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Anal Bioanal Chem (2004) 380: 376–382

DOI 10.1007/s00216-004-2647-5

R EV IE W

Klaus Danzer

A closer look at analytical signals

Received: 6 February 2004 / Revised: 11 April 2004 / Accepted: 19 April 2004 / Published online: 24 June 2004
 Springer-Verlag 2004

Abstract Analytical chemistry will be considered here as Signals are the main object of analysts in all fields of
the measurement science of chemistry that generates, analytical methods and all areas of application. To ob-
treats, and evaluates signals which contain information tain analytical information the analyst generates signals
about the composition and structure of samples. Ana- by a suitable analytical technique by which the sample
lytical information is always obtained from signals. information is encoded into signals. From given signal
Characteristics and peculiarities of analytical signals will properties measured values are taken and these are then
be considered from a very general point of view. A decoded into analytical results, mostly element contents
mathematical model of the influencing of signals will be and their uncertainty or structural information. The
given from which essential performance characteristics general way of obtaining analytical information about
of analytical methods can be derived, e.g. sensitivity, objects under investigation by sampling, analysis, and
cross-sensitivity, specificity, selectivity, and ruggedness evaluation is known as the analytical process, which is
(robustness). shown in Fig. 1.
In contrast with former representations of the ana-
Keywords Analytical signal Æ Sensitivity Æ Cross- lytical process [1, 3, 4, 5] and the chemical measurement
sensitivity Æ Selectivity Æ Specificity Æ Robustness process (CMP [6]), signal generation is inserted as a
separate step. This is because initially signals are pro-
duced by measuring samples and measured values are
then taken from the signals according to procedures that
Introduction (1) select single signals from a signal function, (2)
guarantee the validity of the signals, and (3) take suit-
Analytical chemistry has been defined as chemical dis- able values from them (e.g. signal intensity measured as
cipline which deals with the obtaining of information an integral or height). In addition to the original mea-
about the chemical composition of samples (chemical sured values (measured variables) and the analytical
elements, ions, species, and their structure) [1, 2]. Be- values (original analytical variables, e.g. contents, con-
cause the information process can be seen as the focus of centrations), latent variables are included in the scheme.
this definition, information theory has been used to Latent variables are obtained from real signals by means
build a general theoretical basis of analytical chemistry of mathematical operations (e.g. addition, subtraction,
[3]. But special aspects of analytical chemistry only can eigenanalysis). Latent variables may be appropriate final
be treated in this way—the analytical value, its impor- results of analytical investigations because information
tance and relevance, and the certainty of analytical re- represents not only chemical information but non-
sults. Additional aspects of theoretical fundamentals of chemical information also. Special decisions on quality,
analytical chemistry can be illuminated when the genuineness, authenticity, homogeneity, origin of sam-
emphasis of the above-mentioned definition is put on the ples, or health of patients can be made both on the basis
process of obtaining analytical information. of analytical values and of typical patterns of measured
values expressed by latent variables obtained according
to chemometric procedures. With these extensions of the
K. Danzer analytical processing scheme the central role of signals is
Institute of Inorganic and Analytical Chemistry, expressed and modern techniques of evaluation are
Friedrich Schiller University of Jena, Lessingstr. 8,
7745 Jena, Germany
considered.
E-mail: claus.danzer@jetzweb.de The scheme given in Fig. 1 represents normal ana-
URL: www.clausdanzer.de lytical procedures (off-line analysis). The scheme can be
377

Problem
Sampling strategy Problem solving

Object under study


Sampling Interpretation

Analytical
4 values 6
1 Measuring 2 3 Measuring
Sample Signal Information
sample values
Latent
5 7
variables
1 Sample preparation
2 Measurement
3 Signal belonging, -guarantee, -selection, -parameter
4 Calibration
5 Chemometrics
6 Data evaluation & interpretation
7 Chemometric data analysis

