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Chapter

Modern Sample Preparation

Techniques: A Brief Introduction
Mona Sargazi, Sayyed Hossein Hashemi
and Massoud Kaykhaii

Abstract

Due to fast growth in microprocessors, analytical instrumentations in spectros-

copy, chromatography, microscopy, sensors and microdevices have been subjected
to significant developments. Despite these advances, a sample preparation step
is indispensable before instrumental analysis. Main reasons are low sensitivity of
the instruments, matrix interferences and incompatibility of the sample with the
analytical device. Most of the time spent and most of the errors occurring during a
chemical analysis is on sample preparation step. As a result, any improvements in
this essential process will have a significant effect on shortening the analysis time
and its precision and accuracy and lowering the cost. This introductory chapter
intends to draw the readers’ attention to the importance of sample preparation, the
procedures of sampling and the source of errors that occur in the course of sam-
pling. The chapter then continues with a heading on sample preparation techniques,
including exhaustive and non-exhaustive methods of extraction. Microwave,
sonication and membrane-based extraction techniques are more emphasized as
exhaustive methods and under a new title, miniaturized methods are discussed.
Automation, on-line compatibility and simplification is an important aspect of any
sample preparation and extraction which is discussed at the end of this chapter.

Keywords: sample preparation, matrix interferences, microextraction, automation

1. Introduction

Over the last two decades, efforts in sample preparation have been done to
eliminate organic solvents and perform rapid analysis of combinatorial chem-
istry and biological samples, which require a high level of automation. These
new developments in sample preparation, as a result of miniaturization of the
extraction process, were a reason to extend new solvent-free approaches. Also,
a fundamental understanding of extraction principles has been very important
in the development of novel approaches, which results in new trends in sample
preparation, such as microextraction, miniaturization, and integration of the
sampling and separation. The sampling and sample preparation process, which
is similar to engineering approaches on a smaller scale nevertheless is different
from those related to chromatographic separations or other traditional disciplines
of analytical chemistry, consists of extraction of components of interest from the
sample matrix to an extracting phase. So, the procedure of extraction has a variety
of selectivity, speed, and convenience as a result of the approach and condition

1
Sample Preparation Techniques for Chemical Analysis

used and geometric configurations of the extraction phase [1]. Modernization

of analytical methods and instrumentation made it possible to measure smaller
concentrations of even the most complex molecules and species in complicated
matrices. In addition, improved measurement techniques and tools allow, or often
require, the use of smaller analytical test portions to determine analyte concentra-
tions. Using small test portions face with difficulty in achieving representativeness
of the population, especially in the analysis of trace components, since the qual-
ity of any analytical result, depends on sample representativeness and integrity.
Similar to all measurements, which are accompanied by errors, some typical errors
often occur during sample collection prior to trace analysis [2] but many sources
of error in an analysis can be controlled through the use of blanks, standards, or
reference samples. Neither blank nor standard can repair the damage caused by an
invalid sample [1]. Errors are an integral part of all measurements, which cannot
be eliminated completely but it is possible to estimate the magnitude and nature of
them in order to validate results [3].
In this chapter, an attempt has been made to define the principle of sample
preparation and its importance prior to chemical analysis. The following sections
are dedicated to different methods of sampling and the errors that occur during
sampling and focus on the different techniques in the science of sample prepara-
tion. This chapter is not intended to provide a comprehensive review of the topic of
sample preparation, but it is helpful for learning more about it.

