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Abstract
Calibration is an operation whose main objective is to know the metrological status of a measurement system. Nevertheless, in analytical sciences,
calibration has special connotations since it is the basis to do the quantification of the amount of one or more components (analytes) in a sample, or
to obtain the value of one or more analytical parameters related with that quantity. Regarding this subject, the aim of analytical calibration is to find
an empiric relationship, called measurement function, which permits subsequently to calculate the values of the amount (x-variable) of a substance
in a sample, from the measured values on it of an analytical signal (y-variable). In this paper, the metrological bases of analytical calibration and
quantification are established and, the different work schemes and calibration methodologies, which can be applied depending on the characteristic
of the sample (analyte + matrix) to analyse, are distinguished and discussed. Likewise, the different terms and related names are clarified. A special
attention has been paid to those analytical methods which use separation techniques, in relation with its effect on calibration operations and later
analytical quantification.
2007 Elsevier B.V. All rights reserved.
Keywords: Chemical measurement processes; Metrological and analytical calibration; Analytical quantification; Calibration schemes; Calibration methodologies
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Metrological fundamentals: measurement function for analytical calibration/quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Schemes for analytical calibration/quantification. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Two-standard calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. One-standard calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Methodologies for analytical calibration/quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. External calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Matrix-matched calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Standard addition calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4. Internal calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5. Calibration by internal normalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
33
35
37
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40
42
43
44
45
45
45
1. Introduction
0021-9673/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2007.03.030
34
provide traceability and comparability to the measurement, acting the former as a metrological interface between measurement
standards and analytical results. Nevertheless, in analytical sciences, calibration can be considered from two points of view
as metrological calibration as well as analytical calibration, not
being its requirements and aims similar necessarily. From a practical view, analytical calibration implies to verify or to state
the relationship between the measurement signal and the analyte/s quantity, whereas metrological calibration, based on the
analytical one, is just related to a measuring system understood as a set of one or more measuring instruments and often
other devices, including any reagent and supply, assembled
and adapted to give measured quantity values within specied
intervals for quantities of specied kinds [2]. The metrological
calibration implies the daily evaluation of the metrological performance of a measuring system in order to provide the quality
of the analytical results. Therefore, with a calibrated chemical
measurement system could be possible to obtain good results
although it provides erroneous indications, because these ones
can be corrected due to, in the calibration process, the error
is established. That is why, a metrological calibration leads
to the characterization of a dependence relationship between
the error committed by the measurement system and the value
of the measure, expressed in terms of parameters as deviation, bias, correction, correction factor or calibration factor.
This relationship is only established for the measurement values represented by the calibration standards used, but it can be
extended interpolating into the interval covered by them through
a correction/calibration function. Specific information about the
metrological approach of the calibration in a CMP can be found
in references [3,4].
Calibration in metrology, has been recently defined in a new
revision of the International Vocabulary of Metrology (VIM)
as the operation that, under specied conditions, in a rst step
establishes a relation between the quantity values with measurement uncertainties provided by measurement standards and the
corresponding indications [of a measuring system]1 with associated measurement uncertainties and, in a second step, uses this
information to establish a relation for obtaining a measurement
result from an indication [2] where a measurement standard
is referred to the realization of the denition of a given quantity,
with stated value and measurement uncertainty, used as a reference and it can be provided by a measuring system, a material
measure, or a certied reference material [2]. This new twostep definition generalizes the application of the previous VIMs
definition [5] still in effect, simplifies the wording/phrasing and
improves substantially its understanding. The main innovation
comes from the second step since as the VIM itself quoted, in
this definition the first one has been traditionally perceived as
the proper calibration. As it will be highlighted in this paper, this
second step could include all the analytical operations closely
related with calibration.
The aim of the chemical analysis of an object or a material,
is to obtain analytical information of it represented by the value
35
Fig. 1. Flow-chart showing up the relationships between both analytical calibration, metrological calibration and analytical quantification.
