1、Designation: D3866 12D3866 18Standard Test Methods forSilver in Water1This standard is issued under the fixed designation D3866; 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 ind
2、icates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 These test methods cover the atomic absorption determination of silver in water. Section 34 on Quality Control pertains tothese test methods. Three test method
3、s are given as follows:ConcentrationRange SectionsTest Method AAtomic Absorp-tionChelation-ExtractionA1 to 10 g/L 7 to 15Test Method AAtomic AbsorptionChelation-ExtractionA1 to 10 g/L 7 15Test Method BAtomic Absorp-tionDirect0.1 to 10 mg/L 16 to 24Test Method BAtomic AbsorptionDirect 0.1 to 10 mg/L
4、16 24Test Method CAtomic Absorp-tionGraphite Furnace1 to 25 g/L 25 to 33Test Method CAtomic AbsorptionGraphiteFurnace1 to 25 g/L 25 33A SimilartothatinBrown,E.,Skougstad,M.W.,andFishman,M.J.,“MethodsforCollectionandAnalysisofWaterSamplesforDissolvedMineralsandGases,” Techniquesof Water-Resources Inv
5、estigations of the U.S. Geological Survey, Book 5, Chapter A1, 1970, p. 46.1.2 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values statedgivenin each system are mathematical conversions and may not be exact equivalents; therefore, each syste
6、m shall be used independentlyof the other.parentheses are mathematical conversion to inch-pound units that are provided for information only and are notconsidered standard.1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibil
7、ityof the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine theapplicability of regulatory limitations prior to use. Specific precautionary statements are given in Note 411.5, Note 611.12.1, Note1113.8, and Note 1522.1.1.4 This inte
8、rnational standard was developed in accordance with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Com
9、mittee.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD1976 Test Method for Elements in Water by Inductively-Coupled Argon Plasma Atomic Emission SpectroscopyD2777 Practice for Determination of Precision and Bias of Applicable Test
10、Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD3919 Practice for Measuring Trace Elements in Water by Graphite Furnace Atomic Absorption SpectrophotometryD4691 Practice for Measuring Elements in Water by Flame Atomic Absorption Spectrophotometry1 These test
11、methods are under the jurisdiction of ASTM Committee D19 on Water and are the direct responsibility of Subcommittee D19.05 on Inorganic Constituentsin Water.Current edition approved Sept. 1, 2012Feb. 1, 2018. Published September 2012March 2018. Originally approved in 1979. Last previous edition appr
12、oved in 20072012as D3866 07.D3866 12. DOI: 10.1520/D386612.10.1520/D3866-18.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on th
13、e ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users co
14、nsult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocke
15、n, PA 19428-2959. United States1D4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic ConstituentsD5673 Test Method for Elements in Water by Inductively Coupled PlasmaMass SpectrometryD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Qu
16、ality Control Specifications for Standard Test Methods for Water Analysis3. Terminology3.1 Definition of Term Specific to These Test Methods:3.1.1 laboratory control sample, na solution with a certified concentration of silver.3.1.2 total recoverable silver, nan arbitrary analytical term relating to
17、 forms of silver that are determinable by the digestionmethod that is included in the procedures.3.1 DefinitionsDefinitions: For definition of terms used in these test methods, refer to Terminology D1129.3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.3.2 Definitions
18、 of Terms Specific to This Standard:3.2.1 laboratory control sample, na solution with a certified concentration of silver.3.2.2 total recoverable silver, na descriptive term relating to forms of silver that are determinable by the digestion method thatis included in these test methods.4. Significanc
19、e and Use4.1 The principal adverse effect of silver in the body is cosmetic. It causes argyria, a permanent, blue-gray discoloration of theskin, eyes, and mucous membranes.4.2 Relatively small quantities of silver are bactericidal or bacteriostatic and find limited use in both disinfection of swimmi
