REPORT
The Hierarchy and Relationships
of Analytical
Properties
Miguel Valcárcel and Angel Ríos
Department of Analytical Chemistry
University of Cordoba
14004 Cordoba, Spain
The quality of the analytical infor-
mation produced in a laboratory de-
pends on the quality of the informa-
tion available to m a n a g e r s as they
define the analytical problem, design
the analytical process, and adjust its
features so that the results produced
meet t h e r e q u i r e d objectives (e.g.,
c o m p l i a n c e w i t h l a w s , n o r m s , or
quality control of products and sys-
tems). It is important to have a clear
understanding of analytical proper-
ties such as accuracy and represen-
tativeness as well as their relation-
ship to q u a l i t y in t h e a n a l y t i c a l
process and to the results. These two
facets of a n a l y s i s a r e f r e q u e n t l y
dealt with inconsistently, resulting
in confusion in laboratory work and
in communications w i t h clients or
service users.
The purpose of this REPORT is to
0003-2700/93/0365-781 A/$04.00/0
© 1993 American Chemical Society
establish a hierarchy for analytical
properties, illustrate their mutual
relationships, and describe how the
social and economic considerations of
a given analytical problem affect the
dominance of some properties over
others. As we will see below, dealing
with analytical properties in isola-
tion when designing strategies to ad-
dress specific problems is often inad-
equate and produces erroneous
results.
Types of analytical properties
Quality in the analytical results, the
primary goal of analytical chemistry,
relies heavily on two capital analyti-
cal properties: accuracy and r e p r e -
sentativeness. Accuracy means con-
sistency between the results obtained
and the actual concentration of the
analyte in a particular sample; rep-
resentativeness refers to consistency
between the results and the analyzed
sample as well as between t h e r e -
sults and the definition of the a n a -
lytical problem.
Capital properties rely on another
ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 781 A
group of analytical properties t h a t
we will call basic properties. They
determine the quality of the analyti-
cal process both inside the laboratory
and outside the l a b o r a t o r y d u r i n g
sampling. Basic properties are sensi-
tivity, selectivity, precision, and
sampling; t h e i r definitions can be
found in a number of analytical text-
books and monographs.
The analytical process is also lim-
ited by seemingly less significant ac-
cessory properties. These properties,
however, often have major practical
implications. They include expedi-
t i o u s n e s s , cost-effectiveness, a n d
personnel-related considerations, all
of which affect laboratory output.
Figure 1 shows the two essential
components of analytical quality and
displays capital, basic, and accessory
analytical properties in a hierarchi-
cal m a n n e r . It also outlines the ge-
neric objectives of present-day ana-
lytical chemistry: obtaining larger
amounts of analytical information of
a higher quality by expending less
material, time, and h u m a n re-
REPORT
sources; minimizing risks; and incur-
ring the smallest expenses possible
(i). Whereas capital analytical prop-
e r t i e s a r e associated with r e s u l t s ,
basic and accessory p r o p e r t i e s are
related to the analytical methodology
used.
Analytical properties, whether
viewed individually or collectively,
are not independent of one another.
In fact, they exhibit mutual—and oc-
casionally opposing—relationships.
Attempts to optimize a given analyt-
Personnel
safety/comfort
Figure 1. Goals of analytical chemistry and their relationships to analytical quality
and analytical properties.
Figure 2. Analytical tetrahedra.
782 A · ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993
ical procedure should, in principle,
be aimed a t t h e capital properties.
The m a x i m u m possible sensitivity,
selectivity, and precision should be
achieved, and proper sampling
should be carried out. However, em-
p h a s i s is often placed on saving or
minimizing t i m e , costs, m a t e r i a l s ,
reagents, labor, and hazards, which
l e a d s to g r e a t e r e x p e d i t i o u s n e s s ,
cost-effectiveness, automation, and
p e r s o n n e l safety a n d comfort. The
balance between the objectives as de-
picted in Figure 1 d e t e r m i n e s to a
g r e a t extent how analytical proce-
dures are designed.
