ASTM D3986-17

Standard Test Method for Barium in Brines, Seawater, and Brackish Water by Direct-Current Argon Plasma Atomic Emission Spectroscopy

SIGNIFICANCE AND USE
5.1 All waters containing acid soluble barium compounds are known to be toxic. This test method is useful for the determination of barium in brines, seawater, and brackish waters.  
5.2 Consumption, inhalation, or absorption of 500 to 600 mg of barium is considered fatal to human beings. Lower levels may result in disorders of the heart, blood vessels, and nerves. The drinking water standards set the maximum contaminant level for barium as 2 mg/L barium.
SCOPE
1.1 This test method covers the determination of dissolved and total recoverable barium in brines, seawater, and brackish waters by direct-current argon plasma atomic emission spectroscopy (DCP–AES).  
1.2 This test method has been tested in the range from 10 mg/L to 20 mg/L. Samples shall be diluted to contain concentrations within the calibration range (see 11.1 and 12.5). Higher concentrations can also be determined by changing to a less sensitive emission line.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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 and health practices and determine the applicability of regulatory limitations prior to use.  
1.5 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-May-2017
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: D19 - Water
• Drafting Committee: D19.05 - Inorganic Constituents in Water

Relations

• Replaces: ASTM D3986-11 - Standard Test Method for Barium in Brines, Seawater, and Brackish Water by Direct-Current Argon Plasma Atomic Emission Spectroscopy
• Effective Date: 01-Jun-2017
• Refers: ASTM D1129-13(2020)e2 - Standard Terminology Relating to Water
• Effective Date: 01-May-2020
• Refers: ASTM D3352-15 - Standard Test Method for Strontium Ion in Brackish Water, Seawater, and Brines
• Effective Date: 01-Feb-2015
• Refers: ASTM D4841-88(2013)e1 - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM D4841-88(2013) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 01-Jan-2013
• Refers: ASTM E1097-12 - Standard Guide for Determination of Various Elements by Direct Current Plasma Atomic Emission Spectrometry
• Effective Date: 01-Jun-2012
• Refers: ASTM D5810-96(2011) - Standard Guide for Spiking into Aqueous Samples
• Effective Date: 01-May-2011
• Refers: ASTM D3370-10 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Dec-2010
• Refers: ASTM D1129-10 - Standard Terminology Relating to Water
• Effective Date: 01-Mar-2010
• Refers: ASTM D3352-08a - Standard Test Method for Strontium Ion in Brackish Water, Seawater, and Brines
• Effective Date: 15-Nov-2008
• Refers: ASTM D3370-08 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Oct-2008
• Refers: ASTM D3352-08 - Standard Test Method for Strontium Ion in Brackish Water, Seawater, and Brines
• Effective Date: 15-Aug-2008
• Refers: ASTM D4841-88(2008) - Standard Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
• Effective Date: 15-Jul-2008
• Refers: ASTM D3370-07 - Standard Practices for Sampling Water from Closed Conduits
• Effective Date: 01-Dec-2007
• Refers: ASTM E1097-07 - Standard Guide for Direct Current Plasma-Atomic Emission Spectrometry Analysis
• Effective Date: 01-Nov-2007

Overview

ASTM D3986-17 is the internationally recognized Standard Test Method for Barium in Brines, Seawater, and Brackish Water by Direct-Current Argon Plasma Atomic Emission Spectroscopy. Published by ASTM International, this standard outlines procedures for quantifying both dissolved and total recoverable barium in high-salinity aqueous matrices using direct-current argon plasma atomic emission spectroscopy (DCP-AES). The method ensures accurate detection of barium in environmental samples, which is vital given barium’s toxicity to humans and aquatic ecosystems.

Key Points:

• Scope: Applicable to brines, seawater, and brackish waters.
• Method: Uses DCP-AES, validated in the range of 10–20 mg/L barium; higher concentrations can be determined with alternative emission lines.
• Health Significance: Drinking water should not exceed 2 mg/L barium due to health risks.
• Safety: The method requires safe laboratory practices and careful control of analytical conditions.

