Trends in Analytical Chemistry 71 (2015) 2–8

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

The role of green extraction techniques in Green Analytical Chemistry

Sergio Armenta, Salvador Garrigues, Miguel de la Guardia *
Department of Analytical Chemistry, University of Valencia, Research Building “Jeroni Muñoz”, Dr. Moliner str., 46100, Burjassot, Valencia, Spain

A R T I C L E I N F O A B S T R A C T

Keywords:
Greening extraction techniques to improve the sensitivity and the selectivity of analytical methods is
Green Analytical Chemistry
the sustainable alternative to classical sample-preparation procedures used in the past. In this update,
Extraction
Liquid-liquid extraction
we review the main strategies employed in the scientific literature to reduce deleterious side-effects of
Microextraction extraction techniques. We demonstrate that the evolution of sample-treatment procedures is focused
Sample preparation on the simultaneous improvement of the main analytical features of the method and its practical aspects,
Selectivity including the economic case.
Sensitivity © 2014 Elsevier B.V. All rights reserved.
Side-effect
Solid-phase extraction
Sustainability

Contents

1. The green wave ....................................................................................................................................................................................................................................................... 2

2. Greening analytical procedures ........................................................................................................................................................................................................................ 3
3. Facing the problem of sample treatment ...................................................................................................................................................................................................... 3
4. Green extraction solutions ................................................................................................................................................................................................................................. 4
5. Future trends in green extraction .................................................................................................................................................................................................................... 6
Acknowledgements ............................................................................................................................................................................................................................................... 6
References ................................................................................................................................................................................................................................................................ 7

1. The green wave demand in analysis for a clever combination of environment-

friendly and cheap methodologies (see Fig. 1).
In a changing world, with the tremendous impact of human pres- Based on the 12 principles of GAC [11], many green methods were
ence, the urgent need for sustainability of all of our activities has proposed in recent years, and scientific journals have published
accelerated the evolution from the chemurgical paradigm to the eco- special issues regarding GAC practice in research and applied labo-
logical paradigm in which the environmental side effects of our ratories, as can be observed in Table 1, so creating a wave that
chemical activities must be seriously taken into consideration [1]. modified the concepts and the practice of analysis.
Green Chemistry [2–4] and Green Analytical Chemistry (GAC) [5–9] In summary, GAC has been well accepted by the scientific com-
evolved from the academic sphere to the real world, so there is a munity. However, the change from qualitative to quantitative
tremendous research activity on greening all aspects concerning the observation of the green character of analytical methodologies has
analysis of any kinds of sample, not only those for environmental evolved much more slowly than the scientific production in the field.
studies. We are absolutely convinced that GAC will be really useful In this sense, Life Cycle Assessment (LCA), a holistic tool encom-
in the years ahead. The application of cheap, fast and environmen- passing all environmental exchanges (i.e., resources, energy,
tally safe procedures in environmental, clinical and food analysis emissions, and waste) occurring during all stages of the life cycle
will improve the quality of life in developing countries [10]. So, it of activities, is a useful tool, especially when applied to products
can be seen that GAC has been the key tool to move from the or services for which the life-cycle concept and its stages are clearly
chemurgical paradigm to the ecological paradigm in analytical chem- defined [12]. An additional semi-quantitative criterion was devel-
istry and to create sustainable tools for challenges in the increasing oped by the Green Chemistry Institute (GCI) of the American
Chemical Society (ACS). The criterion was applied to the National
Environmental Methods Index (NEMI), a free Internet-searchable
* Corresponding author. Tel.: +34 96 354 4838; Fax: +34 96 354 4845. database of environmental methods [13]. The profile criterion was
E-mail address: [email protected] (M. de la Guardia). based on four key terms concerning reagents employed as:

http://dx.doi.org/10.1016/j.trac.2014.12.011
0165-9936/© 2014 Elsevier B.V. All rights reserved.
 S. Armenta et al./Trends in Analytical Chemistry 71 (2015) 2–8 3

