ASTM D3831-22

Standard Test Method for Manganese in Gasoline By Atomic Absorption Spectroscopy

SIGNIFICANCE AND USE
5.1 Certain organo-manganese compounds act as antiknock agents when added to gasoline. This test method provides a means for determining the concentration of such a material in a gasoline sample.
SCOPE
1.1 This test method covers the determination of the total manganese content, present as methylcyclopentadienyl manganese tricarbonyl (MMT),2 of gasoline within the concentration range from 0.25 mg/L to 40 mg/L of manganese.  
1.2 This test method is applicable to reformulated gasoline containing up to 12 % volume methyl tertiary butylether or up to 10 % volume ethanol. This test method may not be applicable to highly cracked materials containing greater than 18 % by volume olefins as determined by Test Method D1319 (nondepentanized).  
1.3 This test method has been developed and tested specifically for the determination of MMT in gasoline over the recommended concentration range. Application of the method to other concentration ranges, to the determination of MMT in other materials, or to the determination of other manganese compounds in gasoline have not been tested  
1.4 The values stated in SI units are to be regarded as the standard. The preferred concentration units are mg/L manganese.  
1.5 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. For specific warning statements, see Sections 6 and 7.  
1.6 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: 30-Sep-2022
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• Refers: ASTM D6300-24 - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Mar-2024
• Refers: ASTM D4175-23a - Standard Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 15-Dec-2023
• Refers: ASTM D6299-23a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Dec-2023
• Refers: ASTM D6300-23a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Dec-2023
• Refers: ASTM D6792-23c - Standard Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
• Effective Date: 01-Nov-2023
• Refers: ASTM D6792-23b - Standard Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
• Effective Date: 01-Oct-2023
• Refers: ASTM D4175-23e1 - Standard Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Jul-2023
• Refers: ASTM D7740-20 - Standard Practice for Optimization, Calibration, and Validation of Atomic Absorption Spectrometry for Metal Analysis of Petroleum Products and Lubricants
• Effective Date: 01-Jul-2020
• Refers: ASTM D6300-19a - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
• Effective Date: 01-Dec-2019
• Refers: ASTM D6299-17b - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Dec-2017
• Refers: ASTM D6299-17a - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Nov-2017
• Refers: ASTM D6299-17 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Jan-2017
• Refers: ASTM D6300-16 - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
• Effective Date: 01-Apr-2016
• Refers: ASTM D6300-15 - Standard Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
• Effective Date: 01-Jun-2015
• Refers: ASTM D1319-14 - Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
• Effective Date: 01-Oct-2014

Overview

ASTM D3831-22 is the internationally recognized Standard Test Method for Manganese in Gasoline by Atomic Absorption Spectroscopy. Developed by ASTM International, this standard outlines reliable procedures to determine total manganese content in gasoline, specifically as methylcyclopentadienyl manganese tricarbonyl (MMT). Manganese compounds, especially MMT, function as antiknock agents in gasoline formulations. ASTM D3831-22 ensures precise quantification of manganese concentrations within the range of 0.25 mg/L to 40 mg/L, contributing to quality control, regulatory compliance, fuel formulation, and environmental monitoring.

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Key Topics

• Scope and Applicability

  • Covers the determination of total manganese content as MMT in gasoline.
  • Applicable to reformulated gasoline containing up to 12% methyl tertiary butyl ether (MTBE) or up to 10% ethanol.
  • Not recommended for samples with highly cracked materials containing over 18% olefins.

• Test Method Highlights

  • Utilizes atomic absorption spectroscopy (AAS) at 279.5 nm wavelength.
  • Involves bromine treatment and extraction with methyl isobutyl ketone prior to spectrometric analysis.
  • Calibration standards prepared using organometallic manganese solutions.
  • Provides guidelines for repeatability, reproducibility, and results reporting in mg/L manganese.

• Quality Assurance

  • Stresses the use of stable, representative quality control (QC) samples.
  • Recommends statistical quality management practices and control charting as outlined in related ASTM standards.
  • Emphasizes the need for user-defined safety, health, and environmental protocols.

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Applications

ASTM D3831-22 is essential for laboratories, refineries, and regulatory bodies concerned with:

• Fuel Quality Control

  • Monitoring MMT content in gasoline blends to meet performance and legislative standards.
  • Ensuring antiknock agent levels are within optimal and safe limits.

