1、Designation: D 1246 05Standard Test Method forBromide Ion in Water1This standard is issued under the fixed designation D 1246; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indic
2、ates the year of last reapproval. Asuperscript epsilon (e) 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*1.1 This test method is applicable to the measurement ofbromide ion in water, groun
3、d water, and drinking water.1.2 Samples containing 0.5 mg/L to 1000 mg/L of bromidemay be analyzed by this test method. The concentration rangemay be extended by the dilution of an appropriate aliquot.1.3 The precision and bias statements were determined onnatural and ground waters. It is the respon
4、sibility of the analystto assure the validity of this test method for untested matrices.1.4 A titrimetric and two colorimetric test methods foriodide and bromide were discontinued. Refer to Appendix X1for historical information.1.5 This standard does not purport to address all of thesafety concerns,
5、 if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1066 Practice for Sampling SteamD 1129 Ter
6、minology Relating to WaterD 1193 Specification for Reagent WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed Con-duitsD 4127 Terminology Used with Ion-Selective ElectrodesD 5810 Guide for Spiking
7、 into Aqueous SamplesD 5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminologies D 1129 and D 4127.4. Summary of Test Method4.1 Bromide ion is measured pote
8、ntiometrically using abromide ion-selective electrode in conjunction with a single-junction, sleeve-type reference electrode. Potentials are read ona pH meter having an expanded millivolt scale capable of beingread to the nearest 0.1 mV, or a selective ion meter having adirect concentration scale fo
9、r bromide. For less precise work, apH meter having a millivolt scale capable of being read to thenearest 1.0 mV is adequate, however, no supporting data areavailable.4.2 The electrodes are calibrated in known bromide solu-tions and the concentrations of unknowns are determined insolutions with the s
10、ame background. In most cases, addition ofan ionic strength adjustor to both standards and samples issufficient to maintain constant background ionic strength. Forsamples above 0.1 M in ionic strength, prepare standardsolutions similar to the sample composition.5. Significance and Use5.1 By analysis
11、 for bromide in water, wastewater, andbrackish waters, it is possible to evaluate the origin of thewater, its potential as a source of bromide, and its conditionwith regard to pollution.6. Interferences6.1 Strongly reducing solutions and solutions containingions which form insoluble silver salts may
12、 coat the electrodemembrane. These may be removed by polishing the membranesurface. Sulfide ion and cyanide ion both poison the electrode,and should be removed (see Section 11).6.2 Halide ions form complexes with some metals. Sincethe electrode responds only to free bromide ions, the presenceof any
13、complexing agents lowers the measured concentrations.Concentrations of free metal ions causing a 10 % error of abromide concentration of 8.1 mg/L are bismuth+3, 80 mg/L;1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.05 o
14、n Inorganic Constituentsin Water.Current edition approved Feb. 1, 2005. Published February 2005. Originallyapproved in 1952. Last previous edition approved in 1999 as D 1246 95 (1999).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm
15、.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1*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 Sta
16、tes.cadmium+2, 100 mg/L; lead+2, 1600 mg/L; tin+2, 2400 mg/L;and thallium+3, 4 mg/L.6.3 Chloride ion and hydroxide ion do not interfere whenpresent in the concentrations of up to 400 and 30 000 times thebromide concentration, respectively. There will be no interfer-ence from ammonia when present in
17、concentrations twice thatof bromide, nor from thiosulfate 20 times as concentrated asbromide. Iodide is an interference at a concentration ratio aslow as 2 3 104. Mercury should be absent from samples.7. Apparatus7.1 pH Meter, capable of reading to 0.1 mV, or a selective-ion meter.7.2 Bromide Ion-Se
18、lective Electrode.7.3 Sleeve-Type Single-Junction Reference Electrode, filledwith manufacturers filling solution.7.4 Mixer, magnetic, with a TFE fluorocarbon-coated stir-ring bar.7.5 Laboratory Glassware.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless other
19、wise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high pur
