Anal. Chem.

2010, 82, 7675–7683

Improving the High-Performance Inductively

Coupled Plasma Optical Emission Spectrometry
Methodology through Exact Matching
Michael R. Winchester,* Therese A. Butler, and Gregory C. Turk

Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899

Exact matching is investigated as a means of improving To perform an HP-ICP-OES analysis, a set of calibration standards
high-performance inductively coupled plasma optical and a set of sample solutions of the unknown are gravimetrically
emission spectrometry (HP-ICP-OES), a technique de- prepared so that all standards and samples are nominally the same
veloped at the National Institute of Standards and Tech- with regard to the analyte mass fractions, the internal standard
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nology (NIST) to enable elemental determinations with mass fractions, and the matrix compositions. The sample solutions
relative expanded uncertainty of approximately 0.2% and calibration standards are run on the ICP-OES instrument in
expressed at 95% confidence. “Exact matching” refers to a randomized complete block sequence. In other words, the
the very careful matching of analyte mass fractions, sample solutions and standards are run once each in a randomized
internal standard mass fractions, and matrix compositions sequence, again in a randomized sequence, and so on, until each
among the calibration and unknown sample solutions solution has been run the desired number of times (usually five).
prepared for an analysis. Computer spreadsheet modeling The ratios of the analyte intensities to the internal standard
results and laboratory data involving 16 pairs of analyte intensities are calculated, and the resulting ratios are corrected
and internal standard wavelengths show that exact match- for drift using a unique drift-correction approach.4 The analyte
ing of analyte and internal standard mass fractions mass fraction in the unknown sample is computed from the known
mitigates imprecision and bias that can be caused by even mass fraction of the calibration standards and any observed
subtle nonlinearity in the ICP-OES instrument response. difference between the means of the drift-corrected intensity ratios
Laboratory experiments also demonstrate matrix effects for the sample solutions and the calibration standards. Measure-
caused by small variations in acid composition and by ments involving ICP-OES procedures that are similar to the high-
mass fractions of Na less than 4 mg kg-1, emphasizing performance protocol have been reported by other laboratories.5-9
the need for exact matching of matrix compositions. The HP-ICP-OES technique has become a method of choice
HP-ICP-OES analyses performed at NIST with and for many NIST measurements.10-13 These include certification
without exact matching illustrate that exact matching measurements for NIST reference materials (RMs) and Standard
enables relative expanded uncertainties to be halved Reference Materials (SRMs). For example, the technique has been
to approximately 0.1%. used recently for the certification of the Be mass fraction in SRM
1877 Beryllium Oxide Powder.14 Also, the elemental mass fractions
Approximately a decade ago, the National Institute of Standards of the single-element standard solutions in the SRM 3100 series
and Technology (NIST) in the United States developed a meth- are routinely determined using this approach. The SRMs in the
odology for inductively coupled plasma optical emission spec- 3100 series are important, because they are used by many certified
trometry (ICP-OES) to enable elemental determinations with reference material (CRM) manufacturers to establish meaningful
extraordinarily low uncertainty. Often called “high-performance”
(4) Salit, M. L.; Turk, G. C. Anal. Chem. 1998, 70, 3184–3190.
(HP) ICP-OES, this methodology is capable of routinely providing (5) Kipphardt, H.; Matschat, R.; Rienitz, O.; Schiel, D.; Gernand, W.; Oeter, D.
relative expanded uncertainties on the order of 0.2%, expressed Accredit. Qual. Assur. 2006, 10, 633–639.
as 95% confidence intervals and accounting for all significant (6) Yang, I.; Han, M.-S.; Yim, Y.-H.; Hwang, E.; Park, S.-R. Anal. Biochem. 2004,
335, 150–161.
components of uncertainty, in samples lacking a significantly (7) Rabb, S. A.; Olesik, J. W. Spectrochim. Acta, Part B 2008, 63, 244–256.
interfering matrix. HP-ICP-OES, which has been described in (8) Merson, S.; Evans, P. J. Anal. At. Spectrom. 2003, 18, 372–375.
detail in previous publications,1-3 incorporates a judiciously (9) Simpson, L. A.; Hearn, R.; Merson, S.; Catterick, T. Talanta 2005, 65,
900–906.
chosen internal standard, an efficient drift-correction methodology, (10) Rabb, S. A.; Winchester, M. R.; Yu, L. L. J. Anal. At. Spectrom. 2008, 23,
and gravimetric solution preparation, all within a robust experi- 550–554.
mental design. The technique is based on a single-point calibration. (11) Bertness, K. A.; Wang, C. M.; Salit, M. L.; Turk, G. C.; Butler, T. A.; Paul,
A. J.; Robins, A. H. J. Vac. Sci. Technol., B 2006, 24, 762–767.
(12) Holden, M. J.; Rabb, S. A.; Tewari, Y. B.; Winchester, M. R. Anal. Chem.
* To whom correspondence should be addressed. E-mail: mrw@nist.gov. Fax: 2007, 79, 1536–1541.
301-869-0413. (13) Brennan, R. G.; Rabb, S. A.; Holden, M. J.; Winchester, M. R.; Turk, G. C.
(1) Salit, M. L.; Vocke, R. D.; Kelly, W. R. Anal. Chem. 2000, 72, 3504–3511. Anal. Chem. 2009, 81, 3414–3420.