Key Topics

Importance of Barium Determination

• Health Concerns: Soluble barium compounds are toxic; exposure can cause serious health effects including heart, nerve, and blood vessel disorders.
• Environmental Monitoring: Essential for industries discharging brine waste or monitoring seawater and brackish water quality, supporting compliance with environmental regulations.

Method Highlights

• Sample Preparation: Filtration or acid digestion is used to differentiate dissolved and total recoverable barium.
• Matrix Interferences: High concentrations of calcium or sulfate can interfere, requiring careful calibration or dilution protocols.
• Calibration and Control: Standards and quality control checks (such as calibration blanks, verification standards, and matrix spikes) maintain data accuracy and traceability.

Quality Assurance

• QC Procedures: Regular analysis of laboratory control samples, blanks, and blind samples ensure the validity of test results.
• Precision and Bias: Demonstrated acceptable recovery and repeatability across multiple laboratories and sample types.
• Documentation: Strict adherence is required for sample handling, instrument calibration, and result reporting.

Applications

• Drinking Water Compliance: Used by water utilities to monitor and control barium levels in accordance with health-based standards.
• Industrial Wastewater: Supports industries (e.g., oil and gas, chemical processing) in managing brine effluent and maintaining regulatory compliance.
• Environmental Studies: Applied in marine science and environmental monitoring programs to assess the impact of anthropogenic activities on natural waters.
• Research Laboratories: Provides robust methodology for trace analysis of barium in complex aqueous matrices.

Practical Value

Implementing ASTM D3986-17 helps organizations:

• Detect barium contamination promptly.
• Meet stringent regulatory standards for water quality.
• Protect public health and the environment.
• Demonstrate due diligence and scientific rigor in water quality analysis.

Related Standards

The following standards are referenced or recommended for use in conjunction with ASTM D3986-17 to ensure comprehensive water analysis:

• ASTM D1129: Terminology Relating to Water
• ASTM D1193: Specification for Reagent Water
• ASTM D3352: Test Method for Strontium Ion in Brackish Water, Seawater, and Brines
• ASTM D3370: Practices for Sampling Water from Closed Conduits
• ASTM D4841: Practice for Estimation of Holding Time for Water Samples
• ASTM D5810: Guide for Spiking into Aqueous Samples
• ASTM D5847: Practice for Writing Quality Control Specifications for Water Analysis
• ASTM E1097: Guide for Determination of Elements by DCP-AES

Conclusion

ASTM D3986-17 provides a robust framework for the reliable determination of barium in challenging, high-salinity water samples. Adhering to this standard is critical for water quality professionals, regulatory agencies, and industrial operators to ensure accurate monitoring, regulatory compliance, and public and environmental safety. For full technical implementation, refer to the latest edition as published by ASTM International.

