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Article
Coordinate swapping in standard addition graphs for analytical chemistry:
a simplified path for uncertainty calculation in linear and nonlinear plots
Juris Meija, Enea Pagliano, and Zoltan Mester
Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/ac5014749 • Publication Date (Web): 06 Aug 2014
Downloaded from http://pubs.acs.org on August 12, 2014

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Coordinate swapping in standard addition graphs for analytical chemistry:
5 a simplified path for uncertainty calculation in linear and nonlinear plots
6
7 Juris Meija*, Enea Pagliano, and Zoltán Mester
8
9
10 National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario K1R 0R6, Canada
11 * Corresponding author: juris.meija@nrc.ca
12
13 ABSTRACT
14
15 Uncertainty of the result from the method of standard addition is often underestimated due
16 to neglect of the covariance between the intercept and the slope. In order to simplify the
17
data analysis from standard addition experiments, we propose x-y coordinate swapping in
18
19 conventional linear regression. Unlike the ratio of the intercept and slope, which is the result
20 of the traditional method of standard addition, the result of the inverse standard addition is
21 obtained directly from the intercept of the swapped calibration line. Consequently, the
22 uncertainty evaluation becomes markedly simpler. The method is also applicable to nonlinear
23 curves, such as the quadratic model, without incurring any additional complexity.
24
25
GRAPHICAL ABSTRACT
26
27
28 THE METHOD OF STANDARD ADDITION
29
DIRECT INVERSE
30 REGRESSION REGRESSION
31
x = AMOUNT OF THE
ANALYTE ADDED

32
y = SIGNAL

33
34
35
36
37 x = AMOUNT OF THE y = SIGNAL
–x0
38 ANALYTE ADDED
39 x0 = a0/a1
x0 = –b0
40 u(x0) = x0 u2(a0)/a02 + u2(a1)/a12 + –x0 u(x0) = u(b0)
41 2x.u2(a0)/(a0a1) 1/2
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3 Introduction
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6 It is a common knowledge in analytical chemistry that the instrumental response can be
7 affected by sample matrix. This behaviour leads to biased results when the analytical signal
8 produced from the sample is compared against the calibration graph prepared from matrix-
9 free standard solutions. To overcome this problem, the method of standard addition was
10 introduced in the 1930s.1,2 To date, the method of standard addition remains an essential tool
11
in quantitation especially when isotope dilution cannot be applied. Like any scientific tool,
12
13 the method standard addition has witnessed new developments most notable of which is
14 the concomitant use of the internal standard.3
15
16 To wit, when more than one addition of a standard is performed, the method of standard
17 addition seeks the point with zero response (assuming all signals are corrected for blank
18 contribution), i.e., the analytical result is4,5
19
20
x0 = –xy=0 (1)
21 The calculation of x0 is done by fitting of best line through the observed data {x, y} where x is
22 the amount of the added analyte, and y is the corresponding analytical response. For a
23 commonly used straight line fit, y = a0 + a1x,
24 x0 = a0/a1 (2)
25 which means that the result of the classical standard addition is the ratio of the intercept and
26
the slope of the linear fit. A drawback of this traditional approach is that the uncertainty of
27
28 the analytical result cannot be obtained readily from the fitting parameters a0 and a1. Rather,
29 uncertainty propagation must be performed by combining the uncertainties of a0 and a1.
30 Moreover, because the intercept and the slope are correlated estimates, uncertainty
31 propagation of their ratio must involve the covariance between these two estimates which is
32 not trivial and is often neglected in practice:6-9
33
u2 ( x0 ) u2 (a0 ) u2 (a1 ) cov(a0 , a1 )
34 2
= 2
+ 2
−2 (3)
35 x0 a0 a1 a0 a1
36 where
37
cov(a0 , a1 ) = −x ⋅ u2 (a1 ) (4)
38
39 In general, uncertainty calculations of standard addition results are rather tedious; and
40 publications on the subject are riddled with mathematical equations.3 In addition, several
41 recent studies have focused on a more general problem of nonlinear calibration curves in
42 analytical chemistry.10,11 The metrological aspects of nonlinear calibration curves, however,
43 has not witnessed proper attention largely due to the complexity that this problem poses.
