1、Designation: D1976 12D1976 18Standard Test Method forElements in Water by Inductively-Coupled Argon PlasmaAtomic Emission Spectroscopy1This standard is issued under the fixed designation D1976; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、 revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the determination of dissolved, total-recoverable, or total elements i
3、n drinking water, ground water,surface water, domestic, commercial or industrial wastewaters.wastewaters,2,3 within the following concentration ranges:1.2 It is the users responsibility to ensure the validity of the test method for waters of untested matrices.1.3 Table 1 lists elements for which thi
4、s test method applies, with recommended wavelengths and typical estimated instrumentaldetection limits using conventional pneumatic nebulization.4 Actual working detection limits are sample dependent and as thesample matrix varies, these detection limits may also vary. In time, other elements may be
5、 added as more information becomesavailable and as required.1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is t
6、he responsibilityof the user of this standard to establish appropriate safety safety, health, and healthenvironmental practices and determine theapplicability of regulatory limitations prior to use. For specific hazard statements, see Note 2 and Section 9.1.5 This international standard was develope
7、d 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) Committee.2. Referenced Documents2
8、.1 ASTM Standards:4D1066 Practice for Sampling SteamD1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD4841 Practice
9、 for Estimation of Holding Time for Water Samples Containing Organic and Inorganic ConstituentsD5673 Test Method for Elements in Water by Inductively Coupled PlasmaMass SpectrometryD5744 Test Method for Laboratory Weathering of Solid Materials Using a Humidity CellD5810 Guide for Spiking into Aqueou
10、s SamplesD5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water AnalysisD6234 Test Method for Shake Extraction of Mining Waste by the Synthetic Precipitation Leaching ProcedureD8006 Guide for Sampling and Analysis of Residential and Commercial Water Supply Well
11、s in Areas of Exploration andProduction (E (2) unresolved overlapof molecular band spectra; (3) background contribution from continuous or recombination phenomena; and (4) backgroundcontribution from stray light from line emission of high concentration elements.6.1.1.1 The effects described in 6.1.1
12、 can be compensated for by utilizing a computer correction of the raw data, requiring themonitoring and measurement of the interfering element. The second effect may require selection of an alternate wavelength. Thethird and fourth effects can usually be compensated for by a background correction ad
13、jacent to the analyte line.6.1.1.2 Table 2 lists some interference effects for the recommended wavelengths given in Table 12. The data in Table 2 areintended for use only as a rudimentary guide for the indication of potential spectral interferences. For this purpose, linear relationsbetween concentr
14、ation and intensity for the analytes and the interferents can be assumed.6.1.1.3 Only those interferents listed in Table 2 were investigated. investigated for the analytes in Table 3. The blank spaces inTable 2 indicate that measurable interferences were not observed for the interferent concentratio
15、ns listed in Table 34. Generally,interferences were considered as discernible if the interferent produced interference peaks or background shifts that correspondedto 2 to 5 % of the peaks generated by the analyte concentrations also listed in Table 3.6.1.2 Physical interferences are generally consid
16、ered to be effects associated with the sample nebulization and transportprocesses. Such properties as change in viscosity and surface tension can cause significant inaccuracies, especially in samples thatmay contain high dissolved solids or acid concentrations, or both. The use of a peristaltic pump
17、 may lessen these interferences.If these types of interferences are operative, they must be reduced by dilution of these samples or utilization of standard additiontechniques, or both.TABLE 2 Analyte Concentration Equivalents, mg/L, Arising from Interferents at the 100 mg/L LevelAAnalyte Wavelength,
18、nm InterferentAl Ca Cr Cu Fe Mg Mn Ni Ti VAluminum 308.215 . . . . . . 0.21 . . 1.4Antimony 206.833 0.47 . 2.9 . 0.08 . . . 0.25 0.45Arsenic 193.696 1.3 . 0.44 . . . . . . 1.1Barium 455.403 . . . . . . . . . .Beryllium 313.042 . . . . . . . . 0.04 0.05Boron 249.773 0.04 . . . 0.32 . . . . .Cadmium 2
19、26.502 . . . . 0.03 . . 0.02 . .Calcium 317.933 . . 0.08 . 0.01 0.01 0.04 . 0.03 0.03Chromium 267.716 . . . . 0.003 . 0.04 . . 0.04Cobalt 228.616 . . 0.03 . 0.005 . . 0.03 0.15 .Copper 324.754 . . . . 0.003 . . . 0.05 0.02Iron 259.940 . . . . . 0.12 0.12 . . .Lead 220.353 0.17 . . . . . . . . .Magne
20、sium 279.079 . 0.02 0.11 . 0.13 0.002 0.25 . 0.07 0.12Manganese 257.610 0.005 . 0.01 . 0.002 . . . . .Molybdenum 202.030 0.05 . . . 0.03 . . . . .Nickel 231.604 . . . . . . . . . .Selenium 196.026 0.23 . . . 0.09 . . . . .Silicon 288.158 . . 0.07 . . . . . . 0.01Sodium 588.995 . . . . . . . . 0.08 .