2. What is sampling and sample preparation?

Successful quantitative analysis starts with the sample collection, which is a first
operation in an analytical procedure. The sample in sample collection should be
representative of the bulk material and various sample collection techniques can be
employed depending on the nature of the matrix. For example, in the field of environ-
mental samples, such as soil, air, and water, consideration of representative sampling
right at the point of collection is of great importance because it needs to consider the
intrinsic heterogeneity of most materials. These considerations are highly important
especially in performing analysis of trace and ultra-trace components, which require
sample-specific strategies to obtain a clear and unbiased overview. After sample
collection, it needs to be decided whether the entire sample or a portion of the sample
requires to be analyzed [4]. It should be noted that sampling depends on the location,
depth, and time of the year, which affects the concentration of the sample. Once the
sample is ready for analysis, sample preparation is the next step [3]. Sample prepara-
tion is a crucial step of the analysis process with the ability to detect an analyte at a
level that is appropriate for detection by the instrument. Matrix interferences in this
step can interfere with the detection and measurement of analytes in a way that often
requires to complete separation of the sample matrix from the analyte(s) of interest.
So, the nature of the analyte and the matrix determine the choice of sample prepara-
tion. Figure 1 shows various sample preparation steps that may be employed in sample
preparation in which most analysts use one to four steps for sample preparation,
although, in some cases, more than seven steps may be used [4].
Nowadays, efforts have been done to hyphenate sampling and sample prepara-
tion steps but there are challenges such as multistep procedures involving organic
solvents. So, it is difficult to develop a method to integrate sampling and sample
preparation with separation methods, for the purpose of automation. Therefore,
over 80% of analysis time is currently spent on sampling and sample preparation
steps for complex samples [1, 5].

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Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

Figure 1.
Sample preparation procedures commonly used [4].

3. Importance of sampling and sample preparation

One of the most important parts of the analytical process is sampling, which
is highly dependent on the properties of the analyte and the nature of the sample.
Obtaining correct and informative results from the analytical procedure is a main
purpose of this step. Inappropriate sample collection causes irreparable impairment
that cannot be compensated even by quality assurance measures. Sample contamina-
tion during sample collection is one of the main sources of acquiring invalid data [6].
The decision of where to collect samples, which represents the whole sample, how
to characterize the problems, and choosing a right method of obtaining the right

3
Sample Preparation Techniques for Chemical Analysis

amount of samples, are the critical issues in the sampling step. The purity of the sam-
ple should be ensured before taking a measurement to obtain the optimum results
when using any instrument, irrespective of the technology. For this reason, sample
preparation often involves a cleanup step for “dirty” samples besides extraction pro-
cedure. Sample preparation also includes all treatments to decompose the structure
of the matrix in order to perform the fractionation, isolation, and enrichment of the
proposed analytes. These treatments, which adapt the tested analytes with the detec-
tor to enhance the sensitivity of the detector, are also considered part of the sample
preparation protocol. Emerging some challenging problems with the sample matrix
led analytical chemists to turn to non-traditional technologies, which meet the need
for solvent-free approaches, automation, and miniaturization. These developments
reach some benefits such as in situ analysis of sample, which consequently reduces
the time and errors and thus leads to more accurate, precise, and faster data. In
parallel with the development of new technologies, the fundamental of extraction
principles has advanced, which is in high importance in the development of novel
sample preparation trends. In the case of complex samples, the analytical procedure
consists of several steps including sampling, sample preparation, separation, quan-
tification, statistical evaluation, and decision making. These analytical steps follow
one after another, and the slowest step determines the whole speed of the analytical
process. Since direct analysis cannot produce real results because of interferences
of a matrix of the sample that causes low sensitivity, therefore, modification of the
sample to obtain better analytical results is very important [7, 8].

4. Sampling methods

The aim of sampling methods is to choose a “sample” that represents the popula-
tion. Attempts in sampling methods are ensuring about an equal chance of each part
of the population to be selected for analysis, which requires a random element in
the sampling strategy. These strategies include simple random sampling, systematic
grid sampling, stratified, cluster, and two-stage sampling.
In simple random sampling, the population is divided into a set of units and a
sample is selected unit by unit with an equal probability of selection for each unit at
each draw. In systematic grid sampling, samples are collected from grid areas, which
are as a result of dividing the population into two or three-dimensional grids. When
the purpose of sampling is increasing the probability of locating possible hot spots
in a population, systematic sampling is used.
In two-stage sampling, elementary units are randomly selected within the
population and sample increments are taken from locations within each unit. The
locations may be selected systematically or randomly.
Stratified random sampling is composed of the division of a population into sections
called strata. By designing an efficient and cost-effective sampling plan, the number,
size, and shape of strata are important. When the purpose of sampling is to estimate
more precisely analyte concentration in the population, the uniformity of each stratum
is necessary. So, the number of sample increments needed to define analyte distribution
within each stratum will be reduced. By using systematic sampling, the units occur at
the same relative position in the stratum, while in stratified random sampling, the posi-
tion in the stratum is determined separately by randomization within each stratum.
In survey sampling, a group of distinct and identifiable units in the population
is called a cluster and choosing a group of units as a single unit is called cluster
sampling. In cluster sampling, the population is divided into small groups with each
group serving as a sample unit. The formation of clusters means forming groups of
a heterogeneous nature [6, 9].