36
xspl
1
=
RF
yspl
37
Table 1
More frequent calibration curves and different features for the analytical separation sciences
Calibration curve
Calibration function
Signal blank
Sensitivity
Response factor
Linear
y = bx
y = a + bx
0
a
b [constant]
b [constant]
b [constant]
a/x + b [depends on x]
Parabolic
y = cx2
y = a + cx2
y = a + bx + cx2
0
a
a
2cx [depends on x]
2cx [depends on x]
b + 2cx [depends on x]
cx [depends on x]
a/x + cx [depends on x]
a/x + b + cx [depends on x]
38
x2 (yspl y1 ) x1 (yspl y2 )
y2 y 1
y spl y 1,2
+ x 1,2 ,
b
where b =
y 2 y 1
x2 x 1
being y 1,2 and x 1,2 the global means of the two measured
analytical signals and analyte amounts of the two standards,
respectively, and b is the slope.
When it is known that the intercept is zero, the calibration
factors of both standards are the same and very similar to the
inverse of the slope. Then, the quantification could be easily carried out calculating a pooled calibration factor, CF1,2 , according
to the expressions:
xspl = CFpool y spl ,
where CFpool = CF =
x 1,2
1
=
y 1,2
b
a low test samples number with the aim to minimize the total
analysis time. Whether the number of test samples is great, a
batch processing (of them) can be done.
3.2. One-standard calibration
The calibration could be performed from only one calibrant
when two conditions are fulfilled: (i) the calibration function
must be linear in the interval of analyte amount ranged from
the standard value to zero, and (ii) the blank signal must be
null in the interval previously referred to. So, it is mandatory
to check this last requirement before this calibration scheme
was applied. During the experiment, the calibrant must be replicated twice at least. The quantification is carried out using the
calibration factor calculated from the pair of values, standard
analyte amount/average analytical signal, concerning the calibrant applying the expressions:
x1
xspl = CF y spl , where CF =
y 1
The linearity requirement can be avoided when the analyte
amount in the selected calibration standard is very near to the
one in the sample which is possible when the features of the
sample are previously known. Then the one-standard calibration can be easy going applied (for example, for quality control
of manufactured products).
As for the preceding case, for pesticide residue analysis, it has
been stipulated that one-standard calibration may provide more
accurate results than multi-standard calibration if the detector
response is variable with time [12]. In this case, it must be taking into account that, unless further extrapolation is supported
by evidence of acceptable linearity of the calibration function,
the sample analytical signal should be within 10% of the calibration standard analytical signal if the maximum residue limit
is exceeded; if it is not exceeded, the sample response should be
within 50% of the calibration response.
4. Methodologies for analytical
calibration/quantication
In order to the calibration function, previously established
from standards, could be applied to the samples (Fig. 1), different calibration methodologies [13] can be used, bearing in mind
factors like: (i) the availability of representative standards; (ii)
the analytes nature; (iii) the lack of precision or drift of the measurement system; and (iv) the possibility of disturbance caused
in the output analytical signal by other components concomitants the analyte, considered them individually (interferent) or
in a whole way (matrix effect). Obviously any of the previously
mentioned schemes: multi-, two- or one-standard calibrations
can be applied in all the methodologies.
The calibration standards are prepared from RMs containing
the analyte or a surrogate, that is, a pure substance (compound or element) similar to analyte of interest in chemical
composition, separation and measuring which is taken to be
representative of the native analyte; this must be absent or in
a negligible initial concentration in the sample. The calibration
ya
yIS
39
40
way. In bibliography, EC has been also termed as solvent calibration, standard calibration or even normal calibration.
As external standard (ES), a solution of a RM substance in the
working solvent is used. It usually contains the analyte, although
it is not essential, and the calibration could be carried out from a
surrogate. The use of a surrogate in external calibration is only
appropriate when there are no a RM containing the analyte. An
application, in which two surrogates are used as ES, can be found
in a recent paper on the determination of polyphenols in olive
oil by CE-UV [27].
