ASTM D5863-22

Standard Test Methods for Determination of Nickel, Vanadium, Iron, and Sodium in Crude Oils and Residual Fuels by Flame Atomic Absorption Spectrometry

SIGNIFICANCE AND USE
5.1 When fuels are combusted, metals present in the fuels can form low melting compounds that are corrosive to metal parts. Metals present at trace levels in petroleum can deactivate catalysts during processing. These test methods provide a means of quantitatively determining the concentrations of vanadium, nickel, iron, and sodium. Thus, these test methods can be used to aid in determining the quality and value of the crude oil and residual oil.
SCOPE
1.1 These test methods cover the determination of nickel, vanadium, iron, and sodium in crude oils and residual fuels by flame atomic absorption spectrometry (AAS). Two different test methods are presented.  
1.2 Procedure A, Sections 8–14—Flame AAS is used to analyze a sample that is decomposed with acid for the determination of total Ni, V, and Fe.  
1.3 Procedure B, Sections 15–20—Flame AAS is used to analyze a sample diluted with an organic solvent for the determination of Ni, V, and Na. This test method uses oil-soluble metals for calibration to determine dissolved metals and does not purport to quantitatively determine nor detect insoluble particulates. Hence, this test method may underestimate the metal content, especially sodium, present as inorganic sodium salts.  
1.4 The concentration ranges covered by these test methods are determined by the sensitivity of the instruments, the amount of sample taken for analysis, and the dilution volume. A specific statement is given in Note 1.  
1.5 For each element, each test method has its own unique precision. The user can select the appropriate test method based on the precision required for the specific analysis.  
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard, unless specifically stated. Other units that appear in this standard are included for information purposes only or because they are in embedded pictures that cannot be edited.  
1.7 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. Specific warning statements are given in 8.1, 9.2, 9.5, 11.2, 11.4, and 16.1.  
1.8 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-Nov-2022
• ICS: 75.040 - Crude petroleum
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.03 - Elemental Analysis

Relations

• 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 D4175-23e1 - Standard Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants
• Effective Date: 01-Jul-2023
• 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 D6299-13e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Oct-2013
• Refers: ASTM D4057-06(2011) - Standard Practice for Manual Sampling of Petroleum and Petroleum Products
• Effective Date: 01-Jun-2011
• Refers: ASTM D6299-10 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-10e2 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Mar-2010
• Refers: ASTM D6299-09 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2009
• Refers: ASTM D6299-08 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 15-Oct-2008
• Refers: ASTM D6299-07 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2007
• Refers: ASTM D6299-07e1 - Standard Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance
• Effective Date: 01-Nov-2007
• Refers: ASTM D1193-06 - Standard Specification for Reagent Water
• Effective Date: 01-Mar-2006

Overview

ASTM D5863-22 outlines standardized test methods for the determination of nickel, vanadium, iron, and sodium in crude oils and residual fuels using flame atomic absorption spectrometry (AAS). Developed by ASTM Committee D02 on Petroleum Products, these methods are critical for laboratories, refineries, and quality assurance teams engaged in petroleum analysis. The presence of trace metals in fuel oils can cause corrosion, catalytic deactivation, and degradation of refinery equipment, making accurate measurement essential for fuel quality evaluations and process optimization.

This standard specifies two primary procedures for sample preparation and analysis:

• Procedure A: Utilizes acid decomposition to determine total nickel, vanadium, and iron.
• Procedure B: Employs organic solvent dilution to analyze nickel, vanadium, and sodium, focusing on oil-soluble (dissolved) forms.

Adhering to ASTM D5863-22 supports compliance with international standards and industry regulations, and ensures data comparability across facilities.

