Standard Dilution Analysis: Willis B. Jones, George L. Donati, Clifton P. Calloway, JR., and Bradley T. Jones

Download as pdf or txt
Download as pdf or txt
You are on page 1of 7

Article

pubs.acs.org/ac

Standard Dilution Analysis


Willis B. Jones,† George L. Donati,*,† Clifton P. Calloway, Jr.,‡ and Bradley T. Jones†

Department of Chemistry, Wake Forest University, Winston-Salem, North Carolina 21709, United States

Department of Chemistry, Physics and Geology, Winthrop University, Rock Hill, South Carolina 29733, United States

ABSTRACT: Standard dilution analysis (SDA) is a novel calibration method


that may be applied to most instrumental techniques that will accept liquid
samples and are capable of monitoring two wavelengths simultaneously. It
combines the traditional methods of standard additions and internal
standards. Therefore, it simultaneously corrects for matrix effects and for
fluctuations due to changes in sample size, orientation, or instrumental
parameters. SDA requires only 200 s per sample with inductively coupled
plasma optical emission spectrometry (ICP OES). Neither the preparation of
a series of standard solutions nor the construction of a universal calibration
graph is required. The analysis is performed by combining two solutions in a
single container: the first containing 50% sample and 50% standard mixture;
the second containing 50% sample and 50% solvent. Data are collected in real
time as the first solution is diluted by the second one. The results are used to
prepare a plot of the analyte-to-internal standard signal ratio on the y-axis
versus the inverse of the internal standard concentration on the x-axis. The analyte concentration in the sample is determined
from the ratio of the slope and intercept of that plot. The method has been applied to the determination of FD&C dye Blue No.
1 in mouthwash by molecular absorption spectrometry and to the determination of eight metals in mouthwash, wine, cola, nitric
acid, and water by ICP OES. Both the accuracy and precision for SDA are better than those observed for the external calibration,
standard additions, and internal standard methods using ICP OES.

S tandard dilution analysis (SDA) is a novel calibration


method that may be applied to most instrumental analysis
techniques that will accept liquid samples and are capable of
trometry, where the optical path length is variable and depends
upon the positioning of a sample droplet pressed between two
plates.3 Other common applications involve flowing streams
monitoring more than one wavelength simultaneously. SDA such as gas and liquid chromatography.4,5 The internal standard
combines the traditional methods of standard additions and method will not correct for sample matrix effects, but it will
internal standards. The method of standard additions usually correct for external perturbations as long as the internal
involves the preparation of a series of solutions, each containing standard species has exactly the same response to the
an equal amount of sample but a different amount of added perturbations as the analyte. The method is quicker than
analyte. Since each solution contains the same amount of standard additions, especially if more than one sample is
sample, any effect by the matrix on the analyte should be analyzed. One potential drawback, however, is that the effect of
replicated and corrected. While the mathematics of the method the sample matrix on analyte sensitivity must be exactly the
could be complex depending upon the specific procedure same as its effect on the internal standard. Since the internal
employed,1 it typically boils down to the preparation of a standard calibration curve (a plot of the analyte-to-internal
calibration curve using the prepared solutions and then standard signal ratio versus the concentration of analyte) is
determining the concentration of analyte in the sample from constructed using solutions prepared in pure solvent, the signal
the x-intercept of the line. The method is time-consuming and ratio for a fixed amount of analyte/internal standard must be
cumbersome, especially if more than one sample must be the same in every sample matrix. This often is not the case.
analyzed. On the other hand, it offers a powerful correction if The combination of the standard additions and the internal
the sample matrix significantly affects the analytical signal.2 standard calibration methods has been shown to improve the
Alternatively, if the analytical signal is affected by external results for Cd detection in urine, a typically complex matrix,
factors such as light source fluctuations or changes in sample without sample digestion or any other matrix modification
volume or position, the internal standard method is more using inductively coupled plasma optical emission spectrometry
appropriate. In this case, identical amounts of a judiciously (ICP OES).6 In this case, the calibration methods were
chosen species (internal standard) is added to each analyte combined in the traditional sense: various amounts of a Cd
solution prepared for a calibration curve. The same amount of
internal standard is also added to each sample, which must not Received: November 6, 2014
contain that species naturally. Typical applications for the Accepted: January 19, 2015
internal standard method include infrared absorption spec-