44
45
46 THEORY
47
48 Variable transformation for standard additions
49
50 To the annoyance of many chemists, traditional standard addition regression does not yield
51
the analytical result directly. This problem has been noted before. Notably, Tellinghuisen has
52
53 proposed an alternative approach whereby the variable-of-interest for standard additions, x0,
54 is cast as an explicit variable of the fitting model rather than calculated from the fitting
55 parameters.12,13 The method involves variable transformation from the classical y = a0 + a1x,
56 with x0 = a0/a1, to y = a0(a1 + x) which gives a direct estimate of the standard addition result,
57 i.e., x0 = a1. Likewise, quadratic fitting of y = a0 + a1x + a2x2 can be done with modified
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3 quadratic function, y = a0(a1 + x) + a2(a1 + x)2, which yields x0 = a1. Albeit simple in its concept,
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5
the variable rearrangement from y = a0 + a1x to y = a0(a1 + x) = a0a1 + a0x leads to a nonlinear
6 fitting problem because of the product of both variables, a0a1, which appears in the model
7 equation. As a result, no simple algebraic expressions can provide the results and iterative
8 minimization methods must be employed, such as the Excel SOLVER macro.
9
10 Coordinate swapping
11
12
13 Consider a typical standard addition experiment where x is the vector of the masses of the
14 added standard and y is the vector of the corresponding instrumental responses. Now,
15 instead of fitting y = a0 + a1x, one performs fitting of x = b0 + b1y which is known as the inverse
16 calibration.14 Ordinary least squares fit is obtained by minimizing the sum (a0 + a1xi – yi)2 with
17 a0 and a1 as variables whereas the inverse fit is found by minimizing the sum (b0 + b1yi – xi)2
18 with b0 and b1 as variables. The advantage of the seemingly trivial coordinate swapping
19
20
becomes evident after calculation of x0,inv = –xy=0; x0,inv equals the (negative) intercept of the
21 inverse regression, i.e.,
22 x0,inv = –b0 (5)
23 Consequently, the uncertainty of the analyte concentration x0,inv is the uncertainty of the
24 intercept:
25 u(x0,inv) = u(b0) (6)
26
No additional uncertainty propagation is necessary which obviates the need to evaluate the
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28 covariance between the regression parameters which is necessary when direct regression is
29 employed (see eqs. 3-4).
30
31 Equivalence between direct and inverse regression
32
33 The ordinary least squares minimization is not symmetric with respect to both coordinates.
34
Consequently, many heated discussions have ensued in regards to the numerical differences
35
36 obtained from direct and inverse regressions.14,15 In the context of analytical chemistry, the
37 following two expressions are helpful to establish the metrological compatibility between
38 the results of the direct and inverse linear standard addition models. First, for sufficiently
39 large coefficient of determination (r2) commonly, if not universally, encountered in analytical
40 chemistry,
41
42 u( x0,inv ) / u( x0 ) ≈ r 2 (x)
43 This expression establishes practical equivalence between the uncertainty estimates of direct
44 and inverse standard addition method results. Second, the difference between the results of
45 inverse and direct standard addition methods is:
46
47 x0,inv − x0 = −b1 y (1 − r 2) / r 2 (x)
48 The combination of these two expressions can be empirically approximated as follows:
49 x0,inv − x0 1 − r2
50 ≈ −2 (x)
51 u( x0 ) r2
52 At approximately r2 > 0.8 the two models become metrologically compatible in a sense that
53 the uncertainty of x0 exceeds the numerical difference between the direct and the inverse
54 models, x0,inv – x0. Hence, it is fair to conclude that for all practical applications of analytical
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chemistry, the numerical difference between the results of direct and inverse linear standard
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57 addition plots is irrelevant.
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3 Nonlinear models
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6 Not all analytical methods provide linear response with respect to the amount of the analyte.