Key Topics

• Elemental Analysis in Petrochemical Products: Determination of metal content (Ni, V, Fe, Na) in crude and residual oils is vital for both processing and final product specifications.
• Sample Preparation:
  • Acid decomposition for comprehensive analysis of all forms of metals (Procedure A).
  • Organic solvent dilution for rapid assessment of oil-soluble metals (Procedure B).
• Atomic Absorption Spectrometry (AAS):
  • Utilizes specific wavelengths and flame conditions for each target analyte.
  • Requires proper calibration and use of interference suppressants (e.g., for vanadium).
• Precision and Quality Control:
  • Both methods provide guidelines for repeatability and reproducibility.
  • Emphasis on correct sample handling, calibration checks, and adherence to quality control protocols.
• Significance of Results:
  • Detection of trace metals informs on the potential for fouling, corrosion, and catalyst deactivation.
  • Results assist with quality grading and valuation of feedstock.

Applications

ASTM D5863-22 is widely used for:

• Crude Oil Characterization: Determining metal content prior to refining, which impacts processing strategies and economic value.
• Residual Fuel Quality Assessment: Ensuring that vanadium, nickel, iron, and sodium concentrations are within acceptable limits to minimize equipment damage during combustion.
• Catalyst Protection: Monitoring trace metals to prevent poisoning and deactivation of refining catalysts.
• Corrosion Risk Evaluation: Data from these methods supports maintenance planning for boilers, turbines, and other combustion equipment.
• Regulatory Compliance: Meeting specifications set by environmental and industry authorities for fuel and emissions.

These procedures are suitable for laboratories conducting routine quality checks, research institutions analyzing petroleums, and companies involved in buying, selling, or trading crude oil or heavy fuel oils.

Related Standards

ASTM D5863-22 frequently references and is complemented by the following standards:

• ASTM D1193: Specification for Reagent Water, ensuring all reagents meet required purity.
• ASTM D4057: Practice for Manual Sampling of Petroleum and Petroleum Products, for obtaining representative samples.
• ASTM D4175: Terminology Relating to Petroleum Products, Liquid Fuels, and Lubricants, for standard definitions.
• ASTM D4177: Practice for Automatic Sampling of Petroleum and Petroleum Products.
• ASTM D6299: Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measurement System Performance.

By following ASTM D5863-22 and related standards, organizations ensure the reliability, comparability, and regulatory acceptance of their elemental analyses in petroleum products.