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: D3986 − 17
Standard Test Method for
Barium in Brines, Seawater, and Brackish Water by Direct-
Current Argon Plasma Atomic Emission Spectroscopy
This standard is issued under the fixed designation D3986; 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* D4841 Practice for Estimation of Holding Time for Water
Samples Containing Organic and Inorganic Constituents
1.1 This test method covers the determination of dissolved
D5810 Guide for Spiking into Aqueous Samples
and total recoverable barium in brines, seawater, and brackish
D5847 Practice for Writing Quality Control Specifications
waters by direct-current argon plasma atomic emission spec-
for Standard Test Methods for Water Analysis
troscopy (DCP–AES).
E1097 Guide for Determination of Various Elements by
1.2 This test method has been tested in the range from 10
Direct Current Plasma Atomic Emission Spectrometry
mg/L to 20 mg/L. Samples shall be diluted to contain concen-
trationswithinthecalibrationrange(see11.1and12.5).Higher
3. Terminology
concentrations can also be determined by changing to a less
3.1 Definitions:
sensitive emission line.
3.1.1 For definitions of terms used in this standard, refer to
1.3 The values stated in SI units are to be regarded as
Terminology D1129.
standard. No other units of measurement are included in this
3.2 Definitions of Terms Specific to This Standard:
standard.
3.2.1 continuing calibration blank, n—a solution containing
1.4 This standard does not purport to address all of the
no analytes (of interest) which is used to verify blank response
safety concerns, if any, associated with its use. It is the
and freedom from carryover.
responsibility of the user of this standard to establish appro-
3.2.2 continuing calibration verification, n—a solution (or
priate safety and health practices and determine the applica-
setofsolutions)ofknownconcentrationusedtoverifyfreedom
bility of regulatory limitations prior to use.
from excessive instrumental drift; the concentration is to cover
1.5 This international standard was developed in accor-
the range of calibration curve.
dance with internationally recognized principles on standard-
3.2.3 laboratory control sample, n—a solution with a certi-
ization established in the Decision on Principles for the
fied concentration of barium.
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
3.2.4 total recoverable barium, n—a descriptive term relat-
Barriers to Trade (TBT) Committee. ing to the forms of barium recovered in the acid-digestion
procedure specified in this test method.
2. Referenced Documents
4. Summary of Test Method
2.1 ASTM Standards:
D1129 Terminology Relating to Water
4.1 This test method is dependent upon excitation of the
D1193 Specification for Reagent Water
barium atom by a direct-current plasma source. When the
D3352 Test Method for Strontium Ion in Brackish Water,
excited barium atom decays to a lower energy state it emits
Seawater, and Brines
energy of a wavelength characteristic to the barium atom. The
D3370 Practices for Sampling Water from Closed Conduits
intensity of this emitted radiation will increase in direct
proportion to the concentration of barium in the sample, when
working in the linear response range.
This test method is under the jurisdiction of ASTM Committee D19 on Water
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
4.2 Since the variable and often high concentration of
in Water.
matrix materials in brines, seawater, and brackish water affect
Current edition approved June 1, 2017. Published June 2017. Originally
emission differently, it is a difficult task to prepare standards
approved in 1981. Last previous edition approved in 2011 as D3986 – 11. DOI:
10.1520/D3986-17.
sufficiently similar to the samples. To overcome this problem,
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
the standards are buffered with lithium ion and the samples are
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