ANALYTICAL CHEMISTRY PARADIGM

CHEMURGY
ECOLOGICAL
Maintenance of
main features Green Analytical Parameters
ACCURACY
SENSITIVITY
Additionally

GAC
SELECTIVITY
than
PRECISSION

only
considered
Incorporation of
REDUCTION OF SIDE EFFECTS
• COST Operator REDUCTION OF COSTS
• SAFETY
• SPEED Environment

Fig. 1. Green Analytical Chemistry: shift from chemurgical paradigm to ecological paradigm.

(1) persistent, bioaccumulative and toxic (PBT); 2. Greening analytical procedures

(2) hazardous;
(3) corrosive; and, Remote sensing and direct measurements on untreated samples
(4) the amount and the nature of waste. are the green dream of analysts and many strategies have been
developed for the analysis of target compounds based on the use
A similar criterion includes energy as a key point to be consid- of spectroscopy and electroanalytical signals [17] and image pro-
ered [14]. The addition of energy as a criterion is important due to cessing [18]. However, in most analytical methodologies, sample
the high reliance on non-renewable resources for production of elec- treatment is an unavoidable step and the use of a classical meth-
trical energy. odology, similar to that in Fig. 2 (sampling, sample transport and
In recent years, an ecological scale was developed for the eval- sample preparation before the acquisition of analytical measure-
uation of analytical methods based on the introduction of penalty ments) is absolutely necessary. Typical sample-treatment methods
points [15]. According to it, a 100 score corresponds to a com- include homogenization, filtration, centrifugation, clean-up, analyte
pletely eco-friendly methodology, but subtracting penalty extraction, preconcentration and/or derivatization. On evaluating
points of the method due to the volume and the toxicity of re- the environmental impact of methods, sample preparation is,
agents consumed, energy consumed, emissions, operator hazard by far, the most challenging step regarding both the main
and waste generation. Methods are classified according to the eco- features and the green parameters of the methods. Sample disso-
scale as: lution and analyte extraction involve the use of reagents and
energy, and special care must be taken to select the procedure as
• excellent green analysis (>75 points); simple as possible at room temperature, and the least hazardous
• acceptable green analysis (>50 points); and, reagents. In this context, options for greening methods must be
• inadequate green analysis (<50 points). based on avoidance of the use of toxic reagents and a strong
reductions in consumption of energy and reagents, waste genera-
More recently, a new criterion was proposed to relate the penalty- tion, time taken and operator effort. As a result, minimization and
point values to the volumes of reagents consumed and wastes automation have been the basic tools for greening the analytical
generated using mathematical expressions and to associate the eco- methods.
scale value to a category class (A–G) in a so-called Green Certificate
[16]. 3. Facing the problem of sample treatment

Sample treatment has been the focus of intensive research from

the GAC perspective in the past 20 years, since it is the bottleneck
Table 1 of analytical procedures.
Special issues of journals on Green Analytical Chemistry
It is worth stressing that the sample-preparation step largely de-
Journal Special issue (no. of Year, vol. (no.) termines the quality of the results obtained and is the main
papers) source of systematic errors and random lack of precision of ana-
The Analyst (RSC) Environmentally 1995, 120 (2) lytical methodologies. The sample-treatment step must guarantee
Conscientious Analytical a quantitative recovery of target analytes, avoiding contamination
Chemistry (5)
and providing matrix isolation as far as possible, in order to reduce
Spectroscopy Letters Green Spectroscopy and 2009, 42 (6–7)
Analytical Techniques (18) potential interferences and matrix effects during the measure-
Trends in Analytical Green Analytical Chemistry 2010, 29 (7) ment step.
Chemistry (10) We should notice that there is no universal sample-preparation
Analytical and Bioanalytical Green Analytical Methods 2012, 404 (3) technique suitable for all types of sample, and that sample prepa-
Chemistry (7)
ration depends on the matrix, the nature of analytes and the final
4 S. Armenta et al./Trends in Analytical Chemistry 71 (2015) 2–8

