Designation: D4458 − 15

Standard Test Method for

Chloride Ions in Brackish Water, Seawater, and Brines1
This standard is issued under the fixed designation D4458; 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 (s) indicates an editorial change since the last revision or reapproval.

1. Scope* 3. Terminology
1.1 This test method2 is applicable to the measurement of 3.1 Definitions—For definitions of terms used in this test
chloride in highly mineralized waters such as oil field brines,

LICENSED TO ONGC LIMITED, FOR INTERNAL USE AT THIS LOCATION ONLY, SUPPLIED BY BOOK SUPPLY
method, refer to Terminology D1129.
seawater, and brackish water. The test method is based upon
the titration of chloride with silver nitrate, using a visual 4. Summary of Test Method
indicator.
4.1 This test method is based upon the Mohr procedure for
1.2 Samples containing from 10 to 150 mg of chloride can determining chloride ion with silver nitrate. The chloride
be analyzed by this test method. These levels are achieved by reacts with the silver ion before any silver chromate forms,
dilution as described in the test method. due to the lower solubility of silver chloride. The potassium
1.3 The values stated in SI units are to be regarded as chromate indicator reacts with excess silver ion to form a red
standard. No other units of measurement are included in this silver chromate precipitate. The end point is the appearance of
standard. the first permanent orange color.
1.4 It is the user’s responsibility to assure the validity of the 4.2 This test method is suitable for analyzing solutions with
method for untested types of water. a pH between 6.0 and 8.5.
1.5 This standard does not purport to address all of the 5. Significance and Use
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 5.1 Chloride is present in virtually all oil field brines,
priate safety and health practices and determine the applica- seawaters, and many waste waters. Identification of the origin
bility of regulatory limitations prior to use. of the water and selection of its disposal method may be based
upon the chloride content. The chloride content is also used to
2. Referenced Documents estimate the resistivity of formation waters and to differentiate
between subsurface formations.
2.1 ASTM Standards:3
D1129 Terminology Relating to Water 6. Interferences
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of 6.1 Sulfide, bromide, iodide, thiocyanate, cyanide,
Applicable Test Methods of Committee D19 on Water phosphate, sulfite, carbonate, hydroxide, and iron interfere in
D3370 Practices for Sampling Water from Closed Conduits this test method. Sulfide, sulfite, and thiosulfate can be re-
D5810 Guide for Spiking into Aqueous Samples moved with a peroxide treatment, but usually no attempt is
D5847 Practice for Writing Quality Control Specifications made to remove bromide and iodide because they are usually
for Standard Test Methods for Water Analysis present in insignificant quantities compared to chloride. If
necessary, the pH can be raised and the hydroxides of several
metals, including iron, can be filtered off. Iron, barium, lead,
1
This test method is under the jurisdiction of ASTM Committee D19 on Water and bismuth precipitate with the chromate indicator.
and is the direct responsibility of D19.05 on Inorganic Constituents in Water.
Current edition approved Feb. 1, 2015. Published March 2015. Originally 7. Apparatus
approved in 1985. Last previous edition approved in 2009 as D4458 – 09. DOI:
10.1520/D4458-15. 7.1 Laboratory Glassware.
2
Hillebrand, W. F., Lundell, G. E. F., Bright, H. A., and Hoffman, J. I.,
Applied Inorganic Analysis, 2nd Ed., 732, John Wiley & Sons, Inc., New York, 7.2 Buret, 25-mL capacity.
NY, 1953. 3 For referenced ASTM standards, visit the ASTM website,
www.astm.org, or contact ASTM Customer Service at service@astm.org. For 7.3 Hotplate.
Annual Book of ASTM Standards volume information, refer to the standard’s
Document Summary page on 7.4 Magnetic Stirrer and TFE-fluorocarbon-Coated
the ASTM website. Stirring Bars.