7 When nonlinear response is observed, it is common among chemists to employ empirical
8 polynomials, such as the quadratic function, in order to represent the observed curvature
9 while disregarding the physical basis of the nonlinearity. The difficulty of employing
10 polynomial fitting in standard addition models, however, is in large part due to the
11
complexity of obtaining the analytical results. For example, the analytical result from a
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13 quadratic standard addition fit, y = a0 + a1x + a2x2, is given as16
14 −a1 ± a12 − 4a0 a2
15 x0 = (7)
16 2 a2
17 and the uncertainty calculation is prohibitively complex:
18 u2 (a0 ) q2u2 ( a1 ) d2u2 (a2 )
19 u2 ( x0 ) = + + −
20
z 4a22 z 4a24 z
(8)
21 q cov(a0 , a1 ) d cov(a0 , a2 ) qd cov(a1 , a2 )
22 − + −
a2 z a22 z 2a23 z
23
24 where z = a12 − 4a0 a2 , q = a1 m z , d = a1q − 2a0 a2 , and the regression parameter covariances
25 are calculated as follows:
26
27 2
cov(a0 , a1 ) = u (a1 )
∑ x∑ x 4 − ∑ x2 ∑ x3
(9)
2
28
29
( ∑ x 2 ) − N∑ x 4
2 2
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31 2
cov(a , a ) = u (a )
( ∑ x ) − ∑ x∑ x 3

(10)
0 2 2 2
32 ( ∑ x ) − N∑ x 2

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34 2
N∑ x 3 − ∑ x ∑ x 2
cov(a1 , a2 ) = u (a2 ) 2
(11)
35
36
(∑ x) − N∑ x 2
37 In stark contrast to equations 8-11 for quadratic standard addition model y = a0 + a1x + a2x2,
38 the uncertainty calculation in the inverse approach, x = b0 + b1y + b2y2, remains simple:
39 u( x0,inv ) = u(b0 ) (12)
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41 The simplicity of the inverse fitting is a particularly attractive feature given the growing use
42 of nonlinear calibration functions in analytical chemistry (see Table 1).16-18
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44 Table 1. Comparison of the direct and inverse calibration approaches for the standard addition
45 method.
46 Direct calibration Model Result
47
y = a 0 + a 1x Linear x0 = a0/a1
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49 y = a0 + a1x + a2x2 Quadratic x0 = ( −a1 ± a12 − 4a0a2 ) / 2a2
50 y = (a0 + a1x)/(1 + a2x) x0 = a0/a1
Padé[1,1]
51 2
52 y = (a0 + a1x + a2x )/(1 + a3x) Padé[2,1] x0 = ( −a1 ± a12 − 4a0a2 ) / 2a2
53 Inverse calibration Result
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x = b 0 + b 1y Linear x0,inv = –b0
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56 x = b 0 + b 1 y + b 2y 2 Quadratic x0,inv = –b0
57 x = (b0 + b1y)/(1 + b2y) Padé[1,1] x0,inv = –b0
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3 x = (b0 + b1y + b2y2)/(1 + b3y) x0,inv = –b0
Padé[2,1]
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6 The inverse of the linear model is also a linear model and the same holds true for Padé[1,1]
7 model. Unlike these two functions, however, polynomial models are not invertible. The
8 mathematical form of the fitting model equation, however, is irrelevant for most applications
9 since nonlinear models are used empirically in order to describe the observed curvature
10
between x and y. Consequently, the fitting parameters often carry little physical meaning. In
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12 many cases, nonlinear responses can be made linear by using variable transformation. For
13 example, when the method of standard addition is used in potentiometry, one employs
14 linear fitting function y = a0 + a1lnx, which can be inverted to x = b0 + b1lny.