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Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

5. Sampling errors

Sampling as the most crucial step of each analytical procedure is of high impor-
tance and should be done with the utmost care and expertise. Nevertheless, there are
some typical errors (systematic and random) that can occur from a small percentage
to several orders of magnitude [2]. The sampling error is the error caused by observ-
ing a sample instead of the whole population. The sampling error is the difference
between a sample statistic used to estimate a population parameter and the actual
but unknown value of the parameter. One of the most important systematic errors,
which can occur in the sampling process, is sample contamination. Contamination
can exceed the true levels of the compound analyzed and consequently causes to
obtain invalid results. Therefore, one of the concerns of sampling is to avoid intro-
ducing contamination into the sample. The equipment for sample collection is one
of the main sources of contamination in sampling so a proper sampling device and
container are of great importance for accurate analysis. For example, in the sample
storage step, by storing samples in containers a wide range of chemical or physical
changes can occur such as chemical reactions within components of the sample or
sample components reacting with the containers [6]. Another source of error in
sampling is selecting species, which is representative of the sample. In many envi-
ronmental samples, the concentration of analytes is relatively high, for example, at
the mg.kg−1 level and selecting species considered as bioindicators or biomonitors is
decisive term. Also, some errors are caused by the homogenizing process to reduce
initial values of species into manageable amounts in order to consider them as repre-
sentative analytical subsamples. There is a relation between the sampling error and
particle size of the sample as shown in Figure 2. As it can be seen, a larger sample
size reduces error significantly; however, working with a large amount of sample is
not logical. According to the figure, sampling error for a normal sample is likely to
be between 0.1% and 1% of the whole sample. The sampling error can be minimized
by grinding the particles into fine size with this assumption that there are no issues
relating to the stability of the analytes. It is important to mention that the place of
sampling is very closely linked to a proper sampling strategy. Carefully choosing of a
statistically relevant number and mass of individual samples greatly depends on the
distribution and concentration of the analyte in the collected material [2, 4].

Figure 2.
The relationship between sample error, the number of particles in a sample, and different percentages of
original material sampled [4].

5
Sample Preparation Techniques for Chemical Analysis

6. Sample preparation techniques

Signal detection of the analytical instrument of the target analyte at a low concen-
tration is always challenging because of the highly complicated media and different
interferences from the matrix of any real sample such as biological, food, water, and
environmental samples [10]. Accordingly, it is a need to develop a novel, effective,
fast, inexpensive, and simple sample preparation technique to isolate analyte com-
ponents of the samples and preconcentrate them to a detectable limit [11]. Several
pretreatment techniques including solid phase extraction (SPE) [12], dispersive solid
phase extraction (DSPE) [13], solid phase microextraction (SPME) [14], magnetic
solid phase extraction (MSPE) [15], liquid–liquid extraction (LLE) [16, 17], molecu-
lar imprinted polymer (MIP) [18], stir bar sorptive extraction (SBSE) [19], pipette tip
microsolid phase extraction [20], molecularly imprinted stir bar sorptive extraction
(MIPSB) [21], microwave-assisted extraction (MASE) [22], membrane extraction
[23], solid phase extraction (SPE) [24], supercritical fluid extraction (SFE) [25],
and silver nanoparticle stir bar sorptive extraction [26] have been used widespread
application for preconcentration and isolate trace level compound of complicated
matrices. Before talking in detail about these mainly miniaturized techniques, first
some details about the classification of extraction methods are explained.

7. Exhaustive and non-exhaustive extraction methods

Figure 3 represents the classification of extraction protocols. In exhaustive

extraction methods such as solid phase extraction and liquid–liquid extraction,
analytes are completely transferred to the extraction phase. These methods have
been widely applied as a sample preparation technique in the separation and enrich-
ment of inorganic and organic analytes of water media. Exhaustive extraction
methods do not need calibration because almost all target molecules are transported
into the extracting solvent because of their large volume. Flow systems replaced
batch equilibrium techniques to reduce the consumption of solvent and time. For
example, in dynamic extraction with solvent (Soxhlet extraction) in which extrac-
tion is performed at the solvent boiling point, circulation of the extractant enhances
the extraction power significantly.

