1、Designation: D858 17Standard Test Methods forManganese in Water1This standard is issued under the fixed designation D858; 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 indicates
2、the year of last reapproval. Asuperscript 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.1. Scope*1.1 These test methods cover the atomic absorption deter-mination of dissolved and t
3、otal recoverable manganese inwater and certain wastewaters. Section 34 on Quality Controlpertains to these test methods. Three test methods are given asfollows:Test Method Concentration Range SectionsAAtomic Absorption,Direct0.1 to 5 mg/L 7 to 15BAtomic Absorption,Chelation-Extraction10 to 500 g/L 1
4、6 to 24CAtomic Absorption,Graphite Furnace5to50g/L 25 to 331.2 Test Methods A, B, and C were used successfully onreagent grade and natural waters. Other matrices used in thestudy were brine (Test Method B), effluent from a woodtreatment plant, and condensate from a medium BTU coalgasification proces
5、s (Test Method C). It is the users responsi-bility to ensure the validity of a test method for waters ofuntested matrices.1.3 The values stated in SI units are to be regarded asstandard. The values given in parentheses are mathematicalconversion to inch-pound units that are provided for informa-tion
6、 only and are not considered standard.1.4 This standard does not purport to address all of thesafety concerns, 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 li
7、mitations prior to use. For specific hazardstatements, see 11.7, 20.2, 20.9, and 22.11.1.5 Former Test Method A (Colorimetric) was discontinued.For historical information, see Appendix X1.1.6 This international standard was developed in accor-dance with internationally recognized principles on stand
8、ard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1066 Practice for Sampling SteamD1068 Test Me
9、thods for Iron in WaterD1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD1687 Test Methods for Chromium in WaterD1688 Test Methods for Copper in WaterD1691 Test Methods for Zinc in WaterD1886 Test Methods for Nickel in WaterD1976 Test Method for Elements in Water by Inductivel
10、y-Coupled Argon Plasma Atomic Emission SpectroscopyD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD3557 Test Methods for Cadmium in WaterD3558 Test Methods for Cobalt in WaterD3559 Test
11、Methods for Lead in WaterD3919 Practice for Measuring Trace Elements in Water byGraphite Furnace Atomic Absorption SpectrophotometryD4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD5673 Test Method for Elements in Water by InductivelyCouple
12、d PlasmaMass SpectrometryD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this standard, refer toTerminology D1129.1These test methods
13、are under the jurisdiction of ASTM Committee D19 onWater and are the direct responsibility of Subcommittee D19.05 on InorganicConstituents in Water.Current edition approved June 1, 2017. Published June 2017. Originallyapproved in 1945. Last previous edition approved in 2012 as D858 12. DOI:10.1520/D
14、0858-17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.*A Summary of Changes section appears at the end of t
15、his standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopm
16、ent of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.13.2 Definitions of Terms Specific to This Standard:3.2.1 continuing calibration blank, na solution contain-ing no analytes (of interest) which is used to ver
17、ify blankresponse and freedom from carryover.3.2.2 continuing calibration verification, na solution (orset of solutions) of known concentration used to verify freedomfrom excessive instrumental drift; the concentration is to coverthe range of calibration curve.3.2.3 total recoverable manganese, na d
18、escriptive termrelating to the forms of manganese recovered in the aciddigestion procedure specified in this test standard.4. Significance and Use4.1 Elemental constituents in potable water, receiving water,and wastewater need to be identified for support of effectivepollution control programs. Test
19、 Methods A, B, and C providethe techniques necessary to make such measurements.4.2 Although inhaled manganese dusts have been reportedto be toxic to humans, manganese normally is ingested as atrace nutrient in both food and water. Because it is consideredto be relatively nontoxic to man, as well as