(2) Salit, M. L.; Turk, G. C.; Lindstrom, A. P.; Butler, T. A.; Beck, C. M., II; (14) Winchester, M. R.; Turk, G. C.; Butler, T. A.; Oatts, T. J.; Coleman, C.;
Norman, B. Anal. Chem. 2001, 73, 4821–4829. Nadratowski, D.; Sud, R.; Hoover, M. D.; Stefaniak, A. B. Anal. Chem. 2009,
(3) Salit, M. L.; Turk, G. C. Anal. Chem. 2005, 77, 136A–141A. 81, 2208–2217.

10.1021/ac101471a  2010 American Chemical Society Analytical Chemistry, Vol. 82, No. 18, September 15, 2010 7675
Published on Web 08/26/2010
traceability links from the certified values of their single-element far exceeding the typical 0.2% relative uncertainty attained with
CRMs to the International System of Units (SI). As an aid to HP-ICP-OES. This example illustrates the need for careful
performing HP-ICP-OES analyses for such applications, NIST has matrix matching.
made available a “traceability tool” spreadsheet that guides the NIST has recently completed detailed studies of the benefits
user through the measurement process.3 The traceability tool is afforded through the implementation of exact matching with HP-
now being used by many commercial CRM producers, as well as ICP-OES. The studies involved both exact matching of analyte
other laboratories needing the low uncertainties HP-ICP-OES can and internal standard mass fractions and exact matching of matrix
provide. The traceability tool can be downloaded from the NIST compositions among the solutions prepared for analysis. The
Web site free of charge.15 results are reported in this paper.
HP-ICP-OES was originally developed primarily for relatively
“clean” samples (i.e., samples lacking a significantly interfering EXPERIMENTAL SECTION
matrix). At the time of development, the assumption was made All laboratory experiments were performed using a Perkin-
that ICP-OES is sufficiently immune to matrix effects and small Elmer (Waltham, MA) model 3300DV ICP-OES instrument,
variations in analyte and internal standard mass fractions to negate equipped with a cross-flow nebulizer, a Scott double-pass spray
requirements for very careful matching of standards to samples. chamber fabricated from Ryton, an alumina injector with an inner
Approximate matching was thought to be adequate, especially diameter of 2.0 mm, and a quartz torch. (Identification of
regarding analyte and internal standard mass fractions. However, commercial products in this paper was done in order to specify
we have discovered through long experience that this is often the experimental procedure. In no case does this imply endorse-
untrue. For some combinations of analyte and internal standard ment or recommendation by the National Institute of Standards
lines, the analytical performance of HP-ICP-OES can be improved and Technology.) The plasma was operated using standard
by very carefully matching the matrix characteristics and analyte settings of 1300 W rf power, and plasma, auxiliary, and nebulizer
and internal standard mass fractions among the solutions prepared gas flow rates of 15, 0.5, and 0.80 L min-1, respectively. These
for an analysis. Consequently, in the majority of HP-ICP-OES parameters produced robust plasma giving Mg (II) 280.270 nm
analyses performed currently at NIST, this “exact matching” to Mg (I) 285.213 nm intensity ratios consistently >8. The
approach is employed. values were corrected for the differing Echelle grating diffrac-
Other laboratories have reported use of this sort of exact tion efficiencies at the two wavelengths by multiplying the
matching with ICP-OES methodologies that are similar to the high- observed ratios by 1.85.19 Solutions were delivered to the
performance protocol. In a determination of minor elements in nebulizer by a peristaltic pump at a flow rate of 1.50 mL min-1.
steel, Merson and Evans8 obtained relative expanded uncertainties All spectra were acquired in axial viewing mode unless
(k ) 2) on the order of 1% by matching analyte concentrations to otherwise stated. Spectra were quantified as peak areas with
within 5% relative and matrix Fe concentrations to within 3% two-point background correction.
relative between samples and calibration standards. The effect of All solutions were prepared using Fisher trace metal grade
a 3% change in the Fe concentration on the ratio of the analyte acids and deionized water. The SRMs in the NIST SRM 3100
intensity to the internal standard element intensity was observed series standard solutions were used as sources of the analyte and
to be on the order of the 0.1% measurement precision. On this internal standard elements.
basis, the authors concluded that matching the matrix Fe
concentrations to better than 3% relative would not be beneficial.
RESULTS AND DISCUSSION
In other published work, Simpson et al.9 applied the same
The benefits of exactly matching the analyte and internal
approach to the determination of Ca in human serum, obtaining standard mass fractions and of exactly matching the matrix
a relative expanded uncertainty (k ) 2) of 1.2%. compositions among the solutions prepared for HP-ICP-OES
More recently, Rabb and Olesik studied the use of HP-ICP- analysis were studied in two separate sets of experiments. To be
OES for analyses of samples having complex matrixes.7 To reduce clear, exact matching of the analyte and internal standard mass
matrix effects, they coupled the use of matrix matching, standard fractions does not mean that the mass fractions of the analyte are
addition, and the common analyte internal standard (CAIS) equal to those of the internal standard. Rather, it means that the
technique16-18 with HP-ICP-OES. They found that even a small mass fractions of the analyte are the same among all prepared
amount of an element that is present in samples but absent in solutions (calibrants and unknown solutions), and likewise, the
calibration standards can induce an unacceptable bias in the mass fractions of the internal standard are the same among all
analytical results. Specifically, while studying the determination prepared solutions (calibrants and unknown solutions), even
of Cu using Mn as the internal standard, they found that mass though the analyte mass fractions may be different from the
fractions of Zn as small as 25 mg kg-1 resulted in a 0.56% change internal standard mass fractions.