Fig. 1 The analytical process (chemical measurement process) evaluation and the validity of the environment is given
by the chemical measurement process (analytical pro-
shortened in on-line analysis where the object under cess).
study is measured directly without any sampling From the signal-theoretical point of view, signals
(Fig. 2a) and in in-line analysis, (Fig. 2b) where mea- have to fulfil three functions to gain analytical infor-
surement and control equipment are coupled with and mation:
installed in the object under control [5].
– A syntactic function which describes the relationship
between equivalent signals, the formation of signal
sequences, and the transformation of signals (knowl-
Types of analytical signals edge of the genesis of signals). The syntactic function
characterizes the structurization of signals.
In general, signals are fixed states or processes of – A semantic function which describes the meaning and
material systems. They can, therefore, be differentiated significance of signals and thus their unambiguous
into static and dynamic signals. Examples of static sig- connection with the object to be characterized
nals are scripts, colors, images, pictures, and buildings. (knowledge of coding and decoding, assignment rules,
Dynamic signals result from electrical, thermal, optical, and calibration). The semantic function characterizes
acoustic, or chemical interactions. Nowadays, these the meaning of signals.
signals are converted in each case into electrical signals, – A pragmatic function which determines the relation-
in which form they are treated and transmitted. Finally, ship between signals and persons who receive them.
the essential signal characteristics are recorded in a The pragmatic function characterizes the importance
suitable form. The total process of signal generation and and benefit of signals. All three functions should be
Fig. 2 Chemical measurement process in a on-line analysis and harmonized to obtain the expected information to the
b in-line analysis full extent and to avoid misinterpretation of signals.

(a) (b)
Problem
Problem

Object under study


Object under study

Direct
measurement
Analytical
values Measurement Control

Measuring Measured Control


Signal Information
values results quantity
Latent
values
378

Analytical signals can be classified according to dif- actions energy quanta and particles are exchanged [1].
ferent criteria. First, analytical signals are characterized The generation of analytical signals is a complex
by their generation process. Analytical signals result process that can be considered in three steps, namely
from interactions between the sample constituents and (1) the genesis, (2) the appearance and (3) the presen-
an external interaction system that acts on the sample. tation of signals.
The type of interaction determines the analytical tech- Whereas the genesis can be a chemical reaction,
nique applied. In detail, analytical signals can be the electrochemical or physical process (e.g. neutralization
product of chemical reactions (precipitations, their reaction, electrolysis, absorption and emission of radia-
appearance, color, and crystal shape), changes of colors tion), the appearance step is always a physical phe-
in solutions or flames, and differences between physical nomenon. Independent of the genesis, signals are
quantities (e.g. temperature, potentials, voltages, measured in form of physical quantities like volume,
absorbance). mass, differences of temperatures, and of energy quanta
Nowadays the analyst frequently has to deal with characterized qualitatively and quantitatively by wave-
complex signals in the form of structured signals, signal lengths, frequencies, and intensities. The presentation of
sequences, and signal functions of different dimension- signals take place in the form of values (e.g. hardcopy,
ality [4]. Examples for such complex signals are: spectra data file) and in the form of records of single signals and
of different types (UV–visible, IR, NMR, emission and of signal functions (e.g. spectra, chromatograms, or
absorption spectra, mass spectra), chromatograms (GC, pictures).
LC, HPLC), polarograms, and current–voltage curves. Information in the signal domain is generated from
Types of analytical signal are not only determined by the sample domain as Fig. 3a shows schematically for
their generation, characteristics (static or time-depen- element analysis and Fig. 3b for structure analysis. In all
dent, transient), and complexity but also by their cases the signal functions have diverse characteristics
appearance (their reality). From this point of view we which can be evaluated with regard to the sample. In
can differentiate between single species analysis a definite part (usually a single
signal) is selected from the signal function, as shown in
– Intrinsic signals (manifest signals): real, observable
Fig. 4.
signals from which we can take real measured vari-
From the presented signals characteristic parameters
ables
are taken to transform them into chemical information.
– Latent signals : non-real signals which can be obtained
Apart from the position parameter zA and the intensity
mathematically from real signals, in the simplest cases
parameter yA other characteristics, e.g. signal shape
by differences, ratios, and sums of manifest signals.
Latent signals are realized in the form of latent vari-
ables, e.g. differences between mass numbers in mass
spectrometry, isotope pattern of intensities of molec- (a)
ular peaks, factors, principle components, eigen-
values, and other chemometrically obtainable
quantities
– Hidden signals : non-resolved fine structures of spec-
tral bands or signals covered by background or noise.
Hidden signals can be detected by improving the z z z z