Analytical tetrahedra
The most straightforward and intui-
tive form of graphically displaying
a n a l y t i c a l p r o p e r t i e s involves two
t e t r a h e d r a t h a t s h a r e a vertex and
can be of v a r y i n g sizes r e l a t i v e to
each other (Figure 2). This illustra-
tion provides a useful means of dis-
tinguishing among the three princi-
pal groups of analytical properties,
establishing a hierarchy, and deter-
mining symbiotic and opposing rela-
tionships among them. Figure 2 also
includes sampling, which determines
representativeness.
The vertices of the m a i n t e t r a h e -
dron (left) depict sensitivity, selec-
tivity, and precision; one of its faces
represents accuracy, which relies on
t h e s e t h r e e b a s i c p r o p e r t i e s . This
tetrahedron, together with represen-
t a t i v e n e s s of s a m p l i n g , h a s t h e
greatest statistical weight on analyt-
ical results and is connected with the
objectives of obtaining more and bet-
ter information.
The secondary tetrahedron (right)
has vertices depicting the accessory
analytical properties; one of its faces
r e p r e s e n t s laboratory productivity.
This tetrahedron is related to the ob-
jectives of minimizing time, costs, la-
bor, and hazards.
The balance among analytical
properties illustrated in Figure 2 will
be shifted by the specific elements of
t h e a n a l y t i c a l problem a d d r e s s e d
(e.g., result quality is always in con-
flict with productivity). The balance
between two competing sides repre-
sents a compromise and defines the
c o m p e t i t i v e n e s s of t h e a n a l y t i c a l
laboratory concerned. For example,
although a laboratory may be more
competitive if it can obtain results in
a short time, some accuracy may be
sacrificed. Each l a b o r a t o r y should
determine the most competitive po-
sition of the equilibrium to address a
particular problem.
Shifts in t h e balance depicted in
Figure 2 can be classified by t h r e e
g r o u p s according to w h e t h e r one,
two, or t h r e e analytical properties
a r e to be prioritized. The initially
regular t e t r a h e d r a become irregular
prisms when a vertex, edge, or side
is pulled, l e n g t h e n e d , or expanded
while others are pushed, shortened,
or contracted.
Accuracy and representativeness
As indicated previously, overall qual-
ity in analytical chemistry is deter-
mined by accuracy and r e p r é s e n t a -

Figure 3. Mechanisms for increasing
accuracy by enhancing basic
analytical properties.
(a) Including separation techniques to
preconcentrate analytes of interest and remove
interferences enhances one or more of the three
basic analytical properties, (b) Increasing analysis
precision results in increased accuracy.
tiveness and depends on the quality
of the work performed outside (sam-
pling) and inside the laboratory (the
analytical process).
The influence of sampling on ana-
lytical quality cannot be overstated.
P r o p e r s a m p l i n g is e s s e n t i a l for
achieving the degree of representa-
tiveness appropriate to the analyti-
cal problem and t h u s for providing
quality results. Accuracy in the anal-
ysis of a nonrepresentative sample is
meaningless. For example, an accu-
rate determination of the fat content
of milk in only a few randomly se-
lected packages by use of validated
methodologies based on modern in-
strumentation is not useful analyti-
cal information if the objective is to
determine the fat content of a batch
of 10,000 packs. Appropriate statisti-
cal sampling must be carried out if
the i n f o r m a t i o n produced is to be
r e p r e s e n t a t i v e of t h e problem as a
whole.
Another example involves the
blood potassium concentration deter-
m i n e d from a sample t a k e n from a
patient more t h a n 1 h after a h e a r t
attack. The sample cannot be consid-
ered representative of the patient's
blood potassium concentration at the
time of the heart attack. Representa-
tiveness is therefore an unavoidable
prerequisite and the bottleneck t h a t
controls the entire analytical process:
No other analytical property can be
justified in the absence of representa-
tiveness.
Accuracy is the analytical property
most closely r e l a t e d to l a b o r a t o r y
work in which the chemical composi-
t i o n of a k n o w n s a m p l e is d e t e r -
mined. It is complementary to repre-
s e n t a t i v e n e s s because it allows
specific analytical determinations to
be made about a sample. It also vali-
d a t e s r e p r e s e n t a t i v e n e s s because,
however representative a sample
may be, it is useless if the analytical
information about it is inaccurate.