Figure 3.
Classification of extraction methods. Copyright Wiley-VCH, 2010. Reprinted with permission [1].

6
Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

Non-exhaustive methods including SPME and liquid phase microextraction

(LPME) are based on the principle of equilibrium, pre-equilibrium, and perme-
ation. Although non-exhaustive methods (equilibrium method) such as SPME
are similar to exhaustive equilibrium techniques, the amount of extraction phase
is much smaller than equilibrium exhaustive techniques and is generally used to
separate a small fraction of the analyte from the sample matrix [1].

8. Microwave and sonication extraction

Abu-Samra et al. [27] had already utilized the microwave method to promote the
extraction techniques of liquid phase extraction (LPE). Microwave-assisted extrac-
tion can enormously decrease the extraction time (around 10 min) because micro-
waves directly heat up the solutions (sample and extraction solvent) instead of
containers. The protocol also reduces the solvent consumption and allows multiple
samples. The microwave-assisted extraction (MAE) effectiveness was proved with
compared by general extraction techniques including high-speed homogenization
and mechanical shaking protocols. MAE utilizes a household microwave oven
that can reduce the cost of purchasing a dedicated tool for extraction, including a
polytron-type extractor or an automated pressurized liquid extraction (PLE). If a
flammable organic solvent including acetone is applied as an extraction solvent and
a household microwave is utilized to MAE, sparks that may occur within the range
can cause a fire or explosion. So, it is necessary to take suitable measures including
as preventing the solvent from leaking into the extraction container to minimize
fire and explosion danger [28, 29].
Ultrasonic-assisted extraction (UAE) or sonication extraction (SE) is a mature
extraction methodology that accelerates the process of entering goal analytes in
the solvent by utilizing ultrasound during liquid phase extraction (LPE). Indeed,
ultrasonic extraction is based on mass exchange from the sample into the extraction
phase using ultrasound radiation. Sonication extraction is done by high-frequency
sound waves introduced into a liquid medium and it is associated with the forma-
tion and collapse of tiny bubbles or cavities in the liquid. It has been demonstrated
that the UAE can improve the recovery compared to normal solvent extraction due
to its physicochemical effects such as similar sonication cavitation, disturbance,
fragmentation, emulsification, and erosion [30–32]. The extraction performance of
UAE, MAE, and Soxhlet extraction was compared and the result showed the better
performance of UAE [33]. The technique is a simple and cost-effective method [28].

9. Gas extraction techniques

Purge and trap protocol or dynamic headspace analysis or gas extraction tech-
nique is usually applied as an extraction method for the trace level determination of
volatile analytes present in a liquid sample. The main advantage of the protocol is
its capacity to accept large volumes of sample including the high sorption capacity
of traps; hence, a lower detection limit for volatile organic analytes can be obtained.
In the protocol, the sample is purged using inert gas for a specified time and the
purged compounds are trapped applying an adsorbent trap as shown in Figure 4.
Thermal desorption is utilizing to transfer the target molecules to a next step. Often
before GC detection, an analyte accumulation step, depending on the cry-focusing
unit, is applied. A short capillary is cooled to a sub-ambient temperature usually
with liquid nitrogen or a Peltier system. The step allows to focus the compounds
in a narrow band that is rapidly transferred to GC column using fast thermal

7
Sample Preparation Techniques for Chemical Analysis

desorption. This created a good peak shape and efficiency of separation, so it

increases the resolution as well as the sensitivity of the procedure [34, 35].

