Microchemical Journal 128 (2016) 331–346

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Microchemical Journal

journal homepage: www.elsevier.com/locate/microc

Review article

A review of multivariate designs applied to the optimization of methods

based on inductively coupled plasma optical emission spectrometry
(ICP OES)
Cleber Galvão Novaes a,⁎, Marcos Almeida Bezerra a, Erik Galvão Paranhos da Silva b,
Ana Maria Pinto dos Santos c, Ivana Lago da Silva Romão a,c, João Honorato Santos Neto a
a
Universidade Estadual do Sudoeste da Bahia, Laboratório de Química Analítica, Jequié, Bahia State 45206-190, Brazil
b
Universidade Estadual de Santa Cruz, Departamento de Ciências Exatas e Tecnológicas, Campus Soane Nazaré, Ilhéus, Bahia State 45662-900, Brazil
c
Universidade Federal da Bahia, Grupo de Pesquisa em Química e Quimiometria Instituto de Química, Salvador, Bahia CEP 40170-270, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: This review covers the application of multivariate designs and mathematical-statistical techniques to establish
Received 18 May 2016 optimal conditions of the analytical methods for elemental analysis using inductively coupled plasma optical
Accepted 24 May 2016 emission spectrometry (ICP OES) as a detection technique. The main experimental designs, such as two level fac-
Available online 24 May 2016
torial design, central-composite design, Box Behnken design, Doehlert design and mixtures designs are presented
and discussed in connection to the method stage, in which multivariate designs were used in the instrumental
Keywords:
ICP OES
variable optimization related to plasma, sample decomposition, preconcentration stage and sample introduction
Two level factorial design technique.
Central composite design © 2016 Elsevier B.V. All rights reserved.
Box–Behnken design
Doehlert design
Mixture designs

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
2. Multivariate experimental design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
2.1. Comments regarding the multivariate design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332
2.2. Multivariate experimental designs for variable screening. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
2.3. Multivariate designs for response surface methodology in the study of process variables . . . . . . . . . . . . . . . . . . . . . . . . 333
2.4. Multivariate designs for response surface methodology of mixture variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
2.5. Validation of the fitted mathematical model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
2.6. Multivariate optimization by Simplex method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
3. Multivariate strategic design application in the optimization of analytical methods with ICP OES detection . . . . . . . . . . . . . . . . . . . 336
3.1. Optimization of instrumental parameters regarding plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
3.2. Optimization of the sample preparation stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
3.3. Optimization of preconcentration procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
3.4. Optimization methods for sample introduction in ICP OES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343

1. Introduction

⁎ Corresponding author. Analytical techniques based on the emission of radiant energy by

E-mail address: cgalvaonovaes@gmail.com (C.G. Novaes). the atoms are one of the oldest tools used for multi-elementary

http://dx.doi.org/10.1016/j.microc.2016.05.015
0026-265X/© 2016 Elsevier B.V. All rights reserved.
332 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346
spectrometric analysis. The first source used in emission studies was the
flame, that despite having a low cost and being efficient in the excitation
of some elements, has several disadvantages such as insufficient energy
for atomization and excitement of many analytes, instability, and an en-
vironment rich in reactive species, which cause high background and
the emission of interfering radiation. The plasma sources were devel-
oped for the purpose of analysis by spectrometric emission in the
1960s, and the first spectrometers were introduced in the scientific
equipment market during the mid-1970s [1].
Plasma is a highly energized and electrically neutral gas composed of
ions, electrons and neutral particles. It is usually produced by an argon
stream, that is energized by a high frequency electromagnetic field (or
by microwaves energy) or by a direct current. When this source is com-
bined with high quality spectrometers, it results in a powerful elemental
detection technique. Plasmas produced in these spectrometers usually
have a high temperature (can reach 8.000 K) and a less reactive chem-
ical environment than the atomizer flame. Among the commercially
available spectrometric techniques, the inductively coupled plasma op-
tical emission spectrometry (ICP OES) comes nowadays stands out due
its versatility and detection capacity [2,3].
The high temperature produced by the plasma source allows for a
determination, in highly sensitive manner, of elements that are usually
greatly difficult of being determined through other analytical tech-
niques such as refractory metals or that form refractory oxides [4,5],
rare earth elements [6] and light elements such as boron [7]. In theory,
all elements of the periodic table could be determined by techniques
based on ICP, but, in practice, there are restrictions in the analysis
with elements artificially produced, inert gases and oxygen, due to
their physical and spectral properties [8,9].
The development of analytical methods that use ICP OES as detection
technique requires that the aims of the analysis be clearly defined to take
advantage of all the technical potentialities and to avoid loss of time and
financial resources. Thus, all the stages and characteristics of the method
(type and amount of sample, decomposition method, sample input
method, etc.) should be designed to make it feasible to perform the anal-
ysis and to generate reliable results. Moreover, instrumental variables
such as: radiofrequency (RF), torch configuration (axial or radial), gas
flow, sample aspiration flow, etc. must also be established [10].
Traditionally, the application conditions of an analytical method are
optimized using the univariate optimization. This is characterized by
studying each variable at a time and has as main drawbacks, a large
number of experiments performed (which leads to high consumption
of time and reagents) and the impossibility of evaluating interactions
between studied variables. Recently, multivariate optimization
methods have been gaining ground in the establishment of optimal con-
ditions for the application of an analytical method [11,12]. These
methods are based on mathematical-statistical tools to optimize situa-
tions that involve many variables. Thus, the choice and application of a
particular experimental design based on statistical principles, and asso-
ciated with the scientific expertise of the researcher, allows for the ex-
traction of better information for establishing the conditions that
provide the best results in the application of an analytical method,
using a minimum number of experiments [13,14].
In this review, it is discussed the use of multivariate experimental
designs in the optimization of analytical methods that involve induc-
tively coupled plasma optical emission spectrometry as detection
technique. The use of the main experimental designs and their applica-
tion will be discussed in establishing the best operating conditions at
different stages of the analytical method as well as instrumental vari-
ables related to plasma, preconcentration, digestion and sample
introduction.
2. Multivariate experimental design
Analytical chemistry optimization aims to improve the performance
of a method, ensuring good analytical features such as precision,
accuracy, sensitivity, detection power, among others, and guaranteeing
quality of the results generated. This process is traditionally performed
by changing the levels of so-called independent variables (or simply
variables) and observing the response behavior (also called dependent
variable) [15]. Typical examples of variables are: pH, a reactant's con-
centration, gas flow rate, sample aspiration rate in the equipment,
heating temperature, reaction time, etc. The pH variable, for example,
can be studied on as many levels as are convenient for the research.
For five levels, it could have the values 4.0; 4.5; 5.0; 5.5 and 6.0 or others,
depending on the researcher's goals. As typical responses that may be
optimized, it can mention: analytical signal, the recovery of a particular
substance, yield of a reaction, residual carbon content, final solution
acidity of a digested substance, etc. [16,17].
2.1. Comments regarding the multivariate design
Generally, two main approaches can be distinguished in the applica-
tion of multivariate optimization designs. The first relates to the selec-
tion of the most relevant variables in the analytical process, in other
words, those that will significantly affect the magnitude of the response.
This selection process (screening) is important to rule out variables that
do not contribute significantly to the response and to take a posterior
optimization step only with the variables of interest. The second ap-
proach relates specifically to modeling data obtained by applying a par-
ticular experimental matrix originating from the response surface
methodology (RSM). In this methodology, polynomials functions are
fitted to the data to describe the response behavior as it relates to the
variation in the levels of independent variables [18,19].
Another important aspect when choosing the experimental design is
to recognize the nature of the variables to be optimized. Basically there
are two types of variables: the process variables and the mixtures vari-
ables. The process variables are characterized by the freedom of varying
levels compared to the levels of the other variables, with no restrictions
(at least mathematically) for the combination. Examples of process var-
iables: temperature, pH, agitation rate, heating time, etc. On the other
hand, when working with mixtures variables, this freedom of combina-
tion between levels doesn't exist, because they cannot vary without tak-
ing into consideration the levels of other variables. The variables, in this
case, represent the components of a mixture and the sum of the values
of their levels in each experiment has to be closed in 100%. Examples of
mixtures variables: components proportions (H2O, HNO3 e H2O2) of a
digesting mixture used to decompose plant tissue through microwave
energy. Mixtures designs are used to optimize proportions with two
or more components [20–22].
Finally, one should also consider the amount of responses to be op-
timized. Most papers published about the optical spectrometry works
by optimizing a single response. However, some analytical techniques
such as ICP OES can generate a very large number of responses (e.g. an-
alytical signals corresponding to each particular element or recoveries
from certified samples) and demanding simultaneous optimization.
Among the various multi-response optimization techniques, the one
based on desirability functions stands out. This methodology, proposed
by Derringer and Suich [23], is based on the obtainment of separate re-
sponse surface models for each analyzed response and their predicted
theoretical values are used to calculate the individual desirabilities
that are then transformed to a geometric mean (the overall desirability,
D) as it is shown in Eq. (1). Then, the software makes an extensive
search to optimize the geometric mean.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
n
D¼ d1 d2 d3 …dn ð1Þ
with n representing the number of responses studied in the optimiza-
tion process [24].
Another multi-response function, developed by a group of Brazilian
researchers, called multiple response (MR) has been widely applied in
optimizing analytical strategies involving multi-element determination
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 333