experimental conditions or by chemometric tech- (b)


niques (improvement of analytical resolution and/or
signal-to-noise ratio)

z z z z

Generation of analytical signals Fig. 3 a Relationship between sample domain and signal domain
in elemental analysis. b Relationship between sample domain and
Analytical signals are obtained as a result of interac- signal domain in structure analysis
tions between relevant energy forms and levels of
constituents of the sample (e.g. atoms, ions, molecules)
on the one hand and an external energy system (e.g.
chemical energy, radiation, heat) on the other hand.
The interactions can be elastic or inelastic from the
physical point of view. In elastic interactions no dis-
crete exchange of energy takes place and only struc-
tural changes of energy can be observed and recorded,
e.g. in the form of diffraction, reflection, remission of
radiation or particles. In contrast, in inelastic inter- Fig. 4 Signal parameters
379

and asymmetry, exist and can be measured. In the Contemplating Eq. 4, the partial derivatives of the
following, single signals in a given position zA will be model are of particular interest:
considered which are characterized by an intensity
parameter yA (A means the relevant analyte). These @yA DyA
 ð5aÞ
considerations can be easily generalized for signal @xi;j Dxi;j
sequences and signal functions and, therefore, also for
This partial derivatives represent effects on the signal
multispecies analysis.
(concisely: signal effects) provoked by given species and
factors. In this way, the signal effects:
@yA DyA
Mathematical model of signal appearance eff ðyA Þ ¼  ð5bÞ
@xi;j Dxi;j
The measurement of a sample composed of the analyte characterize specific influences of given species or fac-
A and some other constituents B, C,  , N generates a tors. The situation will be considered first for single-
signal that depends not only on the type and amount of species analysis of a given analyte A.
A but is also influenced to some extent by all the other
constituents. In quantitative analysis the other species
apart from the analyte are called the matrix, in identi- Signal effects
fication and structure analysis one speaks of related
species (neighbouring relations, environment). For the In detail, the signal effects represent various types of
signal parameters the following functional relationships sensitivity of the analytical system:
exist (1a, 1b): 1. The sensitivity of the determination of the analyte A:
zA ¼ f ðA; B; C; . . . ; N Þ ð1aÞ @yA DyA
senðyA Þ ¼ ¼ SAA  ð6Þ
The signal position is composed of a characteristic value @xA DxA
zA0 that is determining for the species A and some which represents the signal effect of the analyte alone
additional changes in position (e.g. chemical shifts), without any contributions to the signal by other species
splittings (e.g. fine structures such as rotation structure and factors. In this way sensitivity is always defined in
of vibration bands), and structuring (e.g. multiplets) analytical chemistry [7]. But, in fact, sen(yA) has to be
which are characteristic of the chemical environment of understood as a kind of ideal sensitivity or net sensitivity
A. The alterations are caused by neighbouring effects, of an analyte determination.
interactions, and couplings, in accordance with natural
laws (multiplet structure). Influencing factors a, b,  , m, 2. Cross sensitivities of the species i=B, C,  , N in form
for example temperature, pressure, solvent, etc., can also of partial sensitivities:
alter the signal position: @yA DyA
partðyA Þ ¼ ¼ SAi  ð7Þ
zA ¼ f ðA; B; C; . . . ; N ; a; b; . . . ; mÞ ð1bÞ @xi Dxi