Although it is r a t h e r difficult to
assess r e p r e s e n t a t i v e n e s s , c e r t a i n
statistical approximations can be ap-
plied to s a m p l i n g t e c h n i q u e s t h a t
make them easier to implement and
more reliable. In m a n y cases, it is
imperative to talk with individuals
both inside and outside the area of
interest and to investigate a variety
of t e c h n i q u e s to e n s u r e a properly
defined analytical question t h a t will
provide results representative of the
scientific, economic, or social prob-
lem a d d r e s s e d . A c c u r a c y , on t h e
other hand, can be evaluated much
more easily by, for example, use of
certified reference materials.
Accuracy and basic analytical
properties
Accurate r e s u l t s rely on a d e q u a t e
sensitivity, the absence of interfer-
ences, and reasonable repeatability/
reproducibility (i.e., low uncertainty)
for the analytical method used. Thus
in Figure 2 the vertices of the face of
the main tetrahedron, which repre-
s e n t s accuracy, coincide w i t h t h e
three basic analytical properties.
In fact, if the a n a l y t e concentra-
tions in the sample are lower t h a n
the detection or quantification limits
achieved, the analytical results will
not be consistent with these limits.
Any perturbations arising from posi-
tive or negative deviations in the an-
alytical signal, whether of an addi-
tive or m u l t i p l i c a t i v e n a t u r e , will
also shift the results from the actual
values. The tetrahedron edge bound
by the sensitivity and selectivity ver-
tices can be markedly lengthened by
including s e p a r a t i o n techniques in
the analytical process; through pre-
concentration a n d interference re-
ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 783 A
moval, such techniques indirectly en-
hance one or more of the three basic
a n a l y t i c a l p r o p e r t i e s ( F i g u r e 3a).
Liquid-liquid extraction is a separa-
tion technique widely used for this
purpose.
Although a given analytical proce-
dure may be highly accurate but not
precise (i.e., the mean of a set of dis-
perse results obtained for the same
sample may coincide with the actual
value), accuracy usually depends on
t h e a b s e n c e of s y s t e m a t i c e r r o r s
arising from low levels of the basic
analytical properties a n d from the
so-called h u m a n factor and indeter-
minate (random) errors. Highly u n -
certain results are also generally not
accurate. T h u s increased precision
results in increased accuracy (Figure
3b); the former can be achieved by
simplifying or a u t o m a t i n g the ana-
lytical process (2). For example, the
use of an automatic sample/standard
introduction system in electrother-
mal vaporization atomic absorption
spectroscopy ensures greater preci-
sion in r o u t i n e analyses compared
with the level of precision achieved
with manual introduction.
Relationships among basic
analytical properties
Figure 4 depicts the opposing rela-
tionships among the three basic ana-
lytical p r o p e r t i e s . E n h a n c i n g one
usually can be achieved only at the
expense of the other two. The central
equilateral triangle represents a bal-
anced situation and can be distorted
to a n isosceles or scalene t r i a n g l e ,
depending on which property is fa-
vored. For comparison, t r i a n g l e
areas have been kept constant. The
most salient relationships among the
three properties are discussed below.
P r e c i s i o n a n d s e n s i t i v i t y . It is
well known t h a t precision decreases
as analyte concentrations decrease.
Figure 4. Relationships among basic
analytical properties.
REPORT
Figure 5 shows an example of the re-
s u l t s from i n t e r c o m p a r i s o n food
analysis e x p e r i m e n t s in which t h e
coefficient of variation increases ex-
ponentially with decreasing analyte
concentration (3). Consequently, a
highly sensitive method will also be
highly variable when applied to trace
and u l t r a t r a c e d e t e r m i n a t i o n s . E r -
rors of ± 10% in the determination of
a few n a n o g r a m s per milliliter of a
drug in blood are quite acceptable;
however, errors made in determining
the same drug at the milligram-per-
gram level in a pharmaceutical prep-
aration should not exceed ± 2%.