[25]. This function has been proposed for the development of a the development of method for determination of refractory metals
preconcentration system for determining cadmium and lead using from: fuels [26], dietetic sweetener [27], soft drinks [28], development
flame atomic absorption spectrometry (FAAS). Currently, some studies of a method for Hg determination from marine invertebrate [29], estab-
have been published in the literature using multiple response and optical lish the conditions for efficient digestion conditions for sediments and
emission spectrometry with inductively coupled plasma with multivari- metals determination [30]. Satured factorial designs (Ex: Plackett–
ate design application. The MR is calculated with the following formula: Burman) also are widely applied such as: establishment of best condi-
  tions in the ultrasonic assisted extraction of metals from sewage sludge
Rx1 Rx2 Rxn [31], development of a wet digestion procedure for metals determina-
MR ¼ þ þ…þ ð2Þ
LSx1 LSx2 LSxn tion from nut [32], among others applications.

with Rx1 as the analytical response of an element in a particular experi- 2.3. Multivariate designs for response surface methodology in the study of
ment and LSx1 as the greatest response in a set of experiments for that process variables
element.
The main purpose of the response surface methodology is to find a
2.2. Multivariate experimental designs for variable screening polynomial that adequately describes the response behavior according
to the levels of the studied variables and allows forecasts to be made
Two types of multivariate designs are widely applied seeking to per- within the defined experimental region of the design [33]. The following
form variable screening: full two level factorial and two level fractional second-order polynomial generally represents the functions that can be
factorial designs. The complete designs are generated by the formula 2k, set, where k is the number of variables, y is the response, xi represents
with base 2 as the number of fixed levels for all variables and k as the the variable levels and b0, bi, bii and bij as the regression parameters of
number of variables. These types of design are performed to assess the independent term, the linear term, the quadratic term and the inter-
whether certain variables or interactions between two or more vari- action term, respectively [34]:
ables affect the response and also allow for an estimation of the magni-
tude of this effect. The full version of the design requires that ∧ X
k X
k X
k
experiments be carried out in all possible combinations of the two levels y ¼ b0 þ bi xi þ bij xi x j þ bii x2i ð3Þ
i¼1 1≤i≤ j i¼1
of each one of the considered k variables [14,18].
When the number of variables to be studied is small, the application
of full factorial designs can be performed with easiness. However, the Some experimental matrices may be used as the basis for establish-
number of necessary experiments can greatly increase when the vari- ing the combination between the levels of the variables to be modeled
ables are large in number. For example, to study six variables in a 26 de- in to the response surface methodology. The adjustment by least
sign, would require 64 experiments. In this case, the number of squares is the most used modeling method to obtain polynomial func-
experiments can be reduced using fractional factorial designs. In them, tions that describe the data behavior [35]. An experimental design ma-
experiments are reduced by a number p, according to the formula trix X and a response vector y obtained after this matrix's application,
2k − p. In the most common case, when the value of p = 1, it results in we have thus the calculation of b parameters that are used in to con-
the so-called half fraction. Thus, for a 26 − 1 design, the number of ex- struct a polynomial function and the following matrix equation:
periments drops to 32 [22]. However, care must be taken in interpreting  −1  
the results of a fractional design, since the effects are confounded with b ¼ XT X XT y ð4Þ
each other. Table 1 shows a complete 24 factorial design and its half frac-
tion 24 − 1, while Fig. 1 illustrates the complete factorial for two vari- Other adjustment methods such as the use of artificial neural net-
ables (1a), three variables (1b) and Fig. 1c shows the fractional works (ANN) can be found in the literature [36–38]. The ANN modeling
factorial design for three variables. has the following advantages: complex relationships modeling, greater
For methods using ICP OES as detection step, full or fractional two- flexibility in regards to the number of data points, have a better predictive
level factorial designs are the most used screener method for study power than the models obtained by regression and the application in
the significance of experimental variables. Three level factorial design mathematical modeling of response surfaces. However, ANN modeling
(TLFD) was already used for selection or optimization of variables: in approach also presents some disadvantages over last square method,
such as, the lack of rigorous validation schemes associated with ANN
models. So, it is difficult really know if the generated model is correct
Table 1
Experimental matrix for the factorial design of two levels for four variables. (a) Full 24 fac-
and reliable confidence interval cannot be calculated to make predictions.
torial design 24 e (b) half fraction 24 − 1. The two level factorial design seen previously may even establish ex-
periments for this modeling. However, due to the small amount of data
Run (a) (b)
points, this matrix allows only the adjustment, by least squares, of func-
x1 x2 x3 x4 x1 x2 x3 x4 tions with linear terms. For the adjustment of quadratic functions, we
01 −1 −1 −1 −1 −1 −1 −1 −1 have experimental designs specially designed for this purpose, such
02 1 −1 −1 −1 1 −1 −1 1 as: three level factorial design, central composite design, Box–Behnken
03 −1 1 −1 −1 −1 1 −1 1 design and Doehlert design.
04 1 1 −1 −1 1 1 −1 −1
05 −1 −1 1 −1 −1 −1 1 1
06 1 −1 1 −1 1 −1 1 −1
• Three level factorial design (TLFD): is generated by the expression 3k,
07 −1 1 1 −1 −1 1 1 −1 k being the number of variables [35]. Thus, TLFD presents three levels
08 1 1 1 −1 1 1 1 1 (−1, 0, and +1) for the study of variables and the experimental ma-
09 −1 −1 −1 1 trix is composed of all three level combinations of these levels. These
10 1 −1 −1 1
designs are used to study few variables (two or three, at most), since
11 −1 1 −1 1
12 1 1 −1 1 the number of experiments required for its application is very large,
13 −1 −1 1 1 making it not economical and efficient on mathematical modeling.
14 1 −1 1 1 These disadvantages led to the development of other designs to adjust
15 −1 1 1 1 the quadratic function. Fig. 2 shows a TLFD for two variables (Fig. 2a)
16 1 1 1 1
and three variables (2b).
334 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346
Fig. 1. Graphical representation of full two level factorial designs to (a) two variables, (b) three variables and (c) fractional factorial design for three variables.
• Box–Behnken design (BBD): data points are located on the
hypersphere equidistant from the center point. Like TLFD, the BBD
has only three levels (−1, 0 and +1). It is a very economical and effi-
cient design for mathematical modeling and the number of experi-
ments is given by the expression k2 + k + n0. The main drawback
pointed out by researchers using BBD is the impossibility to conduct
experiments in points that are located in the cube vertex (Fig. 2c),
which represent interesting combinations that are not computed for
an appropriate response surface [13].
BBD has been applied in the development of methods based on the
determination of analytes by ICP OES such as: development of a pro-
cedure for gallium determination from aluminum matrices [40], opti-
mize, using multi-response approaches, the gas flow rates and
radiofrequency power in the determination of B, Cd, Cr, Fe, Mn and
Zn [41], optimize the zinc extraction parameters from water and bio-
logical matrixes before determination [42], development of a flow in-
jection system coupled to ICP OES for lead determination from waters
[43], optimize a extraction procedure based on ultrasound energy for
Cr and Zn determination from waters, among other applications [44].
• Central composite design (CCD): it can be considered as a combina-
tion of two level factorial and additional designs, like the design of a
star. The number of experiments required for its implementation is
given by the expression 2k + 2 k + n0, with k as number of variables
to be optimized and n0 as the number of replicas of the central point.
Regular CCD allows for all variables to be studied in five levels (−α,
− 1, 0, + 1 e + α). The α values for axial points can be calculated
using the expression α = 2(k − p) / 4. Thus, the distance from the
axial point, when there are three variables for a design with no
fractioning and uniformly rotatable will be 2(3 − 0) / 4 = 1682 [17].
Fig. 3a illustrates the central composite design for two variables and
Fig. 3b for three variables.
Fig. 2. Graphical representations of experimental designs that perform the study of the variables at three levels. (a) Factorial design with three levels for two variables, (b) factorial design
of three levels to three variables and (c) Box–Behnken design.
For tradition, CCD is the most used matrix design for second order
polynomial adjustment in the optimization of analytical methods for
ICP OES determination. For this spectranalytical technique, CCD was
already used to: optimize gas flow rates and the observation height
in the determination of iodine from tablet salt samples [45], metals
and Sn from soft drinks [28], Se in electrolytic manganese [46], Pb,
Ba and Sb from gunshot residuals [10], evaluation of plasma condi-
tions using the Mg II/Mg I ratio [47], development of an on-line
preconcentration system for Cu determination from waters [48],
among others applications.
• Doehlert design (DD): is a very economical and efficient design much
like BBD, and the number of necessary experiments for its execution is
also given by the expression k2 + k + n0. This design is not rotatable
and this can also be noted in that it has different numbers of levels for
each studied variable. This feature is an advantage, for it allows for
greater flexibility and convenience in application. For two variables
(k = 2), DD is represented by the vertices of a regular hexagon
(Fig. 4), plus the central point, defining three levels to one variable
(− 0.866, 0, + 0.866) and five levels to the other (− 1; − 0.5, 0,
+0.5 and +1). When k = 3, the design is represented by a geometric
solid, characterized by alternating square faces with triangular faces,
so called cuboctahedron. Depending on the projection of this solid in
the plane, we can have different experimental mediums with varying
number of levels. One of these matrices can be seen in Table 2, ob-
tained by the plane projection of the solid supported in the triangular
face (Fig. 5b). For this matrix, x1 is studied in five levels (−1, −0.5, 0,
+ 0.5 and + 1), x2 is studied in seven levels (− 0.866, − 0.577,
−0.289; 0; +0.289; +0.577 + 0.866) and x3 is studied in three levels
(−0.816; 0 and +0.816). Another notable feature of the DD is the po-
tential for sequentially, for it is very easy to reuse data points in its dis-
placement to another regions [49].
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 335