in the ratio of the Cu intensity to the Mn intensity. This matrix Exact Matching of Analyte and Internal Standard Mass
effect may seem small. However, it would induce a bias in the Fractions. Laboratory Experiments. The effects of exactly match-
determined Cu concentration of approximately 0.5% relative, ing the analyte and internal standard mass fractions among
(15) Available at https://www-s.nist.gov/srmors/tables/viewTableH.cfm?tableid) solutions were investigated as follows. For each of 16 different
39.
combinations of analyte and internal standard lines, a set of eight
(16) Al-Ammar, A. S.; Barnes, R. M. Spectrochim. Acta, Part B 1998, 53, 1583–
1593. solutions, each 50 mL in volume, was prepared using approximate
(17) Al-Ammar, A. S.; Gupta, R. K.; Barnes, R. M. Spectrochim. Acta, Part B
1999, 54, 1849–1860. (19) Barnard, T. W.; Crockett, M. I.; Ivaldi, J. C.; Lundberg, P. L. Anal. Chem.
(18) Al-Ammar, A. S. Spectrochim. Acta, Part B 2003, 58, 1391–1401. 1993, 65, 1225–1230.

7676 Analytical Chemistry, Vol. 82, No. 18, September 15, 2010
 sensitivity values computed in this way was employed as a
quantitative measure of the variability of those values. Compari-
sons of the variability of the sensitivity values observed for the
two sets of solutions provided a means of assessing the benefits
of exact matching.
As an example, the data for the combination of the Cs (I)
455.528 nm analytical wavelength and the In (I) 325.609 nm
internal standard wavelength is presented in Figure 1. The values
of ICP-OES instrument sensitivity observed for the approximately
matched (i.e., without exact matching) and exactly matched sets
of solutions are plotted, with the eight points in each set
normalized to their respective mean (hereafter called relative
sensitivity values). For this case, exactly matching the analyte and
internal standard mass fractions dramatically improved the preci-
Figure 1. ICP-OES relative sensitivity values observed for sets of sion of the relative sensitivity values.
eight solutions prepared with (closed symbols) and without (open The data for all 16 combinations of analyte and internal
symbols) exact matching of analyte and internal standard mass
standard wavelengths are given in Table 1. There are 17 rows of
fractions. The points for each set of eight solutions are normalized to
the mean. The analytical and internal standard wavelengths were Cs data in the table because data for the combination of Mo as the
(I) 455.528 nm and In (I) 325.609 nm, respectively. The Cs and In analyte and Y as the internal standard were acquired with both
mass fractions in the solutions were 440 and 6 mg kg-1, respectively. axial and radial viewing using the same sets of approximately and
exactly matched solutions. The three analytical lines for S, which
matching, as has been traditionally performed in the implementa- form a multiplet, were observed simultaneously. The third and
tion of HP-ICP-OES at NIST. Additionally, a 400 mL solution was fourth columns in the table give the RSDs of the sets of relative
prepared having nominally the same analyte and internal standard sensitivity values observed for the approximately and exactly
mass fractions as the set of approximately matched solutions. This matched solutions. The fifth column provides the “improvement
single solution was split into eight 50 mL aliquots to form a set of factors” obtained through exact matching, calculated in each case
exactly matched solutions. The two sets of solutions were run in as the RSD of the relative sensitivity values for the approximately
two separate experiments on the ICP-OES instrument. In each matched solutions divided by that for the exactly matched
experiment, a set of solutions was run in a randomized complete solutions. The observed improvement factors range from 0.64 to
block sequence, and the ratios of the analyte intensities to the 51. The RSDs of the nominal analyte and internal standard element
internal standard intensities were calculated and drift-corrected. mass fraction ratios for the approximately matched solution sets
A separate value of the ICP-OES instrument sensitivity, defined ranged from about 2% to about 9%, and the analyte and internal
as the drift-corrected analyte to internal standard intensity ratio standard element mass fractions among the solutions in a given
divided by the ratio of the analyte mass fraction to the internal set were uncorrelated. This is the way solutions for HP-ICP-OES
standard mass fraction (hereafter called the analyte to internal have traditionally been prepared at NIST.
