NEW TRENDS IN FOOD SAMPLE

PREPARATION

S.C.A. COBZAC
“Babes-Bolyai” University, Faculty of Chemistry and Chemical Engineering,
Chemistry Department, 11 Arany Janos, 400028, Cluj-Napoca, Romania
csimona@chem.ubbcluj.ro

1. Introduction

Investigations in food science and technology as well as in food safety require determination
of food composition. The nature of the sample and the reason for the analysis dictate the choice
of analytical methods. The results mainly depend on two operations: obtaining a representative
sample and bringing the sample to a form that can be analyzed. The second operation is known
as sample preparation and, in its simplest form, refers to the transfer of compounds of interest
from food matrix into a liquid phase which can be subjected to chemical analysis.
The goal of sample preparation of solid foods is to obtain an extract that contains the analytes.
This extract or any other liquid sample can be processed for removing the interferences -
operation known as purification or clean-up and/or increasing the concentration of trace
compound beyond the limit of identification or determination - process known as
preconcentration (figure 1).

Fig. 1. Types of extraction techniques in correlation with their purpose

The extraction technique is chosen not only depending on the type of the sample but also on
the volatility of the compound of interest (Figure 2). Table 1 lists some of the techniques used to
prepare the samples.
 Fig. 2. Selection diagram of extraction technique taking into account the properties of analytes
and the nature of sample

Extraction techniques encountered in food sample preparation. Table 1

Technique Abreviation Type of Analyte
sample
Solvent extraction - Solid Volatile
Head-space solid phase microextraction HS-SPME Solid/Liquid Volatile
Purge and trap P&T Liquid Volatile
Head-space single drop microextraction HS-SDME Solid/Liquid Volatile
Maceration - Solid Non- volatile
Soxhlet extraction - Solid Non- volatile
Reflux - Solid Non- volatile
Microwave assisted extraction MAE Solid Non- volatile
Ultrasound assisted extraction UAE Solid Non- volatile
Superfluid extraction SFE Solid Non- volatile
Pressurized liquid extraction PLE Solid Non- volatile
Accelerated solvent extraction ASE Solid Non- volatile
Liquid-liquid extraction LLE Liquid Non- volatile
Liquid-liquid microextraction LLME Liquid Non- volatile
Dispersive liquid-liquid microextraction DLLME Liquid Non- volatile
Single drop microextraction SDME Liquid Non- volatile
QuEChERS (Quick, Easy, Cheap, Effective, QuEChERS Liquid Non- volatile
Rugged, and Safe)
Solid phase extraction SPE Liquid Non- volatile
Dispersive solid phase extraction D-SPE
Solid phase microextraction SPME Liquid Non- volatile
Stir bar sorptive extraction SBSE Liquid Non- volatile
Restricted access media RAM Liquid Non- volatile

The figures of merit of sample preparation efficiency are recovery, preconcentration factor
and selectivity. Sample preparation is the bottleneck of an analytical procedure because it is
tedious and can lead to significant errors.
There are a lot of review article regarding sample preparation of foods for different
contaminant determination [1, 2]
2. Sample preparation for solid food matrices

2.1. Extraction mechanism

Extraction of organic compounds, such as bioactive compounds, additives or contaminants

(antibiotics, pesticides) from a solid food is an equilibrium process in which the analytes are
desorbed from the matrix and dissolve into a solvent. Extraction efficiency depends on three
interdependent parameters:
- Solubility - depends on the type of the solvent, temperature and pressure. Solvent selection
depends on the polarity of the analytes, being preferred those that leave the matrix
unchanged. This kind of extraction is known as selective extraction. Solvents that are
miscible with water can be used for hydrophilic compounds and hydrophobic one for the
organic compounds of like polarity. Usually mixtures of solvents are used.
- mass transfer - refers to analyte transport from the interior of the matrix into the solvent.
There are two processes that occurring: solvent penetration into the matrix and analytes
desorption. Mass transfer depends on the properties of the solvent (diffusion coefficient and
viscosity) and matrix (structure and particle size). High temperature and pressure and
agitation will facilitate mass transfer.
- matrix effects - refers to the interaction of analytes with solid sample. A soluble compound
can be “unextractable” if it is locked in the matrix pores or is strongly bound to the surface.

