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INTRODUCTION
It is common knowledge in analytical chemistry that the
instrumental response can be aected by the sample matrix.
This behavior leads to biased results when the analytical signal
produced from the sample is compared against the calibration
graph prepared from matrix-free standard solutions. To
overcome this problem, the method of standard addition was
introduced in the 1930s.1,2 To date, the method of standard
addition remains an essential tool in quantitation, especially
when isotope dilution cannot be applied. Like any scientic
tool, the method standard addition has witnessed new
developments, most notable of which is the concomitant use
of the internal standard.3
To wit, when more than one addition of a standard is
performed, the method of standard addition seeks the point
with zero response (assuming all signals are corrected for blank
contribution), i.e., the analytical result is as follows:4,5
x 0 = xy = 0
(1)
a02
u 2(a1)
a12
cov(a0 , a1)
a0a1
(3)
(4)
THEORY
Variable Transformation for Standard Additions. To
the annoyance of many chemists, traditional standard addition
regression does not yield the analytical result directly. This
problem has been noted before. Notably, Tellinghuisen has
proposed an alternative approach whereby the variable-ofinterest for standard additions, x0, is cast as an explicit variable
of the tting model rather than calculated from the tting
parameters.12,13 The method involves variable transformation
(2)
u 2 (a 0 )
where,
Analytical Chemistry
Article
u 2(x0) =
qcov(a0 , a1)
qd cov(a1 , a 2)
d cov(a0 , a 2)
+
2
a 2z
a2 z
2a 23z
(6)
(8)
x x 4 x2 x3
cov(a0 , a 2) = u 2(a 2)
cov(a1 , a 2) = u 2(a 2)
( x 2)2 N x 4
(9)
( x 2)2 x x 3
( x)2 N x 2
(10)
N x3 x x2
( x)2 N x 2
(11)
(12)
direct calibration
q2u 2(a1)
u 2 (a 0 )
d 2u 2(a 2)
+
+
z
4a 24z
4a 22z
u(x0,inv)/u(x0) r 2
(7)
a21
x0,inv x0
2a 2
(5)
u(x0,inv) = u(b0)
a12 4a0a 2
a1
y
y
y
y
1 r2
r2
=
=
=
=
a0 + a1x
a0 + a1x + a2x2
(a0 + a1x)/(1 + a2x)
(a0 + a1x + a2x2)/(1 + a3x)
inverse calibration
x
x
x
x
8564
=
=
=
=
b0 + b1y
b0 + b1y + b2y2
(b0 + b1y)/(1 + b2y)
(b0 + b1y + b2y2)/(1 + b3y)
result
x0
x0
x0
x0
=
=
=
=
a0/a1
(a1 (a21 4a0a2)1/2)/2a2
a0/a1
(a1 (a21 4a0a2)1/2)/2a2
result
x0,inv
x0,inv
x0,inv
x0,inv
=
=
=
=
b0
b0
b0
b0
Analytical Chemistry
Article
function
y
y
y
y
y
y
=
=
=
=
=
=
a0x
a0 + a1x
a0 + a1x + a2x2
a0 + a1x + ... + amxm
(a0 + a1x)/(1 + a2x)
(a0 + a1x + a2x2)/(1 + a3x)
=LINEST(y,
=LINEST(y,
=LINEST(y,
=LINEST(y,
=LINEST(y,
=LINEST(y,
x, FALSE, TRUE)
x, TRUE, TRUE)c
x^{0,1,2}, FALSE, TRUE)
x^{0,...,m}, FALSE, TRUE)
x^{0,1,0}*y^{0,0,1}*x^{0,0,1}, FALSE, TRUE)
x^{0,1,2,0}*y^{0,0,0,1}*x^{0,0,0,1}, FALSE, TRUE)
a
For inverse tting x = f(y), all instances of x and y in the LINEST directive have to be interchanged. For example, the inverse linear t is performed
using LINEST(x, y, TRUE, TRUE). bSymbols x and y stand for the data input range. For example, if the values of x and y are in cells A1 to A5 and
B1 to B5, respectively, then the linear t is obtained by entering =LINEST(B1:B5, A1:A5, TRUE, TRUE). Also note that unlike many other
functions which are entered in a singe cell by pressing enter, LINEST is an array function which is entered over several cells (an array) by pressing
ctrl+shift+enter. cAlternatively, one can use =LINEST(y, x^{0,1}, FALSE, TRUE).