Incorporating an analytical sepa-
r a t i o n t e c h n i q u e to i n d i r e c t l y e n -
hance sensitivity and to facilitate the
determination of analyte concentra-
tions below the detection or quantifi-
cation limit of the analytical method
used complicates preliminary opera-
tions and increases the time spent by
the researcher. In addition, precision
is d i m i n i s h e d . D e t e r m i n a t i o n of
trace cadmium in seawater by direct
application of a selective s p e c t r o -
scopic t e c h n i q u e such as g r a p h i t e
furnace atomic absorption spectros-
copy or inductively coupled plasma
atomic emission spectroscopy results
in e r r o r s s m a l l e r t h a n t h o s e ob-
tained when a preconcentration pro-
cedure such as liquid-liquid extrac-
Figure 5. Relationship between the
precision and the concentration level
of the analytes to be determined in the
form of a Horwitz graph.
(Adapted with permission from Reference 3.)
784 A · ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993
tion or ion exchange is used before
spectroscopic analysis.
The standard deviation of the esti-
m a t e for a calibration curve e s t a b -
lishes a statistical relationship be-
tween precision and sensitivity: The
h i g h e r t h e s e n s i t i v i t y (i.e., t h e
greater the curve slope, as defined by
IUPAC), t h e h i g h e r t h e p r e c i s i o n
achieved in the analyte determina-
tion. In fact, at a given signal level
t h e more sensitive method (Figure
6a) provides a less uncertain result
t h a n does the less sensitive method
(Figure 6b), provided both calibra-
t i o n curves h a v e s i m i l a r s t a n d a r d
deviations of the estimate. Also, for a
given curve, t h e h i g h e s t precision
lies in t h e c e n t r a l portion a n d de-
creases toward the ends (quantifica-
tion and u p p e r limit, respectively).
Detection a n d q u a n t i t a t i o n limits,
two ways of defining sensitivity, are
calculated via a p r e c i s i o n - r e l a t e d
parameter: the standard deviation of
the blank.
The relationships between sensi-
tivity and precision discussed above Figure 6. Relationship between
contribute to the uncertainty of the sensitivity and precision in terms of
measuring analytical technique the uncertainty involved at a given
used. Thus weighings on an analyti- signal level in two calibration curves of
cal balance are subject to fixed er- different slope.
rors (e.g., ± 0.1 mg) t h a t will affect (a) More sensitive method, (b) Less sensitive
t h e p r e c i s i o n of t h e m e a s u r i n g method.
method to a n extent inversely pro-
portional to the weighed amount of
sample, reagent, and reaction prod- ganic r a t h e r than inorganic r e -
uct. With other analytical tech- agents); material separation (e.g., by
niques, t h e highest possible preci- combining preconcentration and in-
sion is achieved over a given t e r f e r e n c e r e m o v a l , a s in l i q u i d -
analytical signal range; such is the liquid extraction a n d anodic s t r i p -
case with U V - v i s photometry, where p i n g v o l t a m m e t r y ) ; s e l e c t i o n or
the zone of minimum error is bound alteration of the instrumental tech-
by a b s o r b a n c e v a l u e s b e t w e e n 0.2 nique used (e.g., atomic r a t h e r t h a n
and 0.8 AU. molecular optical techniques or t h e
S e n s i t i v i t y a n d selectivity. Not- use of chemically modified electrodes
w i t h s t a n d i n g t h e i r seemingly d i s - for potentiometric m e a s u r e m e n t s ) ;
tinct n a t u r e s , sensitivity and selec- b i n a r y or t e r n a r y combinations of
tivity are also related and not always the above choices (e.g., pre- and post-
in an opposite m a n n e r . In fact, the column derivatization in chromatog-
difference between additive and mul- raphy, where chemical reactions are
t i p l i c a t i v e i n t e r f e r e n c e s lies in used to enable t h e s e p a r a t i o n a n d
whether the perturbation concerned detection of the solutes, respectively);
affects the slope (sensitivity) of the and use of chemometric techniques in
calibration curve. The more sensitive combination with one or more of the
t h e m e t h o d u s e d to d e t e r m i n e a previous alternatives (e.g., multivari-
given analyte, the more a sample can ate calibration procedures).
be diluted to decrease the concentra- Newly emerging analytical labora-
tions of interferences and hence min- tory instruments tend to incorporate
imize or e l i m i n a t e t h e i r p e r t u r b a - these mechanisms to enhance basic
tions. This approach is widely known a n a l y t i c a l p r o p e r t i e s . T h e u s e of
and exploited in the analysis of clini- nonchromatographic continuous sep-
cal/biological samples; sensitive aration techniques and multichannel
methods call for high initial dilutions detectors as well as the development
(1:10-1:10,000) to minimize the typi- of hyphenated techniques—one p a r t
cal perturbations of macromolecules. of which can be a type of chromatog-
Sensitivity and selectivity can be r a p h y — a n d on-line combined tech-
enhanced by similar mechanisms (4): niques are additional good examples
chemical reactivity (e.g., by using or- in this context.