Table 2
Doehlert experimental matrix obtained by flat projection of Fig. 5b.

Run x1 x2 x3

01 1 0 0
02 0.5 0.866 0
03 0.5 0.289 0.817
04 −1 0 0
05 −0.5 −0.866 0
06 −0.5 −0.289 −0.817
07 0.5 −0.866 0
08 0.5 −0.289 −0.817
09 −0.5 0.866 0
10 0 0.577 −0.817
11 −0.5 0.289 0.817
12 0 −0.577 0.817
Fig. 3. Graphical representations of central composite design for (a) two variables and 13 0 0 0
(b) three variables.

DD has been applied to develop methods based on ICP OES aiming:
optimize the flow rates involved in the performance of sulfur determi-
nation from fuels [50], optimization of operating parameters for Al, Cu,
Mg and Cr determination from wear oil [51], establish the best diges-
tion conditions for metals determination from oil samples [52], min-
eral fertilizers [53], optimize a ultrasound assisted extraction for
metal determination from coconut milk [54], among others applica-
tion. In spite of CCD is the most used experimental matrix, DD has
shown greater versatility, efficiency, practicality and economy in the
optimization of methods using ICP OES as analytical technique.
2.4. Multivariate designs for response surface methodology of mixture
variables
These designs are used to optimize ratios of the components of a mix-
ture. The levels of the mixture variables are mutually dependent and
should provide a constant sum equal to 1. For two variables, this design
can be represented by a line, by two, by an equilateral triangle and by
four lines, forming a tetrahedron [55]. A mixture design for three com-
monly used variables is shown in Fig. 6a and its experimental matrix in
Table 3. The vertices of the triangle represent pure components, the bi-
nary mixtures of two components and the interior, the tertiary mixtures.
When there are situations in which certain combinations of levels
can't be used (e.g. pure component H2O does not allow for the digestion
of a sample), restrictions should be established to define the experimen-
tal region. Restrictions may constitute limits, lower, upper or both.
Within this determined region, new data points are distributed as
evenly and symmetrically as possible to promote efficient modeling.
Additionally, the original proportions may be recalculated within this
Fig. 4. Graphical representation of Doehlert design for two variables.
region, generating the so-called pseudo-components. The pseudo-
components form a new experimental matrix that aids in the adjust-
ment of mathematical functions to the data [22,56]. Fig. 6b represents
the experimental area formed by the restrictions to the minimum
values that the proportions can reach for the three studied variables in
comparison to complete experimental field.
2.5. Validation of the fitted mathematical model
The evaluation of the adjusted mathematical model must be per-
formed to make sure that it is adequate to describe the behavior of the
experimental data. A detailed evaluation of standard coefficient errors
for the equation regression obtained in relation to their confidence in-
tervals must be carried out [39].
One way to accomplish this evaluation is through the analysis of var-
iance (ANOVA), comparing the variation due to treatment (change in the
combination of the levels of the variables) with the random fluctuation of
the answers (random errors) [57]. Through this comparison, it becomes
possible to evaluate the significance of the regression used and the quality
of its adjustment responses. The statistical significance of regression can
be assessed using the ratio between the mean of square of regression
(MSR) and the mean of square of residues (MSr) and comparing the result
with the appropriate value from Fisher's distribution. Additionally, lack of
fit test is also used to evaluate the quality of the model. If the mathemat-
ical model is well fitted to the experimental data, MQFaj should, like
MQep, reflect only the random errors inherent in the system investigated.
It is possible to use the F distribution to assess if there is any significant
difference between these two averages the same way as was done to
evaluate the statistical significance of regression [35].
Other parameters that can be used to observe whether any variation
around the mean and is explained by the regression are: the percentage
of variation explained and residual graphs [49].
The proportion of explained variance is represented as R2, the deter-
mination coefficient, ranging from 0 to 1. This value represents the frac-
tion of the variation which is explained by the lack of model fit. The
closer to 1 the value of the coefficient is, the better the model fit to the ob-
served responses. Although this coefficient is a measure of how the model
adjustment approaches the experimental data, it cannot be used to judge
their lack of adjustment because it does not take into account the number
of degrees of freedom for determining the model [13].
Visual analysis of the residual plots can also generate valuable infor-
mation on the adequacy of the model. If the mathematical model is well
fitted, their residual graphic present a behavior that will suggest a normal
distribution of data. A model generating large magnitude of residuals, it
will not be appropriate to make accurate inferences about the behavior
of the data in the studied experimental field. However, if the model re-
quires some other term, the residue chart presents a behavior that will in-
dicate what type of term should be added to the model [35,39].
336 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346

Fig. 5. Graphical representations of Doehlert design originated by different flat projections of the geometric solid cuboctahedron: (a) design originated of solid projection supported by a
square face, (b) solid projection originated planning supported by a triangular face and (c) planning originated the solid projection backed into a vertex.

2.6. Multivariate optimization by Simplex method
This method allows for optimization of various studied factors with
no need to use specific mathematical-statistical tools, such as required
in the response surface methodology [58]. The Simplex method consists
of a geometric figure (N) dimensions, with each dimension correspond-
ing to a variable to be optimized. The method is very effective when op-
timizing a single response [59]. Simplex optimization is performed by
displacing a geometric figure with k + 1 vertices into an experimental
field toward an optimal region, where k equals the number of variables
in a k-dimensional domain [57]. The original basic algorithm is the sim-
plest and easiest to apply, for it is based only on the reflection move-
ment of the corresponding point of the worst response. The modified
algorithm allows for a greater range of motion and, thus, a more precise
and efficient placement for optimal conditions [16].
3. Multivariate strategic design application in the optimization of
analytical methods with ICP OES detection
The application of first order and second order experimental designs
in the optimization methods involving optical emission spectrometry
with inductively coupled plasma is still recent. The studies here pre-
sented were published in the last twenty years. The use of chemometric
tools has been gaining momentum in the development of analytical
methods [60], especially those involving ICP OES. The amount of

Fig. 6. Graphical representations of (a) mixtures simplex centroid design and (b) mixture design bounded by the following constraints: x1 N 0.1; x2 N 0.2 and x3 N 0.3 compared to the total
experimental field.
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 337