When a multi-standard calibration is performed, the linear
measurement function to estimate from data regression is:
Y = Y0 + S X
which give rise to a calibration curve:
ya,std = aEC + bEC xa,std
where the subscript std are related to calibration standard, the
intercept aEC is the method blank (Y0 ) and the slope bEC is the
sensitivity of the measurement system (S). The quantification
can be then performed from:
xa,spl =
ya,spl aEC
bEC
where the subscript spl are now related to sample. In certain cases, a no-linear calibration function, as polynomial,
exponential, sigmoidal, etc., could be applied.When a signalratio external calibration is performed, the calibration functions
should be established from signal-ratios; e.g. for a linear function, the equation to be fitted is:
ya,std
R
= ystd
= aEC
+ bEC
xa,std
yIS,std
and the quantification equation is:
xa,spl =
(ya,spl /yIS,spl ) aEC
bEC
ya,spl
ya,std
RF
ya,std /xa,std
ya,std /yIS,std
xIS,std R
=
=
=
ystd ;
RFIS
yIS,std /xIS,std
xa,std /xIS,std
xa,std
RCF =
1
RRF
ya,spl
R
= xIS,spl RCF yspl
yIS,spl
It is habitual, but not essential, to add the same amount of internal standard to all the analytical preparations (calibrants and
samples). Then, due to xIS,std = xIS,spl , both terms can be eliminated in the previous equation and a pseudo-relative response
factor (RRF ) or pseudo-relative calibration factor (RCF ) can
be calculated according to:
RRF =
yR
ya,std /yIS,std
= std ;
xa,std
xa,std
xa,spl = RCF
RCF =
1
RRF
R
yspl
ya,spl
R
= RCF yspl
= xa,std R
yIS,spl
ystd
Sm
;
S
and so : sm = p S
ya,spl aMC
bMC
41
Fig. 2. A particular example of the relationship between different types of calibration curve plots: external calibration (EC), matrix-matched calibration (MC),
standard addition calibration (AC) and empirical matrix-matched calibration or
matrix-corrected calibration (MCC ). y0 , method blank signal; ym , matrix blank
signal; ya,spl , signal from actual analyte in sample; xa,spl , actual analyte amount
in sample; aEC , intercept from EC-curve; aMC , intercept from MC-curve; aAC ,
intercept from AC-curve; aYC , intercept from Youden calibration curve (or YCcurve); bEC , slope from EC-curve; bMC , slope from MC-curve; bAC , slope from
AC-curve.
(ya,spl /yIS,spl ) aMC
bMC
This methodology is particularly recommended in procedures for pesticide or drug residue analysis and other
contaminants in food and biological matrices [34,35]. Contrary
to the common belief, the reliability of quantification using
modern analytical techniques as GCMS or even LCMS (or
tandem MS/MS) might not be adequate. Results can be adversely
affected by the lack of selectivity caused by matrix sample effect
on ion suppression.
Owing to the variety of matrices and samples in pesticide
residue analysis, the MC-functions are prepared only in a series
of representative matrices, this is, a sample material or an extract
of a single food or feed used to represent a commodity group as
an indicator of matrix effect in the analysis of broadly similar
commodities. Matrix representativeness is usually determined
among similar biological material (or tissues) according to its
42
content in constituents like, water, acids, sugars, lipids, secondary plant metabolites, etc. The utility of these representative
matrices, has been demonstrated preparing MC calibrations in
cucumber extracts for the determination of 2030 pesticides by
GCMS [36] or LCMS [37] in several vegetable samples.
aAC (y0 + ym )
aAC (y0 + ym )
=
Sm
bAC
aAC aYC
Sm
When the total sample blank is null, the former equation can be
simplified to:
aAC
xa,spl =
bAC
which gives the extrapolated value of the x-intercept. Only in
this case, the analyte amount can be calculated as the quotient
between the intercept and the slope of the AC-curve. This fact
is the basis of the graphic quantification method that generally
appears in text books. Nevertheless, if the total sample blank
nullity is not fulfilled, this last approach can produce serious
errors in the quantification.
