Microwave-Assisted Extraction: © 2018 Elsevier Inc. All Rights Reserved
Microwave-Assisted Extraction: © 2018 Elsevier Inc. All Rights Reserved
Maria Llompart, Carmen Garcia-Jares, and María Celeiro, University of Santiago de Compostela, Santiago de Compostela, Spain
Thierry Dagnac, Galician Agency for Food Quality-Agricultural and Agrarian Research Centre (AGACAL-CIAM), A Coruña, Spain
© 2018 Elsevier Inc. All rights reserved.
Introduction 1
Principles of Microwave-Assisted Extraction 2
Equipment: Components and Extractors 2
Main Components 2
Microwave Systems 3
Closed-vessel microwave systems 4
Open-vessel microwave systems 6
Solvent-free microwave extraction 6
Optimization of the MAE Process 7
Influence of Viscosity, Sample Size, and Sample Nature 7
Temperature and Pressure 7
Solvent Nature 7
Volume of Solvent 8
Extraction Time and Microwave Power 8
Applications 9
References 10
Introduction
Microwave technology finds multiple uses in chemical fields including synthesis of organic, inorganic and organometallic
compounds, catalysis, sample digestion for elemental analysis, solvent extraction, sample drying, moisture measurement, analyte
adsorption and desorption, cleaning up samples, chromogenic reactions, distillation, and microwave plasma atomic spectrometry,
among others.15 It can help reduce the time taken to complete many of the processes mentioned above, and is very suitable for
many types of samples.
The use of microwave energy in chemical analysis first emerged in 19751 to digest biological samples under pressurized
conditions followed by elemental analysis. It was the beginning of the application of microwave radiation in sample preparation.
The development of microwave-assisted extraction (MAE) started one decade later, and the first application of microwave energy
for the extraction of organic compounds was described in 1986,13 for which a domestic appliance was used. In these first studies the
authors propose the use of microwaves to extract crude fat, antinutritives, and pesticides, from food/feed products and soil. This
technique soon gained popularity, mainly due to the introduction in the laboratory of the first commercially available extractors at
the beginning of the 1990s. During this decade MAE was mainly applied to environmental analysis for the extraction of organic and
organometallic pollutants. Applicability of the procedure rapidly expanded to other fields such as natural products and food, and
clinical and pharmaceutical samples, reaching a peak in 2008 as regards the number of published articles.
In MAE, microwave energy is applied to heat solvents in contact with samples (mainly solid samples) achieving the partition of
the target compounds of interest from the sample into the solvent. Extractions are conducted in closed or open vessels where the
sample and solvent are combined and then exposed to microwave energy. The extraction time is significantly reduced when
applying MAE because with microwaves the sample/solvent mixture is directly heated, whereas with classical extraction techniques,
a finite period is needed to heat the vessel before heat is transferred to the solution.
Although the traditional Soxhlet and solvent extraction techniques are still widely accepted, they have inherent limitations and
problems. For example, Soxhlet extraction requires 12–24 h in most cases and uses high volumes of organic solvents (hundreds of
milliliters). In contrast to conventional methods, MAE can reduce the extraction time to less than 20 min and solvent consumption
below 20 mL. MAE allows for the possibility of simultaneously processing multiple samples (up to 12, 24 or even 40 simultaneous
extractions), drastically improving sample throughput. Moreover, the recoveries obtained with MAE are mostly comparable or
higher than those provided by alternative methods. Therefore, MAE largely complies with the minimum criteria required for
modern sample preparation techniques, and provides a very attractive alternative to the conventional approaches.
This article describes the principles, fundamentals, components and equipment used for MAE with special emphasis on the
parameters affecting extraction efficiency. In addition, some of the most important applications focusing on environmental analysis
and the extraction of environmental pollutants, including emerging pollutants and pesticides, as well as the extraction of bioactive
compounds from biological samples will be discussed.
☆
Change History: June 2018. Maria Llompart, Carmen Garcia-Jares, Maria Celeiro, and Thierry Dagnac have updated text, figures, and table and included
bibliography and eliminated further reading.