*A Summary of Changes section appears at the end of this standard

1
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

2
 D4458 −
8. Reagents and Materials
TABLE 1 Aliquot Size for Chloride Determination
8.1 Purity of Reagents—Reagent grade chemicals shall be Specific Gravity Sample Dilution Equivalent Aliquot, mL

used in all tests. Unless otherwise indicated, it is intended that 1.000 to 1.010 None—Take 50 mL for 50
analysis
all reagents shall conform to the specification of the 1.010 to 1.025 None—Take 25 mL for 25
Committee on Analytical Reagents of the American Chemical analysis
1.025 to 1.050 Dilute 25 mL to 100 mL, 12.5
Society, where such specifications are available. 4 Other grades take 50 mL
may be used, provided it is first ascertained that the reagent is 1.025 to 1.090 Dilute 25 mL to 100 mL, 6.25
of sufficiently high purity to permit its use without lessening take 25 mL
1.090 to 1.120 Dilute 25 mL to 500 mL, 1.25
the accuracy of the determination. take 25 mL
1.120 to 1.150 Dilute 25 mL to 1000
8.2 Purity of Water—Unless otherwise indicated, reference mL, take 25 mL
0.625

to water shall be understood to mean reagent water

conforming to Specification D1193, Type I. Other reagent
water types may be used provided it is first ascertained that
the water is of

LICENSED TO ONGC LIMITED, FOR INTERNAL USE AT THIS LOCATION ONLY, SUPPLIED BY BOOK SUPPLY
sufficiently high purity to permit its use without adversely and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
affecting the precision and bias of the test method. Type III
water was specified at the time of round robin testing of this
test method.
8.3 Silver Nitrate Solution, Standard (equivalent to 5 mg
Cl−/mL)—Dissolve 23.9582 g of AgNO3 in approximately 700
mL of water. Add 1 drop concentrated nitric acid (HNO 3) and
dilute to 1 L in a volumetric flask. The HNO 3 will eliminate
any precipitation of silver hydroxide which would change the
concentration. Standardize against sodium chloride (NaCl) by
the procedure described in 8.4. Store in an amber-brown bottle
to protect the solution from light.
8.4 Silver Nitrate Solution, Standard (equivalent to 2 mg
Cl/mL)—For lower chloride concentrations, this more dilute
standard will give a more accurate titration. Dissolve 9.5834 g
of AgNO3 in approximately 700 mL of water. Add 1 drop
concentrated nitric acid (HNO3) and dilute to 1 L in a
volumetric flask. Standardize against sodium chloride (NaCl)
by the procedure described below. Store in an amber-brown
bottle to protect the solution from the light.
8.4.1 Dry 2 to 6 g of high purity (minimum 99.5 %) sodium
chloride crystals at 110°C for 2 h and cool in a desiccator to
room temperature.
8.4.2 Weigh 1.6484 g of the NaCl crystals. Transfer the
crystals into a 1-L volumetric flask, dissolve, dilute, and mix
well. A quantity of 1 mL of this solution provides 1 mg of Cl−.
8.4.3 Pipet 50 mL aliquots of the NaCl solution to
standard- ize the weaker AgNO3 solution (2 mg Cl−/mL)
and dilute to
100 mL with water. Use 100 mL of the NaCl solution to
standardize the more concentrated AgNO 3 solution (5 mg of
Cl−/mL).
8.4.4 Add 1 mL of 5 % indicator solution (see 8.5), 1 g of
sodium bicarbonate powder, and titrate to the appearance of a
permanent orange color preceding a red precipitate. The
analyst must practice this titration to become familiar with this
color.
8.4.5 Determine the indicator blank by substituting 100 mL
of reagent grade water for the sample in 10.3 to 10.6.

4
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

3
 D4458 −
8.4.6 The titre (T) of the silver nitrate solution is given in
the following equation:
mg Cl2 used
T 5 mL AgNO3 required 2
blank
8.4.7 If the titre (T) of the solutions are not exactly 2.0 or
5.0 mg of Cl− per mL AgNO3, it may be desirable to dilute
the solutions if they are too concentrated or add more silver
nitrate if too weak. In either case, restandardize the resulting
solution.
8.5 Potassium or Sodium Chromate, Indicator Solution—
Prepare a 5 % solution (5 g/100 mL) and adjust the pH to 7.0
with HNO3 (1 + 19) or NaHCO3 powder described in 8.6 and
8.7.
8.6 Sodium Bicarbonate (NaHCO3)—Powder to adjust the
sample pH to 8.3.
8.7 Nitric Acid Solution (1 + 19)—Add 1 volume of
HNO3 (sp. gr. 1.42) to 19 volumes water.
8.8 Filter Paper—Purchase suitable filter paper. 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 Practices D3370.

