ASTM D8214-18

Standard Test Method for Forms of Sulfur in Coal by Inductively Coupled Plasma Atomic Emission Spectrometry

SIGNIFICANCE AND USE
5.1 This test method provides for a separation of coal-associated sulfur into two commonly recognized forms: pyritic and sulfate. Organic sulfur is calculated by difference. Results obtained by the test method are used to serve a number of interests, including the evaluation of coal preparation and processing operations designed to reduce coal sulfur levels.
SCOPE
1.1 This test method applies to the determination of sulfate sulfur and pyritic sulfur in coal and calculates organic sulfur by difference. This test method is not applicable to coke or other carbonaceous materials.  
1.2 The values stated in SI units are to be regarded as standard. Non-SI units, if provided, are considered informational and are contained within parentheses  
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 appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.4 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Published
• Publication Date: 31-Oct-2018
• ICS: 75.160.10 - Solid fuels
• Technical Committee: D05 - Coal and Coke
• Drafting Committee: D05.21 - Methods of Analysis

Relations

• Refers: ASTM D7582-24 - Standard Test Methods for Proximate Analysis of Coal and Coke by Macro Thermogravimetric Analysis
• Effective Date: 01-Apr-2024
• Refers: ASTM D121-15(2024) - Standard Terminology of Coal and Coke
• Effective Date: 01-Mar-2024
• Refers: ASTM D7582-15(2023) - Standard Test Methods for Proximate Analysis of Coal and Coke by Macro Thermogravimetric Analysis
• Effective Date: 01-Dec-2023
• Refers: ASTM D3180-15(2023) - Standard Practice for Calculating Coal and Coke Analyses from As-Determined to Different Bases
• Effective Date: 01-Dec-2023
• Refers: ASTM E832-81(2019) - Standard Specification for Laboratory Filter Papers
• Effective Date: 01-Jul-2019
• Refers: ASTM D4239-18 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 01-Sep-2018
• Refers: ASTM D4239-17 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 15-May-2017
• Refers: ASTM D121-15 - Standard Terminology of Coal and Coke
• Effective Date: 01-Sep-2015
• Refers: ASTM D3180-15 - Standard Practice for Calculating Coal and Coke Analyses from As-Determined to Different Bases
• Effective Date: 01-Jan-2015
• Refers: ASTM D4239-14 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 01-Mar-2014
• Refers: ASTM D4239-14e1 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 01-Mar-2014
• Refers: ASTM D4239-13 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 01-Oct-2013
• Refers: ASTM D4239-13e1 - Standard Test Method for Sulfur in the Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion
• Effective Date: 01-Oct-2013
• Refers: ASTM E691-13 - Standard Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
• Effective Date: 01-May-2013
• Refers: ASTM D3180-12 - Standard Practice for Calculating Coal and Coke Analyses from As-Determined to Different Bases
• Effective Date: 01-Apr-2012

Overview

ASTM D8214-18 provides a standardized test method for the determination of sulfur forms in coal using Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). This standard enables laboratories to separately quantify sulfate sulfur and pyritic sulfur, while organic sulfur is determined by calculation. The procedure is specifically applicable to coal and is not intended for use with coke or other carbonaceous materials. The results are instrumental for evaluating coal preparation and processing technologies aimed at reducing sulfur levels, which is a critical factor for regulatory compliance and environmental management in the coal industry.

Key Topics

• Sulfur Forms in Coal: The test distinctly measures sulfate sulfur and pyritic sulfur. Organic sulfur is calculated by subtracting the measured sulfur forms from the total sulfur content, typically determined by a separate combustion analysis.
• Sample Preparation: Coal samples are pulverized to pass through a 250 µm sieve, ensuring representative analysis.
• ICP-AES Analysis: Utilizes advanced plasma emission spectrometry for precise detection and quantification of sulfur and iron, providing sensitivity and accuracy required for routine laboratory analysis.
• Safety and Compliance: Users must implement appropriate safety, health, and environmental practices, considering relevant regulations.
• Precision and Repeatability: The standard defines protocols for repeatability and reproducibility, enhancing the reliability of interlaboratory results.

