1、Designation: D5673 10Standard Test Method forElements in Water by Inductively Coupled PlasmaMassSpectrometry1This standard is issued under the fixed designation D5673; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of las
2、t 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 dissolvedelements in ground water, surface water, and drinking water. Itmay
3、 also be used for the determination of total-recoverableelements in these waters as well as wastewater.21.2 This test method should be used by analysts experiencedin the use of inductively coupled plasmamass spectrometry(ICP-MS), the interpretation of spectral and matrix interfer-ences and procedure
4、s for their correction.1.3 It is the users responsibility to ensure the validity of thetest method for waters of untested matrices.1.4 Table 1 lists elements for which the test method applies,with recommended masses and typical estimated instrumentaldetection limits using conventional pneumatic nebu
5、lization.Actual working detection limits are sample dependent and, asthe sample matrix varies, these detection limits may also vary.In time, other elements may be added as more informationbecomes available and as required.1.4.1 This method covers the analysis of mine dewateringgroundwater and wastew
6、ater effluent in the range of 2120g/L dissolved antimony and 3200 g/L dissolved arsenic.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purport to address all of thesafety concerns, if any, associa
7、ted 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 use.2. Referenced Documents2.1 ASTM Standards:3D1066 Practice for Sampling SteamD1129 Terminology Relating
8、to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specifi
9、cationsfor Standard Test Methods for Water Analysis1This 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. 1, 2010. Published September 2010. Originallyapproved i
10、n 1996. Last previous edition approved in 2005 as D5673 05. DOI:10.1520/D5673-10.2EPA Test Method: Determination of Trace Elements in Waters and Wastes byInductively Coupled PlasmaMass Spectrometry, Method 200.8.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Cus
11、tomer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.TABLE 1 Recommended Analytical Mass and EstimatedInstrument Detection LimitsElementRecommendedAnalytical MassEstimated InstrumentDetection Limit, g/L
12、AAluminum 27 0.05Antimony 121 0.08Arsenic 75 0.9Barium 137 0.5Beryllium 9 0.1Cadmium 111 0.1Chromium 52 0.07Cobalt 59 0.03Copper 63 0.03Lead 206, 207, 208 0.08Manganese 55 0.1Molybdenum 98 0.1Nickel 60 0.2Selenium 82 5.0Silver 107 0.05Thallium 205 0.09Thorium 232 0.03Uranium 238 0.02Vanadium 51 0.02
13、Zinc 66 0.2AInstrument detection limits (3s) estimated from seven replicate scans of theblank (1 % v/v HNO3) and three replicate integrations of a multi-element standard.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C70
14、0, West Conshohocken, PA 19428-2959, United States.E691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodE1601 Practice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical MethodE1763 Guide for Interpretation and Use of Result
15、s fromInterlaboratory Testing of Chemical Analysis Methods3. Terminology3.1 DefinitionsFor definitions of other terms used in thistest method, refer to Terminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 calibration blank, na volume of water containingthe same acid matrix as t
16、he calibration standards (see 11.1).3.2.2 calibration standards, na series of known standardsolutions used by the analyst for calibration of the instrument(that is, preparation of the analytical curve) (see Section 11).3.2.3 calibration stock solution, na solution preparedfrom the stock standard sol
17、ution(s) to verify the instrumentresponse with respect to analyte concentration.3.2.4 dissolved, nthose elements that will pass through a0.45-m membrane filter.3.2.5 interference check sample (ICSA), na solution con-taining matrix elements at environmental levels that result ininterferences on targe
18、t low level analytes.3.2.5.1 DiscussionThe interferences formed in the ICPcan be corrected for by use of element-specific correctionequations or collision cell technology with quadrupole-basedICP-MS, or high resolution ICP-MS.3.2.6 interference check sample (ICSAB), nthe ICSAsolution spiked with 20
19、g/L As and Sb.3.2.7 instrumental detection limit (IDL), nthe concentra-tion equivalent to a signal, which is equal to three times thestandard deviation of the blank signal at the selected analyticalmass(es).3.2.8 internal standard, npure analyte(s) added in knownamount(s) to a solution.3.2.8.1 Discu
