ASTM D3869-15(2023)
(Test Method)Standard Test Methods for Iodide and Bromide Ions in Brackish Water, Seawater, and Brines
Standard Test Methods for Iodide and Bromide Ions in Brackish Water, Seawater, and Brines
SIGNIFICANCE AND USE
4.1 Identification of a brackish water, seawater, or brine is determined by comparison of the concentrations of their dissolved constituents. The results are used to evaluate the origin of the water, determine if it is a possible pollutant or determine if it is a commercial source of a valuable constituent such as iodine or bromine.
SCOPE
1.1 These test methods2 cover the determination of soluble iodide and bromide ions, or both, in brackish water, seawater, and brines. Four test methods are given as follows:
1.1.1 Test Method A for both Iodide and Bromide Ions—Volumetric, for concentrations from 0.2 mg/L to 2000 mg/L iodide and from 5 mg/L to 6500 mg/L bromide (Sections 7 – 15).
1.1.2 Test Method B for Iodide Ion—Colorimetric, for concentrations from 0.2 mg/L to 2000 mg/L iodide (Sections 16 – 25).
1.1.3 Test Method C for Iodide Ion—Selective electrode, for concentrations from 1 mg/L to 2000 mg/L iodide (Sections 26 – 34).
1.1.4 Test Method D for Bromide Ion—Colorimetric, for concentrations from 40 mg/L to 6500 mg/L bromide (Sections 35 – 44).
1.2 Test Method A is intended for use on all brackish waters, seawaters, and brines that contain appreciable amounts of iodide or bromide ions or both. Test Methods B, C, and D, because of their rapidity and sensitivity, are recommended for the analysis of brackish waters, seawaters, and brines in the field and in the laboratory.
1.3 Samples containing from 0.2 mg/L to 2000 mg/L of iodide or 5 mg/L to 6500 mg/L of bromide may be analyzed by these methods.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 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. For specific precautionary statements, see 20.2 and 39.2.
1.6 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
Relations
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: D3869 − 15 (Reapproved 2023)
Standard Test Methods for
Iodide and Bromide Ions in Brackish Water, Seawater, and
Brines
This standard is issued under the fixed designation D3869; 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 1.5 This standard does not purport to address all of the
2 safety concerns, if any, associated with its use. It is the
1.1 These test methods cover the determination of soluble
responsibility of the user of this standard to establish appro-
iodide and bromide ions, or both, in brackish water, seawater,
priate safety, health, and environmental practices and deter-
and brines. Four test methods are given as follows:
mine the applicability of regulatory limitations prior to use.
1.1.1 Test Method A for both Iodide and Bromide Ions—
For specific precautionary statements, see 20.2 and 39.2.
Volumetric, for concentrations from 0.2 mg ⁄L to 2000 mg/L
1.6 This international standard was developed in accor-
iodide and from 5 mg ⁄L to 6500 mg/L bromide (Sections 7 –
dance with internationally recognized principles on standard-
15).
ization established in the Decision on Principles for the
1.1.2 Test Method B for Iodide Ion—Colorimetric, for con-
Development of International Standards, Guides and Recom-
centrations from 0.2 mg ⁄L to 2000 mg ⁄L iodide (Sections 16 –
mendations issued by the World Trade Organization Technical
25).
Barriers to Trade (TBT) Committee.
1.1.3 Test Method C for Iodide Ion—Selective electrode, for
concentrations from 1 mg ⁄L to 2000 mg/L iodide (Sections 26
2. Referenced Documents
– 34).
2.1 ASTM Standards:
1.1.4 Test Method D for Bromide Ion—Colorimetric, for
D1129 Terminology Relating to Water
concentrations from 40 mg ⁄L to 6500 mg/L bromide (Sections
D1193 Specification for Reagent Water
35 – 44).
