1、Designation: D 4190 03Standard Test Method forElements in Water by Direct-Current Plasma AtomicEmission Spectroscopy1This standard is issued under the fixed designation D 4190; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the ye
2、ar of last revision. A number in parentheses indicates 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. Scope*1.1 This test method covers the d
3、etermination of dissolvedand total recoverable elements in water, which includes drink-ing water, lake water, river water, sea water, snow, and Type IIreagent water by direct current plasma atomic emission spec-troscopy (DCP).1.2 The information on precision and bias may not apply toother waters.1.3
4、 This test method is applicable to the 15 elements listedin Annex A1 (Table A1.1) and covers the ranges in Table 1.1.4 This test method is not applicable to brines unless thesample matrix can be matched or the sample can be diluted bya factor of 200 up to 500 and still maintain the analyteconcentrat
5、ion above the detection limit.1.5 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 limitation
6、s prior to use.2. Referenced Documents2.1 ASTM Standards:D 1066 Practice for Sampling Steam2D 1129 Terminology Relating to Water3D 1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 1193 Specification for Reagent Water2D 3370 Practices for Sampling Water from Closed Con-duits2
7、D 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic Constituents2D 5810 Guide for Spiking into Aqueous Solutions2D 5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis4E 1097 Guide for Direct Current Plasma
8、Emission Spec-trometry Analysis33. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 LCS, nlaboratory control standard.3.2.2 total recoverable element, na term relating to formsof each elem
9、ent that are determinable by the digestion methodthat is included in this test method.4. Summary of Test Method4.1 Elements are determined, either sequentially or simul-taneously, by d-c plasma atomic emission spectroscopy.4.2 Matrix enhancement or suppression of the emissionsignal can be minimized
10、by the addition of 2000 mg/L oflithium ion to all standards, samples, and blanks.1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.05 on Inorganic Constituentsin Water.Current edition approved Aug. 10, 2003. Published Septe
11、mber 2003. Originallyapproved in 1982. Last previous edition approved in 1999 as D 4190 99.2Annual Book of ASTM Standards, Vol 11.01.3Annual Book of ASTM Standards, Vol. 3.05.4Annual Book of ASTM Standards, Vol 11.02.TABLE 1 Solutions for AnalysisElement PSolutions for Analysis, g/L123Al 50 100 190B
12、e 50 500 1000B 50 500 1000Cd 1000 50 500Cr 500 1000 50Co 50 500 1000Cu 1000 50 500Fe 500 1000 50Pb 500 200 1000Mn 800 50 300Hg 500 1000 200Ni 50 300 800Sr 600 50 300V 1000 50 400Zn 500 1000 501*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Ha
13、rbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.3 Dissolved elements are determined by atomizing afiltered and acidified sample directly with no pretreatment.4.4 If the sample is clear, total recoverable elements aredetermined in the same manner as dissolved elements excep
14、tthat sample is unfiltered and acidified.4.5 If there are large particles (non-colloidal) the totalrecoverable elements are determined on a portion of the sampleafter a hydrochloric-nitric acid digestion (12.2-12.5). The samedigestion procedure is used to determine all total recoverableelements in t
15、his test method.NOTE 1The volatility of mercury5,6compounds, especially the chlo-rides, makes it necessary to use considerable care in digesting samplescontaining these elements. The samples must not be boiled unlessprovision is made to prevent loss by volatilization.5. Significance and Use5.1 This
16、test method is useful for the determination ofelement concentrations in many natural waters. It has thecapability for the simultaneous determination of up to 15separate elements. High analysis sensitivity can be achievedfor some elements, such as boron and vanadium.6. Interferences6.1 For commonly o
17、ccurring matrix elements the followingspectral interferences have been observed:6.1.1 Calcium, magnesium, and boron interfere with lead at405.78 nm.6.1.2 Calcium interferes with chromium at 425.43 nm.6.1.3 Magnesium interferes with cadmium at 214.44 nm.6.1.4 Iron interferes with cobalt at 345.35 and
18、 240.73 nm.6.1.5 Cobalt interferes with nickel at 341.48 nm.NOTE 2The exact magnitude of these interferences has not beendetermined since it depends on the concentration of the calibrationstandards used and the sample matrix.6.2 Some additional possible interferences are listed inAnnexA2 (TableA2.1)