20、ngpool waters and point-of-use water filters.4.3 ICP-MS or ICP-AES may also be appropriate but at a higher instrument cost. See Test Methods D5673 and D1976.5. Purity of Reagents5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall
21、 conformto the specifications of the Committee on Analytical Reagents of the American Chemical Society, when such specifications areavailable.3 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its usewithout lessening the accuracy o
22、f the determination.5.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water conforming toSpecification D1193, Type I, II, or III water. Type I is preferred and more commonly used. Other reagent water types may be usedprovided it is first ascertain
23、ed that the water is of sufficiently high purity to permit its use without adversely affecting the precisionand bias of the test method. Type II water was specified at the time of round robin testing of these test methods.NOTE 1The user must ensure the type of reagent water chosen is sufficiently fr
24、ee of interferences. The water should be analyzed using thethese testmethod.methods.6. Sampling6.1 Collect the sample in accordance with Practices D3370. The holding time for the samples may be calculated in accordancewith Practice D4841.6.2 Preserve samples for Test Method A with HNO3 (sp gr 1.42)
25、to a pH of 2 or less immediately at the time of collection;normally about 2 mL/L is required. If only dissolved silver is to be determined, filter (11.13) the sample at time of collectionthrough a 0.45-m membrane filter before acidification.NOTE 2Alternatively, the pH may be adjusted in the laborato
26、ry if the sample is returned within 14 days. within 14 days of collection. This couldreduce hazards of working with acids in the field when appropriate.6.3 Do not preserve samples for Test Methods B and C at the time of collection. If only dissolved silver is to be determined,filter the sample throu
27、gh a 0.45-m membrane filter at time of collection. Add cyanogen iodide (CNI) solution to the samples inthe laboratory prior to analysis. For total recoverable silver it is preferable to add the cyanogen iodide to the entire sample to avoida nonhomogeneous solution; therefore, it is advisable to coll
28、ect a discrete sample for silver.3 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.
29、K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.D3866 182TEST METHOD AATOMIC ABSORPTIONCHELATION EXTRACTION7. Scope7.1 This test method4 covers the determination of dissolved and total recoverable silver in most water and wastew
30、aters.7.2 This test method is applicable in the range from 1 to 10 g/Lof silver. The range may be extended by dilution of the originalsample.7.3 This test method has been used successfully with reagent water, natural surface water, and drinking water. The informationon precision and bias may not app
31、ly to other waters. It is the users responsibility to ensure the validity of this test method forwaters of untested matrices.7. Scope7.1 This test method4 covers the determination of dissolved and total recoverable silver in most water and wastewaters.7.2 This test method is applicable in the range
32、from 1 to 10 g/Lof silver. The range may be extended by dilution of the originalsample.7.3 This test method has been used successfully with reagent water, natural surface water, and drinking water. The informationon precision and bias may not apply to other waters. It is the users responsibility to
33、ensure the validity of this test method forwaters of untested matrices.8. Summary of Test Method8.1 Silver is determined by atomic absorption spectrometry. The element, either dissolved or total recoverable, is chelated withammonium pyrrolidine dithiocarbamate (APDC) and extracted with methyl isobut
34、yl ketone (MIBK). The extract is aspirated intoan air-acetylene flame of the spectrophotometer. Total recoverable silver is determined following nitric acid digestion and filtration.9. Interferences9.1 Concentrations of iron greater than 25 mg/L interfere by suppressing the silver absorption.10. App
35、aratus10.1 Atomic Absorption Spectrophotometer for use at 328.1 nm. A general guide for the use of flame atomic absorptionapplications is given in Practice D4691.NOTE 3The manufacturers instructions should be followed for instrumental parameters. Wave-lengths other than 328.1 nm may be used if they