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: D5863 − 22
Standard Test Methods for
Determination of Nickel, Vanadium, Iron, and Sodium in
Crude Oils and Residual Fuels by Flame Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D5863; 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* mine the applicability of regulatory limitations prior to use.
Specific warning statements are given in 8.1, 9.2, 9.5, 11.2,
1.1 These test methods cover the determination of nickel,
11.4, and 16.1.
vanadium, iron, and sodium in crude oils and residual fuels by
1.8 This international standard was developed in accor-
flame atomic absorption spectrometry (AAS). Two different
dance with internationally recognized principles on standard-
test methods are presented.
ization established in the Decision on Principles for the
1.2 Procedure A, Sections 8–14—Flame AAS is used to
Development of International Standards, Guides and Recom-
analyze a sample that is decomposed with acid for the
mendations issued by the World Trade Organization Technical
determination of total Ni, V, and Fe.
Barriers to Trade (TBT) Committee.
1.3 Procedure B, Sections 15–20—Flame AAS is used to
2. Referenced Documents
analyze a sample diluted with an organic solvent for the
determination of Ni, V, and Na. This test method uses oil-
2.1 ASTM Standards:
soluble metals for calibration to determine dissolved metals
D1193 Specification for Reagent Water
and does not purport to quantitatively determine nor detect
D4057 Practice for Manual Sampling of Petroleum and
insoluble particulates. Hence, this test method may underesti-
Petroleum Products
mate the metal content, especially sodium, present as inorganic
D4175 Terminology Relating to Petroleum Products, Liquid
sodium salts.
Fuels, and Lubricants
D4177 Practice for Automatic Sampling of Petroleum and
1.4 The concentration ranges covered by these test methods
Petroleum Products
are determined by the sensitivity of the instruments, the
D6299 Practice for Applying Statistical Quality Assurance
amount of sample taken for analysis, and the dilution volume.
and Control Charting Techniques to Evaluate Analytical
A specific statement is given in Note 1.
Measurement System Performance
1.5 For each element, each test method has its own unique
precision.Theusercanselecttheappropriatetestmethodbased
3. Terminology
on the precision required for the specific analysis.
3.1 Definitions:
1.6 The values stated in SI units are to be regarded as
3.1.1 For definitions of terms used in these test methods,
standard. No other units of measurement are included in this
refer to Terminology D4175.
standard, unless specifically stated. Other units that appear in
this standard are included for information purposes only or
4. Summary of Test Method
because they are in embedded pictures that cannot be edited.
4.1 Procedure A—One to twenty grams of sample are
1.7 This standard does not purport to address all of the
weighed into a beaker and decomposed with concentrated
safety concerns, if any, associated with its use. It is the
sulfuric acid by heating to dryness. The residual carbon is
responsibility of the user of this standard to establish appro-
burned off by heating at 525 °C in a muffle furnace. The
priate safety, health, and environmental practices and deter-
inorganic residue is digested in dilute nitric acid, evaporated to
incipient dryness, dissolved in dilute nitric and made up to
volume with dilute nitric acid. Interference suppressant is
These test methods are under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricantsand are the direct responsibility of
Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2022. Published January 2023. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1995. Last previous edition approved in 2016 as D5863 – 00a (2016). Standards volume information, refer to the standard’s Document Summary page on
DOI: 10.1520/D5863-22. 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
D5863 − 22
added to the dilute nitric acid solution. The solution is
nebulized into the flame of an atomic absorption spectrometer.
A nitrous oxide/acetylene flame is used for vanadium and an
air/acetylene flame is used for nickel and iron. The instrument
is calibrated with matrix-matched standard solutions. The
measuredabsorptionintensitiesarerelatedtoconcentrationsby
the appropriate use of calibration data.
4.2 Procedure B—Sample is diluted with an organic solvent
to give a test solution containing either 5 % (m/m) or 20 %
(m/m) sample. The recommended sample concentration is
dependent on the concentrations of the analytes in the sample.
For the determination of vanadium, interference suppressant is
addedtothetestsolution.Thetestsolutionisnebulizedintothe