SAMPLE

Sampling Avoid as many as possible steps

Remote Sensing
To do
Sample Direct determination
transport

Sample sample dissolution

MODELS

preparation
analyte extraction

Measurement Calibration
Avoid the use of toxic reagents
Alternatively the energy consume
Reduce reagents consume
Data
through waste generation
• AUTOMATION
• MINIATURIZATION
micro extraction
Fig. 2. Strategies for greening an analytical method.

measurement mode. Moreover, an appropriate method for a target using immiscible solvents or solid phases, suitable to extract the
analyte may not be good for comprehensive screening of compounds. analytes selectively.
In recent years, sample-preparation methodologies evolved from In short, there are several strategies proposed in the literature
hard strategies to soft methods based on room-temperature, for analyte extraction [27,28], involving liquid-liquid extraction (LLE)
ultrasound-assisted leaching [19–21] or microwave-assisted diges- [29–31] and solid-phase extraction (SPE) [32,33]. LLE and SPE are
tion using closed systems [22–24], so providing a fast, safe the most widely used techniques for the extraction of liquid samples.
methodology, especially for sample digestion and sample dissolution. In the first type, an appropriate selection of the extraction solvent
Analyte extraction has the double purpose of matrix isolation permits removal of the analyte from the original solution to the new
and analyte preconcentration, and the appropriate selection of sol- phase, directly or after a previous derivatization.
vents and reagents and the control of the preconcentration process From our point of view, SPE is probably the best option to improve
are absolutely necessary in order to: analyte concentration and to separate it from a complex matrix. Gen-
erally, SPE consists of four steps:
• separate quantitatively the target analyte from the matrix; and,
• increase the concentration level of the target analyte in the final • column conditioning;
solution to be measured. • sample loading, which implies analyte retention into the solid
phase;
Sometimes, solid samples are difficult to analyze due to the need • column post-wash; and,
to transfer the target analytes to a liquid phase. Leaching the analyte • analyte elution from the solid phase using an appropriate solvent.
(i.e., solid–liquid extraction or lixiviation) is one of the easiest, most
widely used sample treatments. Classically, leaching has been widely The most common design applied in SPE is the polypropylene
carried out by maceration, based on the correct choice of solvents cartridge with placed sorption phase, which varies in size from
and the use of room temperature or controlled temperature and/ micro-sized disks in 1 mL syringes to 6 mL syringes. SPE can manage
or agitation to increase the solubility of compounds and the rate relatively high volumes of samples for analyte preconcentration being
of mass transfer. In general, heating the system increases the solu- suitable to be eluted on-line with microliters of an appropriate
bilization power of the reagents or solvents used, but involves solvent to do their determination.
environmental side-effects (i.e., energy consumption). Despite the The sample-preparation step can be performed off-line, at-line
extensive use of leaching, it is characterized by long extraction pro- or on-line. At-line procedures are performed with a robotic system
tocols with low efficiency. or autosampler and no manual preparation is required, which is the
In 1879, Franz von Soxhlet developed Soxhlet extraction, which case for off-line systems. On the other hand, on-line procedures
is the most widely used leaching technique [25]. Soxhlet extrac- combine directly the sample-preparation step with the measure-
tion is a primary reference against which performance in new ment mode, usually via a multiport valve.
leaching methods is measured. It is still an attractive option for
routine analysis because of its general robustness and relatively low 4. Green extraction solutions
cost. The Soxhlet system is simple and easy to use, and it enables
the use of a large amount of sample (i.e., 1–100 g). However, the Fig. 3 shows, as a scheme, the different variables to be consid-
main drawbacks are long extraction times and large amounts of ered on greening the extraction steps which, in short, involve the
solvent required, which also mean that the solvent must be evapo- nature and the amount of reagents used and the reduction of the
rated to concentrate the analytes before their determination [26]. energy employed for extraction.
However, when samples are water or aqueous solutions with a As it has been mentioned above, leaching of the analyte from a
complex matrix (e.g., wastewater or seawater, body fluids or juices) solid sample is one of the easiest and most widely used sample treat-
it can be necessary to move from the original solution to a new phase ments. As a consequence, a variety of sample-preparation methods
 S. Armenta et al./Trends in Analytical Chemistry 71 (2015) 2–8 5