When a one-standard addition calibration is made, the
quantification step requires the analysis of at least two test portions, one of them containing an amount of analyte standard
added. Then the sample analyte amount is obtained applying
the next equation which is a particular case of the general one
above explained:
RF =
ya,(spl+add) ya,spl
;
xa,add
CF =
1
RF
ya,spl
ya,(spl+add) ya,spl
being ya,spl and ya,(spl + add) the analyte signals in the original and
the added samples, respectively; and xa,add is the added standard
analyte amount.
As in the previous methodologies, the AC-calibration could
be performed from signals-ratio. The equations for calibration
and quantification are equivalent to the previous ones without
more than to substitute the analytical signals for the respective
analytical signals-ratio.
This type of calibration is the only methodology in which
the results are not affected by systematic matrix errors, independently of the kind and magnitude of the matrix effect, so it
permits to quantify the amount of analytes in any kind of samples. That is why a in-house validation of analytical methods
based on the standard additions and Youden calibrations has
been proposed [40]. Its principal disadvantage lies in the fact that
a calibration for each sample is needed, which implies a lot of
work in routine analysis. To avoid this problem, a simulation of a
bMCC = bAC
yIS,spl
;
xIS,spl
CFIS =
1
RFIS
ya,spl
R
= xIS,spl yspl
yIS,spl
Metrologically, this is the real internal calibration (IC), a onestandard internal calibration methodology formally different to
the signal-ratio calibration; however this last is the most known
application of the use of internal standard in analytical sciences
which sometimes has derived in an inappropriate use of the term
internal calibration.
The preceding equations could be combined and the quantification would be obtained from the following simplified one:
xa,spl =
xIS,spl
R
ya,spl = xIS,spl yspl
yIS,spl
With the aim to enhance the accuracy of the results, a modification of the methodology that uses two internal standards, has
been proposed and it has been called double standard internal
43
method. Initially, the quantification involved the average geometrical value calculation of the two results obtained with each
standard:
xa,spl = ya,spl CFIS1 CFIS2
This equation can be significantly simplified when: (i) two
closely related compounds, upper and lower, of the same
homologous series to which the analyte belongs, are used
as internal standards (e.g. methanol and n-propanol could be
used for ethanol determination); (ii) the analyte and internal standards calibration factors are approximately equals
(CFIS,1 CFa CFIS,2 ), being the product of the relative calibration factors analyte/internal standards around 1 (CF1 CF2 = 1)
due to its differences are compensated each other [42]; and
(iii) both internal standards are added in the same amount,
xIS,1 = xIS,2 = xIS . Then, the analyte amount in the sample can
be calculated according to:
1
R
R
=xIS,spl y1,spl
y2,spl
xa,spl =ya,spl xIS,spl
yIS1,spl yIS2,spl
R and yR represent the analyte/internal standard
where ya,1
a,2
signal-ratios 1 and 2, respectively, obtained from the sample
analysis.
The main advantage argued by the authors, arises from that
this quantification method does not need a previous calibration
(the calibration is implicit in the quantification), so its practical application is very easy. It only requires the addition of
a known and equal amount of both internal standards to each
sample. Once the sample treatment has been finished, the analyte and internal standards signals are measured. The results
obtained show a great accuracy degree, even whether during
sample treatment any analyte losing is produced. Its more important disadvantage lies in the necessity of having two analyte
homologous (internal standards), initially absents in the sample.
To apply an IC the measurement system has to be able to distinguish between the signals from the internal standard(s) and
the very analyte, that is why, both substances must have a different behaviour in the measurement system but similar analytical
properties in order to be measured in a quasi-simultaneous way.
In the same portion of the test sample, the signal of the standard
and the very analyte are measured; from the first one a calibration factor is obtained, which is used to quantify the amount of
analyte from the second signal.
