1、Designation: D858 12Standard 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 Department of Defense.1. Scope*1.1 These test methods cover the atomic absorption deter-mination of dissolved and total
3、recoverable manganese inwater and certain wastewaters. Three test methods are given asfollows:Test Method Concentration Range SectionsAAtomic Absorption, Direct 0.1 to 5 mg/L 7 to 15BAtomic Absorption,Chelation-Extraction10 to 500 g/L 16 to 24CAtomic Absorption, GraphiteFurnace5to50g/L 25to331.2 Tes
4、t 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 process (Test Method C). It is the users responsi-bility to ensure the v
5、alidity of a test method for waters ofuntested matrices.1.3 The values stated in either SI units or inch-pound unitsare to be regarded separately as standard. The values stated ineach system are mathematical conversions and may not beexact equivalents; therefore, each system shall be used inde-pende
6、ntly of the other.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 limitations prior to u
7、se. For specific hazardstatements, see 11.7, 20.2, 20.9, and 22.10.1.5 Former Test Method A (Colorimetric) was discontinued.For historical information, see Appendix X1.2. Referenced Documents2.1 ASTM Standards:2D1066 Practice for Sampling SteamD1068 Test Methods for Iron in WaterD1129 Terminology Re
8、lating 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 WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D1
9、9 on WaterD3370 Practices for Sampling Water from Closed ConduitsD3557 Test Methods for Cadmium in WaterD3558 Test Methods for Cobalt in WaterD3559 Test Methods for Lead in WaterD3919 Practice for Measuring Trace Elements in Water byGraphite Furnace Atomic Absorption SpectrophotometryD4841 Practice
10、for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions of Terms Specific to This Standa
11、rd:3.1.1 total recoverable manganesean arbitrary analyticalterm relating to the recoverable forms of manganese that aredeterminable by the digestion method that is included in theprocedure.3.2 Definitions:3.2.1 For definitions of terms used in these test methods,refer to Terminology D1129.1These tes
12、t methods 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 Sept. 1, 2012. Published September 2012. Originallyapproved in 1945. Last previous edition approved in 2007 as D858 0
13、7. DOI:10.1520/D0858-12.2For 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
14、 at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Significance and Use4.1 Elemental constituents in potable water, receiving water,and wastewater need to be identified for support of effectivepollution con
15、trol programs. Test 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
16、to man, as well as 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 va
17、rious salts and minerals, 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 insurfac
18、e and ground waters.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 on AnalyticalReagents of the American Chemical Society, where suchspecifications are availa
19、ble.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 otherwise indicated, referencesto water shall be understood to mean reagent water conformingto
20、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 the determination. Type II water wasspecified at the time of round-robin testing of this test
21、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 immediately at thetime of collection. If only dissolved manganese is to bedetermined, the sampl
22、e shall be filtered through a 0.45-m (No.325) membrane filter before acidification. The holding time forsamples may be calculated in accordance with Practice D4841.NOTE 1Alternatively, the pH may be adjusted in the laboratory if thesample is returned within 14 days. This could reduce hazards of work
23、ingwith acids in the field when appropriate.TEST METHOD AATOMIC ABSORPTION, DIRECT7. Scope7.1 This 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
24、of the method in aparticular matrix.7.2 This test method is applicable in the range from 0.1 to 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.
25、 Dissolved manganese is determined by atomizinga filtered sample directly with no pretreatment. 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 determinetota
26、l recoverable cadmium (Test Methods D3557), chromium(Test Methods D1687), cobalt (Test Methods 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 th
27、an 100 mg/Lmay interfere.9.2 No interference from SiO2in concentrations up to 100mg/L has been 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 inst
28、ructions for use of the specificcorrection technique should be followed.10. Apparatus10.1 Atomic Absorption Spectrophotometer , for use at279.5 nm.NOTE 3The manufacturers instructions should be followed for allinstrumental parameters. A wavelength other than 279.5 nm may be usedif it has been determ
29、ined 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
30、pressure 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 azeotropic3Reagent Chemicals, American
31、 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., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.