21、Thallium 190.864 0.30 . . . . . . . . .VanadiumZinc292.402213.856.0.05.0.140.005.0.290.02.Vanadium 292.402 . . 0.05 . 0.005 . . . 0.02 .Zinc 213.856 . . . 0.14 . . . 0.29 . .A See Table 34 for concentrations used.D1976 1846.1.2.1 Salt buildup at the tip of the nebulizer is another problem that can o
22、ccur from high dissolved solids. This salt buildupaffects aerosol flow rate that can cause instrumental drift. To control this problem, wet the argon prior to nebulization, use a tipwasher, or dilute the sample.NOTE 1Periodic inspection and cleaning of the nebulizer and torch components are highly r
23、ecommended.6.1.2.2 Reports indicate that better control of the argon flow rate improves instrument performance. This control of the argonflow rate can be accomplished with the use of mass flow controllers.6.1.3 Chemical interferences are characterized by molecular compound formation, ionization effe
24、cts, and solute vaporizationeffects. Normally these effects are not pronounced with the ICPinductively coupled plasma (ICP) technique; however, if observed,they can be minimized by careful selection of operating conditions (incident power, plasma observation position, and so forth), byTABLE 3 Interf
25、erent and Analyte Elemental ConcentrationsTested for InterferentsAAnalytes mg/L Interferentsmg/LAl 10 Al 1 000Al 10As 10 Ca 1 000As 10B 10 Cr 200B 10Ba 1 Cu 200Ba 1Be 1 Fe 1 000Be 1Ca 1 Mg 1 000Ca 1Cd 10 Mn 200Cd 10Co 1 Ni 200Co 1Cr 1 Ti 200Cr 1Cu 1 V 200Cu 1Fe 1Fe 1Mg 1Mg 1Mn 1Mn 1Na 10Ni 10Pb 10Sb
26、 10Se 10Si 1Si 1Tl 10V 1V 1Zn 10A This table indicates concentrations used for interference measurements in Table2.TABLE 4 Interferent Elemental Concentrations for AnalytesTestedAInterferents mg/LAl 1000Ca 1000Cr 200Cu 200Fe 1000Mg 1000Mn 200Ni 200Ti 200V 200A This table indicates concentrations use
27、d for interference measurements in Table2.D1976 185buffering the sample, by matrix matching, and by standard addition procedures. These types of interferences can be highlydependent on matrix type and the specific analyte.6.2 Analysis for silica precludes the use of borosilicate glassware due to pot
28、ential contamination.7. Apparatus7.1 See the manufacturers instruction manual for installation and operation of inductively-coupled argon plasma spectrometers.Table 5 lists elements for which this test method applies, with recommended wavelengths and typical estimated instrumentaldetection limits us
29、ing conventional pneumatic nebulization. Actual working detection limits are sample dependent and as thesample matrix varies, these detection limits may also vary. In time, other elements may be added as more information becomesavailable and as required.7.1.1 Use of a vacuum or purged path is necess
30、ary for determination of sulfur.7.1.2 Use of glass in the sample path may not be acceptable for silica, use of an inert material is recommended to avoid silicacontamination.TABLE X1.15 Suggested Wavelengths and EstimatedDetection LimitsAElement Wavelength,nmAB Estimated detection limit,g/LBCAluminum
31、 308.215 45Arsenic 193.696 53Antimony 206.833 32Barium 455.403 2Barium 455.403 2Beryllium 313.042 0.3Boron 249.773 5Cadmium 226.502 4Calcium 317.933 10Chromium 267.716 7Cobalt 228.616 7Copper 324.754 6Iron 259.940 7Lead 220.353 42Lithium 670.784 4Lithium 670.784 4Magnesium 279.079 30Manganese 257.61
32、0 2Molybdenum 202.030 8Nickel 231.604 15Phosphorous 214.914 76Potassium 766.491 CPotassium 766.491 700Selenium 196.026 75Silica 288.158 27Silver 328.068 7Sodium 588.995 29Strontium 421.552 0.77Sulfur 182.037 3Thallium 190.864 40Vanadium 292.402 8Zinc 213.856 2A Winge, R. K., Fassel, V. A., Peterson,
33、 V. J., and Floyd, M. A., “InductivelyCoupled Plasma-Atomic Emission Spectroscopy,”AnAtlas of Spectral Information,Elsevier Science Publishing Co., Inc., New York, NY, 1985.B The The wavelengths listed are recommended because of their sensitivity andoverall acceptance. Other wavelengths may be subst
34、ituted if they can provide theneeded sensitivity and are treated with the same corrective techniques for spectralinterference (see 6.1.1).C The The estimated detection limits as shown are taken from Winge, Fassel,Winge et al.al.,A USEPA Method 200.7, or task group data. They are given as aguide for