• Regulatory Compliance

  • Supporting adherence to local and international limits on fuel additives such as manganese.
  • Providing standardized methods for reporting and verification to authorities.

• Environmental and Health Assessment

  • Ensuring excessive manganese concentrations are not contributing to air quality issues or health risks.
  • Supporting the transition to cleaner fuels by enabling accurate additive measurement.

• Product Development

  • Assessing new gasoline formulations and their organometallic additive profiles.

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Related Standards

For a comprehensive quality and analytical framework, ASTM D3831-22 references and should be used in conjunction with other standards, including:

• ASTM D1319 - Hydrocarbon types in liquid petroleum products.
• ASTM D4057 / D4177 - Manual or automatic sampling of petroleum products.
• ASTM D4175 - Terminology relating to petroleum products, fuels, and lubricants.
• ASTM D6299 / D6300 - Statistical quality assurance procedures for laboratory data.
• ASTM D6792 - Quality management systems for testing laboratories.
• ASTM D7740 - Optimization and validation of atomic absorption spectrometry for metal analysis.

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By following ASTM D3831-22, laboratories and industry stakeholders gain a trusted, accurate method for measuring manganese in gasoline using atomic absorption spectroscopy. This standard supports global efforts to manage fuel quality, safeguard public health, and comply with environmental regulations in the fuel sector.