© XXXX American Chemical Society A DOI: 10.1021/ac504152x


Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

standard reference solution were added to identical amounts of mACA and SI = mICI), the ratio of the analyte to internal
urine sample, and a constant concentration of an internal standard signals is described by
standard was also added to each solution. While the results
were improved by the combination of the methods, the SA mC m (C std + CAsam) m C sam m C std
= A A = A A = A A + A A
solution preparation was tedious. SDA uses a similar approach, SI mIC I mIC I mIC I mIC I
with the advantage of simplicity. Because of the gradual dilution (1)
obtained by mixing only two solutions, many standard
Notice that this is the equation for a line if we plot y as (SA/
calibration points are obtained in a single run.
SI) versus x as (1/CI). The slope and intercept of this line are
In practice, SDA is performed by continually monitoring two
given by
signals for a solution containing a constant amount of sample
and varying amounts of a standard solution containing both mA CAsam mA CAstd
analyte and internal standard. This may be accomplished in slope = intercept =
mI mIC I (2)
molecular absorption spectrometry by partially filling a cuvette
with a solution containing 50% sample and 50% standard The SDA method is performed by combining a sample
mixture. As data are collected for this solution, a second containing an unknown amount of analyte, with a standard
solution containing 50% sample and 50% solvent is slowly solution containing a fixed ratio of analyte to internal standard
added. Analyte and internal standard signals are collected as the (CAstd/CI = constant). If the relative amount of sample in the
solutions mix in the cuvette. In this case, the relative amount of solution remains constant during the mixing process, then the
sample remains constant (50%) while the relative amount of matrix effects are constant and (mA/mI) is constant. Therefore,
standards added decreases (the standards are diluted). the intercept is also constant.
Similarly, elements may be determined by ICP OES if a The concentration of analyte in the sample is contained in
solution containing 50% sample and 50% standard mixture is the value for the slope of the line and is given simply by
added to the typical sample reservoir. As the peristaltic pump
delivers this sample to the ICP, a solution containing 50% slope C std
CAsam = × A
sample and 50% solvent is added to the same reservoir. Data intercept CI (3)
are collected as the two solutions are mixed. The relative
amount of sample remains constant, while the standards are The final term in eq 3 is the concentration ratio of analyte to
diluted. internal standard in the prepared standard mixture, so the
Gradient dilution techniques have been applied in flow concentration of analyte in the sample is easily obtained from
systems in the past. A calibration procedure for flow injection the calibration plot. Eq 1 demonstrates the types of interference
flame atomic absorption spectrometry was reported in 1998.7 that SDA may correct. Note that the concentration of both the
Later, a gradient ratio standard addition method was reported analyte and the internal standard must be within the linear
for the same technique.8 Some of these ideas were discussed dynamic range of the traditional calibration curve method. Also,
among a set of univariate calibration techniques for flow the signals measured for the analyte and internal standard (SA
injection analysis.9 The same research group has described a and SI) must not include contributions from any other species.
manifold for calibration in flow injection analysis,10 and also a Given these conditions, the SDA method will correct any
technique for flow injection gradient titration.11 More recently, matrix effects that affect the sensitivity of the analyte, any
a gradient dilution method that overcomes matrix interferences chemical interferences that might affect the sensitivity of the
in ICP OES has been described.12 This approach uses an analyte, and any fluctuations caused by variations in the flows of
HPLC pump to dilute the sample provided to the ICP while liquids or gases, light source power, or sample position. The
monitoring two emission lines continually. This allows an SDA method will not correct for spectral interference unless
automated approach to finding the highest sample concen- the magnitude of that interference could be measured
beforehand and subtracted from the appropriate signals.


tration where the matrix effects are minimized.
SDA, on the other hand, requires no flow since the dilution is
performed in a single container. To demonstrate the viability of
EXPERIMENTAL SECTION
the SDA method, six commercial mouthwash samples have Visible Absorption Spectrometry. FD&C Blue No. 1
been analyzed for the presence of FD&C dye Blue No. 1, using (B1) and FD&C Yellow No. 6 (Y6) crystalline dyes were
FD&C dye Yellow No. 6 as the internal standard. Subsequently, obtained from Rainbow Colors, LLC (Windsor, CT). Caution
a suite of eight metals (Al, Cd, Co, Cr, Cu, Fe, Ni, and Pb) has is advised when handling the solid dyes to prevent accidental
been determined in mouthwash, wine, cola, nitric acid, and inhalation. Blue no. 1 also may be harmful to the aquatic
water by ICP OES using Y as the internal standard. environment. An aqueous solution was prepared containing a