 S e l e c t i v i t y a n d p r e c i s i o n . The
uncertainty inherent in the mecha-
nisms described above for enhancing
selectivity is related to the complex-
ity of the analytical process. When
several such mechanisms come into
play, the indeterminate error arising
from each is seen in the final result,
and precision is diminished. Thus if
the selectivity of the methodology in
q u e s t i o n a r i s e s from t h e d e t e c t o r
used (e.g., in single- and multichan-
nel atomic spectroscopy), the analyt-
ical process is simpler a n d h i g h e r
precision is achieved. However, the
precision is decreased when one in-
corporates new chemical reactions or
a separation procedure to increase Figure 7. Distortion of the analytical tetrahedra for boosting (a) accuracy or
the selectivity because it expands the (b) accessory analytical properties.
traceability chain.
U s i n g a s e p a r a t i o n t e c h n i q u e to
remove interferences introduces fur-
ther u n c e r t a i n t y in the final result
because the analytical process is be-
ing expanded or complicated. By au-
tomating the preliminary operations
of the analytical process (2) or by us-
ing h y p h e n a t e d techniques, h u m a n
errors can be minimized. In fact, on-
line combinations of separation tech-
n i q u e s a r e effective m e a n s of i n -
creasing the overall precision
a c h i e v e d by u s i n g t h e c o m b i n e d
techniques in isolation. Thus the co-
efficient of variation associated with
the use of a supercritical fluid ex-
tractor and a gas chromatograph
combined on line is lower t h a n the
summation of those obtained when
the extraction and separation/deter-
mination steps are carried out sepa-
rately.
Appropriate chemometric or sim-
ple m a t h e m a t i c a l t r e a t m e n t s i n -
crease selectivity. U n i v a r i a t e cali-
bration and differential kinetic
methods (e.g., logarithmic extrapola-
tion) (5, 6) are two good choices. As a
rule, the use of these methods results
in poor precision—even poorer t h a n
that obtained from analytical sepa-
ration techniques. However, one can
use t h e s e m e t h o d s to avoid some
stages of the analytical process.
Accuracy and accessory
analytical properties
Figure 8. Relationships among the complementary analytical properties and the
Designing an analytical method by prevalence of one or two of them.
which to achieve high accuracy
Results of enhancing (a) cost-effectiveness, (b) cost-effectiveness and expeditiousness,
means t h a t high levels of the basic (c) expeditiousness, (d) cost-effectiveness and personnel safety/comfort, (e) personnel safety/comfort,
a n a l y t i c a l p r o p e r t i e s m u s t be ob- and (f) expeditiousness and personnel safety/comfort.
tained a t t h e expense of t h e acces-
sory p r o p e r t i e s . As can be seen in
Figure 7a, the m a i n t e t r a h e d r o n is main tetrahedron. This situation re- aspects related to laboratory produc-
distorted when the area of the trian- flects the priorities among the capi- tivity prevail upon the quality of the
g u l a r a c c u r a c y face is i n c r e a s e d , tal, basic, and accessory analytical results.
whereas the secondary tetrahedron properties in Figure 1. The opposite Obtaining immediate analytical
is considerably s h r u n k by shifting s i t u a t i o n (Figure 7b) occurs w h e n results in response to an urgent de-
t h o s e forces p o i n t i n g t o w a r d t h e temporal, economic, and/or personal m a n d (e.g., in t h e clinical field) or

ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 785 A
REPORT
controlling a process in n e a r real
time e n t a i l s sacrificing some accu-
racy. Thus some recent applications
rely on FT-IR spectroscopy to obtain
accurate, reproducible r e s u l t s in as
short a t i m e as possible w i t h m i n i -
mal sample handling and m a n u a l in-
volvement (e.g., on-line process con-
t r o l i n m a n u f a c t u r i n g w o r k [7]).
