Designation: D516 – 11

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 Department of Defense.

1. Scope* D5847 Practice for Writing Quality Control Specifications

1.1 This turbidimetric test method covers the determination for Standard Test Methods for Water Analysis
of sulfate in water in the range from 5 to 40 mg/L of sulfate ion E60 Practice for Analysis of Metals, Ores, and Related
(SO4−−). Materials by Spectrophotometry
1.2 This test method was used successfully with drinking, E275 Practice for Describing and Measuring Performance
ground, and surface waters. It is the user’s responsibility to of Ultraviolet and Visible Spectrophotometers
ensure the validity of this test method for waters of untested 3. Terminology
matrices.
1.3 Former gravimetric and volumetric test methods have 3.1 Definitions—For definitions of terms used in this test
been discontinued. Refer to Appendix X1 for historical infor- method, refer to Terminology D1129.
mation. 4. Summary of Test Method
1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 4.1 Sulfate ion is converted to a barium sulfate suspension
standard. under controlled conditions. A solution containing glycerin and
1.5 This standard does not purport to address the safety sodium chloride is added to stabilize the suspension and
concerns, if any, associated with its use. It is the responsibility minimize interferences. The resulting turbidity is determined
of the user of this standard to establish appropriate safety and by a nephelometer, spectrophotometer, or photoelectric colo-
health practices and determine the applicability of regulatory rimeter and compared to a curve prepared from standard sulfate
limitations prior to use. solutions.

2. Referenced Documents 5. Significance and Use

2.1 ASTM Standards:2 5.1 The determination of sulfate is important because it has
D1066 Practice for Sampling Steam been reported that when this ion is present in excess of about
D1129 Terminology Relating to Water 250 mg/L in drinking water, it causes a cathartic action
D1193 Specification for Reagent Water (especially in children) in the presence of sodium and magne-
D2777 Practice for Determination of Precision and Bias of sium, and gives a bad taste to the water.
Applicable Test Methods of Committee D19 on Water 6. Interferences
D3370 Practices for Sampling Water from Closed Conduits
6.1 Insoluble suspended matter in the sample must be
removed. Dark colors that cannot be compensated for in the
1
This test method is under the jurisdiction of ASTM Committee D19 on Water procedure interfere with the measurement of suspended barium
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents sulfate (BaSO4).
in Water.
Current edition approved Sept. 1, 2011. Published September 2011. Originally 6.2 Polyphosphates as low as 1 mg/L will inhibit barium
approved in 1938. Last previous edition approved in 2007 as D516 – 07. DOI: sulfate precipitation causing a negative interference. Phospho-
10.1520/D0516-11.
2
nates present in low concentrations, depending on the type of
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
phosphonate, will also cause a negative interference. Silica in
Standards volume information, refer to the standard’s Document Summary page on excess of 500 mg/L may precipitate along with the barium
the ASTM website. sulfate causing a positive interference. Chloride in excess 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.

