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Fachbereich Chemiesund Umweltingenieurwesen, Fachhochschule Merseburg, Germany, and Faculty of Chemistry and
Chemical Engineering, Babes -Bolyai University, RO-3400 Cluj-Napoca, Romania
over, the t-test assumes that the errors are independent of the
concentration and have a normal distribution.5,6
To date, different regression procedures have been used for
chemometric evaluation of data from method comparison studies.
Each one has specific theoretical requirements for the data. It is
obvious that the reliability of a procedure depends largely on to
what extent the data can meet these requirements.7,9
Under the premise of a linear relationship between the two
methods in the form of
y ) a0 + a1x
(1)
the estimated values for a0 and a1 are tested against the null
hypothesis a0 ) 0 and a1 ) 1. If the estimated values differ only
by chance from 0 and 1 at a predefined significance level, then
the methods are considered to be equal. A slope significantly
different from unity indicates a proportional error (i.e., a matrix
effect), and an intercept different from zero implies a constant
error (i.e., a blank problem).
The linear regression based on ordinary least-squares presumes that error(Y) . error(X). For the measurements of
method Y, analytical errors are allowed, so that repeated measurements of one sample will scatter perpendicularly to the x-axis
around their expected value on the regression line. The parameters a0 and a1 of the regression equation are determined by
minimizing the sum of squared distances (residuals) between
measurement points and the regression line. The method of leastsquares is sensitive to extreme data points, which may result in
biased values of a0 and a1. A change in the assignment of the
methods to the variables of the regression procedure results in
new parameters which cannot be converted into the old ones by
the regression equation.
A more appropriate approach for method comparison seems
to be the structural relationship model which allows error terms
for both variables. The orthogonal regressionsalso known as the
Deming proceduresis based on the assumption that the standard
deviation of the measurement errors is the same for both methods
and the standardized principal component procedure, considering
(5) Massart, D. J.; Vandeginste, B. M. G.; Deming, S. N.; Michotte, Y.; Kaufman,
L. Chemometrics: A Textbook; Elsevier: Amsterdam, 1988; p 88.
(6) Miller, J. C.; Miller, J. N. Statistics for Analytical Chemistry, 2nd ed.; Ellis
Horwood: Chichester, 1988; p 101.
(7) Passing, H.; Bablok, W. J. Clin. Chem. Clin. Biochem. 1983, 21, 709.
(8) Hartmann, C.; Smeyers-verbeke, J.; Massart, D. L. Analusis 1993, 21, 125.
(9) Kalantar, A. H.; Gelb. B. R.; Alper, J. S. Talanta 1995, 42, 597.
Ax + By + C ) 0
(2)
8.71
7.01
3.28
5.60
1.55
1.75
0.73
3.66
7.35
7.92
3.40
5.44
2.07
2.29
0.66
3.43
0.90
9.39
4.39
3.69
0.34
1.94
2.07
1.38
1.25
6.58
3.31
2.72
2.32
1.50
3.50
1.17
1.81
1.27
0.82
1.88
5.66
0.00
0.00
2.31
1.88
0.44
1.37
7.04
0.00
0.49
0.40
0.00
1.98
10.21
4.64
5.66
19.25
1.29
0.37
2.16
12.53
3.90
4.66
15.86
Examples 2 and 3
Y
X
2.34
1.20
1.88
0.08
0.12
1.12
1.60
22.40
2.16
1.34
2.48
1.22
2.14
0.0026
0.0023
1.05
1.42
26.30
1.99
1.06
1.35
2.04
1.97
1.02
1.45
28.20
22.60
22.37
27.00
1.04
1.89
1.90
0.75
1.16
29.40
23.70
23.30
29.50
Example 4
Y
X
7.32
15.80
5.48
13.00
4.60
9.04
3.29
6.84
0.38
7.27
0.28
1.55
0.06
1.50
1.06
5.19
0.33
7.16
6.80
0.35
7.75
0.14
1.61
0.013
1.63
1.05
5.50
0.054
1.96
0.33
5.54
1.85
3.40
4.19
0.04
3.02
1.33
1.80
0.23
5.21
1.76
3.62
4.07
0.048
3.06
1.35
6.00
5.84
9.90
28.70
14.30
18.80
M(y2) - M(x2) B2 - A2 B A
) )
AB
A B
M(xy)
A
C
y ) - x - ) mx + n
B
B
(3)
In this case, the distance of any point (xi,yi) to the line (2) will
have the following expression:
di2 )
(4)
A 2 + B2
y ) mx + n
(6)
(7)
m2 - wm -1 ) 0
(8)
S)
1
2
A +B
(Ax + By + C)
) min
(5)
i)1
y ) mx + jy - mxj
The minimum of S follows from the approach to zero of the
derivative of S with respect to A, B, and C. From the resulting
system, considering M(x) ) 0, M(y) ) 0, and C ) 0, we obtain
(10) Feldmann, U.; Schneider, B.; Klinkers, H. J. Clin. Chem. Clin. Biochem.