diluted and buffered in the same manner. The standards are
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. used to construct a calibration curve and the concentration of
*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
D3986 − 17
the samples are calculated from this curve. Alternatively, the on analytical reagents of the American Chemical Society,
instrument may be calibrated using a blank and a standard or where such specifications are available. Other grades may be
bracketing standards. The sample concentration can then be used provided it is first ascertained that the reagent is of
read out directly from the instrument. sufficiently high purity to permit its use without lessening the
accuracy of the determination.
4.3 The 455.4-nm line has been found to be the most
satisfactory for analysis. 8.2 Purity of Water—Unless otherwise indicated, reference
towatershallbeunderstoodtomeanreagentwaterconforming
NOTE 1—The barium lines at 230.4 nm, 233.5 nm, and 553.6 nm have
to Type II of Specification D1193. Other reagent water types
been checked and found to be unsatisfactory for this analysis.
may be used provided it is first ascertained that the water is of
4.4 Dissolved barium is determined by filtering the sample
sufficiently high purity to permit its use without adversely
through a 0.45-µm pore size membrane filter (Note 2)atthe
affecting the precision and bias of the test method. Type II
time of sampling. This definition of “dissolved” barium is
water was specified at the time of round robin testing of this
arbitrary since very fine crystals of barium sulfate may pass
test method.
through the membrane filter.
8.3 Barium Solution, Stock(1g/LBa)—Dissolve1.7787gof
NOTE 2—These filters have been found to be contaminated to various
barium chloride dihydrate (BaCl ·2H O) in 100 mL of water,
2 2
degrees with heavy metals depending on the manufacturer. Care should be
add 2 mL of nitric acid (sp gr 1.42) and dilute to 1 L. A
exercised in selecting a source for these filters. It has been found to be a
purchased stock solution of appropriate known purity is also
good practice to wash the filters with nitric acid and then reagent water
acceptable.
before filtering a sample.
4.5 If there are no visible suspended solids in the sample,
8.4 Barium Solution, Standard (50 mg/L)—To 5.0 mL of
total recoverable barium may be determined on an acidified barium stock solution add 5.0 mLof lithium solution (8.8) and
unfiltered sample in the same manner as dissolved barium.
dilute to 100 mLwith HCl (1 + 499) (8.10).Working standards
(11.1) are prepared from this solution.
4.6 When the sample contains suspended solids total recov-
erable barium is determined by an acid digestion step to 8.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
destroy organic and inorganic particulates. chloric acid (HCl).
NOTE 3—If a high reagent blank is obtained for either acid, distill the
5. Significance and Use
acid or use spectrograde acid.
5.1 All waters containing acid soluble barium compounds
8.5.1 Caution—When HCl is distilled, an azeotropic mix-
are known to be toxic. This test method is useful for the
ture is obtained (approximately 6 N HCl).
determination of barium in brines, seawater, and brackish
8.6 Hydrochloric Acid (1 + 499)—Add 1 volume of hydro-
waters.
chloric acid (sp gr 1.19) to 499 volumes of water.
5.2 Consumption, inhalation, or absorption of 500 to 600
8.7 Lithium Carbonate—High-purity lithium carbonate
mg of barium is considered fatal to human beings. Lower
(Li CO ).
2 3
levels may result in disorders of the heart, blood vessels, and
8.8 Lithium Solution (40 g/L Li)—Dissolve 213.0 g of
nerves. The drinking water standards set the maximum con-
Li CO inaminimumamountofhydrochloricacid(spgr1.19)
2 3
taminant level for barium as 2 mg/L barium.
anddiluteto1Lwithwater.Approximately250mLofHCl(sp
gr1.19)isneededtocompletelydissolvethelithiumcarbonate.
6. Interferences
If distilled HCl is used double the amount (see 8.5, Note 3).