Applications

• Coal Quality Assessment: Determines sulfur forms to evaluate raw coal and processed products, supporting quality control in mining operations and coal preparation plants.
• Process Optimization: Valuable for assessing the effectiveness of desulfurization processes and coal cleaning methods by quantifying the reduction of specific sulfur forms.
• Environmental Compliance: Supports emissions reporting and environmental permitting by providing accurate sulfur form content, crucial for controlling sulfur dioxide emissions during combustion.
• Research and Development: Enables laboratories and research institutions to investigate sulfur behavior in coal and develop lower-sulfur fuel options.
• Trade and Specification: Serves as a reference in coal specification contracts, ensuring consistent sulfur content determinations for buyers and sellers.

Related Standards

• ASTM D121 - Terminology of Coal and Coke: Provides standardized terms for coal and coke analysis.
• ASTM D1193 - Specification for Reagent Water: Defines water purity criteria for analytical processes.
• ASTM D2013 - Practice for Preparing Coal Samples for Analysis: Outlines procedures for sample collection and preparation.
• ASTM D3173 - Test Method for Moisture in Analysis Sample of Coal and Coke: Used for moisture determination in coal.
• ASTM D4239 - Test Method for Sulfur in Analysis Sample of Coal and Coke Using High-Temperature Tube Furnace Combustion: Measures total sulfur for comparison and calculation of organic sulfur.
• ISO 5725-6 - Accuracy of Measurement Methods and Results – Part 6: Guidance on accuracy and precision in laboratory analysis.

By following ASTM D8214-18, analysts can reliably quantify sulfur forms in coal, aiding in environmental management, regulatory compliance, and operational efficiency for the coal industry. This test method ensures consistent, accurate, and repeatable results with practical significance for producers, consumers, and regulators. For in-depth procedures and technical requirements, refer to the latest official version of ASTM D8214-18.