MAE is an extraction technique that combines the use of microwave energy and traditional solvent extraction. In MAE microwave
energy is used to heat solvents in contact with solid samples or liquid samples (or to heat samples, e.g., fresh tissues) promoting
partition of the compounds of interest from the sample into the solvent. In contrast to conventional heating, microwaves heat the
solution directly. As a result, temperature gradients are minimal and the heating rate using microwave radiation is faster.
Microwaves are electromagnetic waves made up of two oscillating fields: an electrical field and a magnetic field. The two fields
operate perpendicular to each other and the direction of propagation varies sinusoidally. Microwave energy is a nonionizing
radiation with a frequency range of between 300 and 300,000 MHz (Fig. 1) that causes molecular motion by two mechanisms:
migration of ions and rotation of dipoles. The magnetic field produces the direct action of waves on the material, which is able to
absorb a part of the electromagnetic energy and to transform it into heat.15, 43 All microwave ovens, irrespective of sources or use,
operate at a fixed frequency of 2.45 GHz.
Microwaves heat up the molecules by the dual mechanism of ionic conduction and dipole rotation. Ionic conduction and dipole
rotation usually take place simultaneously both in the solvent and in the sample, which effectively converts microwave energy to
thermal energy. The ionic conduction generates heat due to the resistance of the medium to ion flow. The migration of dissolved
ions causes collisions between molecules because the direction of ions changes as many times as the field changes sign.
The dipole rotation is related to the alternative movement of polar molecules, which try to line up with the electric field (Fig. 2).
Dipolar polarization (also refereed as orientation polarization) is the most significant heating mechanism in microwave extraction.
At 2.45 GHz, realignment of the dipoles of the solvent molecules occurs within a rapidly changing electronic field, typically 4900
million times per second. The solvent molecules try to realign themselves within the electric field. This leads to vibration, and
multiple collisions issuing from this agitation of molecules, which in turn generates energy release, producing heat thought
frictional force and, therefore, increasing the temperature. Heat generation of the sample in the microwave field requires the
presence of a dielectric compound. Only materials or solvents with permanent dipoles are heated by microwaves. As microwave
absorption occurs with the reorientation of permanent dipoles by the electric field, the amount of energy absorbed is proportional
to the solvent dielectric constant (e0 ) that measures the sample ability to absorb microwave energy. The loss factor or dielectric loss
(e00 ) expresses the material ability to dissipate the absorbed energy. In fact, the heat generation in a sample depends on the
dissipation factor (tan d), that measures the efficiency with which different solvents heat up under microwaves. This factor is the
ratio of the sample’s dielectric loss (i.e., the loss factor e00 ) to its dielectric constant (e0 ). Considering tan d, materials can be classified
as: reflective, transparent or absorbent materials.
The effect of microwave energy is strongly dependent on the nature of both the solvent and the matrix. In most cases, the solvent
chosen to perform MAE has a high dielectric constant, so that it strongly absorbs the microwave energy. The compounds with high
dielectric losses are mainly polar compounds. However, in some cases, although is quite uncommon, only the sample matrix may
be heated by the action of microwaves so that the solutes are released in a cold solvent transparent to the microwave energy. For
example, apolar solvents like hexane and chloroform produce no or little heat during microwave exposure. The matrix must be a
good dielectric material, and strongly interacts with the microwaves, as in the case of fresh tissues containing high amount of
water.5, 29 This extraction procedure with transparent microwave solvents may be particularly useful for thermolabile components,
to prevent their degradation. The dielectric properties of several solvents used for MAE are given in Table 1.19
Table 1 Dielectric propertiesa, boiling point, and maximum closed-vessel temperature of several solvents used in MAE
3. The applicator or resonance cavity where the sample is placed. It can be a multimode cavity where microwaves are randomly
dispersed or the waveguide itself. In the latter case, the sample vessel is placed directly inside to focus the microwave radiation
onto the sample.