2.2. Classical extraction techniques

Classical methods include maceration, percolation, reflux and Soxhlet extraction. They are
carried out under atmospheric pressure, with/without heating or mechanic/magnetic stirring.
Maceration consists in keeping in contact the solid sample with the extraction solvent for
several days. Usually it is used for vegetal sample preparation, when mild extraction conditions
are required to protect sensitive bioactive compounds. Percolation, also used for the preparation
of plant samples, is a dynamic extraction technique in which the solvent passes through the
sample bed at a given rate. First extractions of bioactive compounds that take place in the
presence of heating are infusion and decoction. Volatile compounds can be extracted by
hydrodistilation using a Clevenger apparatus [3, 4].
From the classical techniques, reflux extraction is by far the most used. It consists in “boiling”
the sample into a solvent. The solvent vapors are condensed by means of a condenser connected
to the reflux flask. The extraction is more efficient due to the high temperature which leads to
increasing solubility and diffusion coefficient and decreasing solvent viscosity.
Another technique carried out by heating is Soxhlet extraction. The Soxhlet apparatus consists
of three main components: a round-bottomed flask (1), a thimble holder (2) with a siphon
device (4) and a side tube (5) and a reflux condenser (3). The sample is loaded into a porous
cellulous cartridge and placed into the thimble holder (figure 3).
The flask (1) containing the solvent is slightly heated and the generated vapors pass through
the side tube (5) to the reflux condenser (3) where they are condensed. The hot solvent falls into
the thimble chamber (2) where the extraction takes place. When the solvent reaches the top of
the thimble holder, it is drained back into the flask through the siphon (4). The number of
extraction cycles depends on the extraction time and the heating rate. This technique is suitable
for nonvolatile thermostable compounds. Having boiling points higher than the solvent, the
analytes will accumulate in the flask (1). Under these conditions, only the solvent will be
evaporated and condensed, each time the extraction being carried out with fresh solvent
portions. The main drawback of this technique is the long extraction time (6-24 hours).
 Fig. 3. Soxhlet extraction device

Classical techniques are simple and easy to perform but they are high consumers of time and
solvents which are not environmental friendly in most cases.

2.3. Modern extraction techniques

Modern techniques for solid sample preparation, such as accelerated solvent extraction (ASE),
supercritical fluid extraction (SEF), ultrasonic assisted solvent extraction (UAE) and microwave
assisted solvent extraction (MAE), are used to overcome the drawbacks of classical techniques.
The extraction is improved either by increasing the temperature and pressure of the extraction
solvent or due to the effects of the electromagnetic or ultrasonic fields. Despite the high
acquisition cost of the equipment, for a long-term operation and for a large number of analyses,
these techniques may be more economical than classical techniques.

Ultrasonic assisted extraction (UAE), also known as sonication, uses ultrasonic vibration to
facilitate an intimate contact between the sample and the solvent. Over the last twenty years,
UAE has proved to be the predominant technique used in sample preparation of plant materials.
The ultrasound domain can be divided into three frequency ranges, namely:
• power ultrasound (1-100 kHz),
• high frequency ultrasound (100 kHz - 1 MHz)
• diagnosis ultrasound (1 MHz –10 MHz).
The power ultrasound transmitted through a liquid medium affects the distance between the
molecules; the front of the wave creates high positive pressure which compresses the liquid
layers. In contrast, the wave tail creates high negative pressure which forces the molecules to
exceed the critical molecular distance and generate a void space known as cavitations bubbles.
The bubble size is inversely proportional to the frequency - low frequency ultrasound generates
large cavitation bubbles. Under positive pressure the liquid layers are compressed again and the
cavitation bubbles collapse violently, generating high temperatures and pressure. These
conditions generate rapid fluctuations of fluid movement and in consequence significant shear
forces, known as micro-streams, are produced. When the cavitation bubble collapses near a
solid surface, an asymmetric collapse occurs and micro jets with a mechanical effect of several
orders of magnitude larger than a cavitation bubble are produced. Ultrasound of low frequencies
(18-40 kHz) may cause physical disruption of cell walls and particle size reduction. As a result,
the solvent penetrates easier into the cellular material and facilitates the transfer of compounds
from the cell into the solvent. Nowadays, two common laboratory devices for ultrasound
application, bath and probe, are used [5, 6].