20、ity to permit its use without lessening theaccuracy of the determination.8.2 Purity of Water Unless otherwise indicated, referenceto water shall be understood to mean reagent water conformingto Specification D 1193, Type I. Other reagent water types maybe used, provided it is first ascertained that
21、the water is ofsufficiently high purity to permit its use without adverselyaffecting the bias and precision of the test method. Type IIwater was specified at the time of round robin testing of thistest method.8.3 Ionic Strength Adjustor (42.5 g/100 mL NaNO3)In a100-mL volumetric flask, dissolve 42.5
22、 g of sodium nitrate(NaNO3) in water and dilute to volume.8.4 Nickel Sulfate Solution, 1 MIn a 100 mL volumetricflask dissolve 26.3 g of nickel sulfate hexahydrate (NiSO46H2O) in water and dilute to volume.8.5 Sodium Bromide Standard Solution, 1000 mg/LIna1L volumetric flask dissolve 1.288 g dried s
23、odium bromide inwater and dilute to volume.8.6 Sodium Bromide Standard Solutions, (100, 10, and 1mg/L)Dilute 1 volume of the 1000 mg/L bromide standardwith 9 volumes of water to prepare the 100 mg/L standard. Byfurther 1+9 serial dilutions, prepare the 10 and 1 mg/Lstandards.9. Sampling9.1 Collect t
24、he samples in accordance with Practice D 1066and Practices D 3370, as applicable.10. Calibration and Standardization10.1 To 100 mL of the 1, 10, 100, and 1000 mg/L NaBrstandards add 2 mL of the ionic strength adjustor (ISA). If anysamples require treatment for interferences, prepare standardswith th
25、e same background.10.2 Connect and fill electrodes in accordance with manu-facturers instructions.10.3 Transfer the 1 mg/L standard-ISAmixture to a 150 mLbeaker and stir gently using the magnetic mixer. Immerse theelectrodes in the solution and wait 2 min for the potential tostabilize. Record the va
26、lue.10.4 Rinse electrodes thoroughly and repeat for the 10, 100,and 1000 mg/L standard-ISA mixtures. Wait 2 min and recordthe potential.10.5 The calibration curve is generated by plotting onsemilogarithmic graph paper, the potential observed versus theconcentration of the standard used. Note that vo
27、lume correc-tions are incorporated into the calibration, so that samplesanalyzed according to Section 11 of this test method can beread directly.11. Procedure11.1 To any sample containing sulfide or cyanide ion, add0.1 mL nickel sulfate solution to 100 mL sample.NOTE 1This concentration of nickel su
28、lfate will react with 58 mg/Lsulfide and 117 mg/L cyanide.11.2 Transfer 100 mL sample to a 150 mL beaker and add 2mL ionic strength adjustor. Stir thoroughly for 1 min using themagnetic mixer.11.3 Immerse the electrodes in the sample-ISA mixture andwait 2 min for the potential to stabilize. Record t
29、he value.11.4 Read bromide concentration of the sample, in mg/L,directly from the calibration curve. Note that volume correc-tions are incorporated into the calibration.12. Precision and Bias412.1 PrecisionThe overall and single-operator precisionof this test method may be expressed as follows:12.1.
30、1 For Reagent Water:ST5 0.077X 1 1.10, coefficient of correlation 5 1.0SO5 0.067X 1 0.79, coefficient of correlation 5 1.012.1.2 For Water Matrices:ST5 0.064X 1 0.84, coefficient of correlation 5 1.0SO5 0.049X 1 0.09, coefficient of correlation 5 1.0where:ST= overall precision, mg/L,SO= single-opera
31、tor precision, mg/L, andX = concentration of bromide determined.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals,
32、 BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D191078.D 1246 05212.2 The sele
33、cted water matrices included natural waters,ground waters, and tap water. These data on precision and biasmay not apply to waters of other matrices.12.3 BiasRecoveries of known amounts of bromide fromreagent water and selected water matrices were as shown inTable 1.12.4 This information is derived f
34、rom round-robin testing,in which five laboratories, including eight operators, partici-pated. Of the eight sets of data ranked, as described in PracticeD 2777, none was rejected. One operator submitted reagentwater data only. One outlier data point within each set was alsorejected. Four sample level
35、s were run on three days and blankswere obtained for the water used.12.5 This section on precision and bias conforms to PracticeD 2777 77, which was in place at the time of collaborativetesting. Under the allowances made in 1.4 of PracticeD 2777 98, these precision and bias data do meet existingrequ
36、irements for interlaboratory studies of Committee D19 testmethods.13. Quality Control13.1 In order to be certain that analytical values obtainedusing these test methods are valid and accurate within theconfidence limits of the test, the following QC procedures mustbe followed when analyzing bromide.