1
 D516 – 11
5000 mg/L will cause a negative interference. Aluminum, mL 95 % ethanol or isopropanol and 75 g sodium chloride
polymers, and large quantities of organic material present in (NaCl) in a container. Add 50 mL glycerol and mix.
the test sample may cause the barium sulfate to precipitate 8.5 Sulfate Solution, Standard (1 mL = 0.100 mg SO4−−)—
nonuniformly. In the presence of organic matter certain bacte- Dissolve 0.1479 g of anhydrous sodium sulfate (Na2SO4) in
ria may reduce sulfate to sulfide. To minimize the action of water, and dilute with water to 1 L in a volumetric flask. A
sulfate reducing bacteria, samples should be refrigerated at 4°C purchased stock solution of adequate purity is also acceptable.
when the presence of such bacteria is suspected.
9. Sampling
6.3 Although other ions normally found in water do not
appear to interfere, the formation of the barium sulfate suspen- 9.1 Collect the sample in accordance with Practice D1066,
sion is very critical. Determinations that are in doubt may be and Practices D3370, as applicable.
checked by a gravimetric method in some cases, or by the 10. Calibration
procedure suggested in Note 2.
10.1 Follow the procedure given in Section 11, using
7. Apparatus appropriate amounts of the standard sulfate solution prepared
in accordance with 8.5 and prepare a calibration curve showing
7.1 Photometer—One of the following which are given in sulfate ion content in milligrams per litre plotted against the
order of preference. corresponding photometer readings (Note 1). Prepare standards
7.1.1 Nephelometer or turbidimeter; by diluting with water 0.0, 5.0, 10.0, 15.0, 20.0, 30.0, and 40.0
7.1.2 Spectrophotometer for use at 420 nm with light path of mL of standard sulfate solution to 100-mL volumes in volu-
4 to 5 cm; metric flasks. These solutions will have sulfate ion concentra-
7.1.3 Filter photometer with a violet filter having a maxi- tions of 0.0, 5.0, 10.0, 15.0, 20.0, 30.0, and 40.0 mg/L (ppm),
mum near 420 nm and a light path of 4 to 5 cm. respectively.
7.2 Stopwatch, if the magnetic stirrer is not equipped with
an accurate timer. 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
7.3 Measuring Spoon, capacity 0.2 to 0.3 mL.
the cell, lamp, or filter, or if any other alterations of instrument or reagents
7.4 Filter photometers and photometric practices prescribed are made. Check the curve with each series of tests by running two or
in this test method shall conform to Practice E60; spectropho- more solutions of known sulfate concentrations.
tometer practices shall conform to Practice E275.
11. Procedure
8. Reagents 11.1 Filter the sample if it is turbid through a 0.45-µm
8.1 Purity of Reagents—Reagent grade chemicals shall be membrane and adjust the temperature to between 15 and 30°C.
used in all tests. Unless otherwise indicated, it is intended that 11.2 Pipette into a 250-mL beaker 100 mL or less of the
all reagents shall conform to the specifications of the Commit- clear sample containing between 0.5 and 4 mg of sulfate ion
tee on Analytical Reagents of the American Chemical Society.3 (Note 2). Dilute to 100 mL with water if required, and add 5.0
Other grades may be used, provided it is first ascertained that mL of conditioning reagent (Note 1).
the reagent is of sufficiently high purity to permit its use NOTE 2—The solubility of BaSO4 is such that difficulty may be
without lessening the accuracy of the determination. experienced in the determination of sulfate concentrations below about 5
8.2 Purity of Water—Unless otherwise indicated, reference mg/L (ppm). This can be overcome by concentrating the sample or by
to water shall be understood to mean reagent water conforming adding 5 mL of standard sulfate solution (1 mL = 0.100 mg SO4−−) to the
to Specification D1193, Type I. Other reagent water types may sample before diluting to 100 mL. This will add 0.5 mg SO4 to the sample,
which must be subtracted from the final result.
be used provided it is first ascertained that the water is of
sufficiently high purity to permit its use without adversely 11.3 Mix in the stirring apparatus.
affecting the precision and bias of the test method. Type II 11.4 While the solution is being stirred, add a measured
water was specified at the time of round robin testing of this spoonful of BaCl2 crystals (0.3 g) and begin timing immedi-
test method. ately.
8.3 Barium Chloride—Crystals of barium chloride 11.5 Stir exactly 1.0 min at constant speed.
(BaCl2·2H2O) screened to 20 to 30 mesh. To prepare in the NOTE 3—The stirring should be at a constant rate in all determinations.
laboratory, spread crystals over a large watch glass, desiccate The use of a magnetic stirrer has been found satisfactory for this purpose.
for 24 h, screen to remove any crystals that are not 20 to 30 11.6 Immediately after the stirring period has ended, pour
mesh, and store in a clean, dry jar. solution into the cell and measure the turbidity at 30-s intervals
8.4 Conditioning Reagent—Place 30 mL of concentrated for 4 min. Record the maximum reading obtained in the 4-min
hydrochloric acid (HCl, sp gr 1.19), 300 mL reagent water, 100 period.
11.7 If the sample contains color or turbidity, run a sample
blank using the procedure 11.2 through 11.6 without the
3
Reagent Chemicals, American Chemical Society Specifications, American addition of the barium chloride.
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not 11.8 If interferences are suspected, dilute the sample with an
listed by the American Chemical Society, see Annual Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
equal volume of water, and determine the sulfate concentration
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, again. If the value so determined is one half that in the
MD. undiluted sample, interferences may be assumed to be absent.