15
16 Regressions with Excel
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18
19 Calculations using Excel spreadsheets have become commonplace in science.19,20 Many fitting
20 algorithms involve the SOLVER macro which performs minimization of a user-defined function
21 against the user-defined argument. The use of such iterative approaches cannot be subjected
22 to a seamless copy-and-paste for other data, and they do not provide the uncertainty
23 estimates for the parameters. On the contrary, the built-in Excel LINEST function addresses all
24 of the above shortcomings and it can be tailored for both linear and nonlinear model
25
equations. Table 2 summarizes useful LINEST directives in order to perform fitting on linear or
26
27 polynomial models, including the rational Padé functions which were recently introduced for
28 nonlinear standard addition fitting.21
29
30 Table 2. LINEST() fitting of functions commonly encountered in analytical chemistry. a
31 Type Function Excel directive (in English) b
32 Direct y = a0x =LINEST(y, x, FALSE, TRUE)
33
Linear y = a 0 + a 1x =LINEST(y, x, TRUE, TRUE) C
34 2
35 Quadratic y = a 0 + a 1 x + a 2x =LINEST(y, x^{0,1,2}, FALSE, TRUE)
36 Polynomial y = a0 + a1x + … + amxm =LINEST(y, x^{0,…,m}, FALSE, TRUE)
37 Padé[1,1] y = (a0 + a1x)/(1 + a2x) =LINEST(y, x^{0,1,0}*–y^{0,0,1}*x^{0,0,1}, FALSE, TRUE)
38 2
Padé[2,1] y = (a0 + a1x + a2x )/(1 + a3x) =LINEST(y, x^{0,1,2,0}*–y^{0,0,0,1}*x^{0,0,0,1}, FALSE, TRUE)
39
40 a For inverse fitting x = f(y), all instances of x and y in the LINEST() directive have to be
41 interchanged. For example, the inverse linear fit is performed using LINEST(x, y, TRUE,
TRUE).
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b Symbols x and y stand for the data input range. For example, if the values of x and y
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are in cells A1 to A5 and B1 to B5, respectively, then the linear fit is obtained by
44
entering =LINEST(B1:B5, A1:A5, TRUE, TRUE). Also note that unlike many other functions
45 which are entered in a singe cell by pressing enter, LINEST is an array function which is
46 entered over several cells (an array) by pressing ctrl+shift+enter.
47 c Alternatively, one can use =LINEST(y, x^{0,1}, FALSE, TRUE).
48
49
Experimental Part
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52 Bromide was analyzed in certified groundwater reference material by using headspace gas
53 chromatography mass spectrometry (GCMS) after the aqueous derivatization with
54 triethyloxonium tetrafluoroborate at room temperature.22 Iodide ions which are naturally
55 present in the groundwater were used as the internal standard for bromide since both of
56 these anions undergo ethylation in a similar fashion. Experimental details are summarized in
57
58 the Supplementary material and further details can be found elsewhere.23
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Results and discussion
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7 To demonstrate the validity of the coordinate swapping in standard additions, and also to
8 show the usefulness of this approach when dealing with nonlinear standard addition models,
9 determination of bromide in groundwater certified reference material was undertaken using
10 state-of-the-art GCMS method.22 All relevant experimental data are given in Table 3. Symbol
11
mA(AA*) stands for the mass of the sample in the mixture of the sample (A) and standard (A*),
12
13 mA*(AA*) is the mass of the standard in the corresponding mixture, mfinal is the mass of the AA*
14 mixtures after addition of all reagents, and AEtBr and AEtI stand for the peak areas of EtBr and
15 EtI.
16
17 Table 3. Determination of bromide ions in groundwater (BCR-611): data. a
18
19 mA(AA*)/g mA*(AA*)/g mfinal/g AEtBr AEtI
20 2.005 99 0.000 00 2.353 82 14 610 8153
21 2.008 17 0.000 00 2.358 67 14 633 8176
22
2.180 35 0.000 00 2.355 67 13 422 7695
23
24 2.001 74 0.049 49 2.350 62 21 863 8190
25 2.004 35 0.050 05 2.353 49 22 161 8339
26 2.009 60 0.049 89 2.358 09 22 155 8199
27 1.999 61 0.099 24 2.348 73 29 786 8357
28
29 2.005 36 0.099 49 2.354 30 30 806 8652
30 2.009 01 0.099 91 2.358 00 30 427 8432
31 1.999 22 0.148 14 2.346 72 35 088 7983
32 2.002 76 0.148 72 2.351 28 37 794 8531
33
2.006 66 0.148 83 2.354 87 34 243 7731
34
35 1.997 26 0.197 03 2.344 29 42 221 7909
36 2.004 13 0.198 03 2.352 16 46 070 8682
37 2.006 93 0.200 21 2.357 14 38 640 7286
38 – –1
39 a Mass fraction of Br in primary reference standard solution, wA* = 1925(2)k=1 ng g .