20、aquatic life, a limitof 50 g/L has been established in the EPANational SecondaryDrinking Water Regulations. This limit is based primarily onits ability to stain laundry and produce objectionable tastes inbeverages.4.3 Manganese does not occur naturally as a metal but isfound in various salts and min
21、erals, frequently in associationwith iron compounds. Manganese is not mined in the UnitedStates except when manganese is contained in iron ores that aredeliberately used to form ferro-manganese alloys. Manganesesalts are used as fertilizer additives and are commonly found insurface and ground waters
22、.4.4 ICP-MS or ICP-AES may also be appropriate but at ahigher 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 shallconform to the specifications of the Committee
23、 on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.3Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.5.2 Purity of WaterUnless oth
24、erwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D1193, Type I. Other reagent water types maybe used, provided it is first ascertained that the water is ofsufficiently high purity to permit its use without lessening thebias and precision of th
25、e determination. Type II water wasspecified at the time of round-robin testing of this test method.6. Sampling6.1 Collect the sample in accordance with Practice D1066,or Practices D3370 as applicable.6.2 Samples shall be preserved with HNO3(sp gr 1.42),normally about 2 mL/L, to a pH of 2 or less imm
26、ediately at thetime of collection. If only dissolved manganese is to bedetermined, the sample shall be filtered through a 0.45-m (No.325) membrane filter (11.8) before acidification. The holdingtime for samples may be calculated in accordance with PracticeD4841.NOTE 1Alternatively, the pH may be adj
27、usted in the laboratory within14 days of collection. However, acid must be added at least 24 hoursbefore analysis to dissolve any metals that adsorb to the container walls.This could reduce hazards of working with acids in the field whenappropriate.TEST METHOD AATOMIC ABSORPTION, DIRECT7. Scope7.1 T
28、his test method covers the determination of dissolvedand total recoverable manganese and has been used success-fully with reagent and natural water. It is the analystsresponsibility to ensure the validity of the method in aparticular matrix.7.2 This test method is applicable in the range from 0.1 to
29、 5mg/L of manganese. The range may be extended to concentra-tions greater than 5 mg/L by dilution of the sample.8. Summary of Test Method8.1 Manganese is determined by atomic absorption spectro-photometry. Dissolved manganese is determined by atomizinga filtered sample directly with no pretreatment.
30、 Total recover-able manganese in the sample is determined in a portion of thefiltrate obtained after a hydrochloric-nitric acid digestion of thesample. The same digestion procedure is used to determinetotal recoverable cadmium (Test Methods D3557), chromium(Test Methods D1687), cobalt (Test Methods
31、D3558), copper(Test Methods D1688), iron (Test Methods D1068), lead (TestMethods D3559), nickel (Test Methods D1886), and zinc (TestMethods D1691).9. Interferences9.1 Magnesium in concentrations greater than 100 mg/Lmay interfere.9.2 No interference from SiO2in concentrations up to 100mg/L has been
32、observed.9.3 Background correction or chelation-extraction (see TestMethod B) to remove interferences may be necessary todetermine low levels of manganese in some waters.NOTE 2Instrument manufacturers instructions for use of the specificcorrection technique should be followed.10. Apparatus10.1 Atomi
33、c Absorption Spectrophotometer, for use at 279.5nm.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Po
34、ole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D858 172NOTE 3The manufacturers instructions should be followed for allinstrumental parameters. A wavelength other than 279.5 nm may be usedif it has been determined
35、to be equally suitable.10.1.1 Manganese Light SourceMultielement lamps, elec-trodeless discharge lamps, or hollow-cathode lamps have beenfound satisfactory.10.2 Pressure-Reducing ValvesThe supplies of fuel andoxidant shall be maintained at pressures somewhat higher thanthe controlled operating press