mA*(AA*)/g
mfinal/g
AEtBr
AEtI
2.005 99
2.008 17
2.180 35
2.001 74
2.004 35
2.009 60
1.999 61
2.005 36
2.009 01
1.999 22
2.002 76
2.006 66
1.997 26
2.004 13
2.006 93
0.000 00
0.000 00
0.000 00
0.049 49
0.050 05
0.049 89
0.099 24
0.099 49
0.099 91
0.148 14
0.148 72
0.148 83
0.197 03
0.198 03
0.200 21
2.353 82
2.358 67
2.355 67
2.350 62
2.353 49
2.358 09
2.348 73
2.354 30
2.358 00
2.346 72
2.351 28
2.354 87
2.344 29
2.352 16
2.357 14
14 610
14 633
13 422
21 863
22 161
22 155
29 786
30 806
30 427
35 088
37 794
34 243
42 221
46 070
38 640
8153
8176
7695
8190
8339
8199
8357
8652
8432
7983
8531
7731
7909
8682
7286
EXPERIMENTAL SECTION
Bromide was analyzed in certied groundwater reference
material by using headspace gas chromatography mass
spectrometry (GCMS) after the aqueous derivatization with
triethyloxonium tetrauoroborate at room temperature.22
Iodide ions which are naturally present in the groundwater
were used as the internal standard for bromide since both of
these anions undergo ethylation in a similar fashion.
Experimental details are summarized in the Supporting
Information (SI) and further details can be found elsewhere.23
Analytical Chemistry
Article
Table 4. Determination of Bromide in BCR-611 with Standard Addition Method Using Various Direct and Inverse Calibration
Methodsa
yi = AEtBr,i/AEtI,i xi = (mA*(AA*),i/mA(AA*),i) wA*
direct calibration
y = a0 + a1x
y = a0 + a1x + a2x2
y = (a0 + a1x)/(1 + a2x)
y = (a0 + a1x + a2x2)/(1 + a3x)
inverse calibration
x = b0 + b1y
x = b0 + b1y + b2y2
x = (b0 + b1y)/(1 + b2y)
x = (b0 + b1y + b2y2)/(1 + b3y)
equations
result, w(Br)/(ng/g)
complexity of x0b
complexity of u(x0)b
eqs
eqs
eqs
eqs
24
7, 811
s1, s2s3
s4, s5s8
96.45(1.14)
93.15(3.12)
93.50(3.25)
94.93(1.17)
1
8
1
8
30
177
216
460
eqs
eqs
eqs
eqs
5,
5,
5,
5,
96.37(1.14)
93.09(3.34)
92.42(3.21)
94.94(1.12)
1
1
1
1
0
0
0
0
6
6
6
6
Mass fraction of bromide in BCR-611 as determined by the state-of-the-art quadruple isotope dilution GCMS, w(Br) = 96.28(42) ng/g.15 All
uncertainties here are combined standard uncertainties (expressed with coverage factor k = 1). bThe number of elementary arithmetic functions
(addition, multiplication, and exponentiation) needed to obtain x0 or u(x0) starting from the results given by the LINEST function (calculated for
this data set with N = 15). Although the operation count depends on variable rearrangement (e.g., three operations in a b + a b vs two
operations in 2 a b), it nevertheless provides a reasonable estimate of the mathematical complexity at-hand.
a
CONCLUSIONS
Although, strictly speaking, the classical and inverse regressions
are not mathematically equivalent procedures, the distinction
becomes relevant only for data sets that are very noisy or
extremely nonlinear.25 Since this is not a norm in analytical
chemistry, the inverse tting oers signicant advantages to
chemists. Given that the coordinate swapping in standard
addition experiments simplies the data analysis signicantly
over the traditional tting approach, the use of inverse
regression should be embraced in the spirit of Occams razor.
ASSOCIATED CONTENT
S Supporting Information
*
AUTHOR INFORMATION
Corresponding Author
*E-mail: juris.meija@nrc.ca.
Notes
REFERENCES
Analytical Chemistry
Article
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