Microwave solvent assisted extraction (MAE) uses the heat generated by the interaction of
matter with electromagnetic field. The frequency of microwaves rests between 0.3 - 300 GHz.
Radar transmission and telecommunications also use microwave. To avoid the interferences, all
scientific and domestic microwave heaters work at 2.45 or 0.9 GHz.
The magnetic field of microwave radiation interacts with polar molecules and forces the
molecules to rotate and align themselves with the field at a rate of 4.9 x 10 9 times per second.
This oscillation is more vigorous when the molecules have a higher dipole moment. As a result
of the friction between molecules, heat is generated. As a rule, polar solvents such as methanol
can be heated rapidly while nonpolar solvents such as hexane cannot be heated as they do not
absorb microwaves. For extraction, both types of solvent can be used. When polar solvents are
used, the sample is in contact with a hot liquid environment and polar analytes can be extracted.
In this case, the temperature can rise so much that it reaches the boiling point. To avoid the
solvent loose by evaporation closed vessel or open vessel with cooling mantel or condenser can
be used. When transparent solvents are used, nonpolar compounds can be extracted. In this case,
the polar compound (i.e. water) the one that absorbs the radiation is added to the solid sample.
The heating process is inversed - from the sample to the solvent.
The main components of a microwave extraction system include a power supply, a magnetron
(the microwave generator), a waveguide for transmission, a resonant cavity and an extraction
cell (Figure 4).

Fig. 4. Schematic diagram of MAE device

The extraction cells are made of materials that are transparent to microwaves. As mentioned
above, there are two types of microwave cells: closed extraction vessels that can work under
elevated pressure and open vessels which can be used only under atmospheric pressure. A
diagram of a closed-vessel microwave extraction system is presented in figure 5. The oven
contains a carousel with 12 extraction vessels. During extraction, the carousel rotates 360 o like
in domestic microwave heaters.

Fig. 5. Schematic diagram of a closed-vessel microwave extraction system

The interest in this technique regarding the processing of food samples is evidenced by the
considerable number of articles that can be found in the literature [7-9].

Accelerated solvent extraction (ASE), also known as pressurized liquid extraction (PLE),
employs high pressure and high temperature which places solvents near the supercritical region
where the liquid has better extraction characteristics. At high temperatures, the rate of the
extraction process is improved both by increasing the diffusion coefficient of the solvent and its
ability to dissolve the compounds of interest and by concomitant decrease in its viscosity and
surface tension. The role of the pressure is to keep the solvent in the liquid state, below its
boiling point, forcing it to penetrate into the pores of the sample. The ASE apparatus comprises
of an extraction cell placed into an oven, a pump which delivers the solvent, three valves and a
collection vial (figure 6). The pressure at the operating level is achieved by the total or partial
closing of the static valve.

Fig. 6. The schematic diagram of an ASE apparatus

The sample is placed in the extraction cell, the solvent is pumped into the cell until it is filled
and then the system is allowed to equilibrate under static conditions. After a predetermined
time, the extract is pumped out of the cell and, if necessary, the extraction can be continued in
dynamic mode. Lot of review articles and applications can be found in literature regarding
extraction of different contaminants from foods [10, 11].

Supercritical fluid extraction (SFE), an efficient extraction technique of organic compounds

from solid samples, benefits from the properties of supercritical fluids. The physical state of a
substance can be described by a phase diagram which delimits the regions corresponding to
gaseous, liquid and solid states (figure 7). The points along the curves define the equilibrium
between the two phases in contact. In this diagram, the liquid/gas line ends at a point called
critical point. The critical point is defined by a critical temperature T c and a critical pressure p c
beyond which the substance is supercritical.