SOLVENT
SAMPLE
PRESSURE

TEMPERATURE
analyte
SOLVENT

L-L EXTRACTION DERIVATIZATION?

SHAKING
SAMPLE SOLID PHASE

SPE ELUTION SOLVENT

ENERGY?

analyte sample MEMBRANE

membrane

MEMBRANE-MEDIATED ACCEPTING SOLUTION

accepting solution ENERGY?

Fig. 3. Aspects to be considered on greening extraction procedures.

have been developed over the past decades with the objective to namely, they use only microvolumes of organic solvent and thus
improve the extraction performance as well as to reduce overall comply with the requirements of GAC. Another reported LLME
analysis time and cost. Recent developments based on ultrasound- technique, is continuous flow microextraction (CFME). In this
assisted treatments [34,35] enhance the solid-liquid equilibrium, method, the extraction-solvent drop is injected into a glass chamber
reducing the extraction time. Ultrasonic energy causes an effect by a conventional microsyringe and held at the outlet tip of a PTFE
known as cavitation, which generates numerous tiny bubbles in connecting tube, the sample solution flows right through the tube
liquid media and mechanical erosion of solids, including particle and the extraction glass unit to waste, the solvent drop interacts
rupture. Sonication provides an efficient contact between the solid continuously with the sample solution and extraction proceeds si-
and the extractant, usually resulting in a good recovery of the analyte multaneously [48]. In recent years, there has been developed the
[36]. directly-suspended droplet microextraction technique (DSDME) [49]
On the other hand, there are no doubts on the need for a quan- in which a small volume of an immiscible organic solvent is added
titative evaluation of the energy requirements of extraction steps to the surface of the gently stirred aqueous solution. The vortex
and it is one reason to look for greener alternatives to traditional results in the formation of a single droplet at or near the center of
Soxhlet [37]. Pressurized liquid extraction (PLE), also named accel- rotation.
erated solvent extraction (ASE) [38–40] and microwave-assisted Additionally, the use of membrane-mediated [50] extraction tech-
extraction (MAE), can be used instead of Soxhlet for the extrac- niques can favor analyte-extraction processes and move it from the
tion of organic compounds, providing a clear improvement of the original sample to an accepting solution ready to be employed for
extraction processes based on a dramatic reduction in time and tem- analyte measurement. As indicated in Table 2, it involves a simul-
perature and solvent requirements. taneous two-step process and a medium preconcentration, when
Moreover, different alternatives combining the different strate- used on a closed circuit of the accepting phase, which can be rel-
gies previously commented have been developed to overcome the atively easy automatized based on flow-injection analysis (FIA) [51],
main drawbacks of Soxhlet extraction. For instance, high-pressure sequential injection analysis (SIA) [52] or the use of automated
Soxhlet extraction in which the extractants do not reach supercritical syringe systems [53].
conditions and the time required and the solvents consumed are Interesting alternatives to the use of classical organic solvents
dramatically reduced [41]. The combination of Soxhlet and as extraction media have been provided based on ionic liquids
ultrasound-assisted extraction has been developed to take advan- [54–57], agro-solvents, like alcohols or terpenes [58], or the use of
tage of both methodologies and reduce the number of Soxhlet cycles, surfactant solutions [59,60]. The aforementioned procedures provide
greening the methodology [41]. specific solutions for greening classical extraction methods based
Of the attempts to improve Soxhlet performance, the most suc- on the use of alkanes, aromatic hydrocarbons or chlorinated sol-
cessful has been the use of microwaves, being the microwave- vents. However, the deleterious effects of those alternative solvents
assisted Soxhlet extraction the most interesting improvement of are not well known or understood, especially in the case of ionic
conventional Soxhlet extraction [41]. The main limitations over-
come by this approach are the long extraction time periods, the
possibility to automate the procedure and the ability to quantita-
Table 2
tively extract strongly retained analytes.
Comparison of analyte-extraction strategies
On the other hand, the LLE procedure is suitable to be minia-
Liquid-liquid Membrane mediated Solid
turized as, for example, based on the single-drop extraction strategies
[42–45], dispersive liquid–liquid microextraction (DLLME) [46] and Low preconcentration level Medium preconcentration High preconcentration
hollow-fiber liquid-phase microextraction (HF-LPME) [47]. These Single step Simultaneously two steps Two separate steps
Easy automation Relatively easy automation Very easy automation
methods differ in design, but they all have one common feature:
6 S. Armenta et al./Trends in Analytical Chemistry 71 (2015) 2–8