6.1 Calcium interferes in concentrations greater than 300
Store in a cleaned polyethylene or TFE-fluorocarbon bottle.
mg/L, however, this can be overcome by dilution of the
8.9 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
sample. The method of standard additions as described in Test
(HNO ).
Method D3352 will also overcome this interference.
8.10 Nitric Acid (1 + 499)—Add 1 volume of nitric acid (sp
6.2 High concentrations of sulfate anion are also known to
gr 1.42) to 499 volumes of water.
interfere in this test method by causing precipitation of barium
in the form of barium sulfate. 8.11 Filter Paper—Purchase suitable filter paper. Typically
the filter papers have a pore size of 0.45-µm membrane.
7. Apparatus
7.1 See the manufacturer’s instruction manual on installa-
Reagent Chemicals, American Chemical Society Specifications, American
tion and operation of direct-current argon plasma spectrom-
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
eters. Refer to Guide E1097 for information on DCPspectrom-
listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
eters.
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
8. Reagents and Materials 4
The sole source of supply of the apparatus known to the committee at this time
is LI 30 or its equivalent from Spex Industries, Inc., Box 798, Metuchen, NJ 08840.
8.1 Purity of Reagents—Reagent grade chemicals shall be
If you are aware of alternative suppliers, please provide this information to ASTM
used in all tests. Unless otherwise indicated, it is intended that
International Headquarters. Your comments will receive careful consideration at a
reagents shall conform to the specifications of the committee meeting of the responsible technical committee, which you may attend.
D3986 − 17
large amounts (>5 %) of dissolved solids. The amount of reduction in
Material such as fine-textured, acid-washed, ashless paper, or
volume is left to the discretion of the analyst.
glass fiber paper are acceptable. The user must first ascertain
NOTE 6—Many laboratories have found block digestion systems a
that the filter paper is of sufficient purity to use without
useful way to digest samples for trace metals analysis. Systems typically
adversely affecting the bias and precision of the test method.
consist of either a metal or graphite block with wells to hold digestion
tubes. The block temperature controller must be able to maintain unifor-
9. Hazards mity of temperature across all positions of the block. The digestion block
must be capable of maintaining a temperature between 65°C and 95°C.
9.1 As with any method where pumping or aspiration of
For trace metals analysis, the digestion tubes should be constructed of
samples is employed, the viscosity of blank, standards, and
polypropylene and have a volume accuracy of at least 0.5%. All lots of
samples must be controlled within reasonable limits (that is, do tubes should come with a certificate of analysis to demonstrate suitability
for their intended purpose.
not use reagent water standards to analyze oil field brines).
12.4 Cool and filter the samples through fine ashless filter
9.2 To analyze waters containing a high percentage of
paper (8.11) into 100-mL volumetric flasks. Wash the filter
dissolved solids it is necessary to prepare standards and blanks
paper at least three times with water and adjust to 100 mL
with matrices similar to the unknown samples. In many cases
volume.
this is almost impossible and the problem can be solved by
high dilution and introduction of lithium ion as an emission
12.5 Approximate Barium Concentration—Aspirate the
enhancement buffer.
sampleandcompareitsemissionintensitytothatofthebarium
solution standard (50 mg/L, 8.4). It should be stressed that this
10. Sampling
is not an accurate result and is to be used only to calculate the
quantity of sample needed for dilution in 12.6.
10.1 Collect the sample in accordance with Practices
D3370.
12.6 Transf
...