standard mass fraction ratio), was calculated for each of the eight The F-distribution can be used to evaluate the statistical
solutions. The relative standard deviation (RSD) of the eight significance of the improvement factors, because these factors are

Table 1. Improvements in the Precision of ICP-OES Relative Sensitivity Values Obtained by Exactly Matching the
Analyte and Internal Standard Element Mass Fractions among Solutionsa

RSD of relative sensitivity values, %

analyte line internal standard line approximate matching exact matching improvement factorb Rc
Al (I) 396.152 nm Mn (I) 279.482 nm 0.116 0.042 2.8 0.10
Be (I) 265.045 nm Mn (I) 279.482 nm 0.029 0.045 0.64 0.71
Ca (II) 393.366 nm Sc (II) 424.682 nm 0.38 0.53 0.72 0.66
Co (II) 238.892 nm Y (II) 371.030 nm 0.015 0.010 1.5 0.31
Cs (I) 455.528 nm In (I) 325.609 nm 0.697 0.035 20 0.00039
Cu (I) 324.754 nm Mn (I) 279.482 nm 0.087 0.016 5.3 0.021
Ge (I) 265.117 nm In (I) 325.609 nm 0.371 0.033 11 0.0024
Mg (II) 279.553 nm Y (II) 371.030 nm 0.171 0.047 3.6 0.057
Mn (II) 257.610 nm Y (II) 371.030 nm 0.166 0.051 3.3 0.071
Mo (II) 204.598 nm Y (II) 371.030 nm 1.184 0.047 25 0.00018
Mo (II) 204.598 nmd Y (II) 371.030 nmd 0.059 0.059 1.0 0.50
Na (I) 589.592 nm Sr (I) 460.733 nm 0.069 0.061 1.1 0.44
P (I) 213.618 nm Ge (I) 265.117 nm 0.097 0.020 4.8 0.028
S (I) 180.731 nme P (I) 213.618 nm 2.028 0.040 51 0.000018
S (I) 182.034 nme P (I) 213.618 nm 1.047 0.047 22 0.00027
S (I) 182.625 nme P (I) 213.618 nm 0.084 0.041 2.1 0.18
Se (I) 196.026 nm In (I) 325.609 nm 1.761 0.069 26 0.00018
a
See text for further details. b Column 3 divided by column 4. c R gives the probability that the observed improvement factor can be attributed
to random noise, based on the F-distribution. d Radial viewing at 15 mm above the load coil. e Wavelength in vacuum.

Analytical Chemistry, Vol. 82, No. 18, September 15, 2010 7677
Figure 2. Observed dependence of the ICP-OES instrument Figure 3. Relationship between standardized improvement factor
sensitivity on the nominal analyte to internal standard mass fraction and composite nonlinearity score. (See text for explanations of axis
ratios of the solutions in the approximately matched solution set scales.) The data for the three S analytical lines, which constitute a
containing P and Ge. Both the axes have been normalized to their multiplet, were acquired simultaneously. The axially and radially
respective means. The analytical line was P (I) 213.618 nm, and the viewed data for the analyte Mo were obtained using the same sets
internal standard line was Ge (I) 265.117 nm. of approximately and exactly matched solutions.

where mtan is the slope of the tangent to the curve at the analyte
ratios of standard deviations. There are seven degrees of freedom to internal standard mass fraction ratio used during the exact
associated with both the numerator and denominator in each ratio. matching experiments and mlin is the slope of a hypothetical
The final column in Table 1 gives the value of R corresponding line defined by the point on the curve pertaining to this ratio
to each improvement factor, where R states the probability that and the origin. In essence, the tangent is a realization of the
the observed improvement factor can be attributed to random actual ICP-OES instrument response, whereas the hypothetical
noise. From this assessment, 8 of the 17 improvement factors have line represents the ideal, unrealized instrument response. A
R-values of less than 0.05. This means that half of the improvement composite nonlinearity score was then calculated for each exact
factors can be attributed to actual benefits of exact matching with matching experiment by taking the square root of the sum of
a statistical confidence level of 0.95 or greater. Moreover, several the squares of the nonlinearity scores for the analyte and
of the improvement factors are very statistically significant. The internal standard wavelengths.
most extreme example was found when S (I) 180.731 nm was used A quantitative measure of the effect of ICP-OES instrument
as the analytical line and P (I) 213.618 nm was used as the internal response nonlinearity on the improvement factor is illustrated by
standard line. Figure 3. In this graph, the improvement factors from the exact
Close examination of some of the approximately matched data matching experiments are plotted against the composite nonlin-
sets showed that the relative sensitivity values were sometimes earity scores computed as described above. The improvement
dependent on the nominal analyte to internal standard mass factors have been “standardized” by dividing the values in Table
fraction ratios. The data for the approximately matched solution 1 by the corresponding RSDs of the nominal analyte to internal
set using P (I) 213.618 nm as the analytical line and Ge (I) 265.117 standard mass fraction ratios of the solutions in the approximately
nm as the internal standard line are plotted in Figure 2 as an matched sets. This standardization of the improvement factors is
example. In this case, increases in the nominal mass fraction ratio necessary to plot meaningfully the data from the different
resulted in decreases in the relative sensitivity. The dependence experiments on the same ordinate scale. This is because the
was reversed for some other combinations of analyte and internal benefit of exact matching should increase as the degree of
standard wavelengths. Given that HP-ICP-OES is essentially based matching utilized in the preparations of the approximately matched
on a single-point calibration, this behavior implies nonlinearity in sets of solutions deteriorates.
the instrument response for the analytical line, the internal The graph in Figure 3 demonstrates an approximately linear
standard line, or both. Whether the dependence of sensitivity on relationship between the standardized improvement factors and
mass fraction ratio is direct or inverse would depend upon the the composite nonlinearity scores. This relationship shows that
directions and magnitudes of the instrument response curvature nonlinearity in the instrument response to the analyte and/or
for both lines. Curvatures in both directions have been observed internal standard can induce solution-to-solution imprecision when
in our laboratory. solutions in a set are only approximately matched. The data for
To investigate this further, calibration curves were measured the three S analytical wavelengths, which are marked in Figure
for each analytical and internal standard wavelength, and the 3, are especially illuminating in this regard, since they were
degree of nonlinearity, expressed as a percentage, in each curve acquired simultaneously from the same approximately and exactly
was quantified as matched solution sets. Similarly, the data for Mo viewed axially
and radially, also marked in Figure 3, are illustrative, because they
too were acquired using the same solution sets.
nonlinearity ) 100 ( mtan - mlin
mlin ) (1) These laboratory experiments indicate that, for many combina-
tions of analyte and internal standard wavelengths, the quality of
7678 Analytical Chemistry, Vol. 82, No. 18, September 15, 2010
 is half the expanded uncertainties often attained using HP-ICP-
OES analysis.
