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: D516 − 16 D516 − 22

Standard Test Method for

Sulfate Ion in Water1
This standard is issued under the fixed designation D516; 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.

This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope*

1.1 This turbidimetric test method covers the determination of sulfate in water in the range from 55 mg ⁄L to 40 mg/L of sulfate
ion (SO4−−).

1.2 This test method was used successfully with drinking, ground, and surface waters. It is the user’s responsibility to ensure the
validity of this test method for waters of untested matrices.

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1.3 Former gravimetric and volumetric test methods have been discontinued. Refer to Appendix X1 for historical information.

1.4 The values stated in SI units(https://standards.iteh.ai)

are to be regarded as standard. No other units of measurement are included in this standard.

of the user of this standard to establish Document Preview

1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
appropriate safety and healthsafety, health, and environmental practices and determine
the applicability of regulatory limitations prior to use.
1.6 This international standard was developed in accordance with internationally recognized principles on standardization
ASTM D516-22
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
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by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

2. Referenced Documents

2.1 ASTM Standards:2

D1066 Practice for Sampling Steam
D1129 Terminology Relating to Water
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Flowing Process Streams
D4327 Test Method for Anions in Water by Suppressed Ion Chromatography
D5810 Guide for Spiking into Aqueous Samples
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
E60 Practice for Analysis of Metals, Ores, and Related Materials by Spectrophotometry
E275 Practice for Describing and Measuring Performance of Ultraviolet and Visible Spectrophotometers

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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 June 1, 2016Dec. 1, 2022. Published June 2016March 2023. Originally approved in 1938. Last previous edition approved in 20112016 as
D516 – 11.D516 – 16. DOI: 10.1520/D0516-16.10.1520/D0516-22.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [email protected]. 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

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3. Terminology
3.1 Definitions:

3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.

4. Summary of Test Method

4.1 Sulfate ion is converted to a barium sulfate suspension under controlled conditions. A solution containing glycerin and sodium
chloride is added to stabilize the suspension and minimize interferences. The resulting turbidity is determined by a nephelometer,
spectrophotometer, or photoelectric colorimeter and compared to a curve prepared from standard sulfate solutions.

5. Significance and Use

5.1 The determination of sulfate is important because it has been reported that when this ion is present in excess of about 250 mg/L
in drinking water, it causes a cathartic action (especially in children) in the presence of sodium and magnesium, and gives a bad
taste to the water.

5.2 Test Method D4327 (“Test Method of Anions in Water by Suppressed Ion Chromatography”) may be used.

6. Interferences

6.1 Insoluble suspended matter in the sample must be removed. Dark colors that cannot be compensated for in the procedure
interfere with the measurement of suspended barium sulfate (BaSO4).

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6.2 Polyphosphates as low as 1 mg/L will inhibit barium sulfate precipitation causing a negative interference. Phosphonates

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present in low concentrations, depending on the type of phosphonate, will also cause a negative interference.

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6.3 Silica in excess of 500 mg/L may precipitate along with the barium sulfate causing a positive interference.

6.4 Chloride in excess of 5000 mg/L will cause a negative interference.

ASTM D516-22
6.5 Aluminum, polymers, and large quantities of organic material present in the test sample may cause the barium sulfate to
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precipitate nonuniformly.

6.6 Polyphosphates as low as 1 mg/L will inhibit barium sulfate precipitation causing a negative interference. Phosphonates
present in low concentrations, depending on the type of phosphonate, will also cause a negative interference. Silica in excess of
500 mg/L may precipitate along with the barium sulfate causing a positive interference. Chloride in excess of 5000 mg/L will cause
a negative interference. Aluminum, polymers, and large quantities of organic material present in the test sample may cause the
barium sulfate to precipitate nonuniformly. In the presence of organic matter certain bacteria may reduce sulfate to sulfide. To
minimize the action of sulfate reducing bacteria, samples should be refrigerated at 4°C4 °C when the presence of such bacteria is
suspected.

6.7 Although other ions normally found in water do not appear to interfere, the formation of the barium sulfate suspension is very
critical. Determinations that are in doubt may be checked by a gravimetric method in some cases, or by the procedure suggested
in Note 211.2.1.

7. Apparatus

7.1 Photometer—One of the following which are given in order of preference.

7.1.1 Nephelometer or turbidimeter;

7.1.2 Spectrophotometer for use at 420 nm with light path of 44 cm to 5 cm;

7.1.3 Filter photometer with a violet filter having a maximum near 420 nm and a light path of 44 cm to 5 cm.

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7.2 Stopwatch, if the magnetic stirrer is not equipped with an accurate timer.