In contrast, the signal intensity is influenced by the Partial sensitivities characterize signal contributions of
entire matrix: other species than the analyte. The term ‘‘partial sensi-
tivity’’ plays an important role in multispecies analysis
yA ¼ f ðxA ; xB ; xC ; . . . ; xN Þ ð2Þ and has been introduced by Kaiser to characterize
selectivity and specificity of analytical procedures [7, 8].
Accepting a linear model, the signal value is given by:
3. Influences of the factors and parameters j=a, b, c,..., m
yA ¼ yA0 þ SAA xA þ SAB xB þ SAC xC þ    þ SAN xN ð3Þ
@yA DyA
More generally, the signal intensity is also influenced by inflðyA Þ ¼ ¼ IAj  ð8Þ
@xj Dxj
the effects of several factors a, b,..., m of the operating
conditions, for example temperature, pressure, pH va- characterizing specific effects coming from other sources
lue, etc., and instrumental factors. Taking these factors than the accompanying species.
in account the model becomes: Whereas the xI represent
the amounts of the species i=A, B, C,..., N, the xj (j =a,
Analytical characteristics
b, c,  , m) represent the strength of the factor effects.
Mathematical expressions of this kind are well-known in
From the above mentioned three quantities describing
factorial design for finding relevant influences on the
effects on signal intensity, some important characteris-
analyte signal.
tics can be derived.

yA ¼ yA0 þ SAA xA þ SAB xB þ SAC xC þ ::: þ SAN xN þ IAa xa þ IAb xb þ ::: þ IAm xm
ð4Þ
Analyte Other species Influence factors
380

Real sensitivity always play an important role; in agreement with ana-


lytical experience, specificity increases with sensitivity
By the term ‘‘real sensitivity’’ the sum of influences of all and amount of analyte and decreases with increasing
the species (analyte+matrix) and all the factors can be cross-sensitivity and amounts of accompanying species,
characterized. Therefore, the real sensitivity real(yA) and the larger the influences of the disturbing effects are.
represents the total sum of the effects of analyte,
accompanying species, and factors, namely sensitivity,
cross sensitivities, and influences according to Eqs. 6,
Selectivity
7, 8
X
N X
m When more than one species must be analysed in a
realðyA Þ ¼ senðyA ÞxA þ partðyA Þxi þ inflðyA Þxj multicomponent system, selectivity characterizes the
i¼B j¼a ability of the analytical method to detect or to determine
X
N X
m several given species without interference, i.e. indepen-
¼ SAA xA þ SAi xi þ IAj xj ð9Þ dently and undisturbed by each other and by additional
i¼B j¼a constituents in the sample. The term selectivity is widely
used in analytical chemistry but in just the same way as
whereas accompanying species are characterized by specificity more in a verbal sense. A quantitative evalu-
positive quantities part(yA), as a rule, and therefore ation of specificity was given by Kaiser [8] whose defi-
increase the ideal sensitivity, factors might have both nition was improved in Ref. [11]. In simultaneous
effects, that means infl(yA) can be positive and negative. analysis of N species usually (at least) N signals are
The real sensitivity is a suitable characteristic of an evaluated at N sensors (detection channels):
analytical method or technique applicable in real ana-
lytical problems in practice. On the other hand, the yA ¼ yA0 þ SAA xA þ SAB xB þ    þ SAN xN
sensitivity according to Eq. 6 characterizes ideal systems yB ¼ yB0 þ SBA xA þ SBB xB þ    þ SBN xN
containing nothing but the analyte and, therefore, being .. ð11Þ
uninfluenced by all the accompanying components and .
all the influencing factors. All analysts know that there yN ¼ yN 0 þ SNA xA þ SNB xB þ    þ SNN xN
are differences between such ‘‘ideal’’ and real analytical or, in matrix representation:
systems and take this fact into account by extensive
experimental validation studies mostly without consid- y ¼ Sx ð12Þ
eration of theoretical or mathematical backgrounds up
to now. If necessary and possible, not only linear but The sensitivity matrix S (Kaiser’s ‘‘matrix of partial
also nonlinear models are used (e.g. experimental design sensitivities’’ [8]):
and polynomial optimization [9, 10]). Analysts also 0 1
SAA SAB    SAN
deliberately use this fact to improve the sensitivity of a B SBA SBB    C
B SBN C
given procedure, e.g. by addition of substances which S ¼ B .. .. .. .. C ð13Þ
support vaporization or ionization of the analyte. @ . . . . A
SNA SNB  SNN