37、13.2 Calibration and Calibration Verification13.2.1 Analyze at least three working standards containingconcentrations of bromide that bracket the expected sampleconcentration prior to analysis of samples to calibrate theinstrument.13.2.2 Verify instrument calibration after standardization byanalyzin
38、g a standard at the concentration of one of thecalibration standards. Alternately, the concentration of a mid-range standard should fall within 6 15 % of the knownconcentration.13.2.3 If calibration cannot be verified, recalibrate theinstrument.13.3 Initial Demonstration of Laboratory Capability13.3
39、.1 If a laboratory has not performed the test before, or ifthere has been a major change in the measurement system, forexample, new analyst, new instrument, and so forth, a precisionand bias study must be performed to demonstrate laboratorycapability.13.3.2 Analyze seven replicates of a standard sol
40、utionprepared from an Independent Reference Material containing amid-range concentration of bromide. The matrix and chemistryof the solution should be equivalent to the solution used in thecollaborative study. Each replicate must be taken through thecomplete analytical test method including any samp
41、le preser-vation and pretreatment steps. The replicates may be inter-spersed with samples.13.3.3 Calculate the mean and standard deviation of theseven values and compare to the acceptable ranges of bias insection 12.1. This study should be repeated until the recoveriesare within the limits given in
42、section 12.1. If a concentrationother than the recommended concentration is used, refer toPractice D5847 for information on applying the F test and t testin evaluating the acceptability of the mean and standarddeviation.13.4 Laboratory Control Sample (LCS)13.4.1 To ensure that the test method is in
43、control, analyzea LCS containing a mid-range concentration of bromide witheach batch or 10 samples. If large numbers of samples areanalyzed in the batch, analyze the LCS after every 10 samples.The LCS must be taken through all of the steps of the analyticalmethod including sample preservation and pr
44、etreatment. Theresult obtained for the LCS shall fall within 6 15%oftheknown concentration.13.4.2 If the result is not within these limits, analysis ofsamples is halted until the problem is corrected, and either allthe samples in the batch must be reanalyzed, or the results mustbe qualified with an
45、indication that they do not fall within theperformance criteria of the test method.13.5 Method Blank13.5.1 Analyze a reagent water test blank with each batch.The concentration of bromide found in the blank should be lessthan 0.5 times the lowest calibration standard. If the concen-tration of bromide
46、 is found above this level, analysis ofsamples is halted until the contamination is eliminated, and ablank shows no contamination at or above this level, or theresults must be qualified with an indication that they do not fallwithin the performance criteria of the test method.13.6 Matrix Spike (MS)1
47、3.6.1 To check for interferences in the specific matrixbeing tested, perform a MS on at least one sample from eachbatch by spiking an aliquot of the sample with a knownconcentration of bromide and taking it through the analyticalmethod.13.6.2 The spike concentration plus the background concen-tratio
48、n of bromide must not exceed the high calibrationstandard. The spike must produce a concentration in the spikedsample that is 2 to 5 times the bromide concentration in theunspiked sample, or 10 to 50 times the detection limit of thetest method, whichever is greater.13.6.3 Calculate the percent recov
49、ery of the spike (P) usingthe following formula:P 5 100 AVs1 V! BVs# / CVwhere:A = analyte concentration (mg/L) in spiked sample,TABLE 1 Recoveries of Known Amounts of Bromide fromReagent Water and Selected Water MatricesAmountadded,mg/LAmountfound,mg/L6Bias,%StatisticallySignificant(95 % Con-fidenceLevel)Reagent 0.65 0.77 + 18.5 yesWater 1.00 1.19 + 19.0 no92.7 96.4 + 3.99 no864 854 1.16 noWater 0.65 0.80 + 23.1 yes1.00 1.21 + 21.5 yes92.7 95.6 + 3.2 no864 836 3.3 yesD 1246 053B = analyte concentration (mg/L) in unspiked sample,C = concentration (mg/L) o
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