20、ssionThis is used to measure the relativeinstrument response to the other analytes that are componentsof the same solution. The internal standards must be analytesthat are not a sample component.3.2.9 method detection limit (MDL), nthe minimum con-centration of an analyte that can be identified, mea
21、sured andreported with 99 % confidence that the analyte concentration isgreater than zero.3.2.9.1 DiscussionThis confidence level is determinedfrom analysis of a sample in a given matrix containing theanalyte(s).3.2.10 quality control reference solution (QCS), na solu-tion with the certified concent
22、ration(s) of the analytes, preparedby an independent laboratory, and used for a verification of theinstruments calibration.3.2.11 reagent blank, na volume of water containing thesame matrix as the calibration standards, carried through theentire analytical procedure.3.2.12 total-recoverable, na term
23、 relating to forms ofeach element that are determinable by the digestion methodincluded in this procedure (see 12.2).3.2.13 tuning solution, na solution that is used to deter-mine acceptable instrument performance prior to calibrationand sample analysis.4. Summary of Test Method4.1 This test method
24、describes the multi-element determi-nation of trace elements by inductively coupled plasmamassspectrometry (ICP-MS). Sample material in solution is intro-duced by pneumatic nebulization into a radiofrequency plasmawhere energy transfer processes cause desolvation, atomiza-tion, and ionization. The i
25、ons are extracted from the plasmathrough a differentially pumped vacuum interface and sepa-rated on the basis of their mass-to-charge ratio by a quadrupolemass spectrometer. The ions transmitted through the quadru-pole are detected by a continuous dynode electron multiplierassembly and the ion infor
26、mation processed by a data handlingsystem. Interferences relating to the technique must be recog-nized and corrected for (see Section 6 on interferences). Suchcorrections must include compensation for isobaric elementalinterferences and interferences from polyatomic ions derivedfrom the plasma gas,
27、reagents, or sample matrix. Instrumentaldrift as well as suppressions or enhancements of instrumentresponse caused by the sample matrix must be corrected for bythe use of internal standardization.5. Significance and Use5.1 The test method is useful for the determination ofelement concentrations in m
28、any natural waters and wastewa-ters. It has the capability for the determination of up to 20elements. High analysis sensitivity can be achieved for someelements that are difficult to determine by other techniques.6. Interferences6.1 Several types of interference effects may contribute toinaccuracies
29、 in the determination of trace elements. Theseinterferences can be summarized as follows:6.1.1 Isobaric Elemental InterferencesIsobaric elementalinterferences are caused by isotopes of different elementswhich form singly or doubly charged ions of the same nominalmass-to-charge ratio and which cannot
30、 be resolved by the massspectrometer in use. All elements determined by this testmethod have, at a minimum, one isotope free of isobaricelemental interference. Of the analytical isotopes recom-mended for use with this test method (see Table 2), onlymolybdenum-98 (ruthenium) and selenium-82 (krypton)
31、 haveisobaric elemental interferences. If alternative analytical iso-topes having higher natural abundance are selected in order toachieve greater sensitivity, an isobaric interference may occur.All data obtained under such conditions must be corrected bymeasuring the signal from another isotope of
32、the interferingelement and subtracting the appropriate signal ratio from theisotope of interest. A record of this correction process shouldbe included with the report of the data. It should be noted thatsuch corrections will only be as accurate as the accuracy of theisotope ratio used in the element
33、al equation for data calcula-tions. Relevant isotope ratios and instrument bias factorsshould be established prior to the application of any correc-tions.D5673 1026.1.2 Abundance SensitivityAbundance sensitivity is aproperty defining the degree to which the wings of a mass peakcontribute to adjacent
34、 masses. The abundance sensitivity isaffected by ion energy and quadrupole operating pressure.Wing overlap interferences may result when a small ion peakis being measured adjacent to a large one. The potential forthese interferences should be recognized and the spectrometerresolution adjusted to min