Fig. 7. Phase diagram for carbon dioxide

A supercritical fluid behaves like a gas due to its low viscosity and ability to penetrate the
pores and as a liquid due to its density and solvating power. The diffusion coefficient lies
between the values that correspond to the two physical states. The solubility capacity of a
supercritical fluid is influenced by its temperature, pressure and density. When a supercritical
fluid is used as an extraction agent, the process runs faster and with higher extraction yield.
Although many gases can be brought to supercritical state, carbon dioxide (CO 2) is preferred
because it is nontoxic, nonflammable and is available at high purity. It also has a low
supercritical temperature (31oC) and pressure (73 atm). Having a nonpolar molecule, it is used
for extraction of nonpolar and moderately polar compounds. Its solvating power for polar
solutes and compound with high molecular weight can be increased by increasing the
temperature and pressure and/or by adding small quantities (5%) of polar organic solvents such
as methanol, dichloroethylene and acetonitrile.
The basic components of a SFE instrument are: the CO 2 tank, the high-pressure pump, the
extraction cell, the heating oven, the flow restrictor and the extract collector (Figure 8).

Fig. 8. The schematic diagram of a supercritical fluid extractor

The sample is loaded into the extraction cell and then the cell is placed into the heating oven.
The operating pressure is controlled by the restrictor. The extract is collected into a trap or a
collection vial with a solvent. The collection process is carried out at atmospheric pressure when
supercritical CO2 is converted into gas, leaving a concentrated extract. The extraction can be
operated in static or/and dynamic modes. In static mode, the supercritical fluid is held into the
extraction cell for the entire period of time provided for extraction and then released into the
collection device. In the dynamic mode, the supercritical fluid flows through the extraction cell
and is continuously collected. Also in this case the literature abounds both in review articles and
in research articles [12, 13].

In conclusion, the extraction solvent and technique should be chosen taking into account both
the properties of compounds of interest and the properties of the matrix.

3. Sample preparation for liquid food matrices and food extracts

Liquid-liquid extraction (LLE) is one of the most commonly used techniques for liquid
sample preparation. It is so popular because it is simple and provides a high degree of sample
clean-up. The extraction selectivity is easily obtained by through the use of an adequate organic
solvent. Despite its popularity, due to its inherent disadvantages, nowadays, liquid-liquid
extraction is less applied.

3.1. Classical liquid-liquid extraction

Liquid-liquid extraction is an equilibrium process in which the compounds of interest are

partitioned between two immiscible liquid phases. Considering immiscible phases A as the
donor of compound X and phases B as the acceptor phase and the distribution process of
compound X between A and B, the distribution constant K D, according to Nernst, is given by the
following relationship:
KD = [X]B/[X]A

where [X] denote the molar concentration of X at equilibrium state, in each phase. Generally,
one phase is water (A) and the other is an organic solvent (B). According to their hydrophilic
(polar) or lipophilic (non-polar) nature, the components prefer one of these two phases. By
using extraction-reextraction procedures at different pH values, compounds with different
characteristics such as neutral, basic, acidic organic and inorganic, can be separated. Shaking
liquid-liquid extraction is carried out in a simple separation funnel. The components extracted in
the organic phase can be easily concentrated by evaporating the solvent. However, when
considering this technique, drawbacks such as tedious procedures (laborious and time-
consuming), proneness to form emulsion and usage of large volumes of toxic organic solvents
should be highlighted. The development of faster, simpler, inexpensive and more ecological
sample preparation techniques is of major importance in chromatographic analysis [14].
3.1. Modern techniques for liquid sample preparation

Improvement of the performance of liquid sample processing can be achieved in two ways,
which are solvent microextraction (SME) and solid phase extraction (SPE) techniques. The first
one refers to the miniaturization of extractive devices and extraction volumes and the second
consists of replacing the acceptor liquid phase with a solid.

3.1.1. Liquid phase microextraction techniques

Liquid phase microextraction techniques (LPME) can be classified into two categories:
exposed solvent and membrane-protected solvent. The exposed-solvent techniques are: liquid-
liquid microextraction (LLME), liquid-liquid-liquid microextraction (LLLME), single-drop
microextraction (SDME), headspace single drop microextraction (HS-SDME) and dispersive
liquid-liquid microextraction (DLLME). The protected SME include hollow-fiber-two-phase
and hollow-fiber-three-phase microextraction [15-17]

Liquid-liquid microextraction with directly suspended droplet (DSDME) is carried out by

adding to the aqueous sample a drop of an immiscible and low density organic solvent. The
intimate contact between the phases is accomplished by magnetic stirring or sonication. After
the equilibrium was achieved and extraction took place, the system is centrifuged and the phases
are separated. By means of a mycrosyringe, the enriched organic drop is removed (figure 9a). If
the solvent has a relative high solidification point, the system is cooled and then the solid is
removed. This technique is known as solidified floating organic droplet (SFOD) and is
schematically presented in figure 9b.