flame of an atomic absorption spectrometer. A nitrous oxide/
acetylene flame is used for vanadium and an air/acetylene
flame is used for nickel and sodium. The measured absorption
intensities are related to concentrations by the appropriate use
of calibration data.
5. Significance and Use
FIG. 1 Decomposition Apparatus
5.1 When fuels are combusted, metals present in the fuels
can form low melting compounds that are corrosive to metal
parts.Metalspresentattracelevelsinpetroleumcandeactivate
7.2 Prior to weighing, stir the sample and then shake the
catalysts during processing. These test methods provide a
sample in its container. If the sample does not readily flow at
means of quantitatively determining the concentrations of
room temperature, heat the sample to a sufficiently high and
vanadium, nickel, iron, and sodium. Thus, these test methods
safe temperature to ensure adequate fluidity.
can be used to aid in determining the quality and value of the
crude oil and residual oil. PROCEDURE A—FLAME ATOMIC ABSORPTION
AFTER ACID DECOMPOSITION OF THE SAMPLE
6. Purity of Reagents
8. Apparatus
6.1 Reagent grade chemicals shall be used for all tests.
8.1 Atomic Absorption Spectrometer, complete instrument
Unless otherwise indicated, it is intended that all reagents
with hollow cathode lamps and burners with gas supplies to
conform to the specifications of the Committee on Analytical
support air-acetylene and nitrous oxide-acetylene flames.
Reagents of the American Chemical Society where such
(Warning—Hazardous. Potentially toxic and explosive. Refer
specifications are available. Other grades may be used, pro-
to the manufacturer’s instrument manual for associated safety
vided it is first ascertained that the reagent is of sufficiently
hazards.)
high purity to permit its use without lessening the accuracy of
the determination.
8.2 Sample Decomposition Apparatus (optional)—This ap-
paratus is described in Fig. 1. It consists of a borosilicate glass
6.2 When determining metals at concentrations less than
400 mL beaker for the test solution, an air bath (Fig. 2) that
1 mg⁄kg, use ultra-pure grade reagents.
rests on a hot plate and a 250 W infrared lamp supported
6.3 Purity of Water—Unless otherwise indicated, reference
2.5 cm above the air bath. A variable transformer controls the
towatershallbeunderstoodtomeanreagentwaterconforming
voltage applied to the lamp.
to Type II of Specification D1193.
8.3 Glassware—Borosilicate glass 400 mL beakers, volu-
metric flasks of various capacities and pipettes of various
7. Sampling and Sample Handling
capacities. When determining concentrations below 1 mg⁄kg,
7.1 The objective of sampling is to obtain a sample for
allglasswaremustbethoroughlycleaned(orsoakedovernight)
testing purposes that is representative of the entire quantity.
with 5 % HNO and rinsed five times with water.
Only representative samples obtained as specified in Practices
8.4 Electric Muffle Furnace, capable of maintaining 525 °C
D4057 and D4177 shall be used. Do not fill the sample
6 25 °C and sufficiently large to accommodate 400 mL bea-
container more than two-thirds full
kers. The capability of an oxygen bleed is advantageous and
optional.
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
8.5 Steam Bath.
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by theAmerican Chemical 8.6 Temperature Controlled Hot Plate, (optional).
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
8.7 Drying Oven,(optional),explosion-proof,ifusedtoheat
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. crude oils to obtain fluidity.
D5863 − 22
TABLE 1 AAS Conditions for the Determination of Vanadium,
Nickel, and Iron Following Acid Sample Decomposition
Wavelength, Concentration Interference
Element Flame
nm Range, µg/mL Suppressant
Vanadium 318.4 0.5–20 250 µg/mLAl, N O-
Al(NO ) in 5 % C H
3 3 2 2
(V/V)
HNO
Nickel 232.0 0.5–20 None Air-C H
2 2
Iron 248.3 3.0–10 None Air-C H
2 2
10. Preparation of Standards
10.1 Multi-Element Standard—Using the aqueous standard
solutions, prepare a multi-element standard containing
100 mg⁄kg each of vanadium, nickel, and iron. Standards
should be prepared to ensure accuracy and stability and should
be stored in clean containers to safeguard against physical
degradation.
10.2 Working Standards—Prepare at least two working
standards to cover the concentration ranges specified in Table
1. For vanadium, add the specified interference suppressant.
Each working standard must contain 5 % (V⁄V) nitric acid.
Standards should be prepared to ensure accuracy and stability
and should be stored in clean containers to safeguard against
physical degradation.
10.3 Standard Blank,thestandardblankcontains5 %(V/V)
NOTE 1—All parts 16 gage (1.5 mm, 0.060 in.) aluminum. All dimen-