D2777 Practice for Determination of Precision and Bias of
1.2 Test Method A is intended for use on all brackish waters,
Applicable Test Methods of Committee D19 on Water
seawaters, and brines that contain appreciable amounts of
D3370 Practices for Sampling Water from Flowing Process
iodide or bromide ions or both. Test Methods B, C, and D,
Streams
because of their rapidity and sensitivity, are recommended for
D5810 Guide for Spiking into Aqueous Samples
the analysis of brackish waters, seawaters, and brines in the
D5847 Practice for Writing Quality Control Specifications
field and in the laboratory.
for Standard Test Methods for Water Analysis
1.3 Samples containing from 0.2 mg ⁄L to 2000 mg ⁄L of E60 Practice for Analysis of Metals, Ores, and Related
iodide or 5 mg ⁄L to 6500 mg ⁄L of bromide may be analyzed by
Materials by Spectrophotometry
these methods. E200 Practice for Preparation, Standardization, and Storage
of Standard and Reagent Solutions for Chemical Analysis
1.4 The values stated in SI units are to be regarded as
E275 Practice for Describing and Measuring Performance of
standard. No other units of measurement are included in this
Ultraviolet and Visible Spectrophotometers
standard.
3. Terminology
3.1 Definitions—For definitions of terms used in these test
These test methods are under the jurisdiction of ASTM Committee D19 on
methods, refer to Terminology D1129.
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
Constituents in Water.
Current edition approved April 1, 2023. Published April 2023. Originally 4. Significance and Use
approved in 1979. Last previous edition approved in 2015 as D3869 – 15. DOI:
4.1 Identification of a brackish water, seawater, or brine is
10.1520/D3869-15R23.
Additional information is contained in the following references: Collins, A. G., determined by comparison of the concentrations of their
Geochemistry of Oilfield Waters, Elsevier, New York, N.Y., 1975, 496 pp.American
Petroleum Institute, API Recommended Practice for Analysis of Oilfield Waters,
Subcommittee on Analysis of Oilfield Waters, API RP, 45 2nd ed, 1968, 49 pp.Hoke, For referenced ASTM standards, visit the ASTM website, www.astm.org, or
S. H, Fletcher, G. E., and Collins, A. G., “Fluoride and Iodide Selective Electrodes contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Applied to Oilfield Brine Analysis,” US Department of Energy, Report of Standards volume information, refer to the standard’s Document Summary page on
Investigations, BETC/RI-78/7, 1978. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3869 − 15 (2023)
dissolved constituents. The results are used to evaluate the 9. Interferences
origin of the water, determine if it is a possible pollutant or
9.1 Iron, manganese, and organic matter can interfere (Note
determine if it is a commercial source of a valuable constituent
1). They are removed by precipitation and filtration. Remaining
such as iodine or bromine.
traces of iron are masked with fluoride.
NOTE 1—Brines containing surfactants can cause emulsion problems, in
5. Reagents
which case a suitable emulsion breaker can be used.
5.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
10. Apparatus
all reagents shall conform to the specification of the Committee
10.1 Mechanical Bottle Shaker.
on Analytical Reagents of the American Chemical Society,
10.2 Bottles, 200-mL, for use on mechanical shaker.
where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
10.3 Pipets.
sufficiently high purity to permit its use without lessening the
10.4 Hot-Water Bath, thermostatically controlled to 61 °C.
accuracy of the determination.
10.5 Erlenmeyer Flasks, 250-mL.
5.2 Purity of Water—Unless otherwise indicated, reference
to water shall be understood to mean reagent water conforming
11. Reagents and Materials
to Specification D1193, Type I. Other reagent water types may
be used provided it is first ascertained that the water is of
11.1 Acetic Acid, glacial.
sufficiently high purity to permit its use without adversely
11.2 Ammonium Molybdate Solution—Dissolve 2 g of am-
affecting the precision and bias of the test method. Type III
monium molybdate in water and dilute to 100 mL.
water was specified at the time of round robin testing of this
11.3 Bromine Water (Saturated)—Add to 250 mL of water
test method.
slightly more liquid bromine (8 mL to 10 mL) than will
dissolve on shaking. Store in a glass-stoppered amber bottle.
