Designation: C1109 − 10 (Reapproved 2015)

Standard Practice for

Analysis of Aqueous Leachates from Nuclear Waste
Materials Using Inductively Coupled Plasma-Atomic
Emission Spectroscopy1
This standard is issued under the fixed designation C1109; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope 2. Referenced Documents

1.1 This practice is applicable to the determination of low 2.1 ASTM Standards:2
concentration and trace elements in aqueous leachate solutions C859 Terminology Relating to Nuclear Materials
produced by the leaching of nuclear waste materials, using C1009 Guide for Establishing and Maintaining a Quality
inductively coupled plasma-atomic emission spectroscopy Assurance Program for Analytical Laboratories Within the
(ICP-AES). Nuclear Industry
C1220 Test Method for Static Leaching of Monolithic Waste
1.2 The nuclear waste material may be a simulated (non-
Forms for Disposal of Radioactive Waste
radioactive) solid waste form or an actual solid radioactive
D1193 Specification for Reagent Water
waste material.
D7035 Test Method for Determination of Metals and Met-
1.3 The leachate may be deionized water or any natural or alloids in Airborne Particulate Matter by Inductively
simulated leachate solution containing less than 1 % total Coupled Plasma Atomic Emission Spectrometry (ICP-
dissolved solids. AES)
1.4 This practice should be used by analysts experienced in E135 Terminology Relating to Analytical Chemistry for
the use of ICP-AES, the interpretation of spectral and non- Metals, Ores, and Related Materials
spectral interferences, and procedures for their correction. E177 Practice for Use of the Terms Precision and Bias in
ASTM Test Methods
1.5 No detailed operating instructions are provided because 2.2 ISO and European Standards:3
of differences among various makes and models of suitable ISO 1042 Laboratory Glassware—One-mark Volumetric
ICP-AES instruments. Instead, the analyst shall follow the Flasks
instructions provided by the manufacturer of the particular ISO 3585 Borosilicate Glass 3.3—Properties
instrument. This test method does not address comparative ISO 8655 Piston-Operated Volumetric Instruments (6 parts)
accuracy of different devices or the precision between instru-
ments of the same make and model. 3. Terminology
1.6 This practice contains notes that are explanatory and are 3.1 For definitions of pertinent terms not listed here, see
not part of the mandatory requirements of the method. Terminology C859.
1.7 The values stated in SI units are to be regarded as the 3.2 Definitions:
standard. 3.2.1 atomic emission—characteristic radiation emitted by
1.8 This standard does not purport to address all of the an electronically excited atomic species. D7035
safety problems, if any, associated with its use. It is the 3.2.1.1 Discussion—In atomic (or optical) emission
responsibility of the user of this standard to establish appro- spectrometry, a very high-temperature environment, such as a
priate safety and health practices and determine the applica- plasma, is used to create excited state atoms. For analytical
bility of regulatory limitations prior to use. purposes, characteristic emission signals from elements in their
excited states are then measured at specific wavelengths.

1 2
This practice is under the jurisdiction of ASTM Committee C26 on Nuclear For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Fuel Cycle and is the direct responsibility of Subcommittee C26.05 on Methods of contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Test. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved June 1, 2015. Published June 2015. Originally the ASTM website.
3
approved in 1988. Last previous edition approved in 2010 as C1109 – 10. DOI: Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
10.1520/C1109-10R15. 4th Floor, New York, NY 10036, http://www.ansi.org.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 C1109 − 10 (2015)
3.2.2 background correction—process of correcting the in- 3.2.14 linearity check solution(s)—solution(s) containing
tensity at an analytical wavelength for the intensity due to the the elements to be determined at concentrations that cover a
underlying spectral background of a blank. D7035 range that is two to ten times higher and lower than the
3.2.2.1 Discussion—During sample analysis, measurements concentration of these elements in the calibration reference
are made of the background intensity near the peak wavelength solutions. These solutions also contain 1 % (v/v) nitric acid.