19、 so that the analyst may be aware of andtest for them.7. Apparatus7.1 See the manufacturers instruction manual for installa-tion and operation of DCP spectrometers, refer to GuideE 1097 for information on DCP spectrometers.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all
20、tests. Unless otherwise indicated, it is intended thatreagents shall conform to the specifications of the Committeeon Analytical Reagents of the American Chemical Society7where such specifications are available. Other grades may beused, provided it is first ascertained that the reagent is ofsufficie
21、nt purity to permit its use without lessening the accu-racy of the determination.8.2 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water conformingto Type I of Specification D 1193. Other reagent water typesmay be used, provided it is first ascertai
22、ned 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 method.8.3 Stock SolutionsPreparation of stock solutions for eachelement is listed in Annex A3 (
23、Table A3.1) or use commer-cially available, ICP Grade, stock standards.8.4 High Purity Hydrochloric Acid, (HCl), (sp gr 1.19),concentrated hydrochloric acid.8.5 Hydrochloric Acid, (1 + 1)Add one volume of HCl(sp gr 1.19) to one volume of water.8.6 Lithium Carbonate, ultrapure.8.7 Lithium Solution (4
24、0 000 mg/L)Dissolve 213 g ofultrapure lithium carbonate in a minimum amount of HCl (spgr 1.19) and dilute to 1 L with water.8.8 Concentrated Nitric Acid, (HNO3), (sp gr 1.42)High-purity acid can be prepared by distillation of concentrated nitricacid from a sub-boiling quartz still or it can be comme
25、rciallypurchased.8.9 Dilute Nitric Acid, (1+1)Add one volume of HNO3(sp. gr. 1.42) to one volume of water.8.10 Dilute Nitric Acid, (1 + 499)Add one volume ofHNO3(sp gr 1.42) to 499 volumes of water.NOTE 3If a high reagent blank is obtained on either HNO3or HCl,distill the acid or use high purity aci
26、d. When HCl is distilled, an azeotropicmixture is obtained (approximately 6 N HCl); therefore, wheneverconcentrated HCl is specified in the preparation of a reagent or in theprocedure, use double the amount if distilled acid is used.9. Precautions9.1 Emission intensities are affected by changing vis
27、cosityso it is important to control the viscosity of blanks, standards,and samples within reasonable limits. Reagent water standardsshould not be used to analyze oil field brines. Alternatively,matrix matching or the method of additions can be used.9.2 Organic solvents, such as alcohol, acetone, and
28、 methylethyl ketone have been observed to enhance emission intensity.This enhancement effect must be compensated for whenorganic solvents are known to be present. Alternatively, matrixmatching or the method of additions can be used.10. Sampling10.1 Collect the samples in accordance with the applicab
29、lestandards, Practice D 1066, Specification D 1192, or PracticesD 3370.10.2 Preserve the samples by immediately adding highpurity nitric acid to adjust the pH to two at the time ofcollection. Normally 2 mL of HNO3is required per liter ofsample. If only dissolved elements are to be determined, (Note4
30、) filter the sample through a 0.45 m membrane filter beforeacidification. The holding time for the sample may be calcu-lated in accordance with Practice D 4841.5Standard Methods of Chemical Analysis, Editor, N. H. Furman, Vol 1, SixthEdition, pp. 107 and 657.6Smith, G. F., The Wet Chemical Oxidation
31、 of Organic Compositions, The G.Frederick Smith Chemical Co., 1965.7Reagent 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 LaboratoryChemica
32、ls, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia andNational Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.D4190032NOTE 4Depending on the manufacturer, these filters have been foundto be contaminated to various degrees with heavy metals. Care should beexe
33、rcised in selecting a source of these filters. A good practice is to washthe filters with nitric acid and reagent water before filtering a sample.11. Calibration and Standardization11.1 Prepare 100 mL of a blank and at least four standardsolutions to bracket the expected concentration range of thesa
34、mples to be analyzed by diluting 5.0 mL of lithium solution(see 8.7) and an appropriate volume of stock solution withHNO3(1 + 499). Prepare the blank and standards each time thetest is to be run.11.2 Atomize the blank and standards and record the emis-sion intensity or concentration. Atomize HNO3(1