Fig. 9. Principle of directly suspended droplet microextraction (DSDME) and solidified floating
organic droplet (SFOD)

In single-drop microextraction the acceptor phase is represented by a drop of organic solvent

at the tip of a microsyringe needle. After extraction, the drop is retracted into the needle and
injected into an analytical instrument. Two main approaches can be used to carry out SDME:
- by direct immersion (SDME) when the organic droplet is in direct contact with the water
sample, this technique being appropriate for non-volatile analytes (figure 10a)
- from the head-space (HS-SDME) when the needle is placed above the aqueous sample,
this technique being appropriate for volatile analytes (figure 10b).
During the extraction procedure, the drop should remain attached to the needle. The drop
stability is influenced by the cohesive and adhesive forces. Solvents such as isooctane and
toluene are preferred.
 Fig. 9. Schematic diagram for single drop extraction technique:
direct immersion (a); from head-space (b)

Dispersive liquid-liquid extraction (DLLME) is performed by using a mixture of two solvents,

an extraction solvent and a dispersant. The extraction solvent must necessarily be immiscible
with the aqueous sample and it is used in small volumes (hundred microlitres) in the order to
ensure a higher preconcentration factor. The dispersant agent must by miscible with both the
aqueous sample and the extracting solvent, and usually higher volumes than the extraction
volume are used. However, the ratio between the volumes of the two solvents should be
optimized. The volume of the aqueous sample varies between 5-10 mL. The main
characteristics of the extraction system are provided in table 2.

Composition and characteristics of the extraction system in DLLME. Table 2

Solvent Characteristics
Extracting solvent
CCl4 Immiscible with water;
CHCl3 Higher density than water;
CH2Cl2 Good solvent for the analyte;
C2H2Cl4 The type of selected solvent affects KD;
Volume = 5–100 µL; the optimum volume should be determined
so that a high enrichment factor and a sufficient amount for
subsequent determinations are obtained
Dispersing agent
Acetone Miscible with both aqueous sample and extraction solvent;
Methanol Volume = 0.5–1.5 ml; it has a direct influence on: the formation
Ethanol of cloudy "solutions", the degree of dispersion of the extraction
Acetonitrile solvent in the aqueous phase and the efficiency of extraction

When the extraction system is added to the aqueous sample, the dispersant tends to dissolve in
water, forcing the immiscible extraction solvent to form a fine dispersion. The cloudy system
that was formed is separated by centrifugation into two phases. The lower phase is the enriched
one and it is removed using a microsyringe. The extraction steps are presented in figure 10 [18].
It should be mentioned that, as in the case of classical liquid-liquid extraction, it may often be
necessary to carry out several consecutive microextractions.
 Fig. 10. Operation steps in dispersive liquid-liquid microextraction DLLME)

In hallow-fiber microextraction (HFME) the extraction solvent is immobilized in the pores

and in the interior of a polyethylene capillary. The capillary has an inner diameter of 600 µm, a
wall thick of 200 µm, the porosity of about 66% and a pore volume per unit length of 3.3
µm/cm [19]. HFME can be performed in two ways: biphasic and three phase systems (figure
11).

Fig. 11. HFME in biphasic system (a) and three phase system (b)

When the biphasic extraction is performed, the analytes are concentrated into an organic phase
which is not always compatible with HPLC analyses. Contrary, in three phase extraction, the
analytes are transferred from the aqueous sample through the organic solvent into the acceptor
phase, which is also an aqueous phase but of a reversed pH. As shown in figure 12, the steps to
perform HFME are: hallow fiber impregnation, extraction - which is also an equilibrium
process, and desorption. The obtained extract is further analyzed by chromatography.
 Fig. 12. Hallow fiber microextraction steps

3.1.2. Solid phase extraction techniques

In solid phase extraction techniques the extracting/acceptor phase is a solid with adsorbent
properties. There are three main extraction techniques that are carried out on different extraction
devices: cartridge or membrane/disc known as solid phase extraction (SPE), fiber cover with a
sorbent known as solid phase microextraction (SPME) and extraction on stir bar covers with a
sorbent known as stir bar sorbtive extraction (SBSE).