of the analytical lines. Correction of the analytical line peak 3.2.15 non-spectral interference—changes in the apparent
intensity to yield the net line intensity can be made by net signal intensity from the analyte due to physical or
subtraction of either (a) a single intensity measurement per- chemical processes that affect the transport of the analyte to the
formed on the high or low wavelength side of the analytical plasma and its vaporization, atomization, or excitation in the
line (single-point background correction), or (b) an interpo- plasma.
lated background intensity from background measurements
acquired on both the high and low wavelength sides of the 3.2.16 sensitivity—the slope of the linear dynamic range.
analytical line (double-point background correction). 3.2.17 spectral interference—an interference caused by the
3.2.3 bias—between the expectation of the test results and emission from a species other than the analyte of interest.
an accepted reference value. E177 D7035
3.2.4 calibration—the process by which the relationship 3.2.17.1 Discussion—Sources of spectral interference in-
between net signal intensity and elemental concentration is clude spectral line overlaps, broadened wings of intense
determined for a specific element analysis. spectral lines, ion-atom recombination continuum emission,
molecular band emission, and stray (scattered) light effects.
3.2.5 calibration blank solution—calibration solution pre-
pared without the addition of any reference solutions. D7035 4. Summary of Practice
3.2.6 calibration curve—plot of net signal intensity versus
4.1 Aqueous leachates are prepared, using Test Method
elemental concentration using data obtained during calibration.
C1220, for analysis using this practice.
3.2.7 calibration reference solution(s)—solutions contain-
ing known concentrations of one or more elements in 1 % (v/v) 4.2 The general principles of emission spectrometric analy-
nitric acid for instrument calibration. sis are given in Ref (3). In this practice, elemental constituents
of aqueous leachate solutions are determined simultaneously or
3.2.8 critical limit (LC)—minimum significant value of an
sequentially by inductively coupled plasma-atomic emission
estimated net signal or concentration, applied as a discrimina-
spectroscopy (ICP-AES).
tor against background noise. (1)
3.2.9 inductively coupled plasma (ICP)—a high- 4.3 Samples are prepared by filtration if needed to remove
temperature discharge generated by a flowing conductive gas, particulates and acidification to match calibration reference
normally argon, through a magnetic field induced by a load coil solutions. Filtration should be the last resort to clarify a
that surrounds the tubes carrying the gas. D7035 solution since leach studies are designed to determine the
absolute amount of material removed from a waste form by
3.2.10 instrument check solution(s)—solution(s) containing aqueous leaching.
all the elements to be determined at concentration levels
approximating the concentrations in the samples. These solu- 4.4 Additional general guidelines are provided in Guide
tions must also contain 1 % (v/v) nitric acid. C1009, Specification D1193, Terminology C859, and Termi-
3.2.11 interelement correction—a spectral interference cor- nology E135.
rection technique in which emission contributions from inter-
fering elements that emit radiation at the analyte wavelength 5. Significance and Use
are subtracted from the apparent analyte emission after mea- 5.1 This practice may be used to determine concentrations
suring the interfering element concentrations at other of elements leached from nuclear waste materials (glasses,
wavelengths. D7035 ceramics, cements) using an aqueous leachant. If the nuclear
3.2.12 limit of detection (LD)—value for which the false waste material is radioactive, a suitably contained and shielded
negative error is B using a given critical limit. (1) ICP-AES spectrometer system with a filtered exit-gas system
3.2.12.1 Discussion—If the analytical standard deviation is must be used, but no other changes in the practice are required.
constant with respect to concentration, this can be computed as The leachant may be deionized water or any aqueous solution
3.7 times the standard deviation of the analytical results from containing less than 1 % total solids.
ten matrix blank samples spiked at approximately the antici- 5.2 This practice as written is for the analysis of solutions
pated detection limit; otherwise, see references (1, 2)4 for containing 1 % (v/v) nitric acid. It can be modified to specify
additional guidance. the use of the same or another mineral acid at the same or
3.2.13 linear dynamic range—the elemental concentration higher concentration. In such cases, the only change needed in
range over which the calibration curve remains linear to within this practice is to substitute the preferred acid and concentra-
the precision of the analytical method. tion value whenever 1 % nitric acid appears here. It is
important that the acid type and content of the reference and
4
The boldface numbers in parentheses refer to the list of references at the end check solutions closely match the leachate solutions to be
of this standard. analyzed.