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: D3986 − 11 D3986 − 17
Standard Test Method for
Barium in Brines, Seawater, and Brackish Water by Direct-
Current Argon Plasma Atomic Emission Spectroscopy
This standard is issued under the fixed designation D3986; 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*
1.1 This test method covers the determination of dissolved and total recoverable barium in brines, seawater, and brackish waters
by direct-current argon plasma atomic emission spectroscopy (DCP–AES).
1.2 This test method has been tested in the range from 10 mg/L to 20 mg/L. Samples shall be diluted to contain concentrations
within the calibration range (see 11.1 and 12.5). Higher concentrations can also be determined by changing to a less sensitive
emission line.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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 and health practices and determine the applicability of regulatory
limitations prior to use.
1.5 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:
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D3352 Test Method for Strontium Ion in Brackish Water, Seawater, and Brines
D3370 Practices for Sampling Water from Closed Conduits
D4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic Constituents
D5810 Guide for Spiking into Aqueous Samples
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
E1097 Guide for Determination of Various Elements by Direct Current Plasma Atomic Emission Spectrometry
3. Terminology
3.1 Defenitions—Definitions: For definitions of terms used in this test method refer to Terminology D1129.
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 total recoverable barium,continuing calibration blank, n—recoverable barium forms that are determinable by the
digestion method that is included in the procedure.a solution containing no analytes (of interest) which is used to verify blank
response and freedom from carryover.
3.2.2 continuing calibration verification, n—a solution (or set of solutions) of known concentration used to verify freedom from
excessive instrumental drift; the concentration is to cover the range of calibration curve.
3.2.3 laboratory control sample, n—a solution with a certified concentration of barium.
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents in Water.
Current edition approved Sept. 1, 2011June 1, 2017. Published September 2011June 2017. Originally approved in 1981. Last previous edition approved in 20072011 as
D3986 – 07.D3986 – 11. DOI: 10.1520/D3986-11.10.1520/D3986-17.
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
D3986 − 17
3.2.4 total recoverable barium, n—a descriptive term relating to the forms of barium recovered in the acid-digestion procedure
specified in this test method.
4. Summary of Test Method
4.1 This test method is dependent upon excitation of the barium atom by a direct-current plasma source. When the excited
barium atom decays to a lower energy state it emits energy of a wavelength characteristic to the barium atom. The intensity of this
emitted radiation will increase in direct proportion to the concentration of barium in the sample, when working in the linear
response range.
4.2 Since the variable and often high concentration of matrix materials in brines, seawater, and brackish water affect emission
differently, it is a difficult task to prepare standards sufficiently similar to the samples. To overcome this problem, the standards
are buffered with lithium ion and the samples are diluted and buffered in the same manner. The standards are used to construct a
calibration curve and the concentration of the samples are calculated from this curve. Alternatively, the instrument may be
calibrated using a blank and a standard or bracketing standards. The sample concentration can then be read out directly from the
instrument.
4.3 The 455.4-nm line has been found to be the most satisfactory for analysis.
NOTE 1—The barium lines at 230.4 nm, 233.5 nm, and 553.6 nm have been checked and found to be unsatisfactory for this analysis.
4.4 Dissolved barium is determined by filtering the sample through a 0.45-μm pore size membrane filter (Note 2) at the time
of sampling. This definition of “dissolved” barium is arbitrary since very fine crystals of barium sulfate may pass through the
membrane filter.
NOTE 2—These filters have been found to be contaminated to various degrees with heavy metals depending on the manufacturer. Care should be
exercised in selecting a source for these filters. It has been found to be a good practice to wash the filters with nitric acid and then reagent water before
filtering a sample.
4.5 If there are no visible suspended solids in the sample, total recoverable barium may be determined on an acidified unfiltered
sample in the same manner as dissolved barium.
4.6 When the sample contains suspended solids total recoverable barium is determined by an acid digestion step to destroy
organic and inorganic particulates.
5. Significance and Use
5.1 All waters containing acid soluble barium compounds are known to be toxic. This test method is useful for the determination
of barium in brines, seawater, and brackish waters.
5.2 Consumption, inhalation, or absorption of 500 to 600 mg of barium is considered fatal to human beings. Lower levels may
result in disorders of the heart, blood vessels, and nerves. The drinking water standards set the maximum contaminant level for
barium as 2 mg/L barium.
6. Interferences
6.1 Calcium interferes in concentrations greater than 300 mg/L, however, this can be overcome by dilution of the sample. The
method of standard additions as described in Test Method D3352 will also overcome this interference.
6.2 High concentrations of sulfate anion are also known to interfere in this test method by causing precipitation of barium in