7.3 Measuring Spoon, capacity 0.20.2 mL to 0.3 mL.

7.4 Filter photometers and photometric practices prescribed in this test method shall conform to Practice E60; spectrophotometer
practices shall conform to Practice E275.

7.5 Laboratory Glassware—All glassware should be in good condition, clean, and free of contaminating substances.

7.5.1 If the testing is for regulatory purposes, volumetric flasks should be of Type A precision and serialized for quality control
tracking.

7.6 Stirring Apparatus—A magnetic stirrer should be used along with a magnetic stir bar appropriately sized for the labware in
use.

7.7 Weighing Apparatus—A scale or analytical balance of the appropriate accuracy and precision should be used. It should be
calibrated and within its calibration interval.

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 all
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reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society.3 Other
grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening

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the accuracy of the determination.

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Specification D1193, Type I. Other reagent water types may be used Preview
8.2 Purity of Water—Unless otherwise indicated, reference to water shall be understood to mean reagent water conforming to
provided it is first ascertained that the water is of 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.
ASTM D516-22
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8.3 Barium Chloride—Crystals of barium chloride (BaCl2·2H2O) screened to 20 to 30 mesh. To prepare in the laboratory, spread
crystals over a large watch glass, desiccate for 24 h, screen to remove any crystals that are not 20 to 30 mesh, and store in a clean,
dry jar.

8.4 Conditioning Reagent—Place 30 mL of concentrated hydrochloric acid (HCl, sp gr 1.19), 300 mL reagent water, 100 mL
100 mL 95 % ethanol or isopropanol and 75 g sodium chloride (NaCl) in a container. Add 50 mL glycerol and mix.

8.5 Sulfate Solution, Standard (1 mL = 0.100 mg SO4−−)——DissolveDissolve 0.1479 g of anhydrous sodium sulfate (Na2SO4)
in water, and dilute with water to 1 L in a volumetric flask. A purchased stock solution of adequate purity is also acceptable.

8.6 Filter Paper—Purchase suitable filter paper. Typically the filter papers have a pore size of 0.45-µm0.45 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. Sampling

9.1 Collect the sample in accordance with Practice D1066, and Practices D3370, as applicable.

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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 Suggestionssuggestions on the testing of reagents not listed by the American Chemical Society, see
AnnualAnalar 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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10. Calibration

10.1 Follow the procedure given in Section 11, using appropriate amounts of the standard sulfate solution prepared in accordance
with 8.5 and prepare a calibration curve showing sulfate ion content in milligrams per litre plotted against the corresponding
photometer readings (10.2).

10.2 Follow the procedure given in Section 11, using appropriate amounts of the standard sulfate solution prepared in accordance
with 8.5 and prepare a calibration curve showing sulfate ion content in milligrams per litre plotted against the corresponding
photometer readings (Note 1). Prepare standards by diluting with water 0.0, 5.0, 10.0, 15.0, 20.0, 30.0,0.0 mL, 5.0 mL, 10.0 mL,
15.0 mL, 20.0 mL, 30.0 mL, and 40.0 mL of standard sulfate solution to 100-mL100 mL volumes in volumetric flasks. These
solutions will have sulfate ion concentrations of 0.0,0.0 mg 5.0,⁄L, 5.0 mg 10.0,⁄L, 10.0 mg 15.0,⁄L, 15.0 mg 20.0,⁄L, 20.0 mg
30.0,⁄L, 30.0 mg ⁄L, and 40.0 mg/L (ppm), respectively.

NOTE 1—A separate calibration curve must be prepared for each photometer and a new curve must be prepared if it is necessary to change the cell, lamp,
or filter, or if any other alterations of instrument or reagents are made. Check the curve with each series of tests by running two or more solutions of known
sulfate concentrations.

10.2.1 A separate calibration curve must be prepared for each photometer and a new curve must be prepared if it is necessary to
change the cell, lamp, or filter, or if any other alterations of instrument or reagents are made. Check the curve with each series of
tests by running two or more solutions of known sulfate concentrations.

11. Procedure

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11.1 Filter (8.6) the sample if it is turbid through a 0.45-µm0.45 µm membrane and adjust the temperature to between 15 and
30°C.15 °C and 30 °C.