4. The circulator, which allows microwaves to pass only in the forward direction.
The microwave generator is called the magnetron, a term first described by A.W. Hull in 1921. All the commercial systems for the
analytical laboratory, as well as the domestic microwave ovens, emit radiation at a fix frequency of 2.45 GHz. The electromagnetic
energy is conducted from the magnetron to the resonance cavity using a wave guide. The sample placed inside the cavity is therefore
subjected to microwave energy.
Microwave Systems
Microwave-assisted extractors can be classified into two groups, according to the way microwave energy is applied to the sample. In
multimode systems, the microwave radiation is dispersed randomly in a cavity, and so every zone in the cavity, including the sample
or samples that it contains, is irradiated. Single-mode or focused systems allow focusing of the microwave radiation on a restricted
area where the sample is placed for exposure to a much stronger electromagnetic field than in the previous case.24 The most
common one is the closed pressurized multimode system in which the samples are placed inside vessels that are sealed prior to
being subjected to microwave irradiation at high pressure and temperature. Both configurations are presented in Fig. 3.37 These two
technologies are commonly named pressurized MAE and focused MAE, respectively. The focused systems were generally of the
open-vessel type, in which microwaves are applied at atmospheric pressure. Nevertheless, new developments have led to
4 Microwave-Assisted Extraction
(A)
Diffused microwaves (closed system)
Screw
Disc
Diffused Cover
microwaves
Cell Solvent
Sample
Support
Turntable module
(B)
Focused microwaves (open system)
Cooling
Magnetron system
Extraction
Waveguide
cell
Focussed
microwaves
Fig. 3 Schematic view of devices for (A) multimode systems (pressurized) and (B) single-mode or focused systems.37
commercial systems being now available based on multimode configurations at atmospheric pressure, as well as, pressurized
focused systems.
Multimode systems usually incorporate a rotor with a carousel that permits simultaneous extraction of up to 12, 24 or
40 samples (depending on the number of carousel positions). In the single-mode or focused systems simultaneous extraction is
not possible, although some efforts have been made to simultaneous process, up to four samples by splitting the microwave energy
symmetrically among the flasks at the end of the waveguide.
Fig. 4 Working sequence for the preparation of the extraction vessels. Reproduced with permission of Milestone, Inc.
Fig. 5 Commercial extractors from (A) CEM and (B) Milestone. Reproduced with permission of CEM Corporation and Milestone, Inc.
6 Microwave-Assisted Extraction
characteristics. The maximum operation temperature and pressure of the commercially available systems are 300 C and 30 bar
(435 psi), respectively. In most cases, extractions are performed at much lower temperatures (120 C or lower).
The drawbacks or limitations of closed vessel systems include the risk involved in the use of high pressures and temperatures.
Commercial equipment include several security mechanisms, to avoid overpressures and to detect solvent leaks. In addition, the
possible risk of analyte degradation should be considered in the case of thermolabile compounds.
by earth gravity out of the microwave reactor. A cooling system outside the microwave oven continuously condenses the extract.
Whereas traditional processes are carried out in 3 h or more, solvent-free MHG requires less than 30 min. Once the essential oils
have been extracted, they can be analyzed directly by GC–MS. A very large scientific library based on MHG is available and it
includes sample preparation programs and analytical data. These new approaches largely fulfill green chemistry principles achieving
a fast, solventless extraction, obtaining high purity extracts and eliminating the risk of thermal degradation.
In the practical application of MAE, a variety of experimental factors needs to be considered and addressed for a particular system
under investigation. The main variables affecting MAE performance include: nature of the solvent and the matrix; size and moisture
of the sample; solvent volume; microwave power; exposure time; and temperature.5, 6, 25, 36 Advanced optimization strategies often
need to be applied to MAE as it is influenced by many factors that may interact with one another. The use of chemometric tools such
as experiment designs and response surface methodology-RSM allows decreasing the number of experiments needed to assess the
influence of these factors on the MAE process. It consists of applying statistical and mathematical techniques to develop, improve
and optimize the design process.21, 33
Solvent Nature
Another main factor which affects the extraction process is the solvent nature. The solvent selection for MAE is driven not only by the
solubility of the target compounds and by the interaction between solvent and matrix, but also by the microwave absorbing
properties of the solvent. It should have a high selectivity toward the analytes of interest, excluding unwanted matrix components,
and be compatible with the subsequent analysis.