Table 3 Mn and Zn. The optimum conditions obtained for the two responses
Experimental matrix for design mixtures of three variables. (a) Simplex centroid design and the correlation coefficients found were very similar for both de-
that covers all possible experimental field and (b) design generated by restrictions (x1 N
signs. In a 23 factorial design, Santos et al. [66] evaluated the effects of
0.1; x2 N 0.2 and x3 N 0.3) the experimental field.
the RF power, nitric acid concentration and nebulizer stream flow to de-
Run (a) (b) termine uranium in industrial effluents. The RF power was optimized at
x1 x2 x3 x1 x2 x3 1.3 kW, the nebulizer stream flow at 0.9 L min−1 and the nitric acid con-
centration was not significant and fixed at 1.25 mol L−1.
01 1 0 0 0.1 0.2 0.7
02 0 1 0 0.1 0.6 0.3 Other instrumental variables can be optimized in ICP OES. Santelli
03 0 0 1 0.5 0.2 0.3 et al. [50] developed a procedure for determining total sulfur in petro-
04 0.5 0.5 0 0.1 0.4 0.5 leum products (gasoline, kerosene and diesel) and investigated the
05 0.5 0 0.5 0.3 0.2 0.5
plasma gas flow, the sheat gas flow and the oxygen flow in relation to
06 0 0.5 0.5 0.3 0.4 0.3
07 0.333 0.333 0.333 0.233 0.333 0.433 the signal/noise ratio of the instrument though the use of the Doehlert
08 0.666 0.166 0.166 design. The use of oxygen mixed with argon of the plasma is a way to
09 0.166 0.666 0.166 minimize the noise caused by the direct introduction of organic sub-
10 0.166 0.166 0.666 stances in the plasma. The best optimized conditions were: plasma gas
flow (12.0 L min−1), sheat gas flow (0.2 L min− 1) and oxygen flow
(0.035 L min−1). Oliveira et al. [45] applied two 23 designs + Central
published articles involving multivariate optimization has grown expo- Point + Star to assess iodine behavior in a ICP with axial and radial con-
nentially in last few years. figuration. For axial configuration, the maximum sensitivity operation
Among the analytical methods involving the use of some kind of conditions were achieved with applied power of 1300 kW, nebulizing
multivariate optimization, we can cite those seeking better conditions gas flow of 0.8 L min−1 and sample introduction flow of 2.8 mL min−1.
for optimizing instrumental parameters of the ICP related to plasma for- As for the radial configuration, optimal conditions were obtained using
mation, samples digestion, for systems involving preconcentration in a the same RF power and sample introduction flow, nebulizer flow of
line or a batch and strategy optimization of sample introduction in the 0.6 L min−1 and an observation height of 8 mm. The method was ap-
ICP. In the following topics, we discuss some published works with plied for determining iodine in table salt samples, using an axial config-
their characteristics presented by the application of multivariate opti- uration. Table 4 presents other published studies using multivariate
mization methods. optimization and ICP OES.

3.1. Optimization of instrumental parameters regarding plasma 3.2. Optimization of the sample preparation stage

The plasma is defined as a partially ionized gas, has a high electron
density, a high temperature (5000–8000 K) and is electrically conduc-
tive [61]. Plasma can be generated through argon (Ar) or nitrogen
(N2), though the N2 plasma formation is more difficult compared to Ar
plasma, requiring more powerful generators for forming and maintain-
ing the plasma. Some studies mention the use of N2 in the argon plasma
[62,63].
Optimization of plasma-related parameters depends on the energy
required to excite the chemical species. Various instrumental parame-
ters, such as, the observation point, radio frequency power, sample in-
troduction flow rate, auxiliary gas flow rate, nebulizer gas flow rate
and refrigeration gas flow rate, can be adjusted to obtain a plasma
with good performance in the analytes determination [9]. The optimiza-
tion of these variables is often performed using multivariate procedures
and according to the analytical response, may evaluate the ratio noise-
signal, limits of detection and quantification, robustness and sensitivity
[47,64].
Many studies were conducted, simultaneously optimizing radio fre-
quency (RF) power and the flow of the nebulizer gas. Froes et al. [28]
used a 23 factorial design and a central composite design to optimize
the power of the radio frequency, the flow of the nebulizer gas and
the sample stream flow to determine Al, Ba, Ca, Cd, Cr, Cu, K, Mg, Na,
Ni, Pb, Sn and Zn in soda samples. Results showed a better robustness,
obtained by Mg II 280.270 nm/Mg I 285.213 nm, using low nebulizer
flow (0.556 L min− 1) and an increase radio frequency power
(1:43 kW). A 23 central composite design was used by Peixoto et al.
[65] to evaluate the radio frequency power, the nebulizer gas flow and
the auxiliary argon flow. The optimal conditions that allowed for a ro-
bust plasma were: RF power (1200 kW) and nebulizer flow
(0.6 L min−1). The method was applied to determine Al, Ba, Cd, Co, Cr,
Cu, Fe, Mg, Mn, Mo, Ni, P, Pb, and Zn in chocolate milk samples.
A studied by Novaes et al. [41] used complete 24 factorial design and
a Box Behnken matrix to evaluate the performance of two responses
(overall desirability and multiple answers). Four variables were studied
(auxiliary gas stream flow, plasma gas stream flow, nebulizer gas flow
and RF power) to evaluate the behavior of the elements B, Cd, Cr, Fe,
Usually, analytical methods involve a step that submits the sample
to an adequate treatment, seeking digestion, extraction and preparation
of the analyte for analysis [67–72]. This procedure requires a consider-
able time frame and depends on the nature of the sample, the element
concentration, the technique used, the precision and accuracy desired
[73]. Some procedures allow direct sample analysis without digestion
[74–79]. Still, many of these procedures make use of multivariate opti-
mization in some step or another [80].
Methods involving digestion must have characteristics such as: com-
patibility with multi-element techniques, such as ICP OES and ICP-MS;
safety; be in accordance with the principles of the green chemistry;
present high frequency of sampling and be easy to use [81]. In addition,
the digestate should be stable, has low residual acidity, low residual car-
bon content (RCC) and low concentrations of dissolved solids [82].
Different procedures have used the resources of multivariate analy-
sis to optimize better conditions for sample digestion. Momen et al. [32]
used a Plackett–Burman fractional factorial design to optimize seven
factors (HNO3, H2SO4 and H2O2 volumes, digestion time, pre-digestion
time, heating temperature and sample mass). Only eight experiments
were needed to carry out this design. An advantage of this design is to
be able to assess with precision the main effects of a higher number of
factors, using a few experiments without substantial loss of information.
The analytical method developed using HNO3/H2SO4/H2O2 as digestion
mixture was successfully applied to determine Al, Ba, Cd, Cr, Cu, Fe, Mg,
Mn, Pb and Zn in commercial nuts samples.
Two sample digestion systems (ultrasound assisted extraction and
microwave digestion) proposed by Hristozov et al. [31] evaluated the
extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn in a sewage sludge. Both
methods used experimental design. The system using microwaves
was completely optimized using a 25 − 1 fractional factorial design.
The optimum conditions were: pressure of 120 psi, pressure time:
30 min, HNO3 volume: 3 mL, HF volume: 1 mL and HCl volume: 1 mL.
The ultrasound assisted extraction was optimized through the applica-
tion of three experimental designs (fractional Plackett–Burman design,
full factorial design and 32 full factorial design). The optimum condi-
tions were: energy amplitude — 400 W (80%), sonication time
338 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346

Table 4
Recent applications of multivariate design in the optimization of instrumental variables in ICP OES.

