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264 Aufrufe7 SeitenAbstract Analytical chemistry will be considered here as the measurement science of chemistry that generates, treats, and evaluates signals which contain information about the composition and structure of samples. Analytical information is always obtained from signals. Characteristics and peculiarities of analytical signals will be considered from a very general point of view. A mathematical model of the influencing of signals will be given from which essential performance characteristics of analytical methods can be derived, e.g. sensitivity, cross-sensitivity, specificity, selectivity, and ruggedness (robustness).

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Abstract Analytical chemistry will be considered here as the measurement science of chemistry that generates, treats, and evaluates signals which contain information about the composition and structure of samples. Analytical information is always obtained from signals. Characteristics and peculiarities of analytical signals will be considered from a very general point of view. A mathematical model of the influencing of signals will be given from which essential performance characteristics of analytical methods can be derived, e.g. sensitivity, cross-sensitivity, specificity, selectivity, and ruggedness (robustness).

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264 Aufrufe

Abstract Analytical chemistry will be considered here as the measurement science of chemistry that generates, treats, and evaluates signals which contain information about the composition and structure of samples. Analytical information is always obtained from signals. Characteristics and peculiarities of analytical signals will be considered from a very general point of view. A mathematical model of the influencing of signals will be given from which essential performance characteristics of analytical methods can be derived, e.g. sensitivity, cross-sensitivity, specificity, selectivity, and ruggedness (robustness).

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DOI 10.1007/s00216-004-2647-5

R EV IE W

Klaus Danzer

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

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

Direct

measurement

Analytical

values Measurement 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

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

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

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

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

B

self:

10

A

@yA

¼ f ðxi;j Þ ð17Þ

@xi;j

xi

xj

xi

xj

xi

xj

xi

xj

xi

xj

inﬂuences on signals will then be much more diﬃcult.

Strong factor inﬂuences

Low factor inﬂuences

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)

a

382

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

sampling to measurement. Precision is mostly expressed

inversely in form of imprecision by means of absolute or 1. Danzer K, Than E, Molch D (1987) Analytik—Systematischer

relative standard deviation. Nowadays, imprecision Überblick. Leipzig

2. Cammann K (1992) Fresenius J Anal Chem 343:812

should be given by the uncertainty of measurement and 3. Eckschlager K, Danzer K (1994) Information theory in ana-

the analytical result, respectively [14]. lytical chemistry. Wiley, New York

From the signal-related point of view the precision 4. Danzer K (1992) Fresenius J Anal Chem 343:827

should be expressed by the signal-to-noise ratio: 5. Kellner R, Mermet J-M, Otto M, Widmer HM (1998) (eds)

Analytical chemistry. VCH, Weinheim

S yA yA 1 yA 6. Currie LA (1995) IUPAC Commission on Analytical Nomen-

¼ ¼ ¼ ¼ ð18Þ clature, Nomenclature in evaluation of analytical methods

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