32、S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D858 122mixture is obtained (approximately 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
33、(1.0 mL = 1.0 mg Mn)Dissolve 3.076 g of manganous sulfate monohydrate(MnSO4H2O) in a mixture of 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 mg
34、Mn)Dilute 100.0 mLof manganese stock solution to 1 Lwithwater.11.4 Nitric Acid (sp gr 1.42)Concentrated 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:
35、11.6.1 Air, which has been passed through a suitable filter toremove oil, water, and other foreign 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 cyli
36、nder shouldbe replaced at 345 kPa (50 psi).Warning “Purified” gradeacetylene containing a special 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.12. Standardization12.1 Prepare 100
37、 mL each of a blank and at least fourstandard 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
38、, and maximum points for an analyticalcurve.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 13.2.When d
39、etermining dissolved manganese proceed with 13.5.12.3 Aspirate the blank and standards and record the instru-ment readings. Aspirate HNO3(1 + 499) between each stan-dard.12.4 Prepare an analytical curve by plotting the absorbanceof each standard versus its concentration on linear graph paper.Alterna
40、tively read directly in concentration from the instru-ment.13. Procedure13.1 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 with13.5.13.2 Add 5 mL of HCl (sp gr 1.19) to each sample.13.3 Heat the samples on
41、a steam bath or hot plate in awell-ventilated hood until the volume has been reduced to 15or 20 mL, making certain that 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 labo
42、ratories have found block digestion 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 positio
43、ns of the block. For trace metalsanalysis, the digestion tubes should be constructed of polypropylene andhave a volume accuracy of at least 0.5%. All lots of tubes should comewith a certificate of analysis to demonstrate suitability for their intendedpurpose.13.4 Cool and filter the samples through
44、a suitable filterpaper, such as fine-textured, acid-washed, ashless paper into100-mL volumetric flasks. Wash the filter paper two or threetimes with water and adjust to volume.13.5 Set the instrument to zero using reagent blank (zerostandard). Aspirate each filtered acidified sample and standard;rec
45、ord its absorbance or concentration. Aspirate HNO3(1 + 499) between each sample and standard.14. Calculation14.1 Determine the concentration of manganese in eachsample, in milligrams per L, using an analytical curve or,alternatively, read directly in concentration (see 12.4).15. Precision and Bias41
46、5.1 The supporting data on this collaborative study in-cludes reagent and natural water matrices. It is the responsi-bility of the analyst to ensure the validity of the test method ina particular matrix.15.2 The precision of this test method was tested by elevenlaboratories. Five laboratories report
47、ed data for two operators.The precision of this test method is shown in Table 1; the biasis shown in Table 2.15.3 Precision and bias for this test method conform toPractice D2777-77, which was in place at the time of collab-orative testing. Under the allowances made in 1.4 of PracticeD2777-08, these
48、 precision and bias data do meet existingrequirements for interlaboratory studies of Committee D19 testmethods.4Supporting data for Test Methods A and B are available from ASTMInternational Headquarters. Request RR:D19-1034.TABLE 1 Precision and Concentration, Direct AspirationReagent water:Concentr
49、ation (X), mg/L 0.424 2.034 4.053ST0.045 0.177 0.317SO0.021 0.070 0.151Natural water:Concentration (X), mg/L 0.417 2.033 4.076ST0.045 0.179 0.305SO0.037 0.074 0.149D858 123TEST METHOD BATOMIC ABSORPTION,CHELATION-EXTRACTION16. Scope16.1 This test method covers the determination of dissolvedand total recoverable manganese and has been used success-fully with reagent water, tap water, river water, artificialseawater and a synthetic (NaCl) brine. It is the users respon-sibility to ensure the validity of this test method for waters ofother matrice