2
 C1109 − 10 (2015)
5.3 This practice can be used to analyze leachates from contaminants. The acid may be prepared by sub-boiling distil-
static leach testing of waste forms using Test Method C1220. lation (4), or purchased from commercial sources.
7.5 Stock Solutions—May be purchased or prepared from
6. Apparatus metals or metal salts of known purity. Stock solutions should
6.1 Ordinary laboratory apparatus are not listed, but are contain known concentrations of the element of interest rang-
assumed to be present. ing from 100 to 10 000 mg/L.
6.2 Glassware, volumetric flasks complying with the re- 7.6 Calibration Blank Solution, 1 % (v/v) HNO3.
quirements of ISO 1042, made of borosilicate glass complying 7.7 Calibration Reference Solutions, Instrument Check
with the requirements of ISO 3585. Glassware should be Solutions, and Linearity Check Solutions:
cleaned before use by soaking in nitric acid and then rinsing 7.7.1 Prepare single-element or multielement calibration
thoroughly with water. reference solutions by combining appropriate volumes of the
6.3 Filters, inert membrane, having pore size of 0.45 µm or stock solutions in acid-rinsed volumetric flasks. To establish
smaller. the calibration slope accurately, provide at least one solution
6.4 Piston-operated Volumetric Pipettors and Dispensers, with element concentration that is a minimum of 100 times the
complying with the requirements of ISO 8655, for pipetting LD for each element. Add sufficient nitric acid to bring the final
and dispensing of solutions, acids, and so forth. solution to 1 % HNO3. Prior to preparing the multielement
solutions, analyze each stock solution separately to check for
6.5 Bottles, tetrafluoroethylene or polyethylene, for storage strong spectral interference and the presence of impurities (5).
of calibration and check solutions. Take care when preparing the multielement solutions to verify
6.6 Disposable Gloves, impermeable, for protection from that the components are compatible and stable (they do not
corrosive substances. Polyvinyl chloride (PVC) gloves are interact to cause precipitation) and that none of the elements
suitable. present exhibit mutual spectral interference. Transfer the cali-
6.7 Inductively Coupled Plasma-Atomic Emission bration reference solutions to acid-leached FEP TFE-
Spectrometer, computer controlled, with a spectral bandpass of fluorocarbon or polyethylene bottles for storage. Calibration
0.05 nm or less, is required to provide the necessary spectral reference solutions must be verified initially using a quality
resolution. control sample and monitored periodically for stability.
NOTE 3—Solutions in polyethylene bottles are subject to transpiration
NOTE 1—The spectrometer may be of the simultaneous multielement or
losses that may affect the assigned concentration values.
sequential scanning type. The spectrometer may be of the air-path, inert
gas-path, or vacuum type, with spectral lines selected appropriately for use 7.7.2 Prepare the instrument check solution(s) and linearity
with the specific instrument. check solutions in a similar manner.
NOTE 2—An autosampler having a flowing rinse is recommended. 7.7.3 Fresh solutions should be prepared as needed with the
realization that concentrations can change over time. The
7. Reagents and Materials recommended maximum shelf life for calibration reference
7.1 Purity of Reagents—Reagent grade chemicals shall be solutions, instrument check solutions, and linearity check
used in all tests. Unless otherwise indicated, it is intended that solutions is one month.
all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where 8. Sample Preparation
such specifications are available.5 Other grades may be used,
8.1 If necessary to remove solids or suspended colloids,
provided it is first ascertained that the reagent is of sufficiently
filter the leachate through a clean filter, using an inert filter
high purity to permit its use without lessening the accuracy of
support (avoid the use of fritted glass supports). Examine the
the determination.
filtered leachate to verify the absence of visible solids or
7.2 Purity of Water—Unless otherwise indicated, references suspended colloids. The deposit on the filter may be analyzed
to water shall be understood to mean reagent water as defined separately if required.
by Type I of Specification D1193 or water exceeding these
8.2 Prepare filtered and unfiltered aliquots of a calibration
specifications.
blank solution, and compare the results of these aliquots to
7.3 Nitric Acid (specific gravity 1.42)—Concentrated nitric determine whether the filter membrane contributes to the blank
acid (HNO3). level of the filtered solution.