Standards Content (Sample)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D8214 − 18
Standard Test Method for
Forms of Sulfur in Coal by Inductively Coupled
Plasma Atomic Emission Spectrometry
This standard is issued under the fixed designation D8214; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D7582Test Methods for Proximate Analysis of Coal and
Coke by Macro Thermogravimetric Analysis
1.1 This test method applies to the determination of sulfate
E691Practice for Conducting an Interlaboratory Study to
sulfurandpyriticsulfurincoalandcalculatesorganicsulfurby
Determine the Precision of a Test Method
difference. This test method is not applicable to coke or other
E832Specification for Laboratory Filter Papers
carbonaceous materials.
2.2 ISO Standards:
1.2 The values stated in SI units are to be regarded as
ISO 5725-6Accuracy (Trueness and Precision) of Measure-
standard. Non-SI units, if provided, are considered informa-
ment Methods and Results – Part 6: Use in Practice of
tional and are contained within parentheses
Accuracy Values
1.3 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3.1 Fordefinitionsoftermsusedinthistestmethod,referto
priate safety, health, and environmental practices and deter-
Terminology D121.
mine the applicability of regulatory limitations prior to use.
4. Summary of Test Method
1.4 This international standard was developed in accor-
dance with internationally recognized principles on standard-
4.1 Sulfate Sulfur:
ization established in the Decision on Principles for the
4.1.1 Sulfate sulfur is extracted from the analysis sample
Development of International Standards, Guides and Recom-
with a dilute hydrochloric acid solution. The sulfate sulfur in
mendations issued by the World Trade Organization Technical
theextractisdeterminedbyinductivelycoupledplasmaatomic
Barriers to Trade (TBT) Committee.
emission spectrometry (ICP-AES). Sulfates are soluble in
hydrochloric acid, pyritic sulfur and organic sulfur are not
2. Referenced Documents
soluble in hydrochloric acid.
2.1 ASTM Standards:
4.2 Pyritic Sulfur:
D121Terminology of Coal and Coke
4.2.1 Pyritic sulfur is extracted from the pretreated sample
D1193Specification for Reagent Water
with a dilute nitric acid solution. The pyritic sulfur in the
D2013Practice for Preparing Coal Samples for Analysis
extract is determined by correlating extracted iron content,
D3173Test Method for Moisture in theAnalysis Sample of
measured by ICP-AES, as pyritic sulfur content.
Coal and Coke
4.2.2 Monosulfides (pyrites and FeS are disulfides) of iron
D3180Practice for Calculating Coal and Coke Analyses
and elements such as cadmium, lead, vanadium, and zinc can
from As-Determined to Different Bases
be present in coal. In mass fractions up to 100µg⁄g, these
D4239Test Method for Sulfur in the Analysis Sample of
monosulfides do not contribute significantly to the total inor-
4-6
Coal and Coke Using High-Temperature Tube Furnace
ganic sulfide content.
Combustion
Available from International Organization for Standardization (ISO), ISO
Central Secretariat, BIBC II, Chemin de Blandonnet 8, CP 401, 1214 Vernier,
This test method is under the jurisdiction of ASTM Committee D05 on Coal Geneva, Switzerland, http://www.iso.org.
and Coke and is the direct responsibility of Subcommittee D05.21 on Methods of Edwards, A. H., Daybell, G. N., and Pringle, W. J. S., “An Investigation into
Analysis. Methods for the Determination of Forms of Sulfur in Coal,” Fuel, Vol 37,
Current edition approved Nov. 1, 2018. Published January 2019. DOI: 10.1520/ 1958,pp.47-59.
D8214-18. Burns, M. S., “Determination of Pyritic Sulfur inAustralian Coals,” Fuel,Vol
For referenced ASTM standards, visit the ASTM website, www.astm.org, or 49, 1970, pp. 126-133.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Shrimp, N. F., Helfinstine, R. J., and Kuhn, J. K.,“Determination of Forms of
Standards volume information, refer to the standard’s Document Summary page on Sulfur in Coal,” Symposium on Sulfur and Nitrogen in Coal and Oil Shale, 1975,
the ASTM website. pp.99-108.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D8214 − 18
5. Significance and Use 8.4 Filter Paper—Unless otherwise indicated, references to
filterpapershallbeunderstoodtomeanfilterpaperconforming
5.1 This test method provides for a separation of coal-
to Specification E832.
associated sulfur into two commonly recognized forms: pyritic
and sulfate. Organic sulfur is calculated by difference. Results
8.5 Hydrochloric Acid,4.8N(2+3)—Mix two volumes of
obtained by the test method are used to serve a number of
concentratedaqueoushydrochloricacid(HCl,12N)withthree
interests, including the evaluation of coal preparation and
volumes of water.
processing operations designed to reduce coal sulfur levels.
8.6 Nitric Acid,2N(1+7)—Mix one volume of concen-