Solid-phase extraction (SPE) is the most widely used method for preparation of liquid
matrices such as extracts and liquid samples. It is used for cleaning, concentration, changing of
solvents and separating of organic compounds from a number of samples [20, 21]. The
adsorbent is loaded into a cartridge or a barrel between two frits (figure 13a). The nature of the
sorbent is similar to those used in liquid chromatography but different size and geometry (figure
13b). Commercially there are cartridges of different shapes and volumes filled with different
types and amounts of sorbents.

Fig. 13. Solid phase cartridge and sorbent geometrical properties

The selection the sorbent nature (nonpolar, polar or ionic) is made according to the polarity of
the compounds of interest. There are a lot of types of sorbent from inorganics such as florisil
and silica gel to organic ones such as hydrophilic-lipophilic balance (HLB) polymers and
molecular-imprinted polymers (MIP). Another category of sorbents are chemical modified
sorbents which are prepared by bonding different organic compounds onto silica gel surface.
A solid phase extraction is performed in four steps, namely: conditioning, retention, washing
and eluting (figure 14). SPE adsorbents work correctly only if their surface is perfectly clean
and wetted, so the purpose of conditioning is to prepare the sorbent for the optimal adsorption of
the component of interest. Conditioning is performed by passing methanol through the
cartridge.
 Fig.14. Steps of solid phase extraction

Retention is the stage when the component of interest is retained on the surface of the sorbent.
In the sorbent-matrix-sorption system there are interactions between sorbent and analyte (1),
analyte and matrix (2) and sorbent and matrix (3) (figure 15).

Fig. 15. Interation between participants species involved in the retention process

Depending on the relative ratio between these interactions, the analyte can be retained or can
pass through the cartridge without being retained. Removal of the non-specific adsorbed
components is accomplished by washing the sorbent bed with various wash solvents. Elution is
the process by which the components of interest are desorbed from the surface on which it were
been retained.
SEP is an extraction technique in which all of the above mentioned steps are equilibrium
processes. However, due to the large amount of sorbent, the compounds of interest can be fully
recovered in the final extract. In order to achieve this goal each step requires a careful
optimization.

Solid-phase microextraction (SPME) is also a technique for liquid sample preparation. It can
be applied for both volatile and non-volatile analytes. It has a lot of others advantages such as
high sensibility, low background noise (very useful for trace components determination), low
cost, is fast and simple and especially does not use solvents [22, 23].
The extraction device consists of a Hamilton type syringe, the piston/plunger (4) of which
contains a stainless steel wire (2) from which fused silica gel or optic fiber (1) has been bonded
at high temperatures (figure 16).
 Fig. 16. Solid phase microextraction device

The fiber is coated with a sorbent (polyacrylate, polydimethylsiloxane etc.) on which surface
the analytes accumulate. By moving the plunger, the fiber may be exposed or retracted into the
needle. The sorbent is selected according to the polarity of the analyte, polar analytes require
polar coatings. The thickness of the coating is dictated by the molecular weight of the analytes
(Mw), the higher Mw is, the thinner should be the coating.
SPME involves a few simple steps: introducing the SPME device into the sample vial (1),
exposing the fiber and adsorbing the analytes (2), retracting the fiber inside the needle, and
removing the SPME device from the vial (3), inserting the SPME device into the injection port
of a GC (4), fiber exposure and thermodesorption of the analytes (5) and fiber retraction in the
needle and the removal of the SPME device (figure 17).

Fig. 17. Solid phase microextraction steps

Due to the fact that adsorption is an equilibrium process, the maximum amount of analyte that
can be absorbed depends upon KD, coating thickness and equilibration time.
SPME provides the possibility of absorbing the analytes both by direct contact with the
aqueous sample and from the head space (Figure 18).

Fig.18. Design of SPME (a) and HS-SPME (b)

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