Specificity is characterized in an ideal case by diagonal elements


that are different from zero and non-diagonal elements
Specificity is an important characteristic of analytical that are zero (at least approximately).
systems and methods that express qualitatively [5, 11] In analytical practice selectivity can be characterized
and quantitatively [7, 8] their ability to detect or deter- as follows [11]:
mine an individual analyte without interferences from P
N
accompanying species. In agreement with a definition sensðyi Þxi
given in Ref. [8], specificity of the determination of an selðA; B; . . . ; N Þ ¼ i¼A
analyte A concerning the species i=B, C,..., N can be P
N N P
P N
sensðyi Þxi þ partðyij Þxj
characterized as follows: i¼A i¼A j¼A

senðyA ÞxA PN
specðA=B; C; . . . ; N Þ ¼ P Sii xi
senðyA ÞxA þ partðyA Þxi ¼ i¼A
ð14Þ
SAA xA P
N PN
¼ N ð10Þ Sij xj
P i¼A j¼A
SAi xi
i¼A
which expresses the selectivity for a real analytical
Usually, it is not necessary to distinguish between problem depending on all the sensitivities and cross
‘‘theoretical’’ and ‘‘practical’’ specificity as done in Ref. sensitivities of the analytes and their amounts xi and xj.
[8]. For practical purposes the amounts of all the species As for specificity, differentiation between ‘‘theoretical’’
381

and ‘‘practical’’ selectivity, as given in Ref. [11], is of

0.625

0.713

0.831

0.994

0.996
Table 1 Calculated quantities for performance characterization: real sensitivities, real (yA), specificities, spec (A/B,C), ruggedness, rug (yA), and relative ruggedness, rugrel (yA) in case of

rugrel
(A)a
academic interest only. In analytical practice the
amounts of all the sample constituents always determine

16.667
the real analytical selectivity and specificity.

0.167

0.249

0.490

rug (A) means rug (A/B,C,a,b,c), rugrel (A) means rugrel (A/B,C,a,b,c); rug (A/B,C,a,b,c) should be read: ruggedness of the analysis of A with regard to B, C, a, b and c
(A)a
rug

25
(A/B,C)
Ruggedness

0.833

0.998

0.833

0.988

1.00
spec
Methods can only be practically applied when they are
sufficiently robust and insensitive to small variations in

12.02

12.02

10.04

10.02
method conditions, operator skill, and sample compo-

14.0
(yA)
real
sition. This demand is an important validation criterion

different values of signal effects, namely sensitivities, SA i, as well as influences, IA i, amounts of species, xi and strength of influencing factors xj
which has to be proved by experimental evaluation.

12.00
14.00
16.00
10.02
12.02
14.02
12.00
12.02
12.04
10.02
10.04
10.06
10.00
10.02
10.04
S+S
Ruggedness (robustness) has been described verbally
[11] but no quantitative characterization has yet been
presented. Initial stages can be found in Ref. [12] but

S |IA i|xi
that treatment is not general.
The ruggedness can be characterized by means of the

0.04

0.04

0.04
4

4
effect quantities, eff(yA), derived above (Eqs. 6, 7, 8) as
follows:

S IA ixi

0.02

0.02

0.02
rugðA=B; C; :::; N ; a; b; :::; mÞ

2
1 1
¼P
N P
m ¼P
N P
m ð15Þ
jpartðyA Þjxi þ jinflðyA Þjxj jSAi jxi þ jIAj jxj
S SA i xi
i¼B j¼a i¼B j¼a