40
41 In our calculations we use a more elaborate formalism of standard additions which accounts
42 for the (small) differences in the amount of sample in each aliquot, and for the (small)
43 differences in the dilution factors. We also employ an internal standard in order to attain
44
highest precision. More details on this precision-formalism of the standard additions can be
45
46 consulted elsewhere,3,24 and here we give only a brief summary of the variables which are
47 involved in constructing the standard addition plots. When no internal standard is used, the
48 following variables are considered:
49 m mA*(AA*),i
50 yi = final,i AEtBr ,i and xi = w A* (12)
51
mA(AA*),i mA(AA*),i
52 When the internal standard is used, there is no need to account for the sample dilution, and
53 the following variables are considered:
54 A mA*(AA*),i
55 yi = EtBr ,i and xi = w A* (13)
56 AEtI,i mA(AA*),i
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3 The incorporation of the mass fraction of the analyte in the primary standard, wA*, serves to
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simplify the calculations. Such practice is acceptable if the uncertainty of the wA* is negligible.
6 However, when the uncertainty arising from the wA* needs to be explicitly accounted for in
7 the combined uncertainty budget, one can remove the wA* from eqs. 12 and 13. Then, the
8 mass fraction of the analyte in the sample is wA = x0wA*, and the uncertainty is (u(wA)/wA)2 =
9 (u(x0)/x0)2 + (u(wA*)/wA*)2. This way one can ensure that the uncertainty associated with the
10 primary standard is properly incorporated in the uncertainty of the result. For the sake of
11
simplicity, this was not done in this work, also because the uncertainty in the primary
12
13 reference standard, u(wA*), is insignificant in comparison to the uncertainty of the fit for data
14 presented in this work.
15
16 Using data from Table 3, standard addition calculations were performed with four models –
17 linear, quadratic, Padé[1,1], and Padé[2,1] whose equations are given in Table 1. Least squares
18 fitting was performed using LINEST() function as detailed in Table 2. For direct calibration
19
20
functions, the uncertainty of x0 was obtained either from eqs. 3-4 (linear model) or eqs. 8-11
21 (quadratic model). Expressions for the Padé[1,1] and Padé[2,1] parameter covariances are
22 given in the Supplementary material. For all inverse calibration functions, the uncertainty of
23 x0 was obtained directly from LINEST() as per eq. 6. The results are given in Table 4.
24
25 Table 4. Determination of bromide in BCR-611 with standard addition method using various direct and
26 inverse calibration methods. a
27 yi = AEtBr,i/AEtI,i Result, Complexity Complexity
28 Equations
xi = (mA*(AA*),i/mA(AA*),i) wA* w(Br–)/(ng/g) of x0 b of u(x0) b
29
30 Direct calibration
31 y = a 0 + a 1x Eqs. 2, 3-4 96.45(1.14) 1 30
32 y = a 0 + a 1 x + a 2x2
Eqs. 7, 8-11 93.15(3.12) 8 177
33
y = (a0 + a1x)/(1 + a2x) Eqs. s1, s2-s3 93.50(3.25) 1 216
34
35 y = (a0 + a1x + a2x2)/(1 + a3x) Eqs. s4, s5-s8 94.93(1.17) 8 460
36 Inverse calibration
37 x = b 0 + b 1y Eqs. 5, 6 96.37(1.14) 1 0
38
x = b 0 + b 1 y + b 2y 2 Eqs. 5, 6 93.09(3.34) 1 0
39
40 x = (b0 + b1y)/(1 + b2y) Eqs. 5, 6 92.42(3.21) 1 0
2
41 x = (b0 + b1y + b2y )/(1 + b3y) Eqs. 5, 6 94.94(1.12) 1 0
42 a Mass fraction of bromide in BCR-611 as determined by the state-of-the-art quadruple isotope
43 dilution GCMS, w(Br–) = 96.28(42) ng/g.15 All uncertainties here are combined standard
44 uncertainties (expressed with coverage factor k = 1).