35、approximate detection limits. limits for the listed wavelengths. The actualtest method instrumental detection limits are sample dependent sample-dependent and may vary as the sample matrix varies (see 3.2.3).D1976 1868. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall be use
36、d in all tests. Unless otherwise indicated, it is intended thatreagents shall conform to the specifications of the Committee onAnalytical Reagents of theAmerican Chemical Society.5 The highsensitivity of inductively-coupled argon plasma atomic emission spectrometry may require reagents of higher pur
37、ity. Stockstandard solutions are prepared from high purity metals, oxides, or nonhydroscopic reagent grade salts using Types I, II, and IIIreagent water, and ultrapure acids. Other grades may be used, provided it is first ascertained that the reagent is of sufficient purityto permit its use without
38、lessening the accuracy of the determination.8.2 Purity of WaterUnless otherwise indicated, reference to water shall be understood to mean reagent water conforming toType I, II, or III of Specification D1193. It is the analysts responsibility to assure that water is free of interferences. Other reage
39、ntwater types may be used provided it is first ascertained that the water is of sufficiently high purity to permit its use withoutadversely affecting the precision and bias of the test method. Type II water was specified at the time of round robin testing of thistest method.8.3 Aqua RegiaMix three p
40、arts hydrochloric acid (sp gr 1.19) and one part concentrated nitric acid (sp gr 1.42) just beforeuse.NOTE 2Exercise caution when mixing this reagent.reagent, use of a fume hood is recommended.8.4 ArgonWelding grade equivalent or better.8.5 Hydrochloric Acid (sp gr 1.19)Concentrated hydrochloric aci
41、d, ultrapure or equivalent.8.5 Hydrochloric Acid (1 + 1)Add 1 volvolume of hydrochloric acid (sp gr 1.19) ultrapure or equivalent to 1 volvolume ofwater.8.7 Nitric Acid (sp gr 1.42)Concentrated nitric acid, ultrapure or equivalent.8.6 Nitric Acid (1 + 1)Add 1 volvolume of nitric acid (sp gr 1.42) ul
42、trapure or equivalent to 1 volvolume of water.8.7 Nitric Acid (1 + 499)Add 1 volvolume of nitric acid (sp gr 1.42) ultrapure or equivalent to 499 volvolumes of water.8.8 Stock SolutionsPreparation of example stock solutions for each element is listed in Table 46. Use of commerciallyprepared certifie
43、d stock solutions is recommended.8.9 Mixed Calibration Standard SolutionsPrepare mixed calibration standard solutions by combining appropriate volumes ofthe stock solutions in volumetric flasks (see Note 3). Prior to preparing mixed standards, each stock solution should be analyzedseparately to dete
44、rmine possible spectral interference or the presence of impurities. Care should be taken when preparing the mixedstandards to ensure the elements are compatible and stable. It is common practice to have all or nearly all elements in one mixedcalibration standard.NOTE 3Mixed calibration standards wil
45、l vary depending on the number of elements being determined. An example of mixed calibration standardsfor the simultaneous determination of 20 elements is as follows:Mixed Standard Solution Imanganese, beryllium, cadmium, lead, and zincMixed Standard Solution IIcopper, vanadium, iron, and cobaltMixe
46、d Standard Solution IIImolybdenum, arsenic, and seleniumMixed Standard Solution IValuminum, chromium, and nickelMixed Standard Solution Vantimony, boron, magnesium, silver, andthallium8.10 Reagent BlankThis must contain all the reagents and be the same volume as used in the processing of the samples
47、. Thereagent blank must be carried through the complete procedure and contain the same acid concentration in the final solution as thesample solution used for analysis.9. Hazards9.1 The toxicity or carcinogenicity of each reagent used in this test method has not been precisely defined; however, each
48、chemical should be treated as a potential health hazard. Adequate precautions should be taken to minimize personnel exposure tochemicals used in this procedure.10. Sampling10.1 Collect the samples in accordance with Practices D1066 or Practices D3370 as applicable.10.1.1 Analysis for silica preclude
49、s the use of borosilicate glassware due to potential contamination.5 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.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.D1976 18710.2 Preserve the samples by immediately adding nitric acid to adjust the pH to 2 at the
