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Case l:13-cv-01215-EGS Document 1-7 Filed 08/06/13 Page 1 of 4 


A- A- * ★ * 

By Authority Of 


Legally Binding Document 

By the Authority Vested By Part 5 of the United States Code § 552(a) and 
Part 1 of the Code of Regulations § 51 the attached document has been duly 
INCORPORATED BY REFERENCE and shall be considered legally 
binding upon all citizens and residents of the United States of America. 
HEED THIS NOTICE '. Criminal penalties may apply for noncompliance. 

Document Name; 

CFR Section(s): 

ASTM D4239: Standard Test Methods for Sulfur in the 
Analysis Sample of Coal and Coke Using High TemperatuJ* 
Tube Furnace Combustion Methods 
40 CFR 60, Appendix A-7 

Standards Body: American Society for Testing and Materials 

Official Incorporator : 

The Executive Director 
office of the federal register 
washington, d.c. 


Case l:13-cv-01215-EGS Document 1-7 Filed 08/06/13 Page 3 of 4 

Designation: D 4239-97 


Standard Test Methods for 

Sulfur in the Analysis Sample of Coal and Coke Using 
HighTemperature Tube Furnace Combustion Methods^ 

This standard is issued under the fixed designation D 4239; the number immediately following the designation indicates the year of 
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A 
superscript epsilon (i) indicates an editorial change since the last revision or reapproval. 

e' Note — Section 18.4 has been editorially corrected in June 1999. 

1. Scope 

1.1 These test methods cover three alternative procedures 
using high-temperature tube furnace combustion methods for 
the rapid determination of sulfur in samples of coal and coke, 

1.2 These test methods appear in the following order: 


Method /A— High-Temperature Combustion Method with Acid 
Base Titration Detection Procedures 

Method 6— High-Temperature Combustion Method with iodi- 
metric Titration Detection Procedures 

Method C— High-Temperature Combustion Method with Infra- 
red Absorption Detection Procedures 



1.2.1 When automated equipment is used to perform any of 

the three methods of this test method, the procedures can be 
classified as instrumental methods. There are several manufac- 
turers that offer to the coal industry equipment with instrumen- 
tal analysis capabilities for the determination of the sulfur 
content of coal and coke samples. 

1.3 This standard does not purport to address all of the 
safety concerns, if any, associated with its use. It is the 
responsibility of the user of this standard to establish appro- 
priate safety and health practices and determine the applica- 
bility of regulatory limitations prior to use. See 7.8 and 15.2. 

2. Referenced Documents 

2. 1 ASTM Standards: 

D 346 Practice for Collection and Preparation of Coke 

Samples for Laboratory Analysis^ 
D 1193 Specification for Reagent Water^ 
D 2013 Method of Preparing Coal Saniples for Analysis^ 
D 2361 Test Method for Chlorine in Coal^ 
D 3 173 Test Method for Moisture in the Analysis Sample of 

Coal and Coke^ 
D 3176 Practice for Ultimate Analysis of Coal and Coke^ 
D 3180 Practice for Calculating Coal and Coke Analyses 

from As-Determined to Different Bases^ 

' This test method is under the jurisdiction of ASTM Committee D-5 on Coal and 
Coke and is the direct responsibility of Subcommittee DOS. 21 on Methods of 

Current edition approved June 10, 1997. Published May 1998. Originally 
published as D 4239 - 83. Last previous edition D 4239 - 94. 
^ Annual Book of ASTM Standards, Vol 05.05. 
^ Annual Book of ASTM Standards, Vol 1 1 .01 . 