Experimental Optimized parameters Objective of study Analytes Samples References

design

Central Nebulization gas flow rate, sample flow Evaluation of ICP OES with axial or radial Iodine Table salt [45]
composite rate, applied power, and observation height views for determination of iodine in table salt
Factorial design Presence of HNO3, amount of diesel or fuel Development of a method for the Mo, Cr, V, Ti Diesel and fuel oil [26]
23 oil, and the presence of O2 into the Ar determination of refractory metals in diesel
plasma gas flow rate and fuel oil
Factorial design Radio frequency power, and flow nebulizer Analyzing some brands of dietary Na, K, Ca,Mg, Dietetic sweetener [27]
22 sweeteners present in the Brazilian market Fe, Cu, Zn,
and determine the presence of essential ele- Cr, Mn Se,
ments or not, contaminants and potentially Al, Ni, As, Cd,
toxic to the nutritional and toxicological Pb
control
Factorial design Hydrochloric acid concentration, nebulizer Development of a procedure for the direct Ga Bauxites [40]
23 and flow rate and, applied power determination of gallium in aluminum
Box–Behnken matrices employing the reference element
technique for elimination of the aluminum
interference
Factorial design Applied power, carrier gas flow rate, Evaluating five different procedures for the Hg Certified materials (fish tissue, [29]
24 concentrations of HCl and of NaBH4 slurry preparation in order to determine Hg dogfish liver, lobster
in solid samples of very different hepatopancreas, marine sediment,
composition by axial view CV ICP OES lyophilized pig kidney, sewage
sludge, and river sediment)
Factorial design Nebulization gas flow rate, sample flow Determining the mineral composition of soft Al, Ba, Ca, Soft drinks [28]
23 and rate, and applied power drinks with different characteristics (brand, Cd, Cr, Cu, K,
central flavor and the fact of being light, diet, low Mg, Na, Ni,
composite calorie or regular) and evaluate the data Pb, Sn, Zn
obtained employing exploratory analysis
Central Radio frequency power, nebulization flow Applying multivariate optimization to Al, Ba, Cd, Chocolate drink powder [65]
composite rate, and auxiliary argon flow rate evaluate the ICP OES experimental Co, Cr, Cu,
parameters Fe, Mg, Mn,
Mo, Ni, P, Pb,
V, Zn
Factorial design Nebulization gas flow rate, applied power, Applying factorial design and exploratory Al, Ba, Cd, Fruit juice [124]
23 and sample flow rate analysis to optimize a method for the direct Co, Cr, Cu,
determination (without sample Fe, Mn, Ni,
pre-digestion) of micro-elements in fruit Pb, Sb, Sn,
juice Zn
Factorial design Power supplied, sample flow rates, and Finding the optimal set of operational Se Electrolytic manganese [46]
23 and auxiliary Ar flow rate conditions that allow a simple and sensitive
orthogonal method for the determination of Se in
central electrolytic manganese
composite
Factorial design Power supplied, sample flow rates, and Assessing the utility of the flow injection As, Hg, Sb, Electrolytic manganese [125]
23 and auxiliary Ar flow rate hydride generation-ICP OES for the Se, Sn
orthogonal determination of volatile elements as
central routine analysis in industrial laboratories
composite
Factorial design Acid concentration, radio frequency power, Applying factorial designs to evaluate the U Industrial effluent [66]
23 and nebulizer gas flow rate effect of the factors on the emission intensity
for five lines of uranium, employing an axial
viewing with ICP
Doehlert Flow ratios of argon (sheat and plasma gas) Development of an analytical procedure for Total sulfur Gasoline, kerosene and diesel fuel [50]
and oxygen determination of total sulfur content in
petroleum derivatives
Factorial design Auxiliary gas flow, plasma gas flow, Establishing a comparison between a B, Cd, Cr, Fe, — [41]
24 and Box nebulizer gas flow, and radio frequency multiple response function involving Mn, Zn
Behnken power multi-element determinations with the
desirability function D
Central Radio frequency power, nebulizer gas flow Optimization of a method to measure metals Pb, Ba, Sb Gunshot residues [10]
composite and aspiration rate in gunshot residues using multivariate
design optimization
Fractional Radio frequency power, primary and Studyies the copper deposition tendency Cu Mineral oils [126]
factorial auxiliary argon flow, nebulization pressure onto the insulating Kraft paper tapes exerted
design and sample flow rate by two unused oils (a corrosive and a
(25 − 1) non-corrosive one) under defined aging
conditions
Doehlert Applied power, nebulizer gas flow rate, Optimization of the operating conditions of La, Nd, Eu, Geological [127]
sample uptake rate, and observation height an ICP using experimental designs for the Gd, Dy, Er,
determination of rare earth elements Yb
Factorial design Forward power, nebulizer pressure, Optimization of the operating parameters of Al, Cu, Mg, Wear oil (SRM 1085) [51]
24 auxiliary gas flow rate, and sample uptake an ICP for the analysis of samples dissolved Cr, Fe
rate in organic solvents
Three-level Radio frequency power and nebulizer gas Optimization of an analytical method for Al, Ca, Cd, Cr, Dog and cat foods [128]
factorial flow rate determination of the mineral element Cu, Ba, Fe, K,
content of dog and cat food Mg, Mn, P, S,
Sr Zn
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 339

Table 4 (continued)

Experimental Optimized parameters Objective of study Analytes Samples References

design

Central Radio frequency power and nebulizer gas Applying factorial design to evaluate ICP OES Mg II — [47]
composite flow rate plasma conditions through the Mg II/Mg I 280/Mg I
ratio 285 nm
Factorial design Nebulizer gas flow rate, auxiliary gas flow Evaluating the best operating conditions of Na, Ca, Mg, Aqueous extract of crude oil [129]
23 and rate, and radio frequency power an ICP to analyze aqueous extract of crude Sr, Fe
central oil obtained after hot extraction with organic
composite solvents
Fractional Integration time for low emission line, Development of a simple method of Cd, Co, Cr, Eye shadow [130]
factorial integration time for high emission line, cosmetic sample preparation and Cu, Ni
design sample flow rate, sample fow rate during determination of Cd, Co, Cr, Cu and Ni using
(29 − 5) the analyses, pump stabilization time, radio ICP OES
frequency power, auxiliary gas flow rate,
nebulization gas flow rate, cooling gas flow
rate

(20 min), temperature (90 °C), mixture volume (5 mL of HNO3 and 5 mL
of HCl) and magnetic stirring (10 min). The reproducibility and the
analysis period were similar for both extractions. Another procedure in-
volving microwave assisted extraction used a 24 − 1 fractional factorial
design to establish the following conditions: extraction time (17 min),
acid mixture ratio HCl/HNO3 (5:1), acid mixture volume (25 mL) and
microwave power (70%). The method was applied to determine As,
Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in 32 surface sediments of the following
rivers: Asua, Galindo and Nerbioi-Ibaizabal Bilbao estuary, Spain [30].
A digestion method with heating in the digester block was devel-
oped for the extraction of Al, As, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, V and
Zn in certified reference material (oyster tissue — NIST 1566b).
Simplex-centroid mixture design was used to study the effects of the
HCl, HNO3 and H2O2 ratios in the digestion of these samples. The maxi-
mum recovery was obtained for 21.4%, 30.8% and 47.8% ratio, respec-
tively [83].
Santos et al. [84] used the Doehlert design to optimize the extraction
of Ca, Cd, Cu, K, Mg, Mn, Na, Sr and Zn in marine invertebrates samples,
using centrifugation with diluted acids. The best condition set for this
method was: 20 min of centrifugation at 9000 rpm and an acid mixture
(HCl + HNO3 + H3CCOOH) of 1.0 mol L−1. The optimized procedure
was applied in nine samples of oysters, clams and mussels from Bahia
de Todos os Santos, Bahia, Brazil.
The use of a 24 full factorial design to optimize the extraction of Ca, Cu,
Mg, P, S and Zn in lubricating oil samples in microwave ovens with sealed
containers was proposed by Costa et al. [85]. Four factors were studied:
sample mass, digestion time, power applied to microwave radiation and
volume of the oxidant mixture (HNO3 + H2O2). The residual carbon con-
tent and the final acidity were used as responses to the design. Micro-
waves were also used to digest biomass residues of castor (Ricinus
communis), jatropha (Jatropha curcas), radish (Raphanus sativus), sun-
flower (Heliantus annus) and coffee (Coffee arabica) using diluted nitric
acid in a study involving the use of a full factorial design [86]. Optimum
conditions were obtained using 8 mL of HNO3 7,0 mol L−1, heating for
20 min at 180 °C and maximum power of 750 W.
Full factorial design has also been applied in optimizing food sample
digestion procedures [53,87–89], fertilizer [90], diesel oil [52], coal [91],
etc. Table 5 summarizes other studies involving multivariate optimiza-
tion and sample preparation with detection by ICP OES.
3.3. Optimization of preconcentration procedures
Direct determination of trace elements by ICP OES is often made dif-
ficult due to the low concentration of metals in the samples. These prob-
lems can be overcome by using a separation and preconcentration
procedures before detection. To this end, various methods, such as
solid phase extraction (SFE) [92,93], liquid–liquid extraction (LLE) [94,
95], cloud point extraction (CPE) [96,97], electroanalytical deposition
[98,99] and ion exchange [100] have been widely used. Several review
articles have been published exploring the different preconcentration
techniques mentioned.
A microextraction-emulsification microwave assisted system was
studied by Sereshti et al. [44] for the extraction of holmium and ytter-
bium in water samples. The reagent 1-(2-pyridylazo)-2-naphthol
(PAN) was used as a chelating agent. Extraction solvent volume, chelat-
ing agent concentration, pH, ultrasonic radiation time, temperature and
salt concentration were chosen as variables for the application of the
fractional factorial design and the central composite design.
An in-line flow injection system for lead preconcentration using a
mini-column packed with silica gel and functionalized with methyl
thiosalicylate (TS gel) was developed by Zougagh et al. [43]. Five vari-
ables were considered as factors (sample stream flow, eluent stream
flow, eluent concentration, pH and buffer concentration) and were op-
timized by the application of a full factorial design and a Box–Behnken
design. The system was applied to the preconcentration of lead in
water samples. Several preconcentration systems with water samples
applications have been developed using chemometric tools and ICP
OES [42,101–103].
A procedure was developed by Bezerra et al. [104] for simulta-
neous determination of metals trace amounts in saline effluents of
an oil refinery. The procedure is based on the cloud point extraction
(CPE) of Cd, Cr, Cu, Mn, Ni and Pb with the complexing reagent 2-(2-
bromo-piridilazo)-5-dietil-amino-fenol (Br-PADAP in a micellar
phase octylphenoxypolyethoxyethanol (Triton X-114)). The optimiza-
tion of the pH parameters, irradiation time and buffer concentration
was done using the response surface methodology with a Doehlert
matrix.
Araújo et al. [105] developed a procedure for platinum separation in
ferrous matrices using sorption with chloride complexes in polyure-
thane foam. The procedure was optimized using a full factorial design
and a Doehlert matrix. Four variables (foam mass, stirring time, tin chlo-
ride concentrations and chloric acid concentration) were considered as
factors in the extraction optimization. The system was applied to the de-
termination of platinum in iron ore, pure iron and catalysts. Platinum
was also studied in a preconcentration system in line with a polyure-
thane foam column impregnated with thiocyanate [106]. The optimiza-
tion step was carried out using a full factorial design with three variables
(pH, eluent flow and eluent concentration). The method was applied to
the determination of platinum in tap water samples.
Khajeh and Sanchooli [107] developed a nanoparticles adsorbent of
iron oxide and 1-(2-pyridylazo)-2-naphthol as exchange groups of
manganese ions. Four variables (solution pH, amount of the extraction
agent, amount of nanoparticles and time) were considered as factors
in the optimization using a 24 − 1 fractional factorial design and a
340 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346