7.4 Nitric Acid, High-Purity—Nitric acid of higher purity NOTE 4—Step 8.2 may be omitted if none of the samples requires
than reagent grade, specially prepared to be low in metallic filtration.
8.3 Add sufficient high-purity concentrated nitric acid to
bring the leachate sample solution to volume 1 % HNO3. If the
5
Reagent Chemicals, American Chemical Society Specifications, American leachate is known to be a chloride solution, or nitric acid is
Chemical Society, Washington, DC. For suggestions on the testing of reagents not undesirable for other experimental reasons, concentrated hy-
listed by the American Chemical Society, see Analar Standards for Laboratory
drochloric or other mineral acid may be used instead. The acid
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, conditions of the calibration and check solutions used in the
MD. analytical procedure must match those of the leachate sample.

3
 C1109 − 10 (2015)
NOTE 5—It is necessary that quantities of acid and sample be carefully 9.2.4 Best attainable precision.
measured during acidification to allow correction of results to account for
dilution. 9.3 Follow the spectrometer manufacturer’s recommenda-
tion wherever possible in establishing operating conditions.
9. Analytical Conditions For simultaneous multielement systems, the optimum plasma
9.1 Analytical Lines—Suggested analytical lines for typical viewing position and set of operating conditions is usually a
elements are given in Table 1. Additional lines for these and compromise (15). The combination of conditions selected must
other elements of interest, and information about possible be used in all subsequent ICP operations, including determi-
interfering lines, can be found in compilations of analytical nation of LD, calibrations, sample analyses, and performance
lines for ICP-AES (6-14). checks. Systematic use of an appropriate method such as
reference to an atom-to-ion emission intensity ratio (5) to
9.2 Selection of Analytical Conditions—Select an optimum
ensure reproducible conditions is recommended.
combination of analytical lines, background correction
methods, plasma viewing position, and plasma/spectrometer 9.4 Perform at least ten consecutive measurements of a
operating conditions to obtain the following for each element: matrix blank and calculate LD as described in 3.2.12.1.
9.2.1 The lowest attainable LD,
9.5 Perform experiments to determine the linear dynamic
9.2.2 The acceptable linear dynamic range,
range for each element of interest. Use LD and the linear
9.2.3 Avoidance or minimization of spectral and non-
dynamic range as a guide in the preparation of calibration
spectral interference, and
reference solutions and linearity check solutions.
9.6 Estimate the standard deviation for use in establishing
TABLE 1 Suggested Analytical Wavelengths of Typical Elements control limits for each element through repetitive analysis of
for ICP-AESA
the instrument check solution(s). For a particular element,
Suggested Estimated Alternative Estimated
Element Wavelength, Detection Wavelength, Detection these control limits are the known elemental concentration plus
nm Limit, mg/L nm Limit, mg/L or minus a multiple of the standard deviation, based on the
Aluminum 308.22 0.04 237.32 0.03 required confidence limit. For example, a multiple of two times
Americium 283.23 0.01 292.06 >0.01 the standard deviation would provide a confidence limit of
Arsenic 193.70 0.05 189.04 0.01B
Barium 493.41 0.002 455.40 0.001 95 %. Different control limits may be used for individual
Beryllium 234.86 0.0003 313.04 0.0003 samples, or sets of samples, as required by the laboratory. It is
Boron 249.77 0.005 249.68 0.005 recommended that at least ten independent analyses, distrib-
Cadmium 214.44 0.002 ... ...
Calcium 317.93 0.01 393.37 0.0002 uted randomly with respect to time and laboratory operating
Cerium 418.66 0.05 413.76 0.05 conditions, be used to estimate the standard deviation.
Chromium 267.72 0.007 205.55 0.006
Dysprosium 353.17 0.01 205.50 ...
Gadolinium 342.25 0.01 ... ... 10. Calibration
Iron 259.94 0.006 273.96 0.02
Lanthanum 408.67 0.01 379.48 0.01 10.1 Calibration of the Spectrometer System:
Lead 217.00 0.09 220.35 0.04 10.1.1 Follow the spectrometer manufacturer’s instructions
Lithium 670.78 0.002 ... ...