mixture of 6.03 μM B1 (analyte) and 37.6 μM Y6 (internal
standard). Concentrations were recorded to three significant
MATHEMATICAL APPROACH
figures. A modular UV−vis apparatus consisting of a sample
The mathematical approach is straightforward. The analyte holder with integrated light source (tungsten coil lamp), a glass
species (A) in the sample is combined with a standard mixture cuvette, fiber optic, and an USB4000 spectrometer (Ocean
containing both the analyte (A) and an internal standard Optics, Dunedin, FL) was used to analyze the samples. Solution
species (I). Analyte signal (SA) arising from both the sample 1, containing 50% of the standard mixture and 50% sample, was
(sam) and the standard (std) mixture is monitored at one placed in the glass cuvette (1.0 mL aliquot), and the signals at
wavelength, while the internal standard signal (SI, from the 635 nm (analyte) and 480 nm (internal standard) were
standard mixture only) is monitored at a different wavelength. recorded using a 1-s integration time. Then 2.0 mL of solution
Given that the signal in each case is equal to the calibration 2, containing 50% sample and 50% distilled water, were slowly
sensitivity (m) times the concentration of each species (SA = added to the same cuvette using a micropipette with no manual
B DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

or mechanical mixing. The analysis time depended on how fast


solution 2 was added to solution 1 which, in turn, determined
■ RESULTS AND DISCUSSION
Visible Absorption Spectrometry. FD&C Blue No. 1
the number of calibration points obtained (i.e., slower dilutions and FD&C Yellow No. 6 are certified color additives used in
provided more calibration points). In this experiment, typical many foods and consumer products. Since B1 is added as a
runs lasted 90 s, resulting in approximately 50 calibration colorant to relatively simple commercial preparations, it is easy
points. Six commercial mouthwash samples (A−F), each to detect using the traditional technique of visible molecular
containing different amounts of FD&C Blue No. 1 (based on absorption spectrometry. Because it is inexpensive and
the darkness of their blue color), and varying matrix detectable at very low levels using a simple colorimeter, it has
concomitants were analyzed: Listerine Ultraclean (A), Scope been employed in many educational laboratory experiments.
(B), Crest (C), Listerine Fluoride (D), Act (E), and Breath Rx Straightforward calibration techniques have been employed to
(F). For comparison, the same system, samples, standard determine B1 in candies,14 powdered drinks,15,16 and mouth-
solutions, and integration times were used to analyze the wash.17 Of these, mouthwash preparations seem to have the
samples by the traditional methods of external calibration, most variable sample matrices, so these were chosen to evaluate
standard additions, and internal standard. the initial viability of the SDA method.
Atomic Emission Spectrometry. A mixture of metal ions SDA signal profiles for four replicates of sample C are shown
was obtained in two solutions from Teledyne Leeman in Figure 1. Closed points represent the absorbance of the
Laboratories (Hudson, NH). The first solution, used as the
reference standard, consisted of Al, Cd, Cr, Co, Cu, Fe, Ni, Pb
(analytes), and Y (internal standard) at 100 mg/L in 5% (v/v)
HNO3. Yttrium was used in all SDA measurements because it
has been shown to be an effective internal standard for a variety
of analytes and sample types in ICP OES determinations.13 The
second solution was used to spike several samples and check
the efficiency of the SDA method for different matrixes. It was
identical to the first one, with the exception of containing Sc
instead of Y. The sample and reference standard solutions used
in the SDA runs were prepared by diluting the original
solutions 10-fold.
For the SDA method, five samples were spiked with the
multielement solution containing Al, Cd, Cr, Co, Cu, Fe, Ni,
Pb, and Sc: deionized water; 40% HNO3 (v/v) (Fisher
Scientific, TraceMetal grade−caution: use eye and hand
protection when handling concentrated nitric acid); 50% (v/
v) Listerine mouthwash; regular Pepsi (Pepsico, Inc.); red wine Figure 1. Molecular absorbance measured for FD&C Blue No. 1
(Twisted Wine Cellars, Manteca, CA). The reference standard (closed circles) at 635 nm, and FD&C Yellow No. 6 (open circles) at
used in each run was prepared by diluting the Y-containing 480 nm, during the standard dilution analysis of four replicates of
stock solution 1:10 in deionized water. A Prodigy High commercial mouthwash sample C.
Dispersion ICP OES (Teledyne Leeman Laboratories) was
used in all SDA experiments. Emission signals were obtained by
analyte (B1) measured at 635 nm; open points represent the
time-resolved analysis (TRA) at 1 s intervals and over the
absorbance of the internal standard (Y6) measured at 480 nm.
course of 5 min (for a total of 300 data points). The typical Gaps between each run are the times required to replace the
recommended instrumental operating conditions were em- solution and rinse the cuvette. All replicates in this figure were
ployed. used to produce a single SDA calibration plot, which is shown
Four steps were required to apply the SDA method in ICP in Figure 2. The SDA plot has the inverse of the concentration
OES using a single peristaltic pump channel: (i) deionized of Y6 (mM−1) on the x-axis versus the ratio of the absorbance
water was introduced into the plasma for approximately 30 s of B1 and Y6 on the y-axis. In all cases, the concentration of Y6
and a baseline signal was obtained; (ii) a solution containing at any given time was calculated using the absorbance measured
50% sample and 50% standard (solution 1) was then for Y6 at that time (Figure 1) and the maximum absorbance
introduced and the signal increased until a plateau was observed for Y6 prior to the onset of dilution. Therefore,
observed; (iii) after a stable maximum was achieved, the mixing need not be complete prior to data collection, and data
solution containing the blank (50% sample and 50% blank, are collected “on-the-fly”. Notice that despite the complexity of
solution 2) was added to the tube containing solution 1, which the sample matrix, the trendline almost perfectly bisects each
resulted in the gradual dilution of the reference standard; and calibration point, even though all four replicates are included on
(iv) after the signal reached a stable minimum due to the the same graph. In fact, the correlation coefficient for the
dilution of solution 1 by solution 2, deionized water was trendline was 0.9999, and R2 was 0.9998. Regression analysis
introduced once again to rinse the system and ready it for the performed by Microsoft Excel reported a standard error in the
next run. For comparison, the same system and stock solutions slope of only 0.10%. The error in the intercept was 0.16%. The
were used to carry out the traditional methods of external four separate SDA runs gave B1 concentrations in mouthwash
calibration, standard additions, and internal standardization for C with a relative standard deviation of only 0.19%. SDA
the analysis of each sample. For each of the traditional methods, calibration plots for all six mouthwash samples are shown in
five different calibration solutions were used to prepare each Figure 3. Clearly, SDA can provide results with a high degree of
plot. precision.
C DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