10. Membrane extraction

Membrane extraction is an extraction technique that utilizes a microporous

membrane to separate the analytes of the extractant. The materials in the matrix
to be tested pass via the microporous membrane, which are then extracted using
the extractant. Based on the physical and chemical properties of the matrix, the
extractant can be adjusted and selected to achieve better detection results [36]. The
concept of membrane extraction is shown in Figure 5.
Membrane extraction with a sorbent interface (MESI) is considered as an effi-
cient extraction technique since it has not only the ability to isolate the compound
of the real sample, but also indicates advantages such as high selectivity, removal of
the extraction solvent, reduced analysis time, compatibility by gas chromatography
(GC), and applicability to continuous monitoring and automation of industrial
processes. So, the utilization of a MESI method for isolation and enrichment of
target compounds is an area of growing research interest. The membrane extraction
includes two simultaneous steps: the isolation of target compounds of the sample
media using the membrane probe and the stripping of target molecules of the other
side of the membrane utilizing a flowing stripping gas. The membrane acts as a
selective barrier as it allows some compounds and prevents others from passing
via the membrane wall to the analytical sample. MESI-GC has been used to isolate
different samples in various media. A custom-made tools for heating the polymer
and collection, isolate of the degradation products present in the sample’s headspace
was applied (Figure 6) [37]. The treated polymer film was sandwiched as a thin
layer between two aluminum foils near the heating element, which was also covered
by an aluminum foil. The temperature of the heating element was controlled with
an automatic temperature controller. Also, the temperature of the heating element
was determined precisely with a thermocouple wire, which was in contact with the
aluminum foil and connected to the digital thermometer. A polymeric membrane

Figure 4.
Schematic diagram of purge and trap method (adapted from Ref. [34]). Reprinted with kind permission from
Ref. [34] copyright 2020 Taylor & Francis [34].

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Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

Figure 5.
The concept of membrane separation; the analytes are depicted by the circles [37]. Copyright Wiley-VCH, 2003.
Reprinted with permission [37].

Figure 6.
Schematic diagram of MEAI-GC system applied for the polymer degradation and (a), details of the membrane
module (b), main components of the MEAI trap (c). Reprinted by kind permission from Ref. [38]. Copyright
2002 Royal Society of Chemistry.

first extracts the compound from its media. By a porous adsorbent, the analytes are
trapped on a polymeric trap. The extraction membrane acts as a selective barrier
and is generally non-polar, then keeping water away from entering the system. It
also acts as a selective element, since the permeation rates of various analytes vary

9
Sample Preparation Techniques for Chemical Analysis

by the membrane particle. Once the molecules cross the membrane, the carrier gas
stream transports them to the adsorbent interface, where concentration occurs.
The MESI system was included of a membrane extraction probe, an adsorbent
trap, and a capacitive discharge power supply. Figure 6b shows a scheme of the
membrane module. A flat sheet membrane is not self-supportive and so needs
a holder to support it for contact by the system. One side of the membrane was
contacted to the sample and the other to the carrier gas. There are polytetrafluoro-
ethylene (PTFE) washers and stainless steel plates on both sides of the membrane.
In a stainless steel plate, one side of the membrane was supported with a mounted
fine stainless steel wire mesh. Both plates were fastened using three bolts. Via small
diameter PTFE tubing, the carrier gas was combined to the module, which fits
tightly into the PTFE washer. The carrier gas pressure lifted the membrane and
allowed free passage of the gas to the outlet tubing on the opposite side of the mem-
brane surface. After leaving the membrane, the carrier gas and target molecules
proceed to the small trap. The connecting tubes between the membrane module and
the GC injector were deactivated stainless steel tubes. To delete the signal deter-
mined with the detector that could come of the compound absorbed on the walls of
the tubes, the connectors were heated to approximately 120°C applying a heating
tape. In Figure 6c, the design of the micro-trap was presented. The micro-trap was
made by packing a section of stainless steel tubing by the polymer adsorbent. Using
passing an electrical current directly via the wall of the tubing for a few millisec-
onds of the discharge, the trap was heated. The temperature was modified with an
electrical potentiometer charged utilizing the capacitor and utilized to the ends of
metal tubing. The cycle of trapping and heating was repeated automatically using a
timer. The temperature of the trap was set producing minimal decomposition of the
adsorbent [38].