1981, 19, 121.
(11) Bablok, W.; Passing, H. J. Clin. Lab. Aut. 1985, 7, 74.
(12) Ripley, B. D.; Thomson, M. Analyst 1987, 112, 377.
(13) Sarbu, C. Anal. Chim. Acta 1993, 271, 269.
(14) Sarbu, C. Anal. Lett. 1997, 30, 1051.
(15) Onicescu, O. C. R. Acad. Sci. Ser. A 1966, 263, 841.
(16) Onicescu, O.; S tefanescu, V. Informational Statisitics; Editura Tehnica:
Bucures ti, 1979.
(17) Theil, H. Proc. K. Ned. Akad. Wet., Ser. A53 1950, 386.
(18) Maw, R.; Witry, L.; Emond, T. Spectroscopy 1994, 49, 39.
(9)
example 1
example 2
example 3
example 4
y ) 0.544 + 0.845x
x ) -0.299 + 1.089y
y ) -0.162 + 1.063x
x ) 0.203 + 0.899y
y ) -0.194 + 1.084x
x ) 0.193 + 0.920y
y ) 0.005 + 0.890x
x ) -0.167 + 0.631y
y ) -0.081 + 0.839x
x ) 0.171 + 0.918y
y ) -0.066 + 0.795x
x ) 0.148 + 0.937y
iterated weighted
regression (IWLS)
y ) 0.109 + 0.904x
x ) -0.083 + 0.871y
y ) -0.135 + 1.048x
x ) 0.161 + 0.925y
y ) -0.153 + 1.062x
x ) 0.152 + 0.936y
y ) 0.106 + 0.973x
y ) -0.167 + 1.076x
y ) -0.161 + 1.068x
Deming method
y ) 0.412 + 0.881x
y ) -0.194 + 1.087x
y ) -0.202 + 1.085x
y ) 1.402 + 0.698x
2.040x -2.329y + 1 ) 0
y ) 0.429 + 0.876x
x ) -0.490 + 1.141y
-5.545x + 5.090y + 1 ) 0
y ) -0.196 + 1.089x
x ) 0.180 + 0.918x
-5.365x + 4.943y + 1 ) 0
y ) -0.202 + 1.085x
x ) 0.186 + 0.921y
3.856x -5.77y + 1 ) 0
y ) 1.733 + 0.668x
x ) -2.593 + 1.496y
y ) 0.859 + 0.588x
y ) -0.204 + 1.007x
y ) 1.087 + 1.024x
y ) -2.442 + 1.108x
A
pA )
A+B
and
B
pB )
A+B
(10)
The Ho hypothesis is true when E ) 1/2, i.e., when the informational energy is minimal and the two coefficients A and B are equal
in their absolute values. As was shown above, the null hypothesis
is accepted if E ) , where E ) 1/2 represents the theoretical
informational energy, and ) (A2 + B2)/(A + B)2, represents
empirical informational energy. On the other hand, if E * , the
null hypothesis is rejected. Hence, the difference between the
two compared methods is taken as significant.
RESULTS AND DISCUSSION
Some relevant studies concerning the methods comparison in
well-cited papers are considered to compare the advantages of
the new regression method described above.
Illustrative Example 1. To illustrate the characteristics of
performance of the algorithm, taking into account the errors in
both methods in the case of small deviations from homoscedasticity or in the presence of outliers, we refer to data discussed by
Ripley and Thomson12 concerning a set of 30 pairs of determinations of arsenate(V) ion in natural river water (Table 1). The x
values are determined by selective reduction and atomic absorption spectrometry, whereas the y values came from cold trapping
and atomic emission spectrometry. The quoted values are
y ) 2.279 + 0.619x
x ) 0.413 + 1.402y
1 )
i)1
pi2 )
(A2 + B2)
(A + B)2
9.584
19.08
) 0.502
(11)
1279
that one method shows a bias. This conclusion, i.e., the presence
of proportional errors introduced by microwave digestion method,
concerning the analysis of mercury in waste samples was also
recently demonstrated.14
CONCLUSIONS
A new approach for the analysis of method comparison studies
over a wide range of concentrations was discussed and compared
with more or less common regression procedures. All the results
obtained show that the implicit linear function model (ILF) is an
effective method for parameters estimation and methods comparison and can replace the least-squares method and other
proposed approaches. For any given set of data, an evaluation
based on an informational analysis of variance test allows a more
reliable bias detection.
Received for review August 25, 1997. Accepted January
7, 1998.
AC970926Y