Magnesium 279.55 0.0001 279.08 0.03
for forming and stabilizing the plasma. Allow sufficient time
Manganese 257.61 0.001 294.92 0.008 for plasma stabilization before making measurements.
Molybdenum 202.03 0.008 203.84 0.01
Neodymium 406.11 0.1 401.22 0.05
10.1.2 Calibrate the spectrometer system using the calibra-
Neptunium 382.91 0.09 456.04 0.13 tion blank and the appropriate calibration reference solutions,
Nickel 231.60 0.02 221.65 0.01
B
following the same procedure as for sample analysis (see
Phosphorus 214.91 0.08 178.29
Plutonium 300.06 0.03 297.25 0.03
Section 11). Obtain separate intensity measurements at the
Potassium 766.49 0.04 ... ... analytical line peak position while introducing the calibration
Rhodium 343.49 0.06 233.48 0.04 blank and the calibration reference solution. Subtract the
Ruthenium 240.27 0.03 ... ...
Samarium 442.43 0.05 ... ...
analytical line peak intensity determined during analysis of the
Selenium 203.99 0.1 196.03 0.08B calibration blank from that of the calibration reference solution
Silicon 288.16 0.03 212.41 0.02 analysis to determine the net intensity related to concentration.
Sodium 589.00 0.03 330.24 1.9
Strontium 421.55 0.0008 407.77 0.0004
Then check the accuracy of the calibration by analyzing the
Sulfur 180.73 B
... ... instrument check solution(s). The values obtained must fall
Technetium 254.32 0.002 261.00 0.002 within the previously determined control limits (see 9.6) or the
Tellurium 214.28 0.04 214.72 0.2
Thorium 401.91 0.08 ... ...
instrument must be recalibrated. Finally, check calibration
Titanium 337.28 0.007 334.94 0.004 linearity by analyzing the linearity check solutions. The values
Uranium 385.96 0.25 367.01 0.3 obtained must be accurate to within 5 % of the known solution
Vanadium 292.40 0.008 ... ...
Zinc 213.86 0.002 206.20 0.006
concentration for all elements. It is not necessary to check for
Zirconium 343.82 0.008 339.20 0.008 calibration linearity every time the spectrometer is calibrated
A
See Refs (6-14) for a more complete list. Check those references also to identify provided that the analysis conditions have not been altered.
any possible interfering spectral lines from components such as rare earths, 10.1.3 The calibration range for each element should be
actinides, or high-concentration components.
B
Vacuum spectrometer. limited to a linear ratio of the net signal intensity and
concentration.

4
 C1109 − 10 (2015)
10.1.4 Frequency of calibration required depends on instru- precisely and reproducibly. With any instrument, the analyst
ment stability. Common practice is to verify correct calibration must always be alert to the possible presence of unexpected
daily at start-up and to recalibrate whenever the check solu- elements producing interfering spectral lines.
tions analysis indicates the need (see Section 11). 12.1.1 The empirical method of spectral interference cor-
rection uses interference correction factors (17). Interference
11. Procedure
correction factors are determined by analyzing the single-
11.1 Leachate Solution Analysis: element, high-purity stock solutions under conditions matching
11.1.1 Follow the spectrometer manufacturer’s instructions as closely as possible those used for sample analysis. Unless
for forming and stabilizing the plasma. Allow sufficient time plasma conditions can be accurately reproduced from day to
for plasma stabilization before making measurements. day, or for longer periods, interference correction factors found
11.1.2 Analyze samples using the instrument operating to affect the results significantly must be redetermined each
procedure recommended by the manufacturer. A minimum of time samples are analyzed (5, 18, 19).
three sequential spectral integrations is recommended for 12.1.2 Interference correction factors, Kij, are calculated
determining the average (reported) concentration for a single from apparent concentrations observed in the analysis of the
sample analysis. Provide a dilute acid rinse between samples, high-purity stock solutions.