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: D3831 − 22
Standard Test Method for
Manganese in Gasoline By Atomic Absorption
Spectroscopy
This standard is issued under the fixed designation D3831; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of the total
D1319 Test Method for Hydrocarbon Types in Liquid Petro-
manganese content, present as methylcyclopentadienyl manga-
leum Products by Fluorescent Indicator Adsorption
nese tricarbonyl (MMT), of gasoline within the concentration
D4057 Practice for Manual Sampling of Petroleum and
range from 0.25 mg⁄L to 40 mg⁄L of manganese.
Petroleum Products
1.2 This test method is applicable to reformulated gasoline
D4175 Terminology Relating to Petroleum Products, Liquid
containing up to 12 % volume methyl tertiary butylether or up
Fuels, and Lubricants
to 10 % volume ethanol. This test method may not be appli-
D4177 Practice for Automatic Sampling of Petroleum and
cable to highly cracked materials containing greater than 18 %
Petroleum Products
by volume olefins as determined by Test Method D1319
D6299 Practice for Applying Statistical Quality Assurance
(nondepentanized).
and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
1.3 This test method has been developed and tested specifi-
D6300 Practice for Determination of Precision and Bias
cally for the determination of MMT in gasoline over the
Data for Use in Test Methods for Petroleum Products,
recommended concentration range. Application of the method
Liquid Fuels, and Lubricants
to other concentration ranges, to the determination of MMT in
D6792 Practice for Quality Management Systems in Petro-
other materials, or to the determination of other manganese
leum Products, Liquid Fuels, and Lubricants Testing
compounds in gasoline have not been tested
Laboratories
1.4 The values stated in SI units are to be regarded as the
D7740 Practice for Optimization, Calibration, and Valida-
standard. The preferred concentration units are mg/L manga-
tion ofAtomicAbsorption Spectrometry for MetalAnaly-
nese.
sis of Petroleum Products and Lubricants
1.5 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions:
responsibility of the user of this standard to establish appro-
3.1.1 For definitions of terms used in this test method, refer
priate safety, health, and environmental practices and deter-
to Terminology D4175.
mine the applicability of regulatory limitations prior to
use. For specific warning statements, see Sections 6 and 7.
4. Summary of Test Method
1.6 This international standard was developed in accor-
4.1 The gasoline sample is treated with bromine solution
dance with internationally recognized principles on standard-
and diluted with methyl isobutyl ketone. The manganese
ization established in the Decision on Principles for the
content of the sample is determined by atomic absorption
Development of International Standards, Guides and Recom-
spectrometry using an air-acetylene flame at 279.5 nm and
mendations issued by the World Trade Organization Technical
standards prepared from an organo-manganese standard mate-
Barriers to Trade (TBT) Committee.
rial.
4.2 Protocols for using atomic absorption spectrometry are
given in Practice D7740.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved Oct. 1, 2022. Published November 2022. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1979. Last previous edition approved in 2017 as D3831 – 12 (2017). contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
DOI: 10.1520/D3831-22. Standards volume information, refer to the standard’s Document Summary page on
MMT is a registered trademark of Ethyl Corp. the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3831 − 22
5. Significance and Use 7.6 Methyl Isobutyl Ketone, reagent grade. (Warning—
Flammable.Vapor harmful.) (Warning—Solutions of MMTin
5.1 Certain organo-manganese compounds act as antiknock
gasoline are chemically unstable when exposed to light. Low
agents when added to gasoline. This test method provides a
and erratic results may be obtained if the gasoline sample is
means for determining the concentration of such a material in
exposed to light prior to stabilization during analysis.)
a gasoline sample.
7.7 Quality Control (QC) Sample(s),
6. Apparatus
preferably are a portion of one or more gasoline materials that
are stable and representative of the samples of interest.
6.1 Atomic Absorption Spectrometer, capable of scale ex-
pansion and equipped with a manganese hollow-cathode lamp
8. Sampling
for monitoring manganese absorption at 279.5 nm, a premix
slot-type burner with rotatable burner head, and an adjustable
8.1 Take samples of gasoline in compliance with the in-
nebulizer. (Warning—Hazardous. Potentially toxic and explo-
structions in Practice D4057 or D4177 where appropriate.
sive. Refer to the manufacturer’s instrument manual for asso-
Analyze as soon as possible after sampling.
ciated safety hazards.)
9. Calibration
6.2 Vials, up to 40 mL size with polyethylene or TFE-
fluorocarbon-lined caps or glass stoppers.
9.1 Preparation of Working Standards —Prepare four work-
ing standards using the 4.0 mg, 10.0 mg, 20.0 mg, and 40.0 mg
6.3 Pipet, Delivery, 1 mL size.
Mn/L standard manganese solutions described in 7.3.
6.4 Micropipet, 100 µL size, Eppendorf type or equivalent.
9.1.1 Usingamicropipet,add100 µLofbrominesolutionto
6.5 Automatic Pipet,orequivalentdeliverypipet,capableof
each of four separate vials.
delivering 9.0 mL quantities.
9.1.2 Pipet 1 mL of each of the four low-manganese stan-
dards into each of the vials. Mix with the bromine solution by
7. Reagents
swirling the vials.
7.1 Purity of Reagents—Reagent grade chemicals shall be 9.1.3 Deliver 9.0 mL of methyl isobutyl ketone to each of
used in all tests. Unless otherwise indicated, it is intended that
the vials. Mix well.This tenfold dilution of the low-manganese
all reagents shall conform to the specifications of the Commit- standards is the same as the final dilution of the sample.
tee onAnalytical Reagents of theAmerican Chemical Society,
9.2 Preparation of Instrument—Set the atomic absorption
where such specifications are available. Other grades may be
spectrometer operating conditions to those recommended by
used, provided it is first ascertained that the reagent is of
the manufacturer for monitoring manganese absorption at
sufficiently high purity to permit its use without lessening the