11. Miniaturization in sample preparation and extraction

Miniaturization techniques are of increasing interest in almost all aspects of

chemical analysis and especially in sample preparation. They lead to a significant
decrease in analysis time, sample and solvent volume, and consumption of chemi-
cal reagents. Reduction in the quantity of chemical reagents and matrix samples
applied per assay enables higher-throughput assays due to massive parallelization
and multiplex determination versions and after that promulgates the creation of new
procedures using easier handling protocols. Miniaturized SPE and LLE have been
applied for enrichment and isolation of various analytes and have many advantages
including low consumption of solvent, eluent, and sorbent, good extraction effi-
ciency, simple operation versatility. These advantages led to the invention of min-
iaturized modes of SPE and LLE including SPME, SBSE, μSPE, hollow fiber-based
liquid phase microextraction (HF-LPME), LPME, and DLLME [39–41].
Liquid-phase microextraction was first introduced by the Cantwell group
and Dasgupta group in 1996 [42, 43]. As a sample preparation technique derived
from LLE, LPME overcomes the drawbacks of solvent consuming and integrates
sampling, enrichment, and extraction in one step. Compared with LLE, LPME
has a much higher preconcentration factor and the method minimizes the solvent
in scale of microliters. Various types of LPME have been employed to meet the
requirements of determination such as HF-LPME, DLLME, and electromembrane
extraction (EME). In HF-LPME, a porous hollow fiber by the immobilized solvent
is placed between sample and acceptor solution for extraction, which provides high
enrichment and extraction efficiency. The technique has advantages such as high
sensitivity and sample cleanup [44].

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Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

DLLME has excellent enrichment characteristics and is fast. In DLLME,

target compound extraction is practically instantaneous due to the enormous
contact surface between the receptor and donating solvents. To obtain analyte
dispersion, a third solvent should be applied. In DLLME, after adding a proper
volume of extraction and dispersive solvent in the aquatic sample, a cloudy solu-
tion consisting of three solvents (water solution, extraction solvent, and dis-
persive solvent) is formed. After extraction of the target analyte from the water
phase in fine droplets of extraction solvent, the organic phase can be separated
by centrifugation [45, 46].
In EME, target molecules at aqueous media are electrically migrated across a
solvent immobilized porous polymeric liquid membrane called supported liquid.
They can later enter to the acceptor solution with the application of direct current
electric potential. Furthermore, utilizing a transparent liquid free membrane as an
alternative of SLM enables visual screening of the extraction methods. The EME is
a promising procedure for wider applications in analyte analysis and efforts have
been made to improve this extraction method [44].
Solid phase microextraction, as an effective and simple sample preparation, has
been generally used for different real samples since it was proposed by Pawliszyn
et al. in 1990 [47]. The extracting phase attached to the coated fiber has key effects
on the extraction process of the method since the mechanism of the technique is
mainly depending on the absorption equilibrium of the target compounds between
the fiber coating particle and sample solution. Up to date, scientists have employed
a number of coating particles to develop the usage of SPME including graphene
oxide, covalent organic framework, polymer, molecularly imprinted polymer, ionic,
and metal–organic frameworks (MOFs) [17].
Stir bar sorptive extraction is another interesting extraction method. Stir bar
coated by poly-dimethylsiloxane (PDMS), for preconcentration and separation of
the analytes, was first introduced in 1999 with Sandra et al. and called stir bar sorp-
tive extraction (SBSE) [48]. The technique depends on sorption that makes target
compounds partitioning between retaining sorbent (polymer) and liquid or vapor
sample media; hence, originating bulk retention. SBSE is dipped in the sample and
stirred for a defined time. After extraction of the target molecules, it is taken out of
the sample and immerged in a vial including elution solvent and stirs again. In final,
the elution solvent is removed and send to a proper apparatus for determination.
Sampling is carried out with direct insertion of SBSE in liquid or headspace (HS)
sample [49–51]. The mechanism of SBSE is shown in Figure 7.
Pipette tip microsolid phase extraction (PT-μSPE) is one of the most important
extraction techniques of miniaturized SPE that has become a simple and suitable
device for the extraction of different analytes. The pipette tip is proper to be applied

Figure 7.
Schematic of MIP-coated SBSE for naphthalene sulfonates. Reprinted by kind permission from Ref. [52].
Copyright 2018 Taylor and Francis.

11
Sample Preparation Techniques for Chemical Analysis

Figure 8.
Schematic of PT-μSPE for nalidixic acid and acetaminophen [40]. Reprinted by kind permission from Ref.
[40]. Copyright 2020 springer.