Table 5
Recent applications of multivariate optimization applied in the samples digestion and analysis by ICP OES.

Experimental Optimized parameters Objective of study Analytes Samples References

design

Fractionated Microwave power, extraction time, Establishing the digestion procedure by means of an As, Cd, Cr, Cu, Fe, Surface sediments [30]
factorial design volume of acid mixture and the HNO3: open-focused microwave system, and to study the spatial Mn, Ni, Pb, Zn of the estuary of
(24 − 1) HCl volume ratio and temporal distribution of heavy metals in seven Bilbao
different stations along the low estuary channel of Bilbao
Centroid simplex Acid proportions (nitric, acetic and Development of an ultrasound-assisted multielemental Ba, Ca, Cu, Fe, K, Bean [88]
mixture chloride acid) extraction procedure using mixture design Mg, Mn, Sr, Zn
Factorial design 23 Maximum heating power, heating time Developing a simple and fast sample preparation Al, Ca, Cu, Fe, Mg, Gum [131]
and HNO3 volume method to analyze trace elements in gum samples Mn, Ni, Pb, Zn
Plackett–Burman Amplitude, sonication time, temperature, Studying the applicability of an ultrasonic processor Cd, Co, Cr, Cu, Mn, Sewage sludge [31]
volume of acid mixture, acid mixture equipped with an all-glass probe for the total extraction Ni, Pb and Zn
composition bubbling, magnetic stirring of toxic metals
time
Fractionated Pressure, time-at-pressure, HNO3, HF, Comparing the ultrasonic sample pre-treatment method Cd, Co, Cr, Cu, Mn, Sewage sludge [31]
factorial design HCl volume with microwave digestion Ni, Pb and Zn
(25 − 1)
Factorial design 23 Temperature, acid mixture, and time Developing a cavity-microwave-assisted digestion Al, Ba, Ca, Cu, Fe, Press cakes from [86]
methodology for biodiesel press cake samples K, Mg, Mn, Mo, Zn castor, jatropha,
radish, sunflower,
and coffee
Factorial design 22 Concentrations of HNO3 and H2O2 Optimization of an analytical method for determination Al, Ca, Cd, Cr, Cu, Dog and cat foods [128]
of the mineral element content of dog and cat food Ba, Fe, K, Mg, Mn,
P, S, Sr Zn
Factorial design 23 Nitric acid concentration, temperature, Applying multivariate optimization for the development Al, As, Ba, Ca, Co, Bean [132]
and processing time microwave-assisted digestion process using diluted Cr, Cu, K, Mg, Mn,
nitric acid Mo, Ni, P, Pb, Se,
Sr, Zn
Doehlert Mass of diesel oil and the volume of Optimizing a digestion procedure of diesel oil samples Al, Cu, Fe, Ni, Zn Diesel oil [52]
H2O2 for the determination of metals
Factorial design 23 Temperature and volumes of HNO3 and Optimization of a microwave-assisted digestion process Ca, Fe, Mg, Mn, Zn Bean [87]
H2SO4
Simplex centroid HNO3, HCl and H2O2 reagent Development of a digestion method by heating on a Al, As, Ba, Ca, Cd, Oyster tissue [83]
mixture proportions block digestor Co, Cu, Fe, Mg, Mn,
V, Zn
Factorial design 22 Heating time of the infrared lamp and The combined use of infrared radiation and microwave Al, Ca, Cu, Fe, K, Human-feed [89]
HNO3 volume radiation (IR-MW) to increase the amount of organic Mg, Na, P, Zn
samples digested
Factorial design 24 Sample mass, digestion time, Optimization of a microwave-assisted digestion process Ca, Cu, Mg, P, S, Zn Lubricating oil [85]
microwave radiation applied power, using a cavity-oven
and volume of oxidant mixture (HNO3
+ H2O2)
Plackett–Burman (HNO3, H2SO4 and H2O2 volumes), Developing an multi-element analytical method after Cr, Cu, Fe, Mg, Mn, Nut [32]
digestion time, pre-digestion time, appropriate wet digestion procedure using an open Zn, Al, Ba, Cd, Pb
temperature of the hot plate, and sample vessels technique
weight
Factorial design 24 Hydrogen peroxide concentration, Exploring the feasibility of use diluted hydrogen S Coal [91]
microwave temperature, extraction peroxide and microwave radiation for quantitative
time and coal amount extraction of total sulfur
Factorial design 23 Concentration of nitric acid, sonication Development of an ultrasound-assisted multielemental Ca, Cu, Fe, K, Mg, Coconut milk [53]
and Doehlert time and centrifugation speed and time extraction procedure Mn, Na, P, Zn
Factorial design 23 Concentrations of nitric acid, Multivariate optimization of an analytical method to Al, As, Ca, Cd, Cu, Mineral fertilizers [90]
and Doehlert hydrochloric acid and hydrogen determine the mineral composition of mineral fertilizers Fe, Mg, Mn, Na, P,
peroxide Pb, V, Zn
Fractional HNO3 and H2O2 volume, digestion time, Developing a multi-element analytical method after an Al, Ba, Ca, Cu, Fe, Beans [133]
factorial design block temperature and particle size appropriate wet digestion procedure with an open K, Mg, Mn, Ni, P,
(25 − 1) and vessel technique Sr, Zn
Doehlert
Doehlert Concentration of acid mixture (HCl + Developing and apply a centrifugation and Ca, Cd, Cu, K, Mg, Marine invertebrate [84]
HNO3 + H3CCOOH), centrifugation ultrasound-assisted multielemental extraction Mn, Na, Sr, Zn (oyster, mussel and
time, and rotation velocity procedure clam)
Factorial design 23 Sample weight, volume extracting Developing a method for extraction of metal ions P, K, Mg, Ca, Zn, Brazilian rice [134]
solution, and ultrasound time exposure present in rice samples using ammoniacal EDTA solution Mn, Fe, Cu, Mo
Factorial design 23 Agitation, algae weight, and contact Analyzing the influence of agitation, contact time, Pb Industrial Effluents [135]
time amount of algae and type of pretreatment on heavy
metal removal by Arribadas algae
Factorial design 23 Temperature, addition of sulfuric acid, Applying a focused microwave oven for acid digestion of Ba, Ca, Cu, K, Mg, Bovine milk [136]
and number of aliquots of the sample bovine milk samples using a conventional and an Na, P, Zn
gradually added alternative procedure
Factorial design 23 Addition of H2O2, addition of analytes, Evaluating the extraction of elements in solid samples Ba, Cd, Cr, Hg, Pb Raw material [137]
and HNO3 volume using a microwave oven with closed flasks and to evaluation of school
understand the physicochemical parameters involved in supplies
this process
Fractional factorial Sample mass, sonication time, water Developing of a simple, accurate and precise procedure Ca, Cu, Fe, Mg, Zn Fish Muscle Tissue [138]
design (24 − 1) soluble tertiary amines concentration, for extraction of metals from fish samples employing
and factorial and type of acid minimum analyst effort and routine laboratory
design 22 apparatus
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 341