liquids, and must be taken into account in order to identify clearly for the elution of analytes retained on solid phases and, because of
the strengths, the weakness, the opportunities and the threats of that, headspace-based methodologies have been developed for SPME
the alternative extraction process. analysis of volatile and semi-volatile compounds by gas chroma-
Recent advances in SPE extraction involve the evolution of tography (GC) [73–75]. Those procedures can be considered a serious
formats, sorbent types and modes of interaction [61]. Typically, a alternative to the use of solvents in extraction processes and they
commonly utilized format is a polypropylene cartridges consist- should be seriously evaluated in order to quantify the amount of
ing of a 20 μm frit, made of polyethylene or polytetrafluoroethylene, energy consumed and, thus, their environment-friendly character.
at the bottom of the syringe with the relevant sorbent with an In any case, it is clear that the replacement of classical extrac-
additional frit at the top. Alternatives to SPE cartridges include tion procedures with microextraction techniques does not imply only
disks, the SPE pipette tip, 96-well SPE microtiter plates and also a change of scale. It is a new concept in which the amount of sample
small columns, which can be on-line connected to a liquid chro- and reagents used substantially decreases and the speed and
matography (LC) system. From a green perspective, on-line SPE is sustainability of methods are improved. The main trouble is that
preferred. Usually, when it is coupled to a liquid chromatograph, reduction in the sample size can affect the representativeness of an-
it consists of a small pre-column placed in a six-port high- alytical data, especially in the case of the analysis of highly
pressure switching valve. During injection, the sample is pre- heterogeneous samples.
concentrated on a pre-column and later the analytes are eluted
onto the analytical column by valve switches. The main advan- 5. Future trends in green extraction
tages are higher throughput and limited manual processing, as
well as low cost. Pioneering efforts in the automation of extraction procedures
An alternative to SPE is the quick, easy, cheap, effective, rugged through FIA have been demonstrated to be one of the best ways to
and safe (QuEChERS) extraction method [62], which involves reduce operator risks and to avoid environmental side-effects by re-
the extraction of analytes from a homogenized sample using ducing consumption of reagents and generation of waste. However,
an acetonitrile and salt solution and the clean-up of the superna- the microscale of FIA procedures was not enough to assure their
tant using a dispersive SPE (dSPE) technique. This QuEChERS sustainability. Additional efforts in recent years on miniaturiza-
approach offers a user-friendly alternative to traditional LLE tion of extraction also offered an interesting way to improve the
and SPE. greenness of analytical procedures. Recent developments on
The idea of scaling down SPE has led to the development of microfluidic systems [76] and on-chip μSPE include the use of dis-
analytical microextraction procedures. Those methods can be defined posable sorbents using mesofluidic platforms [77], which open new
as non-exhaustive sample-preparation steps using a very small possibilities to green analytical methodologies. So, it is clear that
volume (microliter range or smaller) of extracting phase (solid, semi- in the years ahead much more effort will be made to link these ap-
solid polymeric or liquid material), relative to the sample volume. proaches, which can also be improved by clever selection of the
The field of microextraction gained in significance with the in- phases, solvents and solid, employed in the preconcentration steps
vention of solid-phase microextraction (SPME) in 1990 [63], which to guarantee the inert character of residues and to consume as little
