Al2O3) or

8 H2S + 4 O2  S8 + 8 H2O (1.4)

Sulfur is used in the manufacture of H2SO4, carbon disulfide, sulfites, insecticides,

Table 1.3 Physicochemical Properties of Sulfur

CAS registry ID 7704-34-9

Electronic configuration Ne 3s2 3p4

Ionization energy 10.360 eV

Ionic radius 0.184 (–2) nm; 0.029 (+6)

Energy of first ionization 999.3 kJ/mol

Periodic table group Via

Valences –2, +4, and +6

Melting point 119°C (246.3°F)

Boiling point 444.6°C (832.28°F)

Crystal structure Orthorhombic

Density at 293 K 2.07 g/cm3

BK-AST-MONO11-140027-Chp01.indd 5 5/22/2014 12:16:46 PM

[4] Nadkarni, R. A., “Advances in Elemental Analysis of Hydrocarbon Products,” Analytical

[6] Nadkarni, R. A., “A Review of Modern Instrumental Methods of Elemental Analysis of

BK-AST-MONO11-140027-Chp01.indd 6 5/22/2014 12:16:46 PM

[7] Nadkarni, R. A., “Determination of Inorganic Species in Petroleum Products and

BK-AST-MONO11-140027-Chp01.indd 7 5/22/2014 12:16:46 PM

BK-AST-MONO11-140027-Chp02.indd 9 5/22/2014 12:17:38 PM

Table 2 .1 Analytical Techniques Used for Sulfur Determination in Fossil Fuel

Analytical Technique Coal and Coke Petroleum Products Gaseous Fuels

Combustion–chemical D129, D1266, D6920

2. Analytical Techniques for Sulfur Determination9

3. Analysis of Coal and Coke Products35

4. Analysis of Oil Shales53

5. Analysis of Petroleum Products59

6. Analysis of Lubricants and Additives153

7. Analysis of Gaseous Fuels163

9. Proficiency Testing Programs for Sulfur in Petroleum Products and Lubricants207

Appendix 1 ASTM Standards Cited243

Appendix 2 Index of Description of ASTM Test Methods245

Texas, Colorado, Nevada, Wyoming, and California. It exists in several allotropic

Table 2 .1 Analytical Techniques Used for Sulfur Determination in Fossil Fuel

Table 2.2 International Standards for Sulfur Determination in Petroleum Products

Fig. 2.1 Schematic Diagram of Inductively Coupled Plasma — Atomic Emission

comparison between the sulfur results obtained using the wavelength-

Fig. 2.4 Schematic Diagram of Monochromatic Wavelength Dispersive X-Ray

Fig. 2.6 Typical Ion Chromatogram of a Solution Containing 1 mg/kg of Various