The degree of exact matching required for a specific analysis
depends upon the precise instrument nonlinearity associated with
the analytical and internal standard wavelengths being employed.
Given the wide range of possibilities, it is impractical to attempt
to provide guidance pertaining to each possible situation. Instead,
consider the case in which the instrument response to both the
analyte and internal standard wavelengths is characterized by the
quadratic equation intensity ) -300(mass fraction)2 + 100 000(mass
fraction). This can be considered a worst case scenario, in the
sense that the apparent linearity is still high. The curve is
visually linear, and the coefficient of determination, R2, resulting
from a linear least-squares fit is 0.9997. Therefore, even a
Figure 4. Dependence of the ICP-OES instrument sensitivity on the prudent analyst might incorrectly assume that the instrument
solution analyte to internal standard mass fraction ratio, calculated response is actually linear.
using a spreadsheet model. Both axes have been normalized to their The dependence of the RSD of the relative sensitivity values,
respective means. The line is the result of a least-squares fit to the
RSDRSV, on the RSD of the analyte to internal standard mass
data. (See text for further details.)
fraction ratios, RSDMFR, generated using this model is described
HP-ICP-OES analysis depends upon the degree of matching of by the equation RSDRSV ) 0.026(RSDMFR)2 + 0.031(RSDMFR)
the analyte and internal standard mass fractions among the + 0.000 0002. This equation is useful for quantifying, in this
solutions prepared for the analysis. The data show that exact particular case, the degree of exact matching of the analyte to
matching among the solutions within a given set of calibration internal standard mass fraction ratios among the solutions in
standards or unknown samples in many cases improves solution- a given set (e.g., a set of calibration standards) necessary to
to-solution precision. Variability observed among the data obtained avoid significant solution-to-solution imprecision induced by the
from such solution sets that was previously attributed to real underlying nonlinearity in the instrument response. As stated
irreproducibility in solution preparation (e.g., see Figure 2 and earlier, the expanded uncertainties attained using HP-ICP-OES
related discussion in ref 2) is now seen to have been more likely are generally on the order of 0.2%. Given a coverage factor, k,
due to the deleterious effects of inexact matching. More important, of 2, the combined standard uncertainty is normally on the
the data discussed here imply that exact matching between the order of 0.1%. As a rule of thumb, it may be assumed that
set of calibration standards and the set of unknown samples may RSDRSV should be kept below approximately one-fifth of this
mitigate a potential bias that would otherwise be undetected and value, or 0.02%, to avoid significant solution-to-solution impreci-
not reflected in the uncertainty budget. sion. For this particular case, this means that the solutions must
Spreadsheet Modeling. Further investigations of the effects of be prepared such that RSDMFR is less than or equal to about
ICP-OES instrument response nonlinearity were conducted through 0.6%.
computer spreadsheet modeling. As an example, consider the case The dependence of the relative range of relative sensitivity values,
in which the instrument response to both the analyte and internal RANGERSV, on the relative range of the analyte to internal standard
standard wavelengths is characterized by the quadratic equation mass fraction ratios, RANGEMFR, generated using this model is
intensity ) -50(mass fraction)2 + 100 000(mass fraction). This given by the equation RANGERSV ) 0.0087(RANGEMFR)2 +
case was selected as the example because it is particularly 0.031(RANGEMFR) + 0.000 002. This equation can be used to
instructive. The nonlinearity is visually undetectable, and the quantify, for this particular case, the degree of exact matching
coefficient of determination, R2, for a linear least-squares fit between the mean analyte to internal standard mass fraction
[intensity ) 99 000(mass fraction) + 3000] is 0.999 992. Without ratio of the calibration standards and that of the unknown
plotting the residuals associated with the linear fit, a reasonable sample solutions required to avoid significant analytical bias
analyst would conclude that the instrument response is highly in the HP-ICP-OES analysis. It may be assumed that RANGERSV
linear. The nonlinearity might not even be apparent in the should be kept below 0.02% relative to avoid such bias. This
residual plot when random noise is also present. The composite means that the solutions must be prepared such that the
nonlinearity score for analyte and internal standard lines having relative difference in the mean analyte to internal standard mass
this degree of curvature is 0.71%. Sets of analyte and internal fraction ratio for the calibration standards and that for the
standard mass fractions were generated randomly, all having unknown solutions is less than or equal to about 0.6%.
mean values of 10 mg kg-1, and with the absence of correlation It should be emphasized that, from an analytical viewpoint,
between the analyte and internal standard mass fractions within exactly matching the mean analyte to internal standard mass
a given set. With the use of the hypothetical instrument fraction ratio of the calibration standards to that of the unknown
response, plots like that in Figure 2 were generated for the solutions is generally more important than exactly matching the
various sets. The plot for a set in which the RSD of the analyte to analyte to internal standard mass fraction ratios among a set of
internal standard mass fraction ratios was 6.0% is given in Figure either the calibration standards or the unknown solutions. This
4. As shown, the plot has the same form as the plot in Figure 2. is because the analytical bias induced by a mismatch between
The range of relative sensitivity values observed is 0.10%, which the mean ratios might be undetected and not reflected in the
Analytical Chemistry, Vol. 82, No. 18, September 15, 2010 7679
uncertainty budget for the HP-ICP-OES analysis. In contrast, the regions. Taking such precautions reduces the degree of exact
solution-to-solution imprecision induced by mismatching the ratios matching required.