35、+ 499)between each standard.11.3 Using the instrument software verify that the instru-ment calibration is within user acceptable QC limits.12. Procedure12.1 To determine dissolved elements, add 5.0 mL oflithium solution (see 8.7) to a 100.0 mL volumetric flask andbring to volume with the well-mixed
36、acidified sample. Proceedwith 12.6.12.2 When determining total recoverable elements in solu-tions containing suspended matter or large particles (that is,noncolloidal), add 5.0 mL of HNO3(sp. gr. 1.42) and 5.0 mLof lithium solution to a 100.0-mL sample.NOTE 5When digestion is necessary, subject the
37、standards, sample,and blank to the same procedure.12.3 Add 5.0 mL of HCl (sp. gr. 1.19) to each sample.12.4 Heat the samples in a covered beaker on a steam bathor hot plate until the volume has been reduced to 15 or 20 mL.Take care to see that the samples do not boil. Loss of samplecould result from
38、 bumping or spattering.NOTE 6For samples with high levels of dissolved solids, the amountof reduction in volume is left to the discretion of the analyst.12.5 Cool and filter the samples, if necessary, through a fineashless filter paper into 100.0 mL volumetric flasks. Wash thefilter paper three time
39、s with water and adjust to volume.12.6 Atomize each solution and record its emission intensityor concentration. Atomize HNO3(1 + 499) between samples.13. Calculation13.1 Calculate the concentration of elements in eachsample, in mg/L, using the calibrations established in 11.3.Modern DCP instruments
40、will provide the results in thecalibrated concentration units.13.2 Multiply the results for dissolved elements by thedilution factor of 1.05 to correct for the required addition oflithium solution (12.1).14. Precision and Bias814.1 To facilitate handling and distribution for round robintesting, thre
41、e concentrated solutions were prepared. These wereacidified solutions of 15 elements.14.2 The concentrated solutions, when diluted according todirections, yielded solutions for analysis with the compositionas shown in Table 1. A total of eight laboratories and thirteenoperators participated in this
42、study.14.2.1 Type II water was specified at the time of round robintesting of this test method.14.3 PrecisionThe precision of this test method for theelements tested within their respective ranges of concentrationgiven in Table 1 may be expressed as given in Table 2.14.4 BiasSee Table 3.14.5 This se
43、ction on precision and bias conforms to PracticeD 2777 77 which was in place at the time of collaborativetesting. Under the allowances made in 1.4 of D 2777 98,these precision and bias data do meet existing requirements ofinterlaboratory studies of Committee D19 test methods.15. Quality Control (QC)
44、15.1 In order to be certain that analytical values obtainedusing these test methods are valid and accurate within theconfidence limits of the test, the following QC procedures mustbe followed when analyzing each element.15.2 Calibration and Calibration Verification15.2.1 Analyze at least three worki
45、ng standards containingconcentrations of each element that bracket the expectedsample concentration, prior to analysis of samples, to calibratethe instrument. The calibration correlation coefficient shall beequal to or greater than 0.990. In addition to the initialcalibration blank, a calibration bl
46、ank shall be analyzed at the8Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR: D191079.TABLE 2 PrecisionElement Reagent Water Water of ChoiceAl ST= 0.093X 0.301 ST= 0.108X + 0.424SO= 0.051X + 0.497 SO= 0.044X + 3.18Be ST= 0.066X +
47、 0.354 ST= 0.059X + 2.15SO= 0.025X 0.250 SO= 0.042X 1.43B ST= 0.045X + 9.34 ST= 0.045X + 2.87SO= 0.022X + 3.70 SO= 0.021X + 5.12Cd ST= 0.044X + 6.08 ST= 0.066X + 2.99SO= 0.025X + 4.96 SO= 0.037X + 7.99Cr ST= 0.060X + 2.13 ST= 0.038X + 4.56SO= 0.032X + 1.20 SO= 0.027X + 3.86Co ST= 0.062X + 4.59 ST= 0
48、.085X + 9.55SO= 0.032X + 4.11 SO= 0.040X + 3.99Cu ST= 0.038X + 5.58 ST= 0.049X + 2.75SO= 0.031X + 0.956 SO= 0.039X + 0.644Fe ST= 0.051X + 14.3 ST= 0.053X + 15.7SO= 0.013X + 10.7 SO= 0.034X + 12.2Pb ST= 0.038X + 9.69 ST= 0.037X + 18.3SO= 0.027X + 5.36 SO= 0.016X + 20.7Mn ST= 0.058X + 2.35 ST= 0.034X
49、+ 1.98SO= 0.023X + 3.30 SO= 0.018X + 3.79Hg ST= 0.008X + 22.3 ST= 0.009X + 28.0SO= 0.003X + 14.7 SO= 0.009X + 23.7Ni ST= 0.078X + 5.47 ST= 0.088X + 3.38SO= 0.029X + 7.17 SO= 0.039X 5.54Sr ST= 0.073X + 1.47 ST= 0.024X + 3.56SO= 0.034X + 1.72 SO= 0.021X + 1.27V ST= 0.053X + 1.74 ST= 0.050X + 3.97SO= 0.038X + 0.794 SO= 0.048X 0.156Zn ST= 0.025X + 8.38 ST= 0.022X + 10.9SO=0.011X + 6.67 SO= 0.014X + 9.47where:Sr= overall prevision, g/L,SO= single-operator precision, g/L, andX = concentration of element determined, g/L.D4190033end of the batch run to ensur
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