36、havebeen determined to be equally suitable.10.2 Silver Hollow-Cathode Lamp.10.3 Pressure-Reducing ValvesThe supplies of fuel and oxidant shall be maintained at pressures somewhat higher than thecontrolled operating pressure of the instrument by suitable pressure-reducing valves.11. Reagents and Mate
37、rials11.1 Ammonium Pyrrolidine Dithiocarbamate (APDC) Solution(1 g/100 mL)Dissolve 1.0 g of APDC in 100 mL of water.Prepare fresh before each use.11.2 Bromophenol Blue Indicator Solution (0.1 g/100 mL)Dissolve 0.1 g of bromophenol blue in 100 mL of 50 % ethanolor isopropanol.11.3 Hydrochloric Acid (
38、sp gr 1.19)Concentrated hydrochloric acid (HCl).11.4 Hydrochloric Acid (1 + 49)Add 1 volume of hydrochloric acid (HCl, sp gr 1.19) to 49 volumes of water.11.5 Methyl Isobutyl Ketone (MIBK).NOTE 4Warning: Avoid inhalation and conduct all manipulation in a well-ventilated hood.(WarningAvoid inhalation
39、 and conduct allmanipulation in a well-ventilated hood.)11.6 Nitric Acid (sp gr 1.42)Concentrated nitric acid (HNO3).NOTE 4If a high reagent blank is obtained, distill the HNO3 or use a spectrograde acid.11.7 Silver Solution, Stock (1.0 mL = 100 g Ag)Crush approximately 2 g of silver nitrate (AgNO3)
40、 crystals and dry toconstant mass at 40C. Dissolve 0.1575 g ofAgNO3 in water containing 5 mL of concentrated HNO3 and dilute to 1000 mL. Storein an amber glass bottle. A purchased silver stock solution of appropriate known purity is also acceptable.4 Similar to that in Brown, E., Skougstad, M. W., a
41、nd Fishman, M. J., “Methods for Collection and Analysis of Water Samples for Dissolved Minerals and Gases,”Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1, 1970, p. 46.D3866 18311.8 Silver Solution, Intermediate (1.0 mL = 1.00 g Ag)Dilute 10.0 mL of sil
42、ver stock solution and 5 mL of concentratedHNO3 to 1000 mL with water. Store in an amber glass bottle. A purchased stock solution of adequate purity is also acceptable.11.9 Silver Solution, Standard (1.0 mL = 0.100 gAg)Dilute 100 mLof silver intermediate solution and 5 mLof concentratedHNO3 to 1000
43、mL with water. Prepare fresh before use.11.10 Sodium Hydroxide Solution (100 g/L)Dissolve 100 g of NaOH in water and dilute to 1000 mL.11.11 Oxidant:11.11.1 Air, that has been passed through a suitable filter to remove oil, water, and other foreign substances is the usual oxidant.11.12 Fuel:11.12.1
44、Acetylene-Standard, commercially available acetylene is the usual fuel.Acetone, always present in acetylene cylinders,can affect analytical results.The cylinder should be replaced at 345 kPa (50 psi). (Warning“Purified” grade acetylene containinga special proprietary solvent rather than acetone must
45、 not be used with poly(vinyl chloride) tubing as weakening of the tubing wallscauses a potentially hazardous situation.Warning)see Note 6.)NOTE 6Warning: “Purified” grade acetylene containing a special proprietary solvent rather than acetone must not be used with poly(vinyl chloride)tubing as weaken
46、ing of the tubing walls causes a potentially hazardous situation.11.13 Filter PaperPurchase suitable filter paper. Typically the filter papers have a pore size of 0.45-m membrane. Materialsuch as fine-textured, acid-washed, ashless paper, or glass fiber paper are acceptable. The user must first asce
47、rtain that the filterpaper is of sufficient purity to use without adversely affecting the bias and precision of the test method.12. Standardization12.1 An effective way to clean all glassware to be used for preparation of standard solutions or in the digestion step, or both,is by soaking the glasswa
48、re for 2 h first with HNO3 (1 + 1) and then rinsing with reagent water.12.2 Prepare a blank and sufficient standards containing from 0.0 to 1.0 g of silver by diluting 0.0 to 10.0-mLportions of silverstandard solution to approximately 100 mL.12.3 To determine total recoverable silver, use 125-mL bea
49、kers or flasks, add 5.0 mL of HNO3 (sp gr 1.42), and proceed asdirected in 13.3 through 13.10. To determine dissolved silver use 200-mLvolumetric flasks and proceed as directed in 13.5 through13.10. Treat the blank and each standard in the same manner as the samples.12.4 Construct Read directly in concentration if this capability is provided with the instrument or measure the absorbance ofthe standards or construct an analytical curve by plotting the absorbances of standards versus micrograms of silver. Alternati