later, in 1993, became commercially available. In this technique, a energy as possible.
small amount of extracting phase dispersed on a solid support, nor- One of the key factors in evaluating the sustainability of the dif-
mally, a fused-silica fiber or a metal core, is exposed to the sample, ferent methodologies proposed concerns the correct evaluation of
or its headspace, for a well-defined period of time. environmental risks regarding reagents, wastes and the energy
The several implementations of SPME include mainly open-bed employed. Those factors must be balanced in order to provide si-
extraction concepts, such as agitation mechanism [i.e., stir-bar sorp- multaneously the best analytical features and the smallest
tive extraction (SBSE), stir-rod sorptive extraction (SRSE), stir-cake environmental side-effects. As indicated previously [78], the
sorptive extraction (SCSE), rotating-disk sorptive extraction (RDSE)], greenest methodology is that suitable to solve an analytical problem
dispersed particles into the solution, also called dispersive SPME with the minimum environmental impact, but stress must be placed
(DSPME), and needles. In the last case, in-needle SPME, solid- on the first part of this sentence – finding the solution to the
phase dynamic extraction (SPDE), microextraction by packed sorbent problem.
(MEPS), microextraction in a packed syringe, and fiber-packed- Concerning the reagents used in the extraction steps, efforts
needle microextraction (FNME) have been proposed [64]. should also be made in evaluating new solvents (e.g., agro-solvents,
Novel designs for the SPME include membrane SPME (M- ionic liquids or surfactant solutions), other organized media {e.g.,
SPME) [65], which involved physical separation between the polar crown [79] and crypta ethers, and calixarenes) and lipidic struc-
extraction medium and the analyzed sample by means of a mem- tures (e.g., liposomes and vesicles). The development of new solid
brane. Another membrane-based procedure is polymer-coated phases suitable for use in the selective extraction of target analytes
hollow-fiber membrane (PC-HFM), a simple and inexpensive ex- {e.g., imprinting solid phases [80] and nano-materials [81–83]} will
traction technique that involves coupling HFM with SPME and SBSE contribute to improving the analytical features of the methods and
technology [66]. Another extraction method, membrane extrac- to reducing dramatically the amounts of reagents and energy used.
tion with sorbent interface (MESI) [67], consists of a permeable So, we must be optimistic about the future, and, once again, it will
silicone membrane coupled with an adsorbent trap for sampling be demonstrated that GAC can be a driving force to expand basic
and concentration of organic compounds. research in analytical chemistry, to make an ethical commitment
The use of electrochemically-aided SPME in analytical practice to the environment and to reduce the cost of the analytical methods,
has also been reported [68]. However, this particular technique has thereby contributing to the sustainability of laboratories and
very low extraction efficiency and cannot be coupled to a chro- enterprises.
matographic system, so a new variant, electrosorption-enhanced
SPME (EE-SPME) [69], was proposed in 2007. Advances in Acknowledgements
electrochemically-assisted solid-based extraction techniques were
recently reviewed [70]. Authors acknowledge the financial support the Ministerio de
Special attention must be paid to developments in solvent-free Economía y Competitividad (Project CTQ2011-25743 and Project
extraction methods for sample preparation and analyte separa- CTQ2012-38635) and Generalitat Valenciana (Project PROMETEO-
tion [71,72]. The use of thermal desorption systems is a good option II 2014-077).
 S. Armenta et al./Trends in Analytical Chemistry 71 (2015) 2–8 7

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