ASTM D1246-16(2021)e1

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.
´1
Designation: D1246 − 16 (Reapproved 2021)
Standard Test Method for
Bromide Ion in Water
This standard is issued under the fixed designation D1246; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber 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.
ε NOTE—The WTO caveat was added editorially in December 2021.
1. Scope D1129Terminology Relating to Water
D1193Specification for Reagent Water
1.1 This test method is applicable to the measurement of
D2777Practice for Determination of Precision and Bias of
bromide ion in water, ground water, and drinking water.
Applicable Test Methods of Committee D19 on Water
1.2 Samples containing 0.5 mg/L to 1000 mg/L of bromide
D3370Practices for Sampling Water from Flowing Process
may be analyzed by this test method. The concentration range
Streams
may be extended by the dilution of an appropriate aliquot.
D4127Terminology Used with Ion-Selective Electrodes
1.3 The precision and bias statements were determined on D5810Guide for Spiking into Aqueous Samples
naturalandgroundwaters.Itistheresponsibilityoftheanalyst
D5847Practice for Writing Quality Control Specifications
to assure the validity of this test method for untested matrices. for Standard Test Methods for Water Analysis
1.4 A titrimetric and two colorimetric test methods for
3. Terminology
iodide and bromide were discontinued. Refer to Appendix X1
for historical information.
3.1 Definitions:
3.1.1 For definitions of terms used in this standard, refer to
1.5 The values stated in SI units are to be regarded as
Terminologies D1129 and D4127.
standard. No other units of measurement are included in this
standard.
4. Summary of Test Method
1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4.1 Bromide ion is measured potentiometrically using a
responsibility of the user of this standard to establish appro-
bromide ion-selective electrode in conjunction with a single-
priate safety, health, and environmental practices and deter-
junction,sleeve-typereferenceelectrode.Potentialsarereadon
mine the applicability of regulatory limitations prior to use.
apHmeterhavinganexpandedmillivoltscalecapableofbeing
1.7 This international standard was developed in accor-
read to the nearest 0.1 mV, or a selective ion meter having a
dance with internationally recognized principles on standard-
directconcentrationscaleforbromide.Forlessprecisework,a
ization established in the Decision on Principles for the
pH meter having a millivolt scale capable of being read to the
Development of International Standards, Guides and Recom-
nearest 1.0 mV is adequate, however, no supporting data are
mendations issued by the World Trade Organization Technical
available.
Barriers to Trade (TBT) Committee.
4.2 The electrodes are calibrated in known bromide solu-
2. Referenced Documents tions and the concentrations of unknowns are determined in
solutionswiththesamebackground.Inmostcases,additionof
2.1 ASTM Standards:
an ionic strength adjustor to both standards and samples is
D1066Practice for Sampling Steam
sufficient to maintain constant background ionic strength. For
samples above 0.1 M in ionic strength, prepare standard
This test method is under the jurisdiction ofASTM Committee D19 on Water
solutions similar to the sample composition.
and is the direct responsibility of Subcommittee D19.05 on Inorganic Constituents
in Water.
Current edition approved Nov. 1, 2021. Published December 2021. Originally
5. Significance and Use
approved in 1952. Last previous edition approved in 2016 as D1246–16. DOI:
10.1520/D1246-16R21E01.
5.1 By analysis for bromide in water, wastewater, and
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
brackish waters, it is possible to evaluate the origin of the
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
water, its potential as a source of bromide, and its condition
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. with regard to pollution.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D1246 − 16 (2021)
6. Interferences 8.3 Ionic Strength Adjustor (42.5 g/100 mL NaNO )—In a
100-mL volumetric flask, dissolve 42.5 g of sodium nitrate
6.1 Strongly reducing solutions and solutions containing
(NaNO ) in water and dilute to volume.
ions which form insoluble silver salts may coat the electrode
membrane.Thesemayberemovedbypolishingthemembrane 8.4 Nickel Sulfate Solution, 1 M—In a 100 mL volumetric
surface. Sulfide ion and cyanide ion both poison the electrode,
flask dissolve 26.3 g of nickel sulfate hexahydrate (NiSO ·
and should be removed (see Section 11). 6H O) in water and dilute to volume.
6.2 Halide ions form complexes with some metals. Since
8.5 Sodium Bromide Standard Solution, 1000 mg/L—Ina1
the electrode responds only to free bromide ions, the presence L volumetric flask dissolve 1.288 g dried sodium bromide in
ofanycomplexingagentslowersthemeasuredconcentrations.
water and dilute to volume. Alternatively, certified bromide
Concentrations of free metal ions causing a 10% error of a stock solutions of appropriate known purity are commercially
+3
bromide concentration of 8.1 mg/L are bismuth , 80 mg/L;
available through chemical supply vendors and may be used.