6. Analysis Sample tratednitricacid(HNO ,15.8N)withsevenvolumesofwater.
6.1 The analysis sample is that sample which has been
8.7 Standard Stock Solutions—Stock solutions of
pulverized to pass a 250µm (No. 60) sieve as prepared in
1000µg⁄mL for sulfur and iron are needed for preparation of
accordance with Practice D2013.
dilute standards. Prepare stock solutions from 99.99 % purity
metals or salts. Alternatively, one can use commercially
6.2 Determine the moisture in the analysis sample in accor-
available stock solutions specifically prepared for ICP-AES
dance with Test Method D3173 or Test Methods D7582 to
permit calculation to other bases.
8.8 Internal Standard—Solution of yttrium, 200µg⁄mL in
nitric acid or other suitable element not found in significant
7. Apparatus
mass fractions in the test samples.
7.1 Balance, sensitive to 0.1mg.
7.2 Hot Plate, electric or gas-heated with capability for 9. Procedure for Sulfate Sulfur
temperature control.
9.1 Extraction—Weigh, to the nearest 1mg, a 1g test
7.3 Inductively Coupled Plasma Atomic Emission Spectrom-
specimen and transfer it to a 200mL beaker (tall-form/
eter (ICP-AES)—Eitherasequentialorsimultaneousspectrom-
Berzelius).Add50mLof4.8NHClandafewdropsofethanol
eter is suitable. Because of differences between various makes
to the coal sample. Ethanol facilitates the wetting process.
and models of satisfactory instruments, no detailed operating
Coverthesamplewithawatchglass,placeitonahotplate,and
instructionscanbeprovided.Instead,theanalystshouldfollow
heat at 85°C for 30min while stirring it with a magnetic stir
the instructions provided by the manufacturer of the particular
bar or periodically using a glass stir rod.
instrument.Sensitivity,instrumentaldetectionlimits,precision,
9.2 Filtering—Carefullyfilterthecontentsofthebeakerinto
linear dynamic range, and interference effects shall be inves-
a 250mLto 500mLvacuum flask, using a Type II, Class F or
tigated and established for each analyte on that particular
Gfilterpaper.Washthefilterpaperandcontentswithsufficient
instrument. All measurements shall be within the instrument’s
small volume water washings to ensure the transfer of all the
linear range in which correction factors are valid. It is the
HCl extract to the vacuum flask. Save the filter paper with
responsibility of the analyst to verify that the instrument
extractedresidueforthesubsequentextractionofpyriticsulfur
configurationandoperatingconditionsusedsatisfytheanalyti-
content.
calrequirementsofthistestmethod.Theanalystshallmaintain
qualitycontroldataconfirmingtheinstrumentperformanceand
9.3 Test Solution Preparation—Transfer the filtrate to a
analytical results.
200mL volumetric flask with a glass stir rod. Rinse the
vacuumflaskwithsmallvolumewaterwashingsandtransferto
8. Reagents and Materials
thevolumetricflask.Add10mLof200µg⁄mLyttriumsolution
8.1 Purity of Reagents—Reagent grade chemicals shall be
or appropriate non-interfering internal standard and fill the
used in all tests. Unless otherwise indicated, it is intended that
flask to volume with water. Stopper the flask and mix well.
all reagents shall conform to the specifications of the Commit-
Store the sample solution in washed plastic sample bottles.
tee onAnalytical Reagents of theAmerican Chemical Society,
9.4 Sulfate Blank—Prepare a sulfate blank following the
where such specifications are available. Other grades may be
same procedure and using the same amounts of all reagents as
used, provided that the reagent is of sufficiently high purity to
described above. Save this filter paper for determining the
permit its use without lessening the accuracy of the determi-
pyritic iron blank.
nation.
9.5 Preparation of Calibration Solutions—Prepare a set of
8.2 Purity of Water—Unless otherwise indicated, references
towatershallbeunderstoodtomeanreagentwaterconforming sulfur calibration standards (2.5, 5, 10, 25, 50, 100)µg⁄mL.
to Specification D1193, Type II.
9.5.1 Spectrometric Conditions—Suitable ICP-AES condi-
tions for the determination of sulfur are as follows:
8.3 Ethanol, reagent grade, denatured.
Wavelength 180.731 nm
Wavelength 182.624 nm
Wavelength 182.034 nm
Reagent Chemicals, American Chemical Society Specifications, American
Single integration of 300 s
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
RF Power: 0.8 kW
listed by the American Chemical Society, see Analar Standards for Laboratory
Torch Gas: Coolant 20 L ⁄min
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Aux 0.5 L ⁄min
and National Formulary, U.S. Pharmacopeia Convention, Inc. (USPC), Rockville,
Nebulizer 200 kPa (30 psi)
MD.
D8214 − 18
9.5.2 Measure the emission intensity of the calibration 10.6 Preparation of Calibration Solutions—Prepare a set of
solutions and construct a calibration curve of the emission iron mass calibration standards (10, 20, 30)µg⁄mL.
intensity against the sulfur mass c
...