11.2 Pipette into a 250-mL250 mL(https://standards.iteh.ai)

beaker 100 mL or less of the clear sample containing between 0.50.5 mg and 4 mg of sulfate
ion (Note 211.2.1). Dilute to 100 mL with water if required, and add 5.0 mL of conditioning reagent (Note 110.2.1).
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NOTE 2—The solubility of BaSO4 is such that difficulty may be experienced in the determination of sulfate concentrations below about 5 mg/L (ppm).
This can be overcome by concentrating the sample or by adding 5 mL of standard sulfate solution (1 mL = 0.100 mg SO4−−) to the sample before diluting
to 100 mL. This will add 0.5 mg SO4 to the sample, which must be subtracted from the final result.
ASTM D516-22
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The solubility of BaSO4 is such that difficulty may be experienced in the determination of sulfate concentrations below
about 5 mg/L (ppm). This can be overcome by concentrating the sample or by adding 5 mL of standard sulfate solution (1
mL = 0.100 mg SO4−−) to the sample before diluting to 100 mL. This will add 0.5 mg SO4 to the sample, which must be subtracted
from the final result.

11.3 Mix in the stirring apparatus.

11.4 While the solution is being stirred, add a measured spoonful of BaCl2 crystals (0.3 g) and begin timing immediately.

11.5 Stir exactly 1.0 min at constant speed.

NOTE 1—The stirring should be at a constant rate in all determinations. The use of a magnetic stirrer has been found satisfactory for this purpose.

11.6 Immediately after the stirring period has ended, pour solution into the cell and measure the turbidity at 30-s intervals for 4
min. Record the maximum reading obtained in the 4-min period.

11.7 If the sample contains color or turbidity, run a sample blank using the procedure 11.2 through 11.6 without the addition of
the barium chloride.

11.8 If interferences are suspected, dilute the sample with an equal volume of water, and determine the sulfate concentration again.
If the value so determined is one half that in the undiluted sample, interferences may be assumed to be absent.

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NOTE 4—After dilution, if interferences are still determined to be present alternate methods should be used. It is up to the user to determine appropriate
alternate methods.

11.8.1 After dilution, if interferences are still determined to be present alternate methods should be used. It is up to the user to
determine appropriate alternate methods.

12. Calculation

12.1 Convert the photometer readings obtained with the sample to milligrams per litre sulfate ion (SO4−− ) by use of the calibration
curve described in Section 10.

13. Precision and Bias4

13.1 The precision and bias data presented in this test method meet the requirements of Practice D2777 – 86.

13.2 The overall and single-operator precision of the test method, within its designated range, varies with the quantity being tested
according to Table 1 for reagent water and Table 2 for drinking, ground, and surface waters.

13.2.1 Seven laboratories participated in the round robin at three levels in triplicate, making a total of 21 observations at each level
for reagent water and for matrix water (drinking, ground, and surface water).

13.3 Recoveries of known amounts of sulfate from reagent water and drinking, ground, and surface waters are as shown in Table
3.

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13.3.1 A table for estimating the bias of the test method through its applicable concentration range can be found in Table 4.

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13.3.2 These collaborative test data were obtained on reagent grade water and natural waters. For other matrices, these data may
not apply.

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13.4 Precision and bias for this test method Preview
conforms to Practice D2777 – 86, which was in place at the time of collaborative
testing. Under the allowances made in 1.4 of D2777 – 13, these precision and bias data do meet existing requirements for
interlaboratory studies of Committee D19 test methods.
ASTM D516-22
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14. Quality Control (QC)

14.1 The following quality control information is recommended for the determination of sulfate ion in water.

14.2 Calibration and Calibration Verification:

14.2.1 Analyze at least three working standards containing concentrations of sulfate that bracket the expected sample
concentration, prior to analysis of samples, to calibrate the instrument (see Section 11). The calibration correlation coefficient shall
be equal to or greater than 0.990.

TABLE 1 Overall (ST) and Single-Operator (SO) Standard

Deviations Against Mean Concentration for Interlaboratory
Recovery of Sulfate from Reagent WaterA
Mean Concentration (x¯), Standard Deviation, mg/L
mg/L ST SO
6.6 0.5 0.1
20.4 1.0 0.4
63.7 2.5 1.3
A
The test method is linear to 40 mg/L. Testing at the 63.9 level was accomplished
through dilution as described in 11.2.

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Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:D19-1145. Contact ASTM Customer
Service at [email protected].