among a set of solutions will naturally be reflected in the data HP-ICP-OES analysis requires an initial guess at what the
and, therefore, inherently included in the uncertainty estimation. analyte mass fraction in the unknown sample is likely to be so
As another point, exactly matching only the ratios of the analyte that matching calibration standards can be prepared. If the analyte
mass fractions to the internal standard mass fractions while mass fraction determined through the analysis is too different from
allowing these mass fractions to vary on an absolute scale would the initial guess, it may be advisable to perform a subsequent HP-
be an inadequate approach. This is because the instrument ICP-OES analysis using the determined analyte mass fraction in
responses to the analytical and internal standard wavelengths will place of the initial value. It is difficult to give specific guidance
almost certainly be different. regarding the magnitude of difference that should trigger a
Use of Blanks. To this point in the discussion, the use of blanks subsequent analysis. As a rule of thumb, it is suggested that a
in HP-ICP-OES analysis has not been mentioned. The high- subsequent analysis should be performed when the initial value
performance protocol, as described in previous publications, does falls outside the expanded uncertainty interval, expressed at a level
not include blanks. However, nonzero blank intensity associated of confidence of 95%, associated with the determined value.
with the analyte and/or internal standard wavelength could Exact Matching of Solution Matrix Compositions. The
theoretically have similar effects to those caused by instrument presence of matrix effects in ICP-OES has been recognized almost
response nonlinearity. This is due to the fact that when one or since the time the method was first introduced to the analytical
more nonzero blank intensities apply, the actual slope of the community. It is well-known that analytical accuracy can be
instrument response function is necessarily different from the degraded by these matrix effects and that the conscientious
slope assumed in the analysis. Preliminary spreadsheet modeling analyst may need to take steps to mitigate the consequences. The
confirmed this, but also pointed out that, given even the highest approaches to reducing these consequences that are most often
used include standard addition calibration and matrix matching
blank intensities commonly observed in our laboratory, the
between calibration standards and unknown samples. For a large
severity of the problem seems to be much less than that associated
majority of analytical applications of ICP-OES, percent level or
with even subtle instrument nonlinearity.
poorer uncertainty is acceptable. In these cases, the degree of
The potential for analytically deleterious effects of nonzero
matrix matching required for adequate mitigation of matrix effects
blanks in HP-ICP-OES analysis was investigated in the laboratory.
is usually not high. However, this may not be the case for
Experiments were conducted by running sets of eight exactly
applications of HP-ICP-OES, owing to the fact that target relative
matched solutions and four blanks in a randomized complete block
uncertainties are on the order of 0.2% or better.
sequence on the ICP-OES instrument, calculating and drift-
Matrix effects and the benefits of exactly matching matrix
correcting the analyte to internal standard intensity ratios, and
compositions among the solutions prepared for HP-ICP-OES
computing the relative sensitivity values for each solution, both
analysis were studied as follows. For several combinations of
with and without taking the blank intensities into account. This
analyte and internal standard wavelengths, sets of solutions were
was done for each of the 16 combinations of analyte and internal
prepared having nominally identical analyte and internal standard
standard wavelengths listed in Table 1. An improvement factor,
mass fractions but with systematically varied matrix compositions.
defined as the RSD of the relative sensitivity values obtained using
The solutions in each set were run on the ICP-OES instrument in
the blanks divided by that obtained without using the blanks, was
a randomized complete block sequence for a total of five runs
calculated for each combination. The mean and median improve- per sample. The analyte to internal standard intensity ratios were
ment factors were 0.96 and 0.98, respectively, and the largest value calculated and corrected for drift, and the relative sensitivity values
was only 1.05. These results confirm that the effects of nonzero observed for each solution were computed. Experiments were
blanks on HP-ICP-OES analysis are usually negligible. performed in this way for the two major categories of ICP-OES
Implications. The results presented here show that exact matrix effects that are most relevant to HP-ICP-OES analysis. The
matching of analyte mass fractions and internal standard mass categories of interest are acid effects and concomitant element
fractions among the solutions within a given solution set (e.g., a effects, specifically those of easily ionized elements (EIEs), such
set of calibration standards) and between the set of calibration as Na.