An exclusive feature of IC is that it is possible to carry out the
quantification of several analytes (generally from the same family) in the same sample portion, starting from an only internal
calibration, this is, the internal standard can represent to several
analytes in a simultaneous way in the same sample. As consequence, it would be possible to calculate the (percentage) mass
fraction of each analyte using only the values of the measured
analytical signals by:
ya,spl
xa,spl
FCIS ya,spl
ca,spl (%) = 100 =
100 = 100
xi
(FCIS yi )
yi
where ca,spl indicates the percentage mass fraction of the analyte
a; xa,spl is the mass of this analyte in the sample and ya,spl is
44
the analytical signal due to it. xi,spl represents the sum of the
masses of all the analytes and, yi,spl represents the sum of the
analytical signals attributed to these ones. This strategy is only
possible when the calibration factors are similar for all the analytes, and equal to the calibration factor of the internal standard.
The reliability of internal calibration as calibration/
quantification methodology is based on the ability of the IS to
act as surrogate. In metrological terms, this fact implies that the
response factor (or sensitivity) of the IS is constant and equal
to the calibration factors of each one of the substituted analytes,
into the interval of application of the method. That can be true
for those universal no-specific detectors which respond directly
to the substance amount (mass or concentration), as it happens
with the most classical GC detectors. However, this condition
is harder to fulfil in LC, due to the majority of common detectors used, produce a dissimilar signal amount depending on the
judged analyte. Even, when MS detectors are used, and depending on the ionization system, it could be consider this premise
is satisfied when they work in full-scan mode (not in SIM
mode). In any case, and as far as possible, it is necessary to verify
that this requirement is achieved using a measurement standard
containing both analyte and internal standard.
The main advantage of internal calibration is the reduction
of analysis time, since it only needs one analytical preparation
for calibration and quantification. Moreover, this methodology
permits to make up for the losing of analyte during sample preparation and, in a moderate way, the matrix effect. That is why it is
advisable when at least one of the following circumstances are
produced: (i) the previous preparation sample process is long
and complicated; (ii) a long time for the measure is required
(e.g. chromatogram run time); and (iii) there is no or it is impossible to acquire a material with analyte standard. Obviously, the
main limitation of this methodology is the availability of an adequate IS. As an additional precautionary measure, the amount of
IS must be such its analytical signal (peak area or peak height)
be of the same order that those corresponding to the analyte;
otherwise, significant errors in quantification can be found, over
all if the internal standard signal is not entirely linear.
UE olive oil official analytical methods for the determination of the composition and content of waxes [43], sterols [44],
stigmastadienes [45], and aliphatic alcohols [46], by capillarycolumn gas chromatography, constitute examples of common
application of IC. In those methods, an only calibration IS is
used for the quantification of some analytes of the same chemical
family.
An imaginative proposal recently reported is the echo-peak
internal standard calibration [47]. This is a novel calibration methodology which simulates the use of internal standard
by injecting consecutively, within a short period of time, an
unknown sample and a standard analyte solution. As a result,
the standard analyte peak elutes closely to the sample analyte
peak, thus performing a echo peak. For quantification purposes, a calibration function is obtained from the signal-ratios
of the standard and the reference standard. The concentration of
analyte in the unknown sample is calculated from the peak area
ratio of sample and reference. As an internal standard method,
the echo-peak technique provide the possibility to compensate
CF
xa,std /ya,std
xa,std yIS,std
xa,std
1
=
=
=
R
CFIS
xIS,std /yIS,std
xIS,std ya,std
xIS,std ystd
45
NF =
xref,std yi,std
xref,std / xi,std yi,std
ci,std yref,std
=
cref,std yi,std
We acknowledge financial support from the Spanish Ministerio de Educacion y Ciencia (MEC), Direccion General de
Investigacion (Project No. CTQ2006-15066-C02-02).
xa,spl
ca,spl (%) =
xi,spl
N
CFref ya,spl
100 =
100
N )
(CFref yi,spl
N
ya,spl
NFa ya,spl
= N 100 =
100
(NFi yi,spl )
yi,spl
Acknowledgement
References
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46