with sufficient rinse time to ensure analyte signals return to
K ij 5 ~ A i 2 C i ! /B j (1)
blank concentrations. The calibration blank may be used for
this purpose. If a high concentration of any element is observed where:
in the sample, the calibration blank should be analyzed to Kij = interference correction factors,
verify that no carryover memory effect has occurred. If Ai = apparent concentration observed for element i,
carryover is observed, repeat rinsing until the correct blank Ci = concentration of i observed for the blank, and
value is obtained. After introducing each sample or blank, Bj = actual concentration of interfering element j.
allow sufficient time for complete equilibration before initiat- 12.1.3 Sample concentrations observed for element i (al-
ing data collection. Analysis for elemental concentrations ready corrected for baseline drift) are corrected for spectral
beyond the linear calibration range should be conducted by interferences from elements j, k, and l, for example:
reducing the sample concentration to the linear range by
appropriate dilution and acidification of the sample. S i 5 @ A i 2 ~ ~ B j ·K ij! 1 ~ B k ·K ik! 1 ~ B l ·K il! ! # (2)
11.1.3 Analyze the instrument check solution(s) after every where:
group of ten samples has been analyzed. Precede the analysis
SI = concentration of element i corrected for spectral
of the instrument check solution(s) by analysis of the calibra-
interference,
tion blank to verify that the routine rinse procedure prevents Ai = observed concentration of i,
memory effects from previous sample analyses. Analyze the Bj = observed concentration of interfering element j,
instrument check solution(s) more frequently if nonroutine Bk = observed concentration of interfering element k,
leachate samples or analytical conditions are suspected. The Bl = observed concentration of interfering element l,
concentrations obtained should fall within the control limits Kij = interference correction factor for element j,
(see 9.6). If not, the spectrometer must be recalibrated and all Kik = interference correction factor for element k, and
samples analyzed since the last satisfactory check solution Kil = interference correction factor for element l.
analysis must be reanalyzed. If serious instrumental drift
12.1.4 Interference correction factors may be negative if
occurs, the analysis of samples should be halted and cause of
background correction is employed for element i. A negative
the instability sought and eliminated. Concentrations must fall
Kij can result where an interfering line is encountered at the
within the linear range of each element. Otherwise, samples
background correction wavelength rather than at the peak
must be diluted and reanalyzed.
wavelength. The concentrations of interfering elements j, k,
11.1.4 The stability of the baseline for each element is
and l must have been determined within their respective linear
determined by comparison of successive analyses of the
ranges to approximate the actual concentrations as closely as
calibration blank. The baseline stability should be monitored
possible. Mutual interferences (i interferes with j and j inter-
by periodic analysis of instrument check solution(s). Analysis
feres with i) require iterative or matrix methods for calculation.
for baseline drift is recommended after every group of ten
samples. 12.2 Non-spectral Interference—Non-spectral interference
is not likely to occur in ICP-AES if the matrix of the samples
12. Corrections matches the matrix of the standards. This condition generally
12.1 Spectral Interference—Spectral interference can usu- holds for the low-concentration leachants to which this practice
ally be avoided by judicious choice of analytical wavelengths applies. Further assurance of avoiding non-spectral interfer-
(16). When spectral interference cannot be avoided, the nec- ence can be achieved by preparing all standard solutions using
essary corrections should be made using the empirical method the original leachant solution as the matrix (matrix matched
of spectral interference correction, using either the operating standards) instead of simply pure water or acid.
computer software supplied by the spectrometer manufacturer 12.2.1 If non-spectral interference correction is determined
or the manual method detailed below. The empirical correction to be necessary, the method of standard additions can be used
method cannot be used with scanning spectrometer systems if (20). The method of standard additions is applicable under the
both the analytical and interfering lines cannot be located following conditions:

5
 C1109 − 10 (2015)
12.2.1.1 The chemical and physical form of the analyte in TABLE 2 Standard Deviation of ICP-AES Analysis of Simulated
the standard addition is the same as the analyte in the sample, Leachate Solutions SL-1A
Relative
or the analytical source (ICP) is capable of converting the Element
Concentration, StandardB Standard
analyte in both sample and addition to the same form so that mg/L Deviation, mg/L
Deviation,%
transport, atomization, and excitation processes do not differ; Boron 47.1 0.5 1.06
12.2.1.2 The interference effect is independent of analyte Calcium 0.021 0.0053 24.8C
Cerium 2.01 0.04 1.99
concentration over the concentration range of standard addi- Iron 0.014 0.003 21.4C
tions; and Molybdenum 1.92 0.03 1.56
12.2.1.3 The calibration curve is linear over the concentra- Neodymium 1.60 0.03 1.88
Silicon 18.9 0.18 0.95
tion range of standard additions. Sodium 79.6 1.4 1.76
12.2.2 The method of standard additions involves the addi- Strontium 5.13 0.03 0.58
tion of a known concentration of analyte to the sample. The A
Analytical data from twelve analyses conducted at random times on each of 4
concentration of the addition should be not less than 50 % nor successive days. Each analysis consisted of the average of triplicate contiguous
more than 100 % of the analyte concentration in the sample so burns of the solution (routine procedure).