Figure 2. SDA plot of the four replicates for mouthwash C (Figure 1) plotted as a single run.

Table 1. Concentration and Precision Values for the


Determination of FD&C Blue No. 1 in Six Mouthwash
Samples Using Different Calibration Methodsa
sample EC IS SA SDA
Average Amount of FD&C Blue No. 1 Found (μM)
A 0.74 0.79 0.33 0.54
B 1.1 1.4 2.0 2.1
C 3.2 4.1 3.8 3.6
D 7.2 7.3 7.2 7.6
E 6.2 7.1 7.6 7.9
F 10.7 13.3 10.2 10.1
Precision (% relative standard deviation)
A 5.5 5.4 3.7 0.88
B 1.3 1.4 0.7 0.23
C 1.5 1.2 1.8 0.19
D 1.9 1.9 1.4 0.37
Figure 3. SDA plots for six different mouthwash samples (A−F). Each E 4.3 6.3 5.5 0.44
plot includes multiple replicates. The scale is expanded to show the F 3.2 4.0 1.9 0.39
intercepts more clearly, so many data points fall beyond the limits of average 3.0 3.4 2.5 0.42
the axes (see Figure 2). a
The traditional methods employed five replicates (n = 5), while SDA
employed four replicates analyzed as a single run with 150 calibration
points total (Figure 3).
The concentration of B1 in each sample is contained in the
slope of the SDA line. The amount of B1 in the sample is found
by simply dividing the slope by the relative sensitivities the different sample matrices affect the calibration sensitivities
determined from the intercept (eq 2), or by dividing the for B1 and Y6 to different degrees. Not only does SDA correct
slope by the intercept and then multiplying it by the relative for this effect but it also provides a visual indication of its
concentrations of B1 and Y6 in the standard mixture (eq 3). magnitude (by comparing the intercepts). As expected, SA and
For comparison, the original solutions, blank, samples, and SDA are less sensitive to matrix effects, and their results are
instrumentation used for the SDA determinations were also more closely related. Therefore, the SDA accuracy should be as
used to prepare traditional external calibration (EC), internal good as that measured with the standard additions method,
standard (IS), and standard additions (SA) curves. Results are with the advantage of the enhanced precision provided by the
shown in Table 1. Notice that, generally, %RSD values are correction for fluctuations due to internal standardization.
higher for the EC and IS methods. This most likely happens Results in Table 1 clearly show that the SDA method can be as
because these methods are more severely affected by matrix effective as, or even more effective than, the traditional
effects, and the samples evaluated in these experiments present calibration methods. Considering SDA’s low RSDs, it may
a significant variation in their composition (e.g., sample A has also contribute to higher powers of detection. In addition to
21.6% v/v ethanol; sample C has no ethanol). Notice that these accurate, precise, and sensitive determinations, the SDA
samples have different y-intercepts (Figure 3). This is because method also allows for high sample throughput since only
D DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