nitric acid and any interference suppressant specified in Table
sions are in inches.
1.
Metric Equivalents
10.4 Check Standard—Prepare a calibration check standard
in. mm in. mm
in the same way as the working standards and at analyte
1 25.4 3 ⁄8 98.4
concentrations that are typical of the specimens being ana-
1 ⁄2 38.1 5 127
lyzed.
2 50.8 6 ⁄2 165.1
3 ⁄16 77.8 . .
11. Preparation of Test Solutions
FIG. 2 Air Bath
11.1 Into a beaker, weigh an amount of sample estimated to
contain between 0.0025 mg and 0.12 mg of each metal to be
determined. A typical mass is 10 g. Add 0.5 mL of H SO for
2 4
each gram of sample.
9. Reagents
NOTE 1—If it is desired to extend the lower concentration limits of the
9.1 Aqueous Standard Solutions—Individual aqueous stan-
test method, it is recommended that the decomposition be done in 10 g
dards with 1000 mg⁄kg concentrations of vanadium, nickel,
incrementsuptoamaximumof100 g.Itisnotnecessarytodestroyallthe
and iron, purchased or prepared in acid matrix to ensure organic matter each time before adding additional amounts of the sample
andacid.Whenitisdesiredtodeterminehigherconcentrations,reducethe
stability.
sample size accordingly.
9.2 Nitric Acid—Concentrated nitric acid, HNO .
11.2 Atthesametimepreparereagentblanksusingthesame
(Warning—Poison, oxidizer. Causes severe burns. Harmful or
amount of sulfuric acid as used for sample decomposition.
fatal if swallowed or inhaled.)
Reagent blanks should be carried through the same procedure
9.3 Nitric Acid 50 % (V/V)—Carefully add, with stirring,
as the samples. (Warning—Reagent blanks are critical when
one volume of concentrated nitric acid to one volume of water.
determining concentrations below 1 mg⁄kg. To simplify the
analysis,usethesamevolumeofacidandthesamedilutionsas
9.4 Dilute Nitric Acid, 5 % (V/V)—Carefully add, with
used for the samples. For example, if 20 g of sample is being
stirring, one volume of concentrated nitric acid to 19 volumes
decomposed, use 10 mLof sulfuric acid for the reagent blank.)
of water.
11.3 The use of the air bath apparatus (Fig. 2) is optional.
9.5 Sulfuric Acid—Concentrated sulfuric acid, H SO .
2 4
Place the beaker in the air bath, which is located in the hood.
(Warning—Poison, oxidizer. Causes severe burns. Harmful or
The hot plate is off at this time. Heat gently from the top with
fatal if swallowed or inhaled.)
the infrared lamp (Fig. 1) while stirring the test solution with a
9.6 Aluminum Nitrate, Al(NO ) 9HOH.
3 3
glass rod. As decomposition proceeds (indicated by a frothing
9.7 Potassium Nitrate, KNO . and foaming), control the heat of the infrared lamp to maintain
D5863 − 22
steady evolution of fumes. Give constant attention to each 13.5 Nebulize the test solutions and measure and record the
sample mixture until all risk of spattering and foaming is past. absorbance. If appropriate, blank correct this absorbance by
Then, gradually increase the temperature of both the hot plate subtracting the reagent blank absorbance.
and lamp until the sample is reduced to a carbonaceous ash.
13.6 After measuring absorbances for a test solution, check
theblankstandard.Ifthisdoesnotreadzero,checkthesystem,
11.4 If the air bath apparatus is not used, heat the sample
and then repeat steps 13.2 – 13.5.
and acid on a temperature controlled hot plate.As described in
11.3, monitor the decomposition reaction and adjust the tem-
13.7 Test solutions that give absorbances greater than that
perature of the hot plate accordingly. (Warning—Hot fuming
obtained with the most concentrated working standard must be
concentrated sulfuric acid is very corrosive and a strong
diluted. The dilution must contain interference suppressant at
oxidizing acid. The analyst should work in a well-ventilated
the specified concentrations.
hood and wear rubber gloves and a suitable face shield to
protect against spattering acid.)
14. Quality Assurance/Quality Control (QA/QC)
14.1 Confirm the performance of the instrument and the test
11.5 Place the sample in the muffle furnace maintained at
525 °C 6 25 °C. Optionally, introduce a gentle stream of procedure by analyzing a control QC sample.
14.1.1 When QA/QC protocols are already established in
oxygen into the furnace to expedite oxidation. Continue to heat
until the carbon is completely removed. the testing facility, these may be used to confirm the reliability
of the test result.
11.6 Dissolve the inorganic residue by washing down the
14.1.2 When there is no QA/QC protocol established in the
wallofthebeakerwithabout10 mLofthe1 + 1HNO .Digest
testing facility, Appendix X1 can be used as the QA/QC
on a steam bath for 15 min to 30 min. Transfer to a hot plate
protocol.
and gently evaporate to incipient dryness.
14.2 Usersofthistestmethodareadvisedthat
...

