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Bulgarian Chemical Communications, Volume 44, Number 1 (pp.

5 10) 2012

Green analytical chemistry and its perspectives in Bulgaria


E. H. Ivanova, A. K. Detcheva
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 11 Acad. G. Bontchev Str., 1113 Sofia,
Bulgaria

Received: March 17, 2011; accepted: April 3, 2011

The concept of green chemistry emerged in the 1990s with the aim of minimizing the environmental impact of
chemical activities. The basic principles to which a chemical procedure should correspond in order to be recognized as
environmentally friendly (green) are reviewed. These include reduction of reagent and solvent usage, minimization of
solid, liquid and gaseous materials, produced by the processes involved, reduction of energy and water consumption.
Special emphasis is put on the features of green analytical chemistry, the challenges to the introduction of green
principles to analytical laboratories, the assessment of the environmental impact and the waste management. The
present state and the perspectives of green analytical chemistry in Bulgaria are discussed with an emphasis on the
contributions of Bulgarian researchers in this