Table 5 (continued)

Experimental Optimized parameters Objective of study Analytes Samples References

design

Fractional Microwave power, digestion time, nitric Developing a procedure for partial digestion of bovine Ca, Cu, Fe, Mg, Mn, Bovine tissue [139]
factorial design acid volume, and sample mass tissue using polytetrafluoroethylene micro-vessels Zn
(24 − 1) under microwave radiation
Factorial design 23 Temperature, time, and nitric acid Development of a novel and simple method based on Ca, Na, K, P, Mg, Chocolate bars [140]
concentration acid extraction for the determination of metals by Cu, Mn, Zn
inductively coupled plasma techniques
Factorial design 23 HNO3 concentration, sample mass, and Development of a simple method of cosmetic sample Cd, Co, Cr, Cu, Ni Eye shadow [130]
heating time preparation and determination of Cd, Co, Cr, Cu and Ni
using ICP OES

Box–Behnken design. The method was applied to determine manganese
in barley, wheat and rice flour samples.
Table 6 presents different studies involving multivariate optimiza-
tion variables related to the preconcentration step and ICP OES.
3.4. Optimization methods for sample introduction in ICP OES
One of the most important aspects of good analytical plasma perfor-
mance lies in the sample introduction procedure [47]. Samples can be
introduced in gaseous, liquid and solid forms [108].
The most common procedure for introducing sample in ICP OES is
based on the formation of a liquid aerosol, using pneumatic nebulizers.
However, less than 10% of the solution introduced is converted into use-
ful aerosol with the use of these nebulizers. Other difficulties arise when
highly viscous solutions are used with a high salt content or a low sam-
ple availability [109]. A viable alternative is to produce chemical vapor
generation, transforming the species of interest into a volatile com-
pound, using a chemical reaction that results in hydrides [108–111].
The introduction of hydrides directly into the plasma, provides high
sensitivity and can be associated with systems involving speciation
[112]. Solid samples may be introduced into the plasma via the solid's
wear and tear by an arc, a spark or laser, to produce a vapor that will
be conveyed through an inert gas to the plasma. Different systems are
presented in the literature, such as electrothermal vaporization and
laser ablation [113–116].
Trevizan et al. [47] used a central composite design to evaluate the
performance of two sample introduction systems. Two nebulizers (con-
centric and V-groove) and two nebulization chambers (cyclonic and
Sturman–Masters) were studied to evaluate the robustness of the
plasma as a response through the 280 Mg II/Mg I ratio in an axial ICP.
RF power and nebulization gas flow were the parameters chosen for
this design. Robust conditions were observed at 1.3 kW and
0.9 L min−1 of nebulization gas flow and not robust at 1.0 kW and
0.5 L min−1, respectively. Recoveries between 87 and 107% of Ca, Cu,
Fe, K, Mg, Na, P, S and Zn in skimmed milk were obtained using a V-
groove nebulizer with a Sturman–Masters chamber.
The systems optimization involving the generation of hydride and
cold vapor is very common to achieve optimal conditions for directly in-
troducing steam into plasma. A procedure using the generation of hy-
dride was developed by Lopes et al. [117] for determining bioavailable
selenium and arsenic concentrations in estuarine sediments of the
Guanabara Bay, Rio de Janeiro, Brazil. The optimization was performed
using a two-level factorial design and a Doehlert design to determine
the optimum conditions of the parameters: NaBH4, HCl and the sample
stream flow, along with the nebulizer pressure. Peña-Vásquez et al.
[118] evaluated the generation of steam of Ag, Au, Cd, Cu, Ni and Zn,
using a fractional factorial design (26 − 2) plus two central points to se-
lect the main factors; afterwards, a 24 orthogonal composite
design + star was performed to select optimal values for major factors.
The desirability function was used as a response. The optimal values
established were: [Co] — 1 mg L−1; [HNO3] — 0.43 mol L− 1; [8-
hydroxyquinoline] — 38 mg L− 1; [NaBH4] — 2.24% and nebulizing
flow — 0.74 L min−1. Other studies were also performed to obtain opti-
mal conditions for the generation of hydrides [36,119–121].
Santos et al. [122] proposed the optimization of a cold vapor gener-
ation system with flow injection aimed at determining mercury. Full
factorial design (24) and fractional (25 − 1) were used for optimization
of five variables: HCl and NaBH4 concentrations, HCl and NaBH4 stream
flow and argon stream flow. The procedure was applied to determine
mercury in two certified reference materials (sediment — NIST 2704
and human hair — AIEA 085).
An in line system using high performance liquid chromatography
(HPLC) of ion exchange was coupled to the ICP OES, to determine As
and Se [123]. Three nebulizers and three nebulizing chambers, in
seven combinations, were tested as interfaces. A Doehlert matrix was
applied to specifically evaluate the influence of operational chromato-
graphic parameters and the methodology was applied to determine As
and Se in natural water samples from the province of Santiago del
Estero, Argentina.
Table 7 shows different sample introduction systems, optimized in a
multivariate way, with detection by ICP OES.
4. Conclusion
In this review, we presented a summary of the potentialities that
chemometric tools present in the development of analytical methods
using ICP OES. Here is a compilation of papers published in the past
twenty years, that used some experimental designs in procedures in-
volving this analytical technique, such as: (i) the optimization of condi-
tions for a more robust plasma; (ii) the development of efficient
procedures for sample digestion; (iii) optimization of preconcentration
systems of analytes; and (iv) improvement in the way the sample is in-
troduced into the plasma. The main design types were addressed (com-
plete and fractional factorial, Box Behnken, Doehlert, Simplex, Central
Composite and mixture designs). The number of papers presented in
this review addressing these techniques demonstrates how these tools
are fundamental for success when developing methods. These designs
have numerous advantages such as optimization in a shorter period, ef-
ficiency in the results, generation of a large amount of information from
a small number of experiments, easy to use and the possibility to evalu-
ate the effect of the interaction between the variables, allowing for the
best conditions for the performance of ICP OES analysis.
Acknowledgments
The authors acknowledge grants and fellowships from the Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (307794/
2013), Fundacão de Amparo à Pesquisa do Estado da Bahia (FAPESB)
(5197/2014), and Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior (CAPES) (1368779).
342 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346

Table 6
Recent applications of multivariate optimization applied in preconcentration systems and analysis by ICP OES.