the form of barium sulfate.
7. Apparatus
7.1 See the manufacturer’s instruction manual on installation and operation of direct-current argon plasma spectrometers. Refer
to Guide E1097 for information on DCP spectrometers.
8. Reagents and Materials
8.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that
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.
8.2 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to
Type II of Specification D1193. Other reagent water types may be used provided it is first ascertained that the water is of
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed by
the American Chemical Society, see Annual 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.
D3986 − 17
sufficiently high purity to permit its use without adversely affecting the precision and bias of the test method. Type II water was
specified at the time of round robin testing of this test method.
8.3 Barium Solution, Stock (1g/L Ba)—Dissolve 1.7787 g of barium chloride dihydrate (BaCl ·2H O) in 100 mL of water, add
2 2
2 mL of nitric acid (sp gr 1.42) and dilute to 1 L. A purchased stock solution of adequate appropriate known purity is also
acceptable.
8.4 Barium Solution, Standard (50 mg/L)—To 5.0 mL of barium stock solution add 5.0 mL of lithium solution (8.8) and dilute
to 100 mL with HCl (1 + 499) (8.10). Working standards (11.1) are prepared from this solution.
8.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydrochloric acid (HCl).
NOTE 3—If a high reagent blank is obtained for either acid, distill the acid or use spectrograde acid.
8.5.1 Caution—When HCl is distilled, an azeotropic mixture is obtained (approximately 6 N HCl).
8.6 Hydrochloric Acid (1 + 499)—Add 1 volume of hydrochloric acid (sp gr 1.19) to 499 volumes of water.
8.7 Lithium Carbonate—High-purity lithium carbonate (Li CO ).
2 3
8.8 Lithium Solution (40 g/L Li)—Dissolve 213.0 g of Li CO in a minimum amount of hydrochloric acid (sp gr 1.19) and dilute
2 3
to 1 L with water. Approximately 250 mL of HCl (sp gr 1.19) is needed to completely dissolve the lithium carbonate. If distilled
HCl is used double the amount (see 8.5, Note 3). Store in a cleaned polyethylene or TFE-fluorocarbon bottle.
8.9 Nitric Acid (sp gr 1.42)—Concentrated nitric acid (HNO ).
8.10 Nitric Acid (1 + 499)—Add 1 volume of nitric acid (sp gr 1.42) to 499 volumes of water.
8.11 Filter Paper—Purchase suitable filter paper. Typically the filter papers have a pore size of 0.45-μm membrane. Material
such as fine-textured, acid-washed, ashless paper, or glass fiber paper are acceptable. The user must first ascertain that the filter
paper is of sufficient purity to use without adversely affecting the bias and precision of the test method.
9. Hazards
9.1 As with any method where pumping or aspiration of samples is employed, the viscosity of blank, standards, and samples
must be controlled within reasonable limits (that is, do not use reagent water standards to analyze oil field brines).
9.2 To analyze waters containing a high percentage of dissolved solids it is necessary to prepare standards and blanks with
matrices similar to the unknown samples. In many cases this is almost impossible and the problem can be solved by high dilution
and introduction of lithium ion as an emission enhancement buffer.
10. Sampling
10.1 Collect the sample in accordance with PracticePractices D3370.
10.2 Preserve the samples with high-purity hydrochloric acid to a pH of two or less immediately at the time of collection (about
2 mL/L). If only dissolved barium is to be determined, filter the samples through a 0.45-μm membrane (Note 2) filter before
acidification.
NOTE 4—Alternatively, the pH may be adjusted in the laboratory within 14 days of collection. However, acid must be added at least 24 hours before
analysis to dissolve any metals that adsorb to the container walls. This could reduce hazards of working with acids in the field when appropriate.
11. Standardization and Calculation
11.1 Prepare 100 mL each of a blank and 0.01, 0.02, 0.05, and 0.10 mg/L standards by diluting 5 mL of lithium solution (8.8)
and 20, 40, 100, and 200 μL of barium standard solution (8.4) with HCl (1 + 499). Prepare standards and blank each time the test
is performed.performed, or as determined by Practice D4841.
11.2 Aspirate the blank and standards. Aspirate HNO (1 + 499) between each standard and sample.
11.3 Using the instrument software, verify that the instrument calibration is within user acceptable QC limits and report the
barium concentrations accordingly.
12. Procedure
12.1 When determining dissolved barium the sample should be previously filtered through a 0.45-μm membrane filter (8.11) and
acidified (10.2) then proceed with 12.5.
12.2 When determining total recoverable barium and precipitation has occurred or large amounts of suspended solids are
present, add 5 mL each of nitric acid (sp gr 1.42) and HCl (sp gr 1.19) to 100 mL of the sample and proceed with 12.3 and 12.4.
The sole source of supply of the apparatus known to the committee at this time is LI 30 or its equivalent from Spex Industries, Inc., Box 798, Metuchen, NJ 08840. If
you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting
of the responsible technical committee, which you may attend.
D3986 − 17
12.3 Heat the samples (between 65°C and 95°C) on a steam bath or hot plate below boiling until the volume is reduced to 15
to 20 mL, making certain that the samples do not boil.
NOTE 5—When analyzing samples of brines or samples containing large amounts (>5 %) of dissolved solids. The amount of reduction in volume is
left to the discretion of the analyst.
NOTE 6—Many laboratories have found block digestion syste
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