B
Standard deviation of individual analysis: n = 12 (See Ref. (21), Table 6.11).
that measurement precision will not be degraded and so that C
Concentration of Ca and Fe is approaching the LD.
interferences which exhibit a dependence on analyte/
interfering element ratios will not cause erroneous results. The
method must be applied to all elements in the sample set
individually. Multielement standard addition (21) can be used 13.2 The bias of this practice is dependent on the reliability
if it has been determined that added elements do not produce of the calibration reference solutions, the amount of spectral
interferences. and non-spectral interference, the accuracy of interference
corrections, and the adherence to the calibration drift specifi-
13. Precision and Bias cations (22). Using accurate calibration reference solutions,
13.1 The precision of this practice will depend on the choice and with all necessary corrections applied correctly, the rela-
of instrumentation, analytical wavelengths, operating tive analytical bias for element concentrations that are at least
conditions, etc. Typical values for short-term precision (based ten times the detection limit will be approximately equal to the
on replicate measurements performed at concentrations at least calibration drift.
100 times the LD) range from 0.3 to 2 % relative standard 13.3 Table 2 gives typical data for ICP-AES analyses of a
deviation. Precision degrades with decreasing concentration. simulated leachate used to evaluate analytical precision. (23).

REFERENCES

(1) Currie, L. A., “Nomenclature in Evaluation of Analytical Methods (12) Claudon, X., Birolleau, J. C., Lavergne, M., Miche, B., and Bergey,
Including Detection and Quantification Capabilities,” Pure and Ap- C., Spectrochimica Acta, 1987, Vol 42B, pp. 407–411.
plied Chemistry, 1995, Vol, 67, pp. 1699-1723. (13) DeKalb, E. L., and Edelson, M. C., “Atlas of Atomic Spectral Lines
(2) Gibbons, R. D., and Coleman, D. E., Statistical Methods for Detection of Neptunium Emitted by an Inductively Coupled Plasma,” IS-4953,
and Quantification of Environmental Contamination, John Wiley and Ames Laboratory, Iowa State University, Ames, Iowa, August 1987.
Sons, New York, 2001. (14) Huff, E. A., and Bowers, D. L., Argonne National Laboratory, private
(3) ASTM Methods for Emission Spectrochemical Analysis, ASTM communication.
International, 1967. (15) Berman, S. S., and McLaren, J. W., “Establishment of Compromise
(4) Moody, J. R., and Beary, E. S., “Purified Reagents for Trace Metal Conditions for Multielement Analysis by Inductively Coupled
Analysis,” Talanta, Vol. 29, pp. 1003-1010. Plasma Emission Spectrometry: A Preliminary Report,” Applied
(5) Botto, R. K., “Quality Assurance in Operating a Multielement ICP Spectroscopy, 1978, Vol 32, pp. 273–377.
Emission Spectrometer,” Spectrochimica Acta, 1984, Vol 39B, pp. (16) Larson, G. F., Fassel, V. A., Winge, R. K., and Kniseley, R. N.,
“Ultra-trace Analysis by Optical Emission Spectroscopy: The Stray
95–113.
Light Problem,” Applied Spectroscopy, 1976, Vol 30, pp. 384–391.
(6) Boumans, P. W. J. M., Line Coincidence Tables for Inductively
(17) Boumans, P. W. J. M., “Corrections for Spectral Interferences in
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