1、Designation: D 858 07Standard Test Methods forManganese in Water1This standard is issued under the fixed designation D 858; 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 indicate
2、s 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. Scope1.1 These test methods cover the atomic absorption deter-mination of dissolved and tota
3、l 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 T
4、est 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
5、 validity of a test method for waters ofuntested matrices.1.3 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-bil
6、ity of regulatory limitations prior to use. For specific hazardstatements, see 11.7, 20.2, 20.9, and 22.10.1.4 Former Test Method A (Colorimetric) was discontinued.For historical information, see Appendix X1.2. Referenced Documents2.1 ASTM Standards:2D 1066 Practice for Sampling SteamD 1068 Test Met
7、hods for Iron in WaterD 1129 Terminology Relating to WaterD 1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 1193 Specification for Reagent WaterD 1687 Test Methods for Chromium in WaterD 1688 Test Methods for Copper in WaterD 1691 Test Methods for Zinc in WaterD 1886 Test M
8、ethods for Nickel in WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3557 Test Methods for Cadmium in WaterD 3558 Test Methods for Cobalt in WaterD 3559 Test Methods for Lead in
9、WaterD 3919 Practice for Measuring Trace Elements in Water byGraphite Furnace Atomic Absorption SpectrophotometryD 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD 5810 Guide for Spiking into Aqueous SamplesD 5847 Practice for Writing Quali
10、ty Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 total recoverable manganesean arbitrary analyticalterm relating to the recoverable forms of manganese that aredeterminable by the digestion method which is incl
11、uded in theprocedure.3.2 Definitions:3.2.1 For definitions of terms used in these test methods,refer to Terminology D 1129.4. Significance and Use4.1 Elemental constituents in potable water, receiving water,and wastewater need to be identified for support of effectivepollution control programs. Test
12、 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
13、aquatic life, a limit1These test 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 Aug. 1, 2007. Published August 2007. Originallyapproved in 1945. Last previous edition
14、 approved in 2002 as D 858 02.2For 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.3Withdrawn.1Copyright ASTM Inte
15、rnational, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.of 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 Manganes
16、e does not occur naturally as a metal but isfound in various 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
17、as fertilizer additives and are commonly found insurface 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 America
18、n Chemical Society, where suchspecifications are available.4Other 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
19、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 the water is ofsufficiently high purity to permit its use without lessening thebias and precision of the determination. Type II water wassp
20、ecified at the time of round-robin testing of this test method.6. Sampling6.1 Collect the sample in accordance with Practice D 1066,Specification D 1192, or Practices D 3370 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
21、thetime of collection. If only dissolved manganese is to bedetermined, the sample 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 D 4841.TEST METHOD AATOMIC ABSORPTION, DIRECT7. Scope7.1 This
22、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 5mg
23、/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. Tot
24、al 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 D 3557), chromium(Test Methods D 1687), cobalt (Test Methods D
25、3558), copper(Test Methods D 1688), iron (Test Methods D 1068), lead (TestMethods D 3559), nickel (Test Methods D 1886), and zinc(Test Methods D 1691).9. Interferences9.1 Magnesium in concentrations greater than 100 mg/Lmay interfere.9.2 No interference from SiO2in concentrations up to 100mg/L has b
26、een 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 1Instrument manufacturers instructions for use of the specificcorrection technique should be followed.10. Apparatus10.1 A
27、tomic Absorption Spectrophotometer, for use at 279.5nm.NOTE 2The manufacturers instructions should be followed for allinstrumental parameters. A wavelength other than 279.5 nm may be usedif it has been determined to be equally suitable.10.1.1 Manganese Light SourceMultielement lamps,electrodeless di
28、scharge lamps, or hollow-cathode lamps havebeen found satisfactory.10.2 Pressure-Reducing ValvesThe supplies of fuel andoxidant shall be maintained at pressures somewhat higher thanthe controlled operating pressure of the instrument by suitablevalves.11. Reagents and Materials11.1 Hydrochloric Acid