D 4208 Test Method for Total Chlorine in Coal by the 
Oxygen Bomb Combustion/Ion Selective Electrode 


D 4621 Guide for Accountability and Quality Control in the 

Coal Analysis Laboratory^ 
D5142 Test Methods for the Proximate Analysis of the 

Analysis Sample of Coal and Coke by Instrumental 


3. Summary of Test Methods 

3.1 Method A — High-Temperature Combustion Method with 
Acid-Base Titration Detection Procedures — ^A weighed sample 
is burned in a tube furnace at a minimum operating temperature 
of 1350°C in a stream of oxygen. During combustion, all sulfur 
contained in the sample is oxidized to gaseous oxides of sulfur 
(sulfur dioxide, SO2, and sulfur trioxide, SO3) and the chlorine 
in the sample is released as CI2. These products are then 
absorbed into a solution of hydrogen peroxide (H2O2) where 
they dissolve forming dilute solutions of sulfuric (H2SO4) and 
hydrochloric (HCl) acids. The quantities of both acids pro- 
duced are directly dependent upon the amounts of sulfur and 
chlorine present in the original coal sample. Once the amounts 
of each acid present have been determined, the percentage of 
sulfur contained in the coal may be calculated. 

3.1.1 This method is written to include commercially avail- 
able sulfur analyzers that must be calibrated with appropriate 
standard reference materials (SRMs) to establish recovery 
factors or a calibration curve based on the range of sulfur in the 
coal or coke samples being analyzed. 

Note 1— Elements ordinarily present in coal do not interfere in Method 
A (3.1), with the exception of chlorine; results must be corrected for 
chlorine content of the samples (9.1). 

3.2 Method B — High-Temperature Combustion Method with 
lodimetric Detection Procedures — ^A weighed sample is 
burned in a tube furnace at a minimum operating temperature 
of 1350°C in a stream of oxygen to ensure the oxidation of 
sulfur. The combustion products are absorbed in an aqueous 
solution that contains iodine. When sulfur dioxide is scrubbed 
by the diluent, ttie trace iodine originally present in the solution 
is reduced to iodide, thus causing an increase in resistance. The 
detection system of the instrument consists of a polarized dual 
platinum electrode. Any change in resistance of the solution in 


Case l:13-cv-01215-EGS Document 1-7 Filed 08/06/13 Page 4 of 4 

(iSIb D 4239 

the vessel is detected. Iodine titrant is then added proportion- 
ally to the reaction vessel until the trace excess of iodine is 
replenished and the solution resistance is reduced to its initial 
level. The volume of titrant expended is used to calculate the 
sulfur concentration of the sample. The method is empirical; 
therefore, the apparatus must be calibrated ,by the use of 
standard reference material (SRM). 

3.2. 1 This method is designed to be used with commercially 
available sulfur analyzers, equipped to perform the preceding 
operation automatically, and must be calibrated with an appro- 
priate sample (5.4) based on the range of sulfur in each coal or 
coke sample analyzed. 

Note 2 — Nonautomatic systems may be used with the titration proce- 
dures and calculations performed manually by qualified laboratory tech- 
nicians. The resulting loss in accuracy or speed, or both, would then 

negate the advantages of using the fully automated instrumental approach. 

3.3 Method C-^igh-Temperature Combustion Method with 
Infrared Absorption Detection Procedures — ^The sample is 
burned in a tube furnace at a minimum operating temperature 
of 1350°C in a stream of oxygen to oxidize the sulfur. 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 sulfur dioxide is measured by an 
infrared (IR) absorption detector. Sulfur dioxide absorbs IR 
energy at a precise wavelength within the IR spectrum. Energy 
is absorbed as the gas passes through the cell body in which the 
IR energy is being transmitted: thus, at the detector, less energy 
is received. All other IR energy is eliminated from reaching the 
detector by a precise wavelength filter. Thus, the absorption of 
IR energy can be attributed only to sulfur dioxide whose 
concentration is proportional to the change in energy at the 
detector. One cell is used as both a reference and a measure- 
ment chamber. Total sulfur as sulfur dioxide is detected on a 
continuous basis. This method is empirical; therefore, the 
apparatus must be calibrated by the use of SRMs. 

3.3.1 This method is for use with commercially available 
sulfur analyzers equipped to carry out the preceding operations 
automatically and must be calibrated using standard reference 
material (coal) of known sulfur content based on the range of 
sulfur in each coal or coke sample analyzed. 