35、imize them.6.1.3 Isobaric Polyatomic Ion InterferencesIsobaric poly-atomic ion interferences are caused by ions consisting of morethan one atom that have the same nominal mass-to-charge ratioas the isotope of interest, and which cannot be resolved by themass spectrometer in use. These ions are commo
36、nly formed inthe plasma or interface system from support gases or samplecomponents. Most of the common interferences have beenidentified, and these are listed in Table 3 together with themethod elements affected. Such interferences must be recog-nized, and when they cannot be avoided by the selectio
37、n of analternative analytical isotope, appropriate corrections must bemade to the data. Equations for the correction of data should beestablished at the time of the analytical run sequence as thepolyatomic ion interferences will be highly dependent on thesample matrix and chosen instrument condition
38、s.6.1.4 Physical InterferencesPhysical interferences are as-sociated with the physical processes that govern the transportof the sample into the plasma, sample conversion processes inthe plasma, and the transmission of ions through the plasmamass spectrometer interface. These interferences may resul
39、t indifferences between instrument responses for the sample andthe calibration standards. Physical interferences may occur inthe transfer of solution to the nebulizer (for example, viscosityeffects), at the point of aerosol formation and transport to theplasma (for example, surface tension), or duri
40、ng excitation andionization processes within the plasma itself. High levels ofdissolved solids in the sample may contribute deposits ofmaterial on the extraction, or skimmer cones, or both, reducingthe effective diameter of the orifices and, therefore, iontransmission. Dissolved solids levels not ex
41、ceeding 0.2 %(w/v) have been recommended to reduce such effects. Internalstandardization may be effectively used to compensate forTABLE 2 Recommended Analytical Isotopes and AdditionalMasses That Are Recommended To Be MonitoredIsotopeAElement of Interest27 Aluminum121, 123 Antimony75 Arsenic135, 137
42、 Barium9 Beryllium106, 108, 111, 114 Cadmium52, 53 Chromium59 Cobalt63, 65 Copper206, 207, 208 Lead55 Manganese95, 97,98 Molybdenum60, 62 Nickel77, 82 Selenium107, 109 Silver203, 205 Thallium232 Thorium238 Uranium51 Vanadium66, 67, 68 Zinc83 Krypton99 Ruthenium105 Palladium118 TinAIsotopes recommend
43、ed for analytical determination are underlined. Thesemasses were recommended and are reflected in the precision and bias data.Alternate masses may be used but interferences must be documented.TABLE 3 Common Molecular Ion InterferencesBackground Molecular IonsMolecular Ion Mass Element InterferenceAN
44、H+15 .OH+17 .OH2+18 .C2+24 .CN+26 .CO+28 .N2+28 .N2H+29 .NO+30 .NOH+31 .O2+32 .O2H+33 .36ArH+37 .36ArH+39 .40ArH+41 .CO2+44 .CO2H+45 ScArC+,ArO+52 CrArN+54 CrArNH+55 MnArO+56 .ArOH+57 .40Ar36Ar+76 Se40Ar38Ar+78 Se40Ar2+80 SeMatrix Molecular IonsChloride35ClO+51 V35ClOH+52 Cr37ClO+53 Cr37ClOH+54 CrAr
45、35Cl+75 AsAr37Cl+77 SeSulphate32SO+48 .32SOH+49 .34SO+50 V, Cr34SOH+51 VSO2+,S2+64 ZnAr32S+72 .Ar34S+74 .PhosphatePO+47 .POH+48 .PO2+63 CuArP+71 .Group I, II MetalsArNa+63 CuArK+79 .ArCa+80 .Matrix OxidesBTiO 62 to 66 Ni, Cu, ZnZrO 106 to 112 Ag, CdMoO 108 to 116 CdAMethod elements or internal stand
46、ards affected by molecular ions.BOxide interferences will normally be very small and will only impact the methodelements when present at relatively high concentrations. Some examples of matrixoxides are listed of which the analyst should be aware. It is recommended that Tiand Zr isotopes be monitore
47、d if samples are likely to contain high levels of theseelements. Mo is monitored as a method analyte.D5673 103many physical interference effects. Internal standards shouldhave similar analytical behavior to the elements being deter-mined.6.1.5 Memory InterferencesMemory interferences resultwhen isot
48、opes of elements in a previous sample contribute tothe signals measured in a new sample. Memory effects canresult from sample deposition on the sampler and skimmercones, and from the buildup of sample material in the plasmatorch and spray chamber. The site where these effects occur isdependent on th
49、e element and can be minimized by flushing thesystem with a rinse blank consisting of HNO3(1+49) in waterbetween samples. The possibility of memory interferencesshould be recognized within an analytical run and suitable rinsetimes should be used to reduce them. The rinse times necessaryfor a particular element should be estimated prior to analysis.This may be achieved by aspirating a standard containingelements corresponding to ten times the upper end of the linearrange for a normal sample analysis period, followed byanalysis of the rinse blank