Occasionally, a timely "yes or no" r e -
ply to indicate w h e t h e r a given pa-
r a m e t e r is above or below t h e toler-
a t e d level is m o r e i m p o r t a n t t h a n
obtaining a n accurate analytical re T
suit a few h o u r s l a t e r . S e n s o r s (8)
and screening tests based on i m m u -
noassay (9) a r e additional good ex-
amples.
When economic constraints affect
laboratories or when available equip-
ment is limited, the quality of the r e -
sults suffers. Acquiring and process-
ing analytical signals manually with
poor-quality reagents and r u d i m e n -
t a r y equipment t h a t lacks a d e q u a t e
electronic control adversely influence
t h e accuracy of t h e r e s u l t s . Never-
theless, the best technical means are
no guarantee t h a t results will be ac-
curate unless t h e analytical process
is developed properly, in compliance
Examples of the effects of enhancing one or two accessory
analytical properties
Enhanced property/properties Example
Cost-effectiveness The first step usually taken to cut
laboratory expenses is to reduce
personnel. This results in a heavier
workload for remaining personnel and in a
slower delivery of results (Figure 8a).
Expeditiousness Increasing throughput requires
augmenting laboratory equipment
and compelling staff to work harder
(Figure 8c).
Personnel safety/comfort If political or trade union pressure takes
personnel claims to extremes, costs
immediately rise and throughput falls
(Figure 8e).
Cost-effectiveness and expeditiousness If costs need to be reduced and
throughput raised, the analytical process
is frequently automated fully or partly.
Automation results in staff dismissals and
the assignment of greater responsibilities
to the remaining analysts, who thus
require retraining (Figure 8b).
Expeditiousness and personnel If personnel safety/comfort is not critical
safety/comfort to obtaining the analytical results, the
staff will be under no pressure and none
of the extraordinary and also costly
means needed to maintain a high
throughput will be required (Figure 8f).
Cost-effectiveness and personnel The laboratory budget must be increased
safety/comfort to maintain a high throughput without
altering personnel status (Figure 8d).

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786 A · ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993
with established quality a s s u r a n c e
norms (10).
Accuracy is also affected by t h e
human factor which, despite the high
d e g r e e of a u t o m a t i o n c u r r e n t l y
available at many laboratories, r e -
mains crucial. The ease with which
results are obtained from automatic
analytical methods and the increas-
ing isolation of instrument operators
from the process foster operator er-
rors because of overconfidence in au-
t o m a t e d e q u i p m e n t . These factors
also diminish the attention given to
a critical e v a l u a t i o n of the r e s u l t s
obtained.
Other major human factors are op-
e r a t o r comfort and safety p r e c a u -
tions, the implementation of which
occasionally entails sacrificing some
accuracy to prevent hazards for the
operators and those near them. Such
is the case with routine analyses in-
volving hazardous reagents or meth-
ods. Though the need for accuracy
exists, methodology should be modi-
fied to avoid hazards and the possi-
bility of accidents, and to minimize
the need for the continuous attention
of the operator.
Accessory analytical properties
The accessory properties at the ver-
tices of the productivity t r i a n g u l a r
face of the secondary analytical tet-
rahedron also exhibit opposing rela-
tionships. The imposed or advisable
p r e v a l e n c e of one or two of t h e s e
properties d i s t o r t s t h e e q u i l a t e r a l
t r i a n g u l a r face and hence disturbs
the balance among them.
When an analytical procedure is
designed to enhance one of the three
properties—cost-effectiveness (Fig-
ure 8a), expeditiousness (Figure 8c),
or personnel safety/comfort (Figure
8e)—the other two sides of the r e -
sulting productivity t r i a n g u l a r face
are markedly shortened. If two prop-
erties rather t h a n one are favored—
cost-effectiveness and expeditious-
ness (Figure 8b) or expeditiousness
and personnel safety/comfort (Figure
8f) or cost-effectiveness and person-
nel safety/comfort (Figure 8d)—the
side of t h e r e m a i n i n g p r o p e r t y is
contracted. Examples of such situa-
tions appear in the box on p. 786 A.