standards and the set of unknown sample solutions can mitigate Acid Effects. A representative example of data obtained while
analytically deleterious effects induced by nonlinearity in the ICP- investigating the influence of acid effects on HP-ICP-OES is shown
OES instrument response associated with the analyte and/or in Figure 5. This graph illustrates the inverse linear dependence
internal standard. It is advisable to check experimentally the of the instrument sensitivity on the mass fraction of nitric acid
linearity of instrument response at both wavelengths prior to HP- observed for sample solutions prepared to contain nominally
ICP-OES analysis. Visual examination of a plot of the residuals identical mass fractions of analyte (115 mg kg-1 P) and internal
resulting from a linear fit to the data is one effective approach. standard (18 mg kg-1 Ge). The magnitude of the slope of the
Simply relying upon the value of the correlation coefficient or line implies that to mitigate significant solution-to-solution
coefficient of determination should be avoided, due to insensitivity imprecision, again taken to be represented by an RSD of 0.02%,
to small degrees of curvature. If nonlinearity is found at either the standard deviation of the nitric acid mass fractions among
wavelength, another wavelength should be selected. Alternatively, the solutions in a given set of solutions (e.g., a set of calibration
solutions may be prepared at lower analyte and internal standard standards) should not exceed approximately 0.0007. At a mean
mass fractions to shift the working ranges into more linear nitric acid mass fraction of 0.02, this equates to an RSD of about
7680 Analytical Chemistry, Vol. 82, No. 18, September 15, 2010
 The plot in Figure 6 illustrates a linear dependence of the
instrument sensitivity on the acid composition. The regressed line
in the plot was fitted to the data using the hydrochloric acid mass
fractions as the abscissa values. The equation for a regressed line
fitted using the nitric acid mass fractions would be identical, except
that the sign of the slope would be negative. The magnitude of
the slope of the line implies that keeping solution-to-solution
imprecision below 0.02% RSD requires that the standard deviation
of the nitric and hydrochloric acid mass fractions among the
solutions in a given set be kept below about 0.0002. The RSD
equivalents will, of course, depend upon the mean nitric and
hydrochloric acid mass fraction values. The magnitude of the slope
also implies that keeping analytical bias below 0.02% relative
requires that the absolute difference between the mean mass
Figure 5. Dependence of the observed relative sensitivity of the ICP- fractions of either acid for the set of calibration standards and
OES instrument on the mass fraction of nitric acid for a set of solutions the set of unknown solutions be kept below approximately 0.0002.
prepared to contain identical mass fractions of analyte (115 mg kg-1
EIE Effects. The results of studies concerning the effects of
P) and internal standard (18 mg kg-1 Ge). Error bars represent 95%
confidence intervals calculated from the responses for replicate EIEs on HP-ICP-OES analysis are presented in Figure 7. For these
solutions at each nitric acid mass fraction: analytical wavelength, P studies, sets of solutions were prepared to contain identical analyte
(I) 213.618 nm; internal standard wavelength, Ge (I) 265.117 nm. and internal standard mass fractions and acid compositions but
with varying mass fractions of Na. The source of Na used was
SRM 3152a sodium standard solution, lot no. 010728. Importantly,
this SRM does not contain any of the analytes or internal standards
at mass fractions that could significantly perturb the analyte or
internal standard compositions of the prepared solutions. The plots
for the analyte P and internal standard Ge in Figure 7a and for
the analyte Cu and internal standard Mn in Figure 7b clearly
indicate linear dependences of ICP-OES instrument sensitivity on
Na mass fractions varying between 0 and 4.0 mg kg-1. The two
sets of data plotted in Figure 7b, which were acquired on two
separate days using two separate sets of solutions, show that this
dependence is reproducible. To the authors’ knowledge, EIE
effects at such small mass fractions of an easily ionized element
have never before been demonstrated. However, these results are
consistent with the extreme sensitivity of Cu analysis to the
Figure 6. Dependence of the observed relative sensitivity of the ICP-
OES instrument on the nitric and hydrochloric acid mass fractions presence of Zn mass fractions as small as 25 mg kg-1 reported
for a set of solutions prepared to contain identical total acid (nitric by Rabb and Olesik.7 Given the magnitudes of the slopes of
plus hydrochloric) mass fractions of 0.02 and identical mass fractions the fitted lines in these two plots, maintaining 0.02% or lower
of analyte (115 mg kg-1 P) and internal standard (18 mg kg-1 Ge).
RSDs arising from solution-to-solution imprecision would
The line was fitted to the data using the hydrochloric acid mass
fractions as the abscissa values. Error bars represent 95% confidence require that the solutions within a given set be prepared such
intervals calculated from the responses of replicate solutions at each that the standard deviations of the Na mass fractions do not
acid composition: analytical wavelength, P (I) 213.618 nm; internal exceed 0.4 and 0.2 mg kg-1 for the P/Ge and Cu/Mn pairs,
standard wavelength, Ge (I) 265.117 nm.
respectively. Also, avoiding analytical bias larger than 0.02%
relative would require that the mean Na mass fraction of the
3.5%. The magnitude of the slope of the line also implies that
avoidance of significant analytical bias, again taken to be 0.02% calibration standards differ from that of the unknown solutions
relative, would require that the absolute difference between by less than 0.4 and 0.2 mg kg-1 for the P/Ge and Cu/Mn
the mean nitric acid mass fractions of the set of calibration pairs, respectively. It is possible that the necessity of matching
standards and the set of unknown solutions not exceed 0.0007. the Na mass fractions so closely might be somewhat alleviated
Similar dependences were observed for other combinations of through “buffering”, whereby a large amount of Na would be
analyte and internal standard wavelengths, though the depen- intentionally and precisely added to all solutions.
dence was in some cases direct, rather than inverse. In contrast to the plots in panels a and b of Figure 7, the data
Another representative example of acid effect data obtained for the Ca/Sc pair in Figure 7c do not demonstrate a dependence
in this work is given in Figure 6. In this case, all solutions were of the ICP-OES instrument sensitivity on Na mass fraction at a
again prepared to contain 115 mg kg-1 P as the analyte and 18 statistical significance level of P ) 0.05, as indicated by the fact
mg kg-1 Ge as the internal standard. The sum of the mass that the 95% confidence interval for the slope of the fitted line,
fractions of nitric acid and hydrochloric acid in each solution 0.00018 ± 0.00021 kg mg-1, overlaps zero. This is probably due
was 0.02, though the portion that was nitric acid was varied. to the fact that, unlike P (IP ) 10.5 eV) and Cu (IP ) 7.7 eV),
Analytical Chemistry, Vol. 82, No. 18, September 15, 2010 7681
 of calibration standards and the set of unknown sample solutions.