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: D5863 − 00a (Reapproved 2016) D5863 − 22
Standard Test Methods for
Determination of Nickel, Vanadium, Iron, and Sodium in
Crude Oils and Residual Fuels by Flame Atomic Absorption
Spectrometry
This standard is issued under the fixed designation D5863; 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 These test methods cover the determination of nickel, vanadium, iron, and sodium in crude oils and residual fuels by flame
atomic absorption spectrometry (AAS). Two different test methods are presented.
1.2 Test Method Procedure A, Sections 78–1314—Flame AAS is used to analyze a sample that is decomposed with acid for the
determination of total Ni, V, and Fe.
1.3 Test Method Procedure B, Sections 1415–1920—Flame AAS is used to analyze a sample diluted with an organic solvent for
the determination of Ni, V, and Na. This test method uses oil-soluble metals for calibration to determine dissolved metals and does
not purport to quantitatively determine nor detect insoluble particulates. Hence, this test method may underestimate the metal
content, especially sodium, present as inorganic sodium salts.
1.4 The concentration ranges covered by these test methods are determined by the sensitivity of the instruments, the amount of
sample taken for analysis, and the dilution volume. A specific statement is given in Note 1.
1.5 For each element, each test method has its own unique precision. The user can select the appropriate test method based on
the precision required for the specific analysis.
1.6 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this
standard.standard, unless specifically stated. Other units that appear in this standard are included for information purposes only or
because they are in embedded pictures that cannot be edited.
1.7 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. Specific warning statements are given in 7.18.1, 8.29.2, 8.59.5, 10.211.2,
10.411.4, and 15.116.1.
1.8 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.
These test methods are under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricantsand are the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved April 1, 2016Dec. 1, 2022. Published May 2016January 2023. Originally approved in 1995. Last previous edition approved in 20112016 as
D5863 – 00a (2011).(2016). DOI: 10.1520/D5863-00AR16. 10.1520/D5863-22.
*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
D5863 − 22
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
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
3. Terminology
3.1 Definitions:
3.1.1 For definitions of terms used in these test methods, refer to Terminology D4175.
4. Summary of Test Method
4.1 Test Method Procedure A—One to twenty grams of sample are weighed into a beaker and decomposed with concentrated
sulfuric acid by heating to dryness. The residual carbon is burned off by heating at 525 °C in a muffle furnace. The inorganic
residue is digested in dilute nitric acid, evaporated to incipient dryness, dissolved in dilute nitric and made up to volume with dilute
nitric acid. Interference suppressant is added to the dilute nitric acid solution. The solution is nebulized into the flame of an atomic
absorption spectrometer. A nitrous oxide/acetylene flame is used for vanadium and an air/acetylene flame is used for nickel and
iron. The instrument is calibrated with matrix-matched standard solutions. The measured absorption intensities are related to
concentrations by the appropriate use of calibration data.
4.2 Test Method Procedure B—Sample is diluted with an organic solvent to give a test solution containing either 5 % (m/m) or
20 % (m/m) sample. The recommended sample concentration is dependent on the concentrations of the analytes in the sample. For
the determination of vanadium, interference suppressant is added to the test solution. The test solution is nebulized into the flame
of an atomic absorption spectrometer. A nitrous oxide/acetylene flame is used for vanadium and an air/acetylene flame is used for
nickel and sodium. The measured absorption intensities are related to concentrations by the appropriate use of calibration data.
5. Significance and Use
5.1 When fuels are combusted, metals present in the fuels can form low melting compounds that are corrosive to metal parts.
Metals present at trace levels in petroleum can deactivate catalysts during processing. These test methods provide a means of