+2 +2 +2
cadmium , 100 mg/L; lead , 1600 mg/L; tin , 2400 mg/L;
8.6 Sodium Bromide Standard Solutions, (100, 10, and 1
+3
and thallium , 4 mg/L.
mg/L)—Dilute 1 volume of the 1000 mg/L bromide standard
6.3 Chloride ion and hydroxide ion do not interfere when
with 9 volumes of water to prepare the 100 mg/Lstandard. By
presentintheconcentrationsofupto400and30 000timesthe
further 1+9 serial dilutions, prepare the 10 and 1 mg/L
bromide concentration, respectively. There will be no interfer-
standards.
ence from ammonia when present in concentrations twice that
of bromide, nor from thiosulfate 20 times as concentrated as
9. Sampling
bromide. Iodide is an interference at a concentration ratio as
9.1 Collect the samples in accordance with Practice D1066
−4
low as 2×10 . Mercury should be absent from samples.
and Practices D3370, as applicable.
7. Apparatus
10. Calibration and Standardization
7.1 pH Meter, capable of reading to 0.1 mV, or a selective-
10.1 To 100 mL of the 1, 10, 100, and 1000 mg/L NaBr
ion meter.
standards add 2 mLof the ionic strength adjustor (ISA). If any
7.2 Bromide Ion-Selective Electrode.
samples require treatment for interferences, prepare standards
with the same background.
7.3 Sleeve-Type Single-Junction Reference Electrode, filled
with manufacturer’s filling solution.
10.2 Connect and fill electrodes in accordance with manu-
facturer’s instructions.
7.4 Mixer, magnetic, with a TFE fluorocarbon-coated stir-
ring bar.
10.3 Transferthe1mg/Lstandard-ISAmixturetoa150mL
beaker and stir gently using the magnetic mixer. Immerse the
7.5 Laboratory Glassware.
electrodes in the solution and wait 2 min for the potential to
stabilize. Record the value.
8. Reagents
10.4 Rinseelectrodesthoroughlyandrepeatforthe10,100,
8.1 Purity of Reagents—Reagent grade chemicals shall be
and 1000 mg/Lstandard-ISAmixtures. Wait 2 min and record
used in all tests. Unless otherwise indicated, it is intended that
the potential.
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
10.5 Follow manufacturer instructions for calibrating
where such specifications are available. Other grades may be
selective-ion meters with a direct reading of concentration
used, provided it is first ascertained that the reagent is of
capabilities. For pH meters, generate a calibration curve by
sufficiently high purity to permit its use without lessening the
creating a calibration curve on semilogrithmic graph paper or
accuracy of the determination.
by creating a plot of mV potential versus log(10) concentra-
tion. Note that volume corrections are incorporated into the
8.2 Purity of Water—Unless otherwise indicated, reference
calibration,sothatsamplesanalyzedaccordingtoSection11of
towatershallbeunderstoodtomeanreagentwaterconforming
this test method can be read directly.
to Specification D1193,Type I. Other reagent water types may
be used, provided it is first ascertained that the water is of
11. Procedure
sufficiently high purity to permit its use without adversely
affecting the bias and precision of the test method. Type II
11.1 To any sample containing sulfide or cyanide ion, add
water was specified at the time of round robin testing of this
0.1 mL nickel sulfate solution to 100 mL sample.
test method.
NOTE 1—This concentration of nickel sulfate will react with 58 mg/L
sulfide and 117 mg/L cyanide.
11.2 Transfer100mLsampletoa150mLbeakerandadd2
Reagent Chemicals, American Chemical Society Specifications, American
mLionic strength adjustor. Stir thoroughly for 1 min using the
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory magnetic mixer.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
11.3 Immerse the electrodes in the sample-ISAmixture and
and National Formulary,U.S.PharmaceuticalConvention,Inc.(USPC),Rockville,
MD. wait 2 min for the potential to stabilize. Record the value.
´1
D1246 − 16 (2021)
11.4 Read bromide concentration of the sample, in mg/L, 13. Quality Control
directly from the meter. Note that volume corrections are
13.1 In order to be certain that analytical values obtained
incorporated into the calibration.
using these test methods are valid and accurate within the
confidencelimitsofthetest,thefollowingQCproceduresmust
12. Precision and Bias
be followed when analyzing bromide.
12.1 Precision—The overall and single-operator precision
13.2 Calibration and Calibration Verification:
of this test method may be expressed as follows:
13.2.1 Analyze at least three working standards containing
12.1.1 For Reagent Water:
concentrations of bromide that bracket the expected sample
S 50.077X11.10, coefficientofcorrelation 51.0
T concentration prior to analysis of samples to calibrate the
S 50.067X10.79, coefficientofcorrelation 51.0
O
instrument.
13.2.2 Verifyinstrumentcalibrationafterstandardizationby
12.1.2 For Water Matrices:
analyzing a standard at the concentration of one of the
S 50.064X10.84, coefficientofcorrelation 51.0
T
calibration standards. Alternately, the concentration of a mid-
S 50.049X10.09, coefficientofcorrelation 51.0
O
range standard should fall within 6 15 % of the known
where:
concentration.
13.2.3 If calibration cannot be verified, recalibrate the
S = overall precision, mg/L,
T
instrument.
S = single-operator precision, mg/L, and
O
X = concentration of bromide determined.
13.3 Initial Demonstration of Laboratory Capability:
12.2 The selected water matrices included natur
...