279.5 nm using an air-acetylene flame. This test method
accuracy of the determination.
assumes that good operating procedures are followed. Design
7.2 Bromine Solution—Add reagent grade bromine to an differences between spectrometers make it impractical to
equal volume of cyclohexane. (Warning—Bromine can cause
exactly specify required instrument settings.
severe and painful burns when it contacts the skin. In addition
9.2.1 Nebulizemethylisobutylketoneintotheflame.Adjust
to other precautions, wear protective gloves in preparing the
thenebulizer(sampleflowrate),acetylene,andairflowratesto
solution and prepare, store, and use it in a well-ventilated
give a lean, nonluminous flame.
hood.)
9.2.2 With methyl isobutyl ketone as a blank, nebulize, in
turn, the four working standards.
7.3 Manganese Standard Solution 400 mg Mn/
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D3831 − 12 (Reapproved 2017) D3831 − 22
Standard Test Method for
Manganese in Gasoline By Atomic Absorption
Spectroscopy
This standard is issued under the fixed designation D3831; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope Scope*
1.1 This test method covers the determination of the total manganese content, present as methylcyclopentadienyl manganese
tricarbonyl (MMT), of gasoline within the concentration range from 0.25 mg ⁄L to 40 mg ⁄L of manganese.
1.2 This test method is applicable to reformulated gasoline containing up to 12 % volume methyl tertiary butylether or up to 10 %
volume ethanol. This test method may not be applicable to highly cracked materials containing greater than 18 % by volume olefins
as determined by Test Method D1319 (nondepentanized).
1.3 This test method has been developed and tested specifically for the determination of MMT in gasoline over the recommended
concentration range. Application of the method to other concentration ranges, to the determination of MMT in other materials, or
to the determination of other manganese compounds in gasoline have not been tested
1.4 The values stated in SI units are to be regarded as the standard. The preferred concentration units are mg/L manganese.
1.5 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use. use. For specific warning statements, see Sections 56 and 67.
1.6 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.
2. Referenced Documents
2.1 ASTM Standards:
D1319 Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4175 Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis.
Current edition approved May 1, 2017Oct. 1, 2022. Published June 2017November 2022. Originally approved in 1979. Last previous edition approved in 20122017 as
D3831 – 12.D3831 – 12 (2017). DOI: 10.1520/D3831-12R17.10.1520/D3831-22.
MMT is a registered trademark of Ethyl Corp.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3831 − 22
D6300 Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products, Liquid Fuels, and
Lubricants
D6792 Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
D7740 Practice for Optimization, Calibration, and Validation of Atomic Absorption Spectrometry for Metal Analysis of
Petroleum Products and Lubricants
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in this test method, refer to Terminology D4175.
4. Summary of Test Method
4.1 The gasoline sample is treated with bromine solution and diluted with methyl isobutyl ketone. The manganese content of the
sample is determined by atomic absorption spectrometry using an air-acetylene flame at 279.5 nm and standards prepared from an
organo-manganese standard material.
4.2 Protocols for using atomic absorption spectrometry are given in Practice D7740.
5. Significance and Use
5.1 Certain organo-manganese compounds act as antiknock agents when added to gasoline. This test method provides a means for
determining the concentration of such a material in a gasoline sample.
6. Apparatus
6.1 Atomic Absorption Spectrometer, capable of scale expansion and equipped with a manganese hollow-cathode lamp for
monitoring manganese absorption at 279.5 nm, a premix slot-type burner with rotatable burner head, and an adjustable nebulizer.
(Warning—Hazardous. Potentially toxic and explosive. Refer to the manufacturer’s instrument manual for associated safety
hazards.)
6.2 Vials, up to 40 mL size with polyethylene or TFE-fluorocarbon-lined caps or glass stoppers.
6.3 Pipet, Delivery, 1 mL size.
6.4 Micropipet, 100 μL size, Eppendorf type or equivalent.
6.5 Automatic Pipet, or equivalent delivery pipet, capable of delivering 9.0 mL quantities.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
7.2 Bromine Solution—Add reagent grade bromine to an equal volume of cyclohexane. (Warning—Bromine can cause severe and
painful burns when it contacts the skin. In addition to other precautions, wear protective gloves in preparing the solution and
prepare, store, and use it in a well-ventilated hood.)
7.3 Manganese Standard Solution 400 mg Mn/L—Dissolve the appropriate amount of organometallic manganese standard in
methyl isobutyl ketone to give a standard solution of 400 mg Mn/L.
Reagent Chemicals, American Chemical Society SpecificationsACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, , American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
D3831 − 22
7.4 Manganese, Standard Solution 4.0 mg, 10.0 mg, 20.0 mg, and 40.0 mg Mn/L—Dilute the 400 mg ⁄L standard manganese
solution with methyl isobutyl ketone using volumetric glassware to give the desired lower concentration manganese standard
solutions.
7.5 Organometallic Manganese Standard—Pre-prepared commercially available organometallic stock solutions have been found
to be satisfactory.
7.6 Methyl Isobutyl Ketone, reagent grade. (Warning—Flammable. Vapor harmful.) (Warning—Solutions of MMT in gasoline
are chemically unstable when exposed to light. Low and erratic results may be obtained if the gasoline sample is exposed to light
prior to stabilization during analysis.)
7.7 Quality Control (QC) Sample(s),
preferably are a portion of one or more gasoline materials that are stable and representative of the samples of interest.
8. Sampling
8.1 Take samples of gasoline in compliance with the instructions in Practice D4057 or D4177 where appropriate. Analyze as soon
as possible after sampling.
9. Calibration
9.1 Preparation of Working Standards —Prepare four working standards using the 4.0 mg, 10.0 mg, 20.0 mg, and 40.0 mg Mn/L
standard manganese solu
...