quantitatively determining the concentrations of vanadium, nickel, iron, and sodium. Thus, these test methods can be used to aid
in determining the quality and value of the crude oil and residual oil.
6. Purity of Reagents
6.1 Reagent grade chemicals shall be used for all tests. Unless otherwise indicated, it is intended that all reagents 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.
6.2 When determining metals at concentrations less than 1 mg ⁄kg, use ultra-pure grade reagents.
6.3 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to Type
II of Specification D1193.
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.
Reagent Chemicals, American Chemical Society Specifications,ACS 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.
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FIG. 1 Decomposition Apparatus
7. Sampling and Sample Handling
7.1 The objective of sampling is to obtain a sample for testing purposes that is representative of the entire quantity. Only
representative samples obtained as specified in Practices D4057 and D4177 shall be used. Do not fill the sample container more
than two-thirds full
7.2 Prior to weighing, stir the sample and then shake the sample in its container. If the sample does not readily flow at room
temperature, heat the sample to a sufficiently high and safe temperature to ensure adequate fluidity.
TEST METHOD PROCEDURE A—FLAME ATOMIC ABSORPTION AFTER ACID DECOMPOSITION OF THE
SAMPLE
8. Apparatus
8.1 Atomic Absorption Spectrometer, complete instrument with hollow cathode lamps and burners with gas supplies to support
air-acetylene and nitrous oxide-acetylene flames. (Warning—Hazardous. Potentially toxic and explosive. Refer to the
manufacturer’s instrument manual for associated safety hazards.)
8.2 Sample Decomposition Apparatus (optional)—This apparatus is described in Fig. 1. It consists of a borosilicate glass 400 mL
beaker for the test solution, an air bath (Fig. 2) that rests on a hot plate and a 250 W infrared lamp supported 2.5 cm above the
air bath. A variable transformer controls the voltage applied to the lamp.
8.3 Glassware—Borosilicate glass 400 mL beakers, volumetric flasks of various capacities and pipettes of various capacities.
When determining concentrations below 1 mg ⁄kg, all glassware must be thoroughly cleaned (or soaked overnight) with 5 % HNO
and rinsed five times with water.
8.4 Electric Muffle Furnace, capable of maintaining 525 °C 6 25 °C and sufficiently large to accommodate 400 mL beakers. The
capability of an oxygen bleed is advantageous and optional.
8.5 Steam Bath.
8.6 Temperature Controlled Hot Plate, (optional).
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NOTE 1—All parts 16 gage (1.5 mm, 0.060 in.) aluminum. All dimensions are in inches.
Metric Equivalents
in. mm in. mm
1 25.4 3 ⁄8 98.4
1 ⁄2 38.1 5 127
2 50.8 6 ⁄2 165.1
3 ⁄16 77.8 . .
FIG. 2 Air Bath
8.7 Drying Oven, (optional), explosion-proof, if used to heat crude oils to obtain fluidity.
9. Reagents
9.1 Aqueous Standard Solutions—Individual aqueous standards with 1000 mg ⁄kg concentrations of vanadium, nickel, and iron,
purchased or prepared in acid matrix to ensure stability.
9.2 Nitric Acid—Concentrated nitric acid, HNO . (Warning—Poison, oxidizer. Causes severe burns. Harmful or fatal if
swallowed or inhaled.)
9.3 Nitric Acid 50 % (V/V)—Carefully add, with stirring, one volume of concentrated nitric acid to one volume of water.
9.4 Dilute Nitric Acid, 5 % (V/V)—Carefully add, with stirring, one volume of concentrated nitric acid to 19 volumes of water.
9.5 Sulfuric Acid—Concentrated sulfuric acid, H SO . (Warning—Poison, oxidizer. Causes severe burns. Harmful or fatal if
2 4
swallowed or inhaled.)
9.6 Aluminum Nitrate, Al(NO ) 9HOH.
3 3
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TABLE 1 AAS Conditions for the Determination of Vanadium,
Nickel, and Iron Following Acid Sample Decomposition
Wavelength, Concentration Interference
Element Flame
nm Range, μg/mL Suppressant
Vanadium 318.4 0.5–20 250 μg/mL Al, N O-
Al(NO ) in 5 % C H
3 3 2 2
(V/V)
HNO
Nickel 232.0 0.5–20 None Air-C H
2 2
Iron 248.3 3.0–10 None Air-C H
2 2
9.7 Potassium Nitrate, KNO .
10. Preparation of Standards
10.1 Multi-Element Standard—Using the aqueous standard solutions, prepare a multi-element standard containing 100 mg ⁄kg