4. Significance and Use 

4.1 Determination of sulfur is, by definition, part of the 
ultiniate analysis of coal. 

4.2 Results of the sulfur analysis are used to serve a number 
of interests: evaluation of coal preparation, evaluation of 
potential sulfur emissions from coal combustion or conversion 
processes, and evaluation of the coal quality in relation to 
contract specifications, as well as other scientific purposes. 

4.3 The instrumental analysis provides a reliable, rapid 
method for determining the concentration of sulfur in a lot of 
coal or coke and are especially applicable when results must be 
obtained rapidly for the successful completion of industrial, 
beneficiation, trade, or odier evaluations. 

5. Sample 

5.1 The sample shall be the material pulverized to pass No. 
60 (250-pm) sieve and mixed thoroughly in accordance with 
Method D 2013 or Practice D 346. 

Note 3 — It may be difficult to meet the precision statements of Section 
18 when high mineral content coals are ground to pass 60 mesh. When the 
precision of analysis required cannot be obtained, it is recommended that 
the coals be ground to pass through a No. 100 (150-pm) sieve. The 
reduced particle size should result in a more homogeneous sample. 

5.2 A separate portion of the analysis sample should be 
analyzed for moisture content in accordance with Test Method 
D3173, so that calculation to other than die as-determined 
basis can be made. 

5.3 Procedures for converting as-determined sulfur values 
obtained from the analysis sample to other bases are described 
in Practices D 3 1 76 and D 3 1 80. 

5.4 Standard Reference Material (SRM) such as SRM Nos. 
2682 through IGiS-SulJur in Coal^ which consist of four 
different coals that have been individually crushed and ground 
to pass a 60-mesh sieve, and bottled in 50-g units, or other 
commercially available reference coals with a certified sulfur 


6. Apparatus 

6.1 Tube Furnace — Capable of heating 150- to 175-mm 
area (hot zone) of the combustion tube (6.2) to at least 1350°C. 
It is usually heated electrically using resistance rods, a resis- 
tance wire, or molybdenum disilicide elements. Specific di- 
mensions may vary with manufacturer's design. 

Note 4 — Induction furnace techniques may be used provided it can be 
shown that they meet the precision requirements of Section 18. 

6.2 Combustion Tube — Approximately 28-mm internal di- 
ameter with a 3-mm wall thickness and 750 mm in length made 
of porcelain, zircon, or muUite. It must be gas-tight at working 
temperature. The combustion may be carried out in a tapered- 
end tube that is closely connected to the gas absorber by high 
temperature tubing with gastight joints. Acceptable configura- 
tions include connecting the tapered-end tube directly to the 
elbow of the fritted gas bubbler or to a 10/30., standard 
taper-ground joint that is attached to a heat resistant glass right 
angle bend. The temperature at the tapered end of the tube 
should be maintained high enough to prevent condensation in 
the tube itself. 

6.2.1 Alternatively, a high-temperature straight refractory 
tube may be used, if available. It requires a silica adaptor (6. 1 1 ) 
with a flai-ed end that fits inside the combustion tube and serves 
as an exit for the gases. 

6.3 Flowmeter, for measuring an oxygen flow rate up to 2.0 

6.4 Sample Combustion Boats, must be made of iron-free 
material and of a convenient size suitable for the dimensions of 

"Available from the Office of Standard Reference Materials, Room B314, 
Chemistry BIdg., National Bureau of Standards, Washington, DC 20234. 

^ Based on the method of Mott, R. A., and y/jlkinson, H. C, "Determination of 
Sulfur in Coal and Coke by the Sheffield High temperature Method," Fuel Fuel B, 
Vol. 35, 1956, p. 6. This method is designed for the rapid determination of sulfur in 
coal and coke. It is not applicable to coals or coal density fractions that have been 
subjected to treatment with chlorinated hydrocarbons because of the potentially high 
acidity of the combustion gases.