one standard solution needs to be prepared, and the sample is


diluted only twice (once with blank and once with this standard
solution).
Atomic Emission Spectrometry. Figure 4 shows the
emission signals obtained for Al in a mouthwash matrix, Fe in a

Figure 5. SDA plots for Al in mouthwash, Fe in nitric acid, and Pb in


wine.

times. Since the concentration of all eight analytes spiked in the


samples was the same (10 mg/L), the results were combined
for each matrix, and the different calibration methods were
compared. As one would expect, the SDA results were similar
Figure 4. Emission signals obtained for Al in a mouthwash matrix, Fe
in a HNO3 matrix, and Pb in a wine matrix during an SDA run. to the ones from the standard additions method, and both were
superior to the other calibration strategies (Table 2). The main
HNO3 matrix, and Pb in a wine matrix during an SDA run Table 2. Limits of Detection and Concentrations of Eight
using ICP OES. As discussed previously, in the first 30 s of each Metals Found Using Different Calibration Methods
run, deionized water is introduced into the ICP to establish a
blank baseline. Solution 1 is then introduced into the plasma EC IS SA SDA n
until a stable maximum is achieved. At 120 s into the run, an Limit of Detection, mg/L
aliquot of solution 2 is added to solution 1, which results in the Al, 396.15 nm 0.2 0.6 0.1 0.08 5
gradual decrease of the emission intensities, giving rise to the Cd, 214.44 nm 0.1 0.4 0.3 0.03 5
“SDA region” of Figure 4. Note the 15 s delay between the Co, 228.62 nm 0.2 0.6 0.3 0.01 5
solution mixing and the beginning of the SDA region as the Cr, 267.72 nm 0.1 0.4 0.3 0.02 5
solution travels through the tubing, to the nebulizer, and into Cu, 324.75 nm 0.1 0.5 0.3 0.02 5
the plasma. At 210 s, water is again introduced into the ICP to Fe, 259.94 nm 0.2 0.3 0.3 0.08 5
prevent memory effects. This cleaning step continues until the Ni, 221.65 nm 0.3 0.2 0.3 0.03 5
300 s mark, when the system is ready for the next run. Pb, 220.35 nm 0.3 0.3 0.3 0.08 5
Similar to the molecular absorption determinations described Average Concentration of Eight Metals Found, mg/L
previously, the ratio between analyte and internal standard (10 mg/L of each metal added)
signal intensities is plotted against the inverse of the internal water 10.0 10.9 10.1 10.2 24
standard concentration. Again, the concentration of internal nitric acid 9.1 11.6 8.9 9.8 24
standard at any given time is calculated by comparing the mouthwash 13.4 12.6 11.2 10.3 24
emission signal of the internal standard in the SDA region cola 10.0 11.6 9.5 9.5 24
(Figure 4) with the signal prior to the onset of dilution. Figure wine 14.6 13.4 11.2 10.5 24
5 shows the SDA plots created from data in the “SDA region” average 11.4 12.0 10.2 10.1 120
of Figure 4 and using Y as the internal standard.
As observed in Figure 4, the SDA region stretches over advantages of the SDA method when compared to standard
approximately 30 s. Because a data point is collected every additions are its simplicity, its superior sample throughput, and
second, a total of 30 standard calibration points is obtained. the possibility of correcting for variations in physical parameters
Some of these points are not shown in Figure 5 for clarity, but associated with the sample and its environment during the
the trendline is constructed from all of the points. Because the analysis.
standard reference solution used in all experiments contains 10 The limits of detection (LOD) were calculated by analyzing
mg/L of all elements, the ratio between analyte and Y five blank samples and multiplying the standard deviation of the
concentrations in the standard is equal to 1. Thus, the results by 3. In all cases, the blank was the matrix without the
concentrations of analytes in the samples are calculated simply analytes added. The results for SDA were slightly better than
by dividing the calibration curve slopes by their intercepts (eq those obtained by the other calibration methods (Table 2).
3). This fact may be related to SDA characteristics such as the large
The SDA results were compared to the standard additions, number of calibration points used for the blank (30 points for
external calibration, and internal standard methods. To prevent SDA compared to 5 points for SA, for example) and minimal
any bias during data collection, the Time Resolved Analysis sample manipulation, which may result in lower standard
feature was used in all experiments with the same integration deviations. In addition, blank measurements to determine LOD
E DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