The extraction solvents available for MAE are usually limited to those that absorb microwaves (solvents with permanent dipole
moments), although the use of solvent mixtures (with and without dipoles) extend MAE applications to a larger variety of potential
solvent mixtures.
8 Microwave-Assisted Extraction
MAE of nonpolar compounds usually entails the adoption of a compromise since, although these compounds are more readily
dissolved in nonpolar solvents such as n-hexane, the interaction of microwaves with the solvent depends on its dielectric properties
(see Table 1). This requires the use of a mixture of solvents of different polarity in many cases. For example, one of the most suitable
solvents for MAE of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs)
is a mixture of hexane and acetone. This mixture, in a proportion 1:1 (v/v) is the recommended in the US EPA 3546 method.12
Hexane is an example of microwave transparent solvent whereas acetone or ethanol is an excellent microwave absorbing solvent.
Therefore, the selection of the organic solvents should account for three facts:
1. The microwave-absorbing properties of the solvent (and the ability of the solvent to convert this energy into heat). As microwave
absorption occurs owing to the reorientation of permanent dipoles by the electric field, the amount of energy absorbed is
proportional to the dielectric constant (e0 ) of the solvent. In practice, most of the time, the absorption is also proportional to the
solvent polarity. Apart from absorbing the energy, the solvent must be able to convert this energy into heat, so the efficiency of
the conversion process is dependent on the dielectric factor loss (e00 ). The overall efficiency of heating is then expressed by the
dissipation factor (tan d).
2. Preferably the solvent should have a high selectivity toward the analyte of interest excluding unwanted matrix components.
3. The interaction of the solvent with the matrix.
In order to achieve optimum extraction yields by MAE, analytes can be extracted according to three different mechanisms15:
(a) Mechanism I: the sample could be immersed in a single solvent or mixture of solvents that absorb microwave energy strongly.
(b) Mechanism II: the sample could be extracted in a combined solvent containing solvents with both high and low dielectric losses
mixed in various proportions.
(c) Mechanism III: samples that have a high dielectric loss (i.e., samples with high water content) can be extracted with a microwave
transparent solvent.
Most MAE applications involve the use of polar solvents or mixtures of nonpolar–polar solvents and water, including the humidity
of biological matrices themselves (following the third extraction mechanism). Regarding water, although its power of solubility for
organic compounds is not as high as those of organic solvents, its interaction with microwaves is much higher due to its high
dielectric constant, thus providing, in some applications, high extraction efficiencies, and environmentally friendliness.
In specific cases such as in the extraction of organometallic compounds, the use of methanol acidified with acetic acid allows
organometals to be extracted in a rapid, efficient manner with no degradation.
The new incorporation of heating elements, such as stirring bars (5 20 mm), in WeflonTM (Milestone) or Carboflon® (CEM)
makes it possible to perform extractions with microwave transparent solvents at high temperatures (indirect heating). In this way,
methods (e.g., Soxhlet protocols) that involve nonpolar solvents which are microwave transparent can be performed easily without
any change in the current solvent scheme.
Recently, some alternative solvents, such as ionic liquids (ILs), have been proposed for MAE of pesticides, environmental
pollutants and natural compounds.14, 18, 42 ILs, composed of bulky organic cations and inorganic or organic anions, can efficiently
absorb and transfer the microwave energy. They have attracted much research interest for a variety of applications, thanks to their
excellent properties: negligible vapor pressure, good thermal stability, wide liquid range, tunable viscosity and miscibility with water
and organic solvents, as well as good solubility and extractability for various organic compounds. Thus, ILs have been used as
attractive “green” alternatives to conventional volatile organic solvents.
Volume of Solvent
In conventional extractions, a higher volume of solvent will usually increase the recovery of the analyte. However, in MAE, the same
approach may lead to lower recoveries, probably due to an inadequate mixing of the solvent with the matrix by the microwaves. The
selection of solvent volume depends on the type and the size of sample, but, on average, it may be about 10-fold lower than those
used in classical extractions, but always considering that the solvent volume must be sufficient to ensure that the whole sample is
immersed.