No attempt was made in this work to reduce matrix effects
through judicious selections of sample introduction components
or other experimental parameters. It is possible that sensitivity
to matrix effects can be reduced through such selections,20
thereby alleviating to some extent the need for exact matrix
matching. It may also be possible to employ the crossover point
concept recently described by Chan and Hieftje21,22 to help
overcome this issue.
Improvements in Analytical Performance of HP-ICP-OES
with Exact Matching. The final question to be addressed in this
paper regards the amounts by which HP-ICP-OES precision and
bias are improved through the use of exact matching. The answer
to this question will vary with the particular analysis. However, a
consideration of the certifications of the SRMs in the NIST SRM
3100 series is instructive. This SRM series consists of single-
element solutions for each of 67 elements. HP-ICP-OES has been
used by NIST as a major component of the certification strategy
for a large majority of these SRMs for over a decade, with well
over 100 analyses having been performed. The development and
implementation of exact matching began in late 2005. To assess
improvements in the results of HP-ICP-OES analyses of these
SRMs afforded by exact matching, a survey was performed of
historical data for the period from 1999 through the present. The
mean and median of the set of relative expanded uncertainties,
expressed at a level of confidence of 95%, obtained prior to the
implementation of exact matching are 0.23% and 0.19%, respec-
tively (n ) 65). The corresponding statistics for results obtained
afterward are 0.11% and 0.08%, respectively (n ) 49). Therefore,
the use of exact matching has resulted in a general decrease in
the relative expanded uncertainties associated with the HP-ICP-
OES analyses by approximately a factor of 2.
In some cases, the expanded uncertainty associated with a
given HP-ICP-OES analysis may not be significantly affected by
the use of exact matching. This is because the uncertainty budget
can be dominated by components of uncertainty that are unaf-
fected by exact matching, such as the uncertainty associated with
the purity assay of the source material used to prepare calibration
standards. Even in such cases, exact matching is advisable,
because of the possibility of avoiding an otherwise undetected
bias.
Figure 7. Dependences of the observed relative sensitivity of the Finally, it should be mentioned that an additional component
ICP-OES instrument on Na mass fraction for sets of solutions of uncertainty might be required in the uncertainty budget in the
containing (a) 115 mg kg-1 P as the analyte and 18 mg kg-1 Ge as event that adequate exact matching cannot be assured. This
the internal standard, (b) 7 mg kg-1 Cu as the analyte and 28 mg
situation is more likely to arise in terms of exact matrix matching
kg-1 Mn as the internal standard, and (c) 0.3 mg kg-1 Ca as the
analyte and 1.8 mg kg-1 Sc as the internal standard. In panel b, the than exact matching of analyte and internal standard mass
two sets of data were taken on two different days using two different fractions.
sets of solutions. In panel c, the uncertainty in the slope is a 95%
confidence interval. Error bars represent 95% confidence intervals
CONCLUSIONS
calculated from the responses of replicate solutions at each Na matrix
composition. Wavelengths monitored were P (I) 213.618 nm, Ge (I)
The results reported in this paper show that optimal imple-
265.117 nm, Cu (I) 324.754 nm, Mn (I) 279.482 nm, Ca (II) 393.366 mentation of HP-ICP-OES requires careful attention to certain
nm, and Sc (II) 424.682 nm. aspects of the preparation of calibration standards and unknown
sample solutions. Specifically, the analyte mass fractions, internal
Ca (IP ) 6.1 eV) can be considered an EIE, with an ionization
standard mass fractions, and matrix compositions of the solutions
potential that is not very different from that of Na (IP ) 5.1
eV). (20) Todolı́, J. L.; Gras, L.; Hernandis, V.; Mora, J. J. Anal. At. Spectrom. 2002,
Implications. These data show that HP-ICP-OES analysis may 17, 142–169.
(21) Chan, G. C.-Y.; Hieftje, G. M. Spectrochim. Acta, Part B 2008, 63, 355–
be improved by employing exact matrix matching among the 366.
solutions within a given solution set, as well as between the set (22) Chan, G. C.-Y.; Hieftje, G. M. J. Anal. At. Spectrom. 2010, 25, 282–294.

7682 Analytical Chemistry, Vol. 82, No. 18, September 15, 2010
within a given set (e.g., a set of calibration standards) and between a level of confidence of 95%, for HP-ICP-OES analysis. This
the set of calibration standards and the set of unknown sample represents an improvement of a factor of 2 compared to HP-ICP-
solutions should be exactly matched. The exactness of matching OES analysis performed without exact matching.
needed can be reduced somewhat by ensuring that the instrument
response to the analyte and internal standard wavelengths are as
linear as possible and by taking steps to reduce matrix effects. Received for review June 3, 2010. Accepted August 17,
When properly implemented, exact matching enables the routine 2010.
attainment of 0.1% relative expanded uncertainties, expressed at AC101471A

Analytical Chemistry, Vol. 82, No. 18, September 15, 2010 7683