6. Sampling
11.4 Calcium Carbonate (CaCO ), powdered.
6.1 Collect the sample in accordance with Practices D3370.
11.5 Calcium Oxide (CaO), anhydrous powdered.
TEST METHOD A—VOLUMETRIC FOR IODIDE
AND BROMIDE 11.6 Hydrochloric Acid (1 + 1)—Add 1 volume of HCl (sp
gr 1.19) to 1 volume of water.
7. Scope
11.7 Hydrochloric Acid (1 + 3)—Add 1 volume of HCl (sp
7.1 This test method is applicable to brackish waters, gr 1.19) to 3 volumes of water.
seawaters, and brines, and is recommended for such waters
11.8 Hydrochloric Acid (1 + 199)—Add 1 volume of HCl
containing appreciable amounts of iodide or bromide, or both.
(sp gr 1.19) to 199 volumes of water.
The test method can be used for concentrations as high as 2000
11.9 Methyl Red Indicator Solution (0.1 g/L)—Dissolve
mg/L iodide and 6500 mg/L bromide.
0.01 g of water-soluble methyl red in water and dilute to 100
mL.
8. Summary of Test Method
11.10 Potassium Fluoride (KF·2H O), crystalline.
8.1 Iodide in the sample is oxidized with bromine to iodate
in a buffered solution, the excess bromine is decomposed with
11.11 Potassium Iodide (KI), crystals, free of iodates when
sodium formate, and the iodate reacts with added iodide to
tested in accordance with American Chemical Society (ACS)
form iodine which is titrated with sodium thiosulfate.
specifications.
8.2 Iodide and bromide are oxidized to iodate and bromate,
11.12 Sodium Acetate Solution (275 g/L)—Dissolve 275 g
respectively, with hypochlorite. The excess hypochlorite is
of sodium acetate trihydrate (NaC H O ·3H O) in water, to
2 3 2 2
destroyed with sodium formate, leaving iodate and bromate to
dilute to 1 L, and filter.
react with added iodide to liberate iodine which is titrated with
11.13 Sodium Chloride (NaCl), crystals, which, in addition
sodium thiosulfate.
to satisfying ACS specifications, must be free of iodide, iodate,
8.3 The bromide concentration is calculated by difference
bromide, and bromate.
between the iodide and combined iodide and bromide deter-
11.14 Sodium Formate Solution (500 g/L)—Dissolve 50 g
minations.
of sodium formate (NaCHO ) in hot water and dilute to 100
mL. This solution must be freshly prepared.
11.15 Sodium Hypochlorite Solution—Use a fresh commer-
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
cial sodium hypochlorite or bleach solution containing ap-
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by the American Chemical proximately 5 % NaClO.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
11.16 Sodium Thiosulfate Solution (0.1 N)—Prepare and
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
copeial Convention, Inc. (USPC), Rockville, MD. standardize as directed in Practice E200.
D3869 − 15 (2023)
11.17 Sodium Thiosulfate Solution (0.01 N)—With a cali- 12.10 Adjust the pH of the solution with HCl (1 + 3) (11.7)
brated pipet transfer 25 mL of the 0.1 N Na S O solution to a pH between 5.5 and 6.0. Heat at 90 °C for 10 min. (A small
2 2 3
(11.16) into a 250-mL volumetric flask. Dilute to the mark with amount of undissolved CaCO should remain at this point.)
water that has been freshly boiled and cooled then mix well.
12.11 Remove the flask and cautiously add 10 mL of
This solution shall be prepared not more than 2 days before it
sodium formate solution (11.14), return the flask to the water
is to be used.
bath, and keep the contents hot for 5 min more. Observe the
11.18 Starch Indicator Solution—Make a paste of 6 g of timing closely. Rinse down the inside of the flask with a few
arrowroot or soluble iodometric starch with cold water. Pour millilitres of water and allow the solution to cool to room
the paste into 1 L of boiling water. Add 20 g of KOH, mix temperature. Do not use a water bath.
thoroughly, and allow to stand for 2 h. Add 6 mL of glacial
12.12 Add 3 drops of ammonium molybdate solution (11.2),
acetic acid. Mix again and add sufficient HCl (sp gr 1.19) to
0.5 g of KF (11.10) (if iron is present), 0.5 g of KI (11.11), mix
adjust the pH to 4.0. Store in a glass-stoppered bottle. Starch
until dissolved, and acidify with 15 mL of HCl (1 + 1) (11.6).
solution prepared in this manner will remain chemically stable
12.13 Titrate the sample (12.7) for iodide or the sample
for at least 1 year.