in SDA begin with a relatively large analyte signal from the method may randomly result in artificially high or low values,
standard. This might help minimize small signal fluctuations the average amount found is similar to that for SDA. However,
from the background, which would be more prominent in the the average percent error is significantly worse for SA (Table
absence of an analytical signal. Furthermore, if the measure- 3). In addition, SDA provides improvements in precision,
ment is shot-noise-limited, as might be the case for an emission calculated as percent relative standard deviation, when
measurement using an internal standard, a larger initial signal compared to all three calibration methods.
should result in a lower LOD. On the other hand, the SDA For this proof of concept work, we have chosen two different
method is time-limited (a single point per second is collected in techniques that are widely used and that can suffer from severe
ICP OES, for example). The traditional methods might employ matrix effects. ICP-based methods are especially sensitive to
longer integration times to improve detection limits. such effects,18,19 and we have intentionally chosen complex
Table 3 displays the results of all four calibration methods matrices, with diverse compositions, to demonstrate the
separated by element. Individual entries in the table are an capabilities of SDA in comparison to the traditional calibration
methods.
Table 3. Concentration of Eight Metals, Accuracy, and
Precision Found Using Different Calibration Methods
EC IS SA SDA n
■ CONCLUSION
Standard dilution analysis is simple and effective, providing
Average Concentration Found, mg/L (10 mg/L added)
superior accuracy, precision, and sample throughput when
Al 12.1 12.6 9.5 9.5 15
compared to other traditional calibration methods. It offers the
Cd 11.7 12.2 11.0 10.5 15 best of both worlds: it simultaneously corrects for matrix effects
Co 11.8 12.3 10.2 10.0 15 due to the sample concomitants (as with standard additions)
Cr 11.0 11.6 10.3 10.2 15 and for fluctuations due to changes in sample size, orientation,
Cu 11.6 12.3 9.5 9.7 15 or instrumental parameters (as with internal standard). SDA
Fe 11.2 11.8 10.5 10.3 15 requires no instrument modifications or special strategies for
Ni 11.1 11.7 10.4 10.2 15 widely used techniques such as molecular absorption
Pb 11.0 11.6 10.1 9.9 15 spectrometry and ICP OES. It can be applied to most
average 11.4 12.0 10.2 10.1 120 instrumental analysis techniques that will accept liquid samples
Accuracy (average percent error) and are capable of simultaneous multianalyte determinations.
Al 24.8 26.1 4.8 5.0 15 The novel approach proposed by SDA is rapid, requiring less
Cd 20.8 22.2 16.0 7.3 15 than 3 min to analyze each sample by mixing two solutions in a
Co 19.6 23.3 11.5 4.2 15 single container. That container may be the cuvette in a
Cr 15.5 16.4 10.4 4.3 15 molecular absorption experiment or the sample tube in an ICP
Cu 16.4 23.4 7.8 3.8 15 OES experiment. Since the same amount of sample is always
Fe 20.1 17.6 10.8 4.5 15 present during the measurement, the relative effect of the
Ni 18.7 17.5 12.4 4.9 15 matrix on analytes and internal standard is not a concern. This
Pb 18.9 15.8 12.0 4.0 15 makes the selection of a suitable internal standard trivial. As
average 19.3 20.3 10.7 4.7 120 shown in this proof of concept work, the SDA method may be
Precision (percent relative standard deviation) successfully used in molecular and atomic spectrometry
techniques.