36、ure of the instrument by suitablevalves.11. Reagents and Materials11.1 Hydrochloric Acid (sp gr 1.19)Concentrated hydro-chloric acid (HCl).NOTE 4If a high reagent blank is obtained, distill the HCl or usespectrograde acid. (WarningWhen HCl is distilled, an azeotropicmixture is obtained (approximatel
37、y 6 NHCl.) Therefore, whenever con-centrated HCl is specified in the preparation of a reagent or in theprocedure, use double the amount specified if distilled acid is used.)11.2 Manganese Solution, Stock (1.0 mL = 1.0 mg Mn)Dissolve 3.076 g of manganous sulfate monohydrate(MnSO4H2O) in a mixture of
38、10 mL of HNO3(sp gr 1.42) and100 mL of water. Dilute to 1 L with water. A purchasedmanganese stock solution of appropriate known purity is alsoacceptable.11.3 Manganese Solution, Standard (1.0 mL = 0.1 mgMn)Dilute 100.0 mLof manganese stock solution to 1 Lwithwater.11.4 Nitric Acid (sp gr 1.42)Conce
39、ntrated nitric acid(HNO3).NOTE 5If a high reagent blank is obtained, distill the HNO3or usespectrograde acid.11.5 Nitric Acid (1 + 499)Add 1 volume of HNO3(sp gr1.42) to 499 volumes of water.11.6 Oxidant:11.6.1 Air, which has been passed through a suitable filter toremove oil, water, and other forei
40、gn substances, is the usualoxidant.11.7 Fuel: Acetylenestandard, commercially availableacetylene is the usual fuel. Acetone, always present in acety-lene cylinders, can affect analytical results. The cylinder shouldbe replaced at 345 kPa (50 psi). (Warning“Purified” gradeacetylene containing a speci
41、al proprietary solvent other thanacetone should not be used with poly(vinyl chloride) tubing asweakening of the tubing walls can cause a potentially hazard-ous situation.)11.8 Filter PaperPurchase suitable filter paper. Typicallythe filter papers have a pore size of 0.45-m membrane.Material such as
42、fine-textured, acid-washed, ashless paper, orglass fiber paper are acceptable. The user must first ascertainthat the filter paper is of sufficient purity to use withoutadversely affecting the bias and precision of the test method.12. Standardization12.1 Prepare 100 mL each of a blank and at least fo
43、urstandard solutions to bracket the expected manganese concen-tration range of the samples to be analyzed by diluting themanganese standard solution with HNO3(1 + 499). Prepare thestandards each time the test is to be performed, and select so asto give zero, middle, and maximum points for an analyti
44、calcurve.NOTE 6It is recommended that the blank (zero standard) be comparedwith reagent grade water to avoid the possibility of using a high blank.12.2 When determining total recoverable manganese add0.5 mL of HNO3(sp gr 1.42) and proceed as directed in 13.3.When determining dissolved manganese proc
45、eed with 13.6.12.3 Aspirate the blank and standards and record the instru-ment readings. Aspirate HNO3(1 + 499) between each stan-dard.12.4 Read directly in concentration if this capability isprovided with the instrument or measure the absorbance of thestandards and prepare an analytical curve by pl
46、otting theabsorbance of each standard versus its concentration on lineargraph paper.13. Procedure13.1 An effective way to clean all glassware to be used forpreparation of standard solutions or in the digestion step, orboth, is by soaking the glassware overnight with HNO3 (1 + 1)and then rinse with r
47、eagent.13.2 Measure 100.0 mL of a well-mixed acidified sampleinto a 125-mL beaker or flask.NOTE 7If only dissolved manganese is to be determined, start with13.6.13.3 Add 5 mL of HCl (sp gr 1.19) to each sample.13.4 Heat the samples (between 65C to 95C) on a steambath or hot plate below boiling in a
48、well-ventilated hood untilthe volume has been reduced to 15 or 20 mL, making certainthat the samples do not boil.NOTE 8For brines and samples with high levels of suspended matter,the amount of reduction in volume is left to the discretion of the analyst.NOTE 9Many laboratories have found block diges
49、tion systems auseful way to digest samples for trace metals analysis. Systems typicallyconsist of either a metal or graphite block with wells to hold digestiontubes. The block temperature controller must be able to maintain unifor-mity of temperature across all positions of the block. The digestion blockmust be capable of maintaining a temperature between 65C to 95C. Fortrace metals analysis, the digestion tubes should be constructed ofpolypropylene and have a volume accuracy of at least 0.5 %. All lots oftubes should come with a certificat