The sample to solvent ratio frequently employed ranges from 1:10 to 1:50 (w:v), but this ratio has to be adapted and optimized
for each raw material. The nature of the matrix in which the analytes of interest are present can play an important role toward the
extraction yield.
sample–extractant contact. In these conditions, the application of microwaves over short, intermittent periods results in substan-
tially increased extraction efficiency relative to the continuous application of microwaves.
Usually, increasing extraction time beyond the optimal range does not improve the extraction efficiency, and may even decrease
the analyte recoveries (e.g., thermolabile compounds). Recently, more powerful microwave platforms that incorporate two
magnetrons, allowing power of up to 1900 W, have become available in the market.
Applications
The use of MAE has been mainly focused on extracting complex samples, and it is continuously expanding in several research areas
highlighting environmental analysis, food analysis, and the extraction of bioactive compounds from natural sources. MAE is easy to
implement and rapid, and provides good extraction efficiencies similar to or higher than those obtained with classical techniques
(i.e., Soxhlet or liquid–liquid extraction) and other more recent techniques (i.e., supercritical fluid extraction or pressurized liquid
extraction).
Regarding environmental analysis, the first applications of MAE described the determination of pesticides, PAHs, and PCBs in
soils and sediments.13, 23, 28 Since then, many other environmental contaminants have been efficiently extracted such as phenols
and organometallic compounds.10, 20, 38 The EPA method 3546 “Microwave Extraction” was proposed in 2000 for the extraction of
semivolatile organic compounds, including organophosphorus pesticides, organochlorine pesticides, chlorinated herbicides,
phenoxyacid herbicides, substituted phenols, PCBs, and polychlorinated dibenzodioxins/polychlorinated dibenzofurans, which
can then be analyzed by chromatographic procedures.12, 17 This MAE method can also be applied to the extraction of additional
target analytes. Recently, the use of microwaves for the extraction of contaminants of emerging concern has attracted great
interest.19, 36 MAE methods for flame retardants, surfactants, pharmaceutical and personal care products have been developed
because of the relative ease in optimizing the extraction parameters, and because of the automation, high efficiency and sample
throughput they afford. A rapid and simple method for the analysis of polybrominated diphenyl ethers (PBDEs) in house dust
samples based MAE and GC–MS/MS was optimized using a multifactorial experimental design approach (Fig. 7). In this method
the use of an aqueous NaOH phase in combination with a nonpolar organic phase (hexane) allowed an efficient extraction of
PBDEs from dust reducing chromatographic background. The final hexane extracts could be analyzed after a simple one-step
cleanup procedure with Florisil. Method accuracy was demonstrated by the analysis of a certified reference material (Fig. 7).33
BC
AB
AA
D:[NaCI] BDE-47
BDE-99
C:Temperature
BDE-153
B:Volume
A:pH
0 2 4 6 8 10 12
Standardized effect
1200
MAE values
Concentration (ng g−1)
600
400
200
0
BDE-47 BDE-100 BDE-99 BDE-85 BDE-154 BDE-153
Fig. 7 MAE of polybrominated diphenyl ethers (PBDEs). (Upper) Pareto chart showing the influence of main effects and interactions for three selected PBDEs;
(Below) Analysis of a CRM urban dust material contaminated with PBDEs.
10 Microwave-Assisted Extraction
In food analysis, microwave extractions allow food to be dried, extracted and concentrated with a single equipment and minimal
sample manipulation. Many applications of microwave-assisted extraction are devoted to isolating trace organic pollutants from
food, although MAE has also been used in food ingredients analysis such as the flavor composition of musts,7 amino acids in
vegetables,16 pectin from waste mango peel,31 and fatty acids from vegetable oils and animal fats,32 among other applications.