(12.12) for combined iodide and bromide with 0.01 N sodium
11.18.1 If a proprietary starch indicator powder is used, it
thiosulfate solution (11.17) using starch indicator (11.18).
shall be so indicated in reporting the results of the analysis.
Disregard any return of blue color after the endpoint.
11.19 Filter Paper—Purchase suitable filter paper. The user
must first ascertain that the filter paper is of sufficient purity to
13. Calculation
use without adversely affecting the bias and precision of the
13.1 Calculate the concentration of iodide and bromide ions
test method.
in milligrams per litre as follows:
13.2 Iodide:
12. Procedure
C 5 E 2 D
12.1 To remove iron, manganese, and organic matter from
the sample, add exactly 100 mL of sample to a bottle. Add 1 g
where:
of calcium oxide (11.5), stopper, and place the mixture in a
C = corrected millilitres of Na S O solution,
2 2 3
shaker for 1 h. Allow the mixture to stand overnight and filter
E = millilitres of Na S O , sample solution, and
2 2 3
on a dry folded filter (11.19), discarding the first 20 mL that
D = millilitres of Na S O blank solution.
2 2 3
come through. Brines with specific gravities less than 1.009
CN
may be filtered without standing overnight. Prepare a blank in 2
I , mg/L 5 × 21150
S
the same manner.
where:
12.2 Transfer an aliquot of the filtrate containing 1 mg to 2
mg of iodide to a 250-mL Erlenmeyer flask. Add sufficient N = normality of Na S O solution, and
2 2 3
S = millilitres of sample.
water to provide a total volume of 75 mL.
12.3 Add 3 drops of methyl red indicator (11.9). Add HCl 13.3 Bromide:
(1 + 199) (11.8) dropwise until the mixture is just slightly acid.
C 5 E 2 D
12.4 Add 10 mL of sodium acetate solution (11.12), 1 mL of
CN
Br , mg/L 5 × 13320 2 X
glacial acetic acid (11.1), 4 mL of bromine water (11.3), and
S
allow to stand for 5 min.
where:
12.5 Add 2 mL of sodium formate solution (11.14), blow
−
X = concentration of I as determined above.
out any bromine vapor from the neck of the flask, and wash
down the sides with water. 5
14. Precision and Bias
12.6 When the solution is completely colorless, add 0.2 g of
14.1 The overall precision (S ) and single-operator preci-
T
KF (11.10) and 0.5 g of KI (11.11). Mix until dissolved and add
sion (S ) of this test method within their designated ranges vary
o
15 mL of HCl (1 + 1) (11.6).
with the quantity being tested in accordance with Table 1 and
12.7 For final treatment and titration of the sample, proceed Table 2.
as directed in (12.13).
14.2 The bias of the test method determined from recoveries
12.8 To determine the combined iodide and bromide, trans- of known amounts of iodide and bromide in a series of
fer an aliquot of the filtrate (12.1) containing 1 mg to 2 mg of prepared standards are given in Table 1 and Table 2.
bromide to a 250-mL Erlenmeyer flask. Add sufficient water to
NOTE 2—The precision and bias estimates are based on the interlabo-
make the total volume 75 mL.
ratory study on four artificial brine samples containing various amounts of
iodide, bromide, and interfering ions as shown in Table 3. Two analysts in
12.9 If necessary add sufficient NaCl (11.13) to produce a
3-g chloride content. Add, in order, 10 mL of sodium hypo-
chlorite solution (11.15) and approximately 0.4 g of CaCO
3 5
Supporting data have been filed at ASTM International Headquarters and may
(11.4) (or enough so that approximately 0.1 g will remain after
be obtained by requesting Research Report RR:D19-1061. Contact
...
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