Al 30.5 17.4 2.9 3.5 15
Cd 24.4 10.9 18.8 7.7 15
Co 21.0 8.0 13.9 5.1 15 AUTHOR INFORMATION
Cr 18.7 5.9 12.7 4.5 15 Corresponding Author
Cu 15.6 9.7 7.6 3.3 15 *E-mail: donatigl@wfu.edu. Tel: +1 336 758-4815. Fax: +1 336
Fe 25.6 12.7 13.5 5.0 15 758-4656.
Ni 22.6 9.4 14.9 5.8 15
Notes
Pb 22.4 9.3 13.8 4.9 15
The authors declare no competing financial interest.


average 19.8 9.3 13.3 5.8 120

REFERENCES
average of 15 SDA runs: five sample matrixes, n = 3. As (1) Bader, M. J. Chem. Educ. 1980, 57, 703−706.
observed in Table 2, SDA and standard additions present (2) Harvey, D. J. Chem. Educ. 2002, 79, 613−615.
similar results. Purely from a recovery standpoint, SDA (3) Veening, H. J. Chem. Educ. 1966, 43, 319−320.
provides results of a slightly better accuracy than those of (4) Rice, G. W. J. Chem. Educ. 1987, 64, 1055−1056.
standard additions and significantly better than those obtained (5) Magee, J. A.; Herd, A. C. J. Chem. Educ. 1999, 76, 252.
with the other methods. However, when average percent errors (6) Davis, A. C.; Alligood, B. W.; Calloway, C. P., Jr.; Jones, B. T.
are compared, SDA accuracies are superior to the standard Appl. Spectrosc. 2005, 59, 1300−1303.
addition (SA) values by a factor of 2 and to the other methods (7) Koscielniak, P. Anal. Chim. Acta 1998, 367, 101−110.
by a factor of 4. This may be explained by the number of data (8) Koscielniak, P.; Kozak, J. Anal. Chim. Acta 2002, 460, 235−245.
(9) Koscielniak, P. Anal. Chim. Acta 2001, 438, 323−333.
points used to construct the plots for each method. The SDA (10) Koscielniak, P.; Wierczorek, M.; Kozak, J.; Herman, M. Anal.
plots are prepared using 30 data points, one collected each Chim. Acta 2007, 600, 6−13.
second during the SDA region of the dilution. The SA method (11) Wojtowicz, M.; Kozak, J.; Koscielniak, P. Anal. Chim. Acta 2007,
employs a calibration curve prepared from only five solutions. 600, 78−83.
Therefore, the best fit is superior with the SDA method and the (12) Cheung, Y.; Schwartz, A. J.; Hieftje, G. M. Spectrochim. Acta,
accuracy is better. Since the quality of the best fit in the SA Part B 2014, 100, 38−43.

F DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX
Analytical Chemistry Article

(13) Zachariadis, G. A.; Vogiatzis, C. Appl. Spectrosc. Rev. 2010, 45,


220−239.
(14) Aurian-Blajeni, B.; Sam, J.; Sisak, M. J. Chem. Educ. 1999, 76,
91−92.
(15) Sigmann, S. B.; Wheeler, D. E. J. Chem. Educ. 2004, 81, 1475−
1478.
(16) Thomasson, K.; Lofthus-Herschman, S.; Humbert, M.;
Kulevsky, N. J. Chem. Educ. 1998, 75, 231−233.
(17) Siegrist, E.; Anderson, G. J. Chem. Educ. 1997, 74, 567−568.
(18) Montaser, A.; Golightly, D. W., Ed. Inductively Coupled Plasmas
in Analytical Atomic Spectrometry, 2nd ed.; Wiley-VCH: New York,
1992.
(19) Montaser, A., Ed. Inductively Coupled Plasma Mass Spectrometry,
1st ed.; Wiley-VCH: New York, 1998.

G DOI: 10.1021/ac504152x
Anal. Chem. XXXX, XXX, XXX−XXX

You might also like