Experimental Optimized parameters Objective of study Analytes Samples References

design

Factorial design 24 pH, amount of extractant, amount of Development of a procedure after extraction by magnetic Zn Water and [42]
and nanoparticles, and adsorption time nanoparticles biological
Box–Behnken
Factorial design 24 Mass of 1-(2-pyridylazo)-2-naphthol, pH, Development of a procedure for preconcentration of vanadium V, Cu Seawater [103]
and Doehlert active carbon mass, and shaking time and copper, based on solid-phase extraction of vanadium (IV),
vanadium (V) and copper (II) ions as
1-(2-pyridylazo)-2-naphthol (PAN) complexes by active
carbon
Factorial design 25 Sample flow rate, eluent flow rate, eluent Development of a flow injection system for the on-line Pb Water [43]
and concentration, pH and buffer concentration preconcentration of lead by sorption on a microcolumn packed
Box–Behnken with silica gel funtionalized with methylthiosalicylate (TS-gel)
Factorial design 24 Foam mass, shaking time, stannous Applying a procedure for separation of platinum from ferrous Pt Ferrous [105]
and Doehlert chloride concentration and hydrochloric matrices using sorption as chloride complexes on polyurethane matrices
acid concentration foam
Factorial design 23 pH, loading flow rate, and eluent Applying factorial design for optimization of the experimental Pt Water [106]
concentration variables of an on-line preconcentration system based on
solid-phase extraction of platinum as thiocyanate complex
onto polyurethane foam
Central composite pH, sample flow rate, and eluent Developing of an on-line preconcentration procedure using Cu Water [48]
concentration solid phase extraction on a minicolumn filled with ethyl vinyl
acetate
Factorial design 23 Temperature, pH, and biosorbent dosage Evaluating Typha domingensis phytomass and its biosorption Fe3+, Zn2+ Water [141]
capacity for iron and zinc ions present in a mixed metal ions
solution
Factorial design 23 Eluent concentration, eluent flow rate, and Development of a novel method for the determination of Pb by Pb Drinking water [142]
surfactant concentration on-line cloud point extraction coupled to ICP OES with
ultrasonic nebulization
Fractional factorial Volume of extraction solvent, pH, salt Development of a simple and efficient method of Cr, Zn Water [44]
design (25 − 1) concentration, extraction temperature, and ligandless-ultrasound-assisted emulsification microextraction
and sonication time for the simultaneous preconcentration of chromium and zinc
Box–Behnken
Mixed factorial Amount of sample, contact time, and liquid Developing a method to obtain robust information on short Na, K, Mg, Volcanic ashes [143]
to solid ratio term leaching behavior of volcanic ashes Ca, Si, Al, V,
Mn, Fe, Co
Factorial design 24 Sample flow rate, reagent flow rate, eluent Studying a separation/preconcentration procedure using solid Zn Water [144]
and central concentration, and reagent concentration phase extraction coupled to zinc vapor generation
composite
Fractional factorial Volume of extraction and disperser Applying dispersive liquid–liquid microextraction for Cr, Cu,Ni, Natural waters [145]
design (25 − 1) solvents, pH, concentration of salt, and simultaneous preconcentration of chromium, copper, nickel Zn
concentration of the chelating agent and zinc
Fractional factorial pH of solution, amount of extractant, Development of a magnetic nanoparticle adsorbent that uses Mn Cereal [107]
design (24 − 1) amount of nanoparticles, and time iron oxide nanoparticles as the core and
and 1-(2-pyridylazo)-2-naphthol
Box–Behnken
Fractional factorial Volume of extraction solvent, ultrasonic Applying ultrasound-assisted emulsification microextraction Al, Cu, Fe, Oscillatoria, [102]
design (26 − 2) time, extraction temperature, salt for simultaneous extraction of trace levels using sodium Zn, Juncus littoralis
and concentration, concentration of ligand, and diethyldithiocarbamate trihydrate as a chelating agent and tissues and
Box–Behnken pH tetrachloroethylene as an extraction solvent water
Fractional factorial Volume of extraction solvent, Optimizing an ultrasound-assisted Yb3+, Water [146]
design (26 − 1) concentration of chelating agent, pH, emulsification-microextraction system to simultaneous Ho3+
and central ultrasonic time, temperature, and extraction of holmium and ytterbium using
composite concentration of salt 1-(2-pyridylazo)-2-naphthol as chelating agent
Doehlert pH and irradiation time Development of an analytical procedure of separation and Cd, Cr, Cu, Oil-refinery [104]
preconcentration using cloud point extraction Mn, Ni, Pb effluent
4
Factorial design 2 pH, eluent concentration, and sample flow Development of a dual-bed resin solid phase extraction for Ag, Al, As, Gasoline [147]
rate preconcentration of Ag, Al, As and Cr using Dowex 50 W-x8 Cr
and Dowex 1-x8 as metal ion sorbents
Factorial design 24 Sample pH, chelating agent concentration, Optimizing an hollow fiber-liquid phase microextraction Ag, Al, As, Diesel and [148]
and extraction time, and stripping solution method for the simultaneous extraction and preconcentration Mn, Ti gasoline
Box–Behnken concentration of Ag, Al, As, Mn and Ti as ammonium pyrrolidine
dithiocarbamate complexes
Factorial design 23 Concentration of KMnO4, sonication time, Development of a pre-concentration and separation method Pb River water [101]
and Doehlert and concentration of MnSO4 using ultrasound assisted co-precipitation with manganese
dioxide
Fractional factorial pH, sample flow rate, buffer concentration, Development of a method for solid phase extraction on Mo Water [149]
design (25 − 1) eluent concentration, and eluent flow L-tyrosine immobilized on carbon nanotubes
and central
composite
Factorial design 23 Chelating agent concentration, surfactant Developing a cloud point extraction method to Cd, Co, Cu, Saline [150]
concentration, and the pH of the solution preconcentration of metals in produced water using Ni, Pb, Zn produced
8-hydroxyquinoline as the chelating agent water
 C.G. Novaes et al. / Microchemical Journal 128 (2016) 331–346 343

Table 7
Recent applications of multivariate optimization applied in sample introduction systems and analysis by ICP OES.

Experimental design Optimized parameters Objective of study Analytes Samples References

Factorial design 24 and Sample flow rate, pressure of nebulizer, Development of a procedure for Se, As Estuarine sediments [117]
Doehlert NaBH4 flow rate, and HCl flow rate determination of bioavailable concentrations
of selenium and arsenic using a concomitant
metals analyzer device to perform hydride
generation
Doehlert Radio frequency power and nebulizer gas Evaluating and improve the analytical As, Se Natural water [123]
flow rate potentiality of the direct interfacing of ion
exchange — high performance liquid
chromatography
Fractional factorial HCl concentration, NaBH4 concentration, HCl Construction of a glass homemade system for Hg Buffalo river [122]
design (25 − 1) and flow rate, NaBH4 flow rate and argon flow the separation of the liquid and gas phases, sediment (NIST
factorial design 24 rate designed as an alternative to the commercial 2704) and human
system for use with the ICP OES equipment hair (IAEA 085).
mercury determination
Central composite HCl concentration, NaBH4 concentration, and Chemical generation and transport of vapors As, Sb, Bi, Ge, Sn, — [121]
carrier gas flow rate of As, Sb, Bi, Ge, Sn, Se, Te, and Hg in a Se, Te, Hg
multivariate way
Placket–Burman Concentration of thiourea, concentration of Determination of the level of arsenic and As, Sb Sea-water [119]
lanthanum in the samples, HCl antimony in sea-water by axial ICP OES with
concentration, NaBH4 concentration, continuous hydride generation after
trapping buffer pH, elution flow, flow rate of performing pre-reduction with thiourea and
carrier gas, knotted reactor length, and buffer carrying out a pre-concentration by
flow/sample flow co-precipitation with lanthanum in a knotted
reactor
Fractional factorial NaBH4 concentration, cobalt concentration, Multivariate optimization of the main Ag, Au, Cd, Cu, Ni, — [118]
design (26 − 1) and oxine concentration, injection Ar flow, type parameters which might affect Ag, Au, Cd, Cu, Zn
orthogonal central of acid, and acid concentration Ni and Zn vapor generation
composite
Central composite Radio frequency power and nebulizer gas Applying a factorial design to evaluate plasma Ca, Cu, Fe, K, Mg, Non-fat milk powder [47]
flow rate conditions employing the Mg II 280/Mg I 285 Na, P, S, Zn
nm intensity ratio in an axial ICP using
different sample introduction devices: a
concentric or a V-groove nebulizer and a
cyclonic or a Sturman–Masters spray
chamber
Orthogonal central Carrier gas flow rate, acid concentration, Evaluating the performance of a new hydride Se Reference materials [120]
composite sample flow rate, NaBH4 concentration, generator for hydride forming elements for (not-fat milk powder,
reductor flow rate, Ni concentration, Co determination by ICP oyster tissue, human
concentration, and Cu concentration urine, and sediments)
Plackett–Burman and Sample and NaBH4 uptake rate, aerosol Inserting pre-evaporation tube between a As, Ba, Be, Bi, Cd, Standard reference [151]
central composite carrier gas flow rate, relative plasma multi-mode sample introduction system and Co, Cr, Cu, Fe, Ge, materials (Montana
observation height, NaBH4 concentration, the plasma torch to improve the Hg, Mn, Mo, Ni, soil and fish protein)
HNO3 concentration simultaneous determination of hydride Pb, Sb, Sn, V, W,
forming and other elements Zn
Factorial design 22 NaBH4 concentration, and HCl concentration Development of a method for the As, Hg, Sb, Se, Sn Sediment slurries [152]
simultaneous determination of As, Hg, Sb, Se
and Sn using on-line chemical vapor
generation and Ge(IV) as internal standard
Fractional factorial Sample, reagent, buffer and acid flow rates, Development of a preconcentration system to Se Water, energy drinks, [112]
design (27 − 3), and acid, buffer and reagent concentrations determine inorganic selenium species after wine and tea
fractional factorial separation by a column filled with polyvinyl
design (24 − 1) and chloride with lanthanum hydroxide
central composite co-precipitation

NaBH4 — Sodium borohydride; HCl — Hydrochloric acid; HNO3 — Nitric acid.

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