0.02

0.02
The ruggedness will be the higher the lower the cross

0
sensitivities and the strengths of influences are. The
range of the quantity ruggedness is from 0 to infinity,
SAA

10

10

10

10

10

10
according to the definition (15). For realistic assessment
it may be of advantage to use a relative quantity, the

0.01

0.01

0.01
relative ruggedness which can take values between 0
1
1

1
c

and 1:

0.01

0.01

0.01
rugrel ðA=B; C; :::; N ; a; b; :::; mÞ
1
b

1
senðyA ÞxA
¼ PN Pm
ð16Þ
0.01

0.01

0.01
senðyA ÞxA þ jpartðyA Þjxi þ jinflðyA Þjxj
i¼B j¼a
a

2
1

¼S P SAA xA P
AA xA þ jSAi j xi þ jIAj j xj
0.01

0.01
C

0
For ambitious investigation and validation it should be
taken into account that effects on signals are frequently
0.01

0.01

not constant but depend on the influencing quantity it-


B

self:
10
A

@yA
¼ f ðxi;j Þ ð17Þ
@xi;j
xi
xj

xi
xj

xi
xj

xi
xj

xi
xj

Phenomenological and mathematical treatment of


influences on signals will then be much more difficult.
Strong factor influences

Strong factor influences

For ruggedness this dependence is evident and has been


Low factor influences

Low factor influences

Low factor influences

described, e.g. by Wünsch [13], as being characterized by


a so-called cathedral function, see Fig. 5.
Strong matrix

Strong matrix
Low matrix

Low matrix
influences

influences

influences

influences

No matrix
sens (yA) = SAA
part (yA) = SA i

influence
infl (yA) = IA j
(1)

(2)

(3)

(4)

(5)

Fig. 5 Cathedral function of robustness according to Wünsch [13]


a
382

It is also well-known that sometimes interactions


appear between the accompanying species themselves Summary
and with given factors. This can be taken into account
by interaction terms SA,BC xB xC and IA,ab xa xb, Accepting the central role of signals, the object of ana-
respectively, in Eqs. 3 and 4 as it is known from models lytical chemistry can be defined as the generation,
of experimental design [9]. If significant, such interaction treatment, and evaluation of signals from which infor-
terms must be included into the calculation of the rele- mation on the composition of samples is obtained. This
vant performance characteristics. statement can be made more precise by additional
explanation on the temporal and spatial changes that
Example In Table 1 an example is shown which illus- might be studied [1]. Characterization of analytical
trates the consequences of different quantities of signal chemistry as ‘‘a science of signal production and inter-
effects, namely sensitivities, SA i, and influences, IA i, and pretation’’ was first given by E. Pungor [15, 16].
amounts of species, xi, on real sensitivity, real(yA), Signals are the main object of analytical work. Ana-
specificity spec (A/B,C), and ruggedness, rug (A/ lysts generate signals by various analytical techniques to
B,C,a,b,c). obtain information on sample composition and struc-
It can be seen that ruggedness and specificity increase ture. By use of signal-related considerations basic signal
as expected when the amounts of interfering species B effects can be described and mathematically quantified.
and C decrease and the strength of influences a, b, and c Important analytical characteristics like (ideal) analyte
decrease. On the other hand, the real sensitivity as the sensitivity and cross sensitivities of accompanying spe-
sum of all signal effects, decreases with decreasing dis- cies can be explained in the same way as real sensitivity,
turbing effects. ruggedness, and specificity. Generalization to multispe-
cies analyses also defines selectivity. Signal-to-noise ratio
characterizes the precision of analytical procedures and
Precision
determines basic performance characteristics like limits
of detection and quantification.
Analytical methods are characterized primarily by their
precision. The precision is determined by the reproduc-
ibility of the analytical procedure, that means of the
complete standard operation procedure (SOP) from References
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2. Cammann K (1992) Fresenius J Anal Chem 343:812
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the analytical result, respectively [14]. lytical chemistry. Wiley, New York
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