45 b The number of elementary arithmetic functions (addition, multiplication, and
46 exponentiation) needed to obtain x0 or u(x0) starting from the results given by the LINEST()
47 function (calculated for this dataset with N = 15). Although the operation count depends on
48 variable rearrangement (e.g., three operations in a×b + a×b vs two operations in 2×a×b), it
49 nevertheless provides a reasonable estimate of the mathematical complexity at-hand.
50
51 In general, one can observe that the numerical results of inverse calibration approach differ
52 negligibly from the corresponding results obtained from the direct fitting of analytical signal
53 against the mass of the added analyte. In addition, all results agree with the value established
54
from the state-of-the-art isotope dilution measurements.22 The calculation of the x0 values
55
56 and their uncertainty estimates, however, is significantly simpler from the inverse
57 regressions. Table 4 summarizes the minimum number of elementary arithmetic functions
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3 needed to obtain xo or u(x0) starting from the results given by the LINEST() function. In all
4
5
cases the inverse approach provides answers without any additional calculations whereas
6 direct fitting of y over x requires considerable amount of additional calculations in order to
7 obtain x0 and u(x0). In the well-cited publication on the standard addition method, Bader
8 reflects that “once mathematical complexity sets in, it is easy to make mistakes”.7 In this
9 vein, it is hoped that the marked simplicity of the inverse approach will result in a wider use
10 of this technique and spur the much-needed evaluation of the metrological performance of
11
nonlinear standard addition models. With the increased nonlinearity in the standard addition
12
13 curves, one should expect more discrepancies between the results of the various empirical
14 nonlinear models and also between the direct and inverse calibration approaches. In such
15 situations, the analysts will be reminded to re-evaluate the chosen method of analysis or the
16 adequacy of the measurement model equation.
17
18 Conclusions
19
20
21 Although strictly speaking the classical and inverse regressions are not mathematically
22 equivalent procedures, the distinction becomes relevant only for datasets that are very noisy
23 or extremely nonlinear.25 Since this is not a norm in analytical chemistry, the inverse fitting
24 offers significant advantages to chemists. Given that the coordinate swapping in standard
25 addition experiments simplifies the data analysis significantly over the traditional fitting
26
approach, the use of inverse regression should be embraced in the spirit of Occam’s razor.
27
28
29 References
30
31 (1) Hohn, H. Chemische Analysen mit dem Polarographen, 1937, Springer: Berlin
32 (2) Kelly, W. R.; Pratt, K. W.; Guthrie, W. F.; Martin, K. R. Anal. Bioanal. Chem. 2011, 400, 1805–
33 1812.
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(3) Hauswaldt, A.-L.; Rienitz, O.; Jährling, R.; Fischer, N.; Schiel, D.; Labarraque, G.;
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36 Magnusson, B. Accred. Qual. Assur. 2012, 17, 129–138.
37 (4) Harris, D. C. Quantitative Chemical Analysis, 4th ed, 1995, Freeman: New York
38 (5) Tellinghuisen, J. Analyst 2005, 130, 370–378.
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2010, 25, 624–630.
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51 (14) Tellinghuisen, J. Fres. J. Anal. Chem. 2000, 368, 585–588.
52 (15) Shukla, G.K. Technometrics 1972, 14, 547–553.
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55 (18) Gorazda, K.; Michalowska-Kaczmarczyk, A. M.; Asuero, A. G. Talanta 2013, 116, 927–930.
56 (19) Harris, D. C. J. Chem. Educ. 1998, 75, 119–121.
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(20) Kragten, J. Analyst 1994, 119, 2161–2165.
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3 (21) Bartkovjak, J.; Karovicova, M. Meas. Sci. Rev. 2001, 1, 63–65.
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