Method Extraction phase Sample phase Sampling mode

SBSE Sorbent coated on stir bar Environment or water Direct

sample

SDME Single drop Environment, water, and Direct or headspace

gas sample

DLLME Organic solvent Environment or water Direct

sample

LPME Liquid phase Environment or water Direct

sample

SPME Polymeric extracting phase Environment, water, and Direct, headspace,

coated on a fused silica fiber gas sample and membrane

Table 1.
Some of miniaturized sample preparation techniques.

as a SPE column due to its special conical shape using various diameters in two ends.
Normally, a bigger pipette tip is immersed in a small one to obtain a novel cartridge
and used as μSPE [53, 54]. Schematic of PT-μSPE for nalidixic acid and acetamino-
phen extraction is depicted in Figure 8.
Table 1 shows the comparison of some of the miniaturized sample preparation
methods.

12. Automation

The aim of miniaturized methods is a drastic reduction in solvent consumption

and samples, based on the green chemistry protocols. However, they sometimes
consist of steps such as centrifugation, drawn and drop cycles, and vortexing
which are regarded as disadvantages. Hence, even considering all non-automated
micromethods benefits, they are still related to multiple steps, increasing the anal-
ysis time, complexity, and propensity of analytical errors. So, automated methods
are explained basically to be simpler, faster, and further environmentally friendly
than traditional and miniaturized methods. For the goal, various strategies for

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DOI: http://dx.doi.org/10.5772/intechopen.100715

automation methods have been introduced in the last decades, such as the automa-
tion of SPE (online SPE) and with tailoring the microextraction protocols in order
toward its automation such as automated SPME, in-tube SPME, automated SBSE,
and so on. Fully automated SPME injection systems are commercially available
now from different companies. It will be possible theoretically that a technique
depending on SPME could be adapted to work by another microextraction tech-
nique, for example, by microextraction by packed sorbent (MEPS) once the same
adsorbents such as C18 or C8 can be packed inside the MEPS’s syringe, which is
applied as coated phase on SPME fibers. Hence, after preliminary tests to enough
the values of the parameters including extraction cycles and solvent volume, the
protocols could be transferred between these two methods and to other sorbent-
based techniques as well [55].

13. Conclusion

Evaluating chemical analytes in complex media is a challenging task, which

needs highly accurate sample preparation techniques. The development of these
methods created miniaturization techniques with features such as providing lower
detection limits, wider linear range, and improvement of selectivity and speed.
Nevertheless, the intense sample handling remains an important gap that may
even impair the performance of the techniques since the equilibrium between
analytes can be easily disturbed. In this chapter, we tried to explain some major
sample preparation techniques, both exhaustive and non-exhaustive methods.
Also, sample collection and pretreatment are discussed as critical steps, which
may impair the correct analytes detection despite the sample preparation method
applied. Improvement of sample preparation using smaller samples, and the volume
of solvent, reduction of analysis time, miniaturization, compatibility to different
analytical instruments and automation, is still a major part of research in chemi-
cal analysis. Besides automation, the application of “green” solvents such as ionic
liquids and deep eutectic solvents likely will find more demands in the extraction.
Solventless and flow-through sample preparation methods are also of interest,
which is expected to find more importance in the near future. Advances in mem-
brane technology will affect extraction techniques as well. In the next chapters of
this book, the reader will find some recent researches currently under investigation
to achieve these goals in sample preparation.

Acknowledgements

We gratefully acknowledge team members for their essential contribution over

the years.

Conflict of interest

The authors declare no conflict of interest.

13
Sample Preparation Techniques for Chemical Analysis

Author details

Mona Sargazi1, Sayyed Hossein Hashemi2 and Massoud Kaykhaii1*

1 Faculty of Sciences, Department of Chemistry, University of Sistan and

Baluchestan, Zahedan, Iran

2 Faculty of Marine Science, Department of Marine Chemistry, Chabahar Maritime

University, Chabahar, Iran

*Address all correspondence to: kaykhaii@gmail.com

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

14
Modern Sample Preparation Techniques: A Brief Introduction
DOI: http://dx.doi.org/10.5772/intechopen.100715

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