29、(sp gr 1.19)Concentrated hydro-chloric acid (HCl).NOTE 3If a high reagent blank is obtained, distill the HCl or usespectrograde acid. (WarningWhen HCl is distilled, an azeotropicmixture is obtained (approximately 6 NHCl). Therefore, whenever con-centrated HCl is specified in the preparation of a rea
30、gent 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 10 mL of HNO3(sp gr 1.42) and100 mL of water. Dilute to 1 L with water. A purchased stock
31、solution of appropriate purity is also acceptable.11.3 Manganese Solution, Standard (1.0 mL = 0.1 mgMn)Dilute 100.0 mL of manganese stock solution to 1 Lwith water.11.4 Nitric Acid (sp gr 1.42)Concentrated nitric acid(HNO3).NOTE 4If a high reagent blank is obtained, distill the HNO3or usespectrograd
32、e acid.4Reagent 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, BDH Ltd., Poole, Dorset, U.K., and the United States Pha
33、rmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D85807211.5 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 foreign substance
34、s, is the usualoxidant.11.7 Fuel:Acetylenestandard, commercially available acetylene isthe usual fuel. Acetone, always present in acetylene cylinders,can affect analytical results. The cylinder should be replaced at50 psig (345 kPa).Warning“Purified” grade acetylene con-taining a special proprietary
35、 solvent other than acetone shouldnot be used with poly(vinyl chloride) tubing as weakening ofthe tubing walls can cause a potentially hazardous situation.12. Standardization12.1 Prepare 100 mL each of a blank and at least fourstandard solutions to bracket the expected manganese concen-tration range
36、 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 analyticalcurve.NOTE 5It is recommended that the blank (zero standard) be compared
37、with 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 determining dissolved manganese proceed with 13.5.12.3 Aspirate the blank and standards and record the instru-m
38、ent 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.Alternatively read directly in concentration from the instru-ment.13. Procedure13.1 Measure 100.0 mL of a well-mixed
39、acidified sampleinto a 125-mL beaker or flask.NOTE 6If 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 a steam bath or hot plate in awell-ventilated hood until the volume has been reduced to 15or 20 mL, making cer
40、tain that the samples do not boil.NOTE 7For brines and samples with high levels of suspended matter,the amount of reduction in volume is left to the discretion of the analyst.13.4 Cool and filter the samples through a suitable filterpaper, such as fine-textured, acid-washed, ashless paper into100-mL
41、 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;record its absorbance or concentration. AspirateHNO3(1 + 499) between each sample and s
42、tandard.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 Bias515.1 The supporting data on this collaborative study in-cludes reagent and natural wat
43、er 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 reported data for two operators.The precision of this test method is shown in Table 1; the
44、biasis shown in Table 2.15.3 Precision and bias for this test method conform toPractice D 2777-77, which was in place at the time ofcollaborative testing. Under the allowances made in 1.4 ofPractice D 2777-06, these precision and bias data do meetexisting requirements for interlaboratory studies of
45、CommitteeD19 test methods.TEST 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
46、. It is the users respon-sibility to ensure the validity of this test method for waters ofother matrices.16.2 This test method is applicable in the range from 10 to500 g/L of manganese. The range may be extended toconcentrations greater than 500 g/L by dilution of the sample.17. Summary of Test Meth
47、od17.1 Manganese is determined by atomic absorption spec-trophotometry. The element, either dissolved or total recover-able, is chelated with pyrrolidine dithiocarbamic acid andextracted with chloroform. The extract is evaporated to dry-ness, treated with hot HNO3to destroy organic matter, dis-solve
48、d in HCl, and diluted to a specified volume with water. Aportion of the resulting solution is then atomized into theair-acetylene flame of the spectrophotometer. The digestionprocedure summarized in 8.1 is used to determine totalrecoverable manganese.5Supporting data for Test Methods A and B are ava
49、ilable from ASTMInternational Headquarters. Request RR: D19-1034.TABLE 1 Precision and Concentration, Direct AspirationReagent water:Concentration (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 0.149D85807318. Interferences18.1 See Section 9.19. Apparatus19.1 All items of apparatus described in Section 10 arerequired.20. Reagents and Materials20.1 Bromcresol Green Indicator Solution (1 g/L)Dissolve 0.1 g of bromcresol green in 100 mL of 20 %