Regarding the analysis of trace organic pollutants from food and environmental samples, a recent review on advances in MAE
highlights that trace pesticides (e.g., avermectin, pyrethroid, triazines, and organochlorine), aromatic fused-ring compounds
(e.g., PBDEs, PAHs and heterocyclic aromatic amines (HAAs)), and trace pharmaceuticals and hormones (e.g., sulfonamides,
fluoroquinolones, and estrogens) constitute the three main categories for analysis.40 It is worthy to note that the three top countries
publishing papers on MAE of pesticide residues from plants are Spain, China, and Portugal.27 One interesting trend is the
combination of MAE with microextraction techniques such as dispersive liquid–liquid microextraction (DLLME), which allows
further concentration and clean-up before analysis.35, 41 In this way, three polar HAAs have been determined in hamburger patties
after optimization of the factors affecting the extraction, and using HPLC for the analysis; good performance in terms of linearity,
recovery, precision, and better detection limits (0.06–0.21 ng/g) than previously reported methods have been reported.2 Also, MAE
followed by DLLME and HPLC has been proposed for the analysis of PAHs in smoked rice,26 and pesticides from litchi fruits.41
As one of the main trends of the emerging bio-economy, consumers across the world increasingly demand safe, natural products
for personal care, health, food, well-being, and beauty. This translates into massive demand of botanical extracts (secondary
metabolites) obtained through extraction processes radically greener than conventional solid–liquid extraction using hydrocarbon
solvents.9 The so-called microwave-assisted processes (MAP) was originally developed and patented by Canada’s Federal Depart-
ment of the Environment for the direct extraction of compounds from dried as well as fresh materials of biological origin.29,30 The
process is applicable to many types of tissue for example, plant material for flavoring and fragrance purposes such as pepper mint,
seaweeds; various types of vegetables, such as, onions, garlic and the like; and other tissues like animal tissues to extract pigments,
oils, etc.
MAE has gained enormous popularity for the recovery of various active compounds from plant materials, especially with the
newer add-ons or technological modifications incorporated into MAE systems, which enhance extraction efficiency and ensure a
greener implementation. Such improvements include integrating MAE with other technologies, for example, ultrasound assisted
extraction (UAE), negative pressure cavitation (NPC), enzyme assisted extraction (EAE), hydrodiffusion extraction (HDE), and SFE,
or replacement of extraction medium with suitable alternatives including ionic liquids, deep eutectic solvents, and nonionic
surfactants.11 Solvent-free MAE arose as a sustainable technology in achieving the objectives of green chemistry for the extraction
of plant material since the internal water within the plant material is heated allowing the destruction of plant cells containing
bioactive compounds which are released and transferred outside the plant material. The technique has been applied to the
extraction of essential oils from menthe, rosemary, and citrus peel, and polyphenols from onions.8
Research on MAE of medicinal plants has been largely on the design and development of optimum conditions for the maximum
yield of target bioactive compound followed by comparison with conventional techniques. After 2010, at least half of the published
papers on MAE were based on extraction of bioactive compounds from plants, clearly showing that polyphenols, flavonoids, and in
general antioxidants have been the most dominant components considered.27 To prevent degradation due to excessive heat,
temperature exposition during MAE should be minimized. Over the years, improvement of MAE methodologies has resulted in
better outputs in terms of prevention of flavonoid degradation.34 Recently it was reported that an equipment using a slot end
coaxial antenna into the microwave applicator provided an effective cooling system, and when applied to the extraction of sea
buckthorn leaves, demonstrated higher values of total phenolic content and antioxidant power when compared with extracts
obtained by conventional MAE.4
MAE is used extensively for extraction of botanicals since it has the additional advantage to be useful for both polar and
nonpolar compounds. In a recent critical comparison of extraction techniques used for botanicals MAE was the technique mostly
applied to extract anthocyanins and polyphenols, and the second after Soxhlet to extract flavonoids.3 This paper also reflects the
number of patented procedures of botanicals extraction being Soxhlet the most patented technique followed by SFE and MAE.
By-products of the agrifood industry such as wine and juice are being regarded as a source of bioactive compounds, mainly
flavonoids. MAE has been successfully employed to extract anthocyanins39 from them and other bioactive compounds.
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