10. Procedure
10.1 Filter (8.8) the sample to remove any insoluble or
suspended materials.
10.2 Pipet an aliquot of sample into a 150-mL Erlenmeyer
flask. Dilute to 100 mL with water. Refer to Table 1 for
approximate volume.
10.3 Measure the pH and adjust to near neutral.
10.4 Add1g of sodium bicarbonate and stir to dissolve.
The pH should be between 6.5 and 8.0.
10.5 Add 1 mL of 5 % chromate indicator.
10.6 Titrate with one of the silver nitrate solutions to a
permanent orange color preceding the brick red colored pre-
cipitate.
NOTE 1—Endpoint detection may be improved by selecting
background and lighting conditions that enhance color contrast between
the solution and precipitate.

4
 D4458 −
TABLE 2 Determination of Precision and Bias of Chloride Ions in
Synthetic Brines 13.2.2 Verify titrant concentration after standardization by
analyzing a standard at a mid-range concentration. The mea-
Amount Amount Statistically sured concentration of a mid-range sample should fall within
Added, Found, Significant
615 % of the known concentration.
mg/L mg/L So mg/L ST mg/L % ± Bias (95 %
Confidence
13.2.3 If standardization cannot be verified, restandardize
Level) the solution.
994 995 0.0 0.0 + 0.10 no 13.2.4 It is recommended to analyze a blank and continuing
48 324 47 868 130 340 −0.94 yes calibration verification (CCV) at a 10 % frequency. The
143 524 142 959 740 1 450 0.39 no
results should fall within the expected precision of the method
or 615
% of the known concentration.
10.7 Record the volume of AgNO3 required to the end 13.3 Initial Demonstration of Laboratory Capability:
point and calculate the chloride content. 13.3.1 If a laboratory has not performed the test before, or

LICENSED TO ONGC LIMITED, FOR INTERNAL USE AT THIS LOCATION ONLY, SUPPLIED BY BOOK SUPPLY
if there has been a major change in the measurement system,
11. Calculation
for example, new analyst, new instrument, and so forth, a
11.1 Calculate the chloride content as follows: precision and bias study must be performed to demonstrate
~mL AgNO3 used 2 B! 3 T 31000 laboratory capability.
mg Cl2/L 5 mL sample 13.3.2 Analyze seven replicates of a standard solution
prepared from an Independent Reference Material containing a
where:
mid-range concentration of chloride. The matrix and
T = titre, mg Cl−/mL of AgNO3, and chemistry of the solution should be equivalent to the solution
B = indicator blank, as determined in 8.4.5.
used in the collaborative study. Each replicate must be taken
12. Precision and Bias5 through the complete analytical test method including any
sample preser- vation and pretreatment steps.
12.1 Precision—The overall and single operator precision 13.3.3 Calculate the mean and standard deviation of the
of this test method varies with the quantity being tested in seven values and compare to the acceptable ranges of bias in
accordance with Table 2. Table 2. This study should be repeated until the recoveries are
12.2 Bias—Recoveries of known amounts of chloride in within the limits given in section Table 2. If a concentration
synthetic brines are given in Table 2. other than the recommended concentration is used, refer to
12.3 The information in Table 2 is derived from round Practice D5847 for information on applying the F test and t
robin testing in which five laboratories, including eight test in evaluating the acceptability of the mean and standard
operators, participated. Of eight data sets ranked as described deviation.
in Practice D2777, none was rejected. One data point out of 13.4 Laboratory Control Sample (LCS):
seventy-two was rejected. Three synthetic brines were 13.4.1 To ensure that the test method is in control, prepare
analyzed, on each of three days, at chloride levels and analyze a LCS containing a mid-range concentration of
representative of the range of the test method. chloride with each batch (laboratory defined or twenty
samples). The laboratory control samples for a large batch
12.4 These data may not apply to waters of other matrices.
should cover the analytical range when possible. The LCS
12.5 Precision and bias of this test method conforms to must be taken through all of the steps of the analytical method
Practice D2777 – 77, which was in place at the time of including sample preservation and pretreatment. The result
collaborative testing. Under the allowances made in 1.4 of obtained for the LCS shall fall within 615 % of the known
D2777 – 13, these precision and bias data do meet existing concentration.
requirements for interlaboratory studies of Committee D19 13.4.2 If the result is not within these limits, analysis of
test methods. samples is halted until the problem is corrected, and either all
the samples in the batch must be reanalyzed, or the results
13. Quality Control must be qualified with an indication that they do not fall
13.1 In order to be certain that analytical values obtained within the performance criteria of the test method.
using these test methods are valid and accurate within the 13.5 Method Blank:
confidence limits of the test, the following QC procedures 13.5.1 Analyze a reagent water test blank with each
must be followed when analyzing chloride. laboratory-defined batch. The concentration of chloride found
13.2 Calibration and Calibration Verification: in the blank should be less than 0.5 times the lowest
13.2.1 Standardize the titrant as directed above. calibration standard. If the concentration of chloride is found
above this level, analysis of samples is halted until the
5
Supporting data have been filed at ASTM International Headquarters and may contamination is eliminated, and a blank shows no
be obtained by requesting Research Report RR:D19-1115. Contact ASTM Customer contamination at or above this level, or the results must be
Service at service@astm.org. qualified with an indication that they do not fall within the
performance criteria of the test method.