Quality compromises
M e e t i n g t h e d e m a n d s imposed on
the information produced by an ana-
lytical l a b o r a t o r y r e q u i r e s t h a t a
compromise be m a d e b e t w e e n t h e
two c o m p o n e n t s of t h e a n a l y t i c a l
chemistry/quality binomial: external
quality, which refers to the proper-
ties of the monitored product or ser-
vice, a n d i n t e r n a l q u a l i t y , w h i c h
deals with the analytical process and
the results produced.
External quality may result from
compliance with legislation or qual-
ity requisites for a production pro-
cess. It directly affects a n a l y t i c a l
quality, which depends on capital,
basic, and accessory analytical prop-
erties. As we have seen, analytical
quality can be approached in various
ways, depending on the a n a l y t i c a l
problem. From a strictly theoretical
point of view, the situation in Figure
8a can be considered i d e a l — a t the
least, one should reach the balanced
situation shown in Figure 2. How-
ever, the facts may justify the situa-
tion depicted in Figure 8a for the an-
a l y t i c a l l a b o r a t o r y to m e e t t h e
d e m a n d s posed by t h e a n a l y t i c a l
problem derived from the economic
or social problem addressed.
The c u r r e n t requirement t h a t all
l a b o r a t o r y activities be in w r i t t e n
form necessitates managerial plan-
ning. In m a n y cases t h i s r e q u i r e -
ment is imposed by law, and often a
company produces a quality manual
whereby the specific priorities affect-
ing the analytical properties graphi-
cally related by the two t e t r a h e d r a
are to be established via s t a n d a r d
o p e r a t i o n a l procedures (SOPs). In
R&D and in pharmaceutical industry
laboratories, priorities are imposed
by o r g a n i z a t i o n s such as the Food
and Drug Administration or the Or-
ganization for Economic Cooperation
and Development in the form of Good
Laboratory Practices. On the other
h a n d , in analytical R&D l a b o r a t o -
ries, such as those a t u n i v e r s i t i e s
where new analytical methods and
technological innovations are devel-
oped, the goal is to characterize each
of the analytical properties inherent
in the new method or technique ac-
cording to quality control norms.
Final remarks
In the foregoing discussion, we have
strived to establish a h i e r a r c h y of
analytical properties as well as their
relationships to one another and the
two analytical quality components.
In addition, we have underscored the
need to accurately define objectives
w h e n d e s i g n i n g a n a l y t i c a l proce-
dures. Although a number of the in-
dividual factors dealt with here are
well known, they have rarely been
considered together or in a system-
atic m a n n e r d e s p i t e t h e fact t h a t
t h e y a r e m o s t likely t h e u l t i m a t e
foundation of analytical chemistry.
This view can be of use to basic and
applied researchers in planning and
managing laboratories as well as in
teaching analytical science.
ANALYTICAL CHEMISTRY, VOL. 65, NO. 18, SEPTEMBER 15, 1993 · 787 A
References
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1992, 343, 814.
(2) Valcârcel, M.; Luque de Castro, M. D.
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(3) Horwitz, W.; Kamps, L. R.; Boyer,
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(4) Valcârcel, M.; Rios, A. Analusis 1990,
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Miguel Valcârcel (left) has been a profes-
sor at the University of Cordoba since
1976. He received his B.S. degree in
chemistry and his Ph.D. in analytical
chemistry (1971) from the University of
Sevilla (Spain). Valcarcel's research in-
terests include the automation of analyti-
cal processes, flow injection methods,
(bio)chemical sensors, nonchromato-
graphic continuous separation tech-
niques, and the implementation of quality
systems in the analytical laboratory. He is
the author or co-author of about 400 re-
search papers, six textbooks, and three
monographs.
Angel Rios (right) is an assistant profes-
sor in the Department of Analytical
Chemistry at the University of Cordoba.
He received his B.S. degree in chemistry
(1980) and his Ph.D. in analytical chem-
istry (1983) from that university. His re-
search interests include automated flow
systems and the implementation and ap-
plication of quality principles in control
and R&D analytical laboratories.