each of vanadium, nickel, and iron. Standards should be prepared to ensure accuracy and stability and should be stored in clean
containers to safeguard against physical degradation.
10.2 Working Standards—Prepare at least two working standards to cover the concentration ranges specified in Table 1. For
vanadium, add the specified interference suppressant. Each working standard must contain 5 % (V ⁄V) nitric acid. Standards should
be prepared to ensure accuracy and stability and should be stored in clean containers to safeguard against physical degradation.
10.3 Standard Blank, the standard blank contains 5 % (V/V) nitric acid and any interference suppressant specified in Table 1.
10.4 Check Standard—Prepare a calibration check standard in the same way as the working standards and at analyte
concentrations that are typical of the specimens being analyzed.
11. Preparation of Test Solutions
11.1 Into a beaker, weigh an amount of sample estimated to contain between 0.0025 mg and 0.12 mg of each metal to be
determined. A typical mass is 10 g. Add 0.5 mL of H SO for each gram of sample.
2 4
NOTE 1—If it is desired to extend the lower concentration limits of the test method, it is recommended that the decomposition be done in 10 g increments
up to a maximum of 100 g. It is not necessary to destroy all the organic matter each time before adding additional amounts of the sample and acid. When
it is desired to determine higher concentrations, reduce the sample size accordingly.
11.2 At the same time prepare reagent blanks using the same amount of sulfuric acid as used for sample decomposition. Reagent
blanks should be carried through the same procedure as the samples. (Warning—Reagent blanks are critical when determining
concentrations below 1 mg ⁄kg. To simplify the analysis, use the same volume of acid and the same dilutions as used for the
samples. For example, if 20 g of sample is being decomposed, use 10 mL of sulfuric acid for the reagent blank.)
11.3 The use of the air bath apparatus (Fig. 2) is optional. Place the beaker in the air bath, which is located in the hood. The hot
plate is off at this time. Heat gently from the top with the infrared lamp (Fig. 1) while stirring the test solution with a glass rod.
As decomposition proceeds (indicated by a frothing and foaming), control the heat of the infrared lamp to maintain steady
evolution of fumes. Give constant attention to each sample mixture until all risk of spattering and foaming is past. Then, gradually
increase the temperature of both the hot plate and lamp until the sample is reduced to a carbonaceous ash.
11.4 If the air bath apparatus is not used, heat the sample and acid on a temperature controlled hot plate. As described in 10.311.3,
monitor the decomposition reaction and adjust the temperature of the hot plate accordingly. (Warning—Hot fuming concentrated
sulfuric acid is very corrosive and a strong oxidizing acid. The analyst should work in a well-ventilated hood and wear rubber
gloves and a suitable face shield to protect against spattering acid.)
11.5 Place the sample in the muffle furnace maintained at 525 °C 6 25 °C. Optionally, introduce a gentle stream of oxygen into
the furnace to expedite oxidation. Continue to heat until the carbon is completely removed.
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11.6 Dissolve the inorganic residue by washing down the wall of the beaker with about 10 mL of the 1 + 1 HNO . Digest on a
steam bath for 15 min to 30 min. Transfer to a hot plate and gently evaporate to incipient dryness.
11.7 Wash down the wall of the beaker with about 10 mL of dilute nitric acid (5 % V/V). Digest on the steam bath until all salts
are dissolved. Allow to cool. Transfer quantitatively to a volumetric flask of suitable volume and make up to volume with dilute
nitric acid. This is the test solution.
11.8 Pipette aliquots of the test solution into two separate volumetric flasks. Retain one flask for the determination of nickel and
iron. To the other flask add aluminum interference suppressant for vanadium determination (refer to Table 1) and dilute up to mark
with dilute nitric acid (5 % V/V). Similarly, prepare a reagent blank solution for vanadium analysis.
12. Preparation of Apparatus
12.1 Consult the manufacturer’s instructions for the operation of the atomic absorption spectrometer. This test method assumes
that good operating procedures are followed. Design differences
...