3
 D4458 −
13.6 Matrix Spike (MS):
results must be qualified with an indication that they do not
13.6.1 To check for interferences in the specific matrix fall within the performance criteria of the test method.
being tested, perform a MS on at least one sample from each
laboratory-defined batch by spiking an aliquot of the sample NOTE 2—Acceptable spike recoveries are dependent on the concentra-
tion of the component of interest. See Guide D5810 for additional
with a known concentration of chloride and taking it through information.
the analytical method.
13.7 Duplicate:
13.6.2 The spike concentration plus the background 13.7.1 To check the precision of sample analyses, analyze a
concen- tration of chloride must not exceed the high sample in duplicate with each laboratory-defined batch. If the
calibration standard. The spike must produce a concentration concentration of the analyte is less than five times the
in the spiked sample that is 2 to 5 times the analyte detection limit for the analyte, a matrix spike duplicate (MSD)
concentration in the unspiked sample, or 10 to 50 times the should be used.
detection limit of the test method, whichever is greater. 13.7.2 Calculate the standard deviation of the duplicate
13.6.3 Calculate the percent recovery of the spike (P) using values and compare to the precision in the collaborative study
the following formula: using an F test. Refer to 6.4.4 of Practice D5847 for informa-

LICENSED TO ONGC LIMITED, FOR INTERNAL USE AT THIS LOCATION ONLY, SUPPLIED BY BOOK SUPPLY
P 5 100 @ A ~ Vs1V ! 2 BVs # /CV tion on applying the F test.
13.7.3 If the result exceeds the precision limit, the batch
where: must be reanalyzed or the results must be qualified with an
A = analyte concentration (mg/L) in spiked sample, indication that they do not fall within the performance criteria
B = analyte concentration (mg/L) in unspiked sample, of the test method.
C = concentration (mg/L) of analyte in spiking solution,
Vs = volume (mL) of sample used, and 13.8 Independent Reference Material (IRM):
V = volume (mL) of spiking solution added. 13.8.1 In order to verify the quantitative value produced by
the test method, analyze an Independent Reference Material
13.6.4 The percent recovery of the spike shall fall within (IRM) submitted as a regular sample (if practical) to the
the limits, based on the analyte concentration, listed in Guide laboratory at least once per quarter. The concentration of the
D5810, Table 1. If the percent recovery is not within these IRM should be in the concentration mid-range for the method
limits, a matrix interference may be present in the sample chosen. The value obtained must fall within the control limits
selected for spiking. Under these circumstances, one of the established by the laboratory.
following remedies must be employed: the matrix interference
must be removed, all samples in the batch must be analyzed 14. Keywords
by a test method not affected by the matrix interference, or 14.1 brackish water; brines; chloride ion; seawater; silver
the nitrate

SUMMARY OF CHANGES

Committee D19 has identified the location of selected changes to this standard since the last issue
(D4458 – 09) that may impact the use of this standard. (Approved Feb. 1, 2015.)

(1) Added 8.8. (3) Revised Section 13.

(2) Revised the equation in 11.1.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the
risk of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years
and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional
standards and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a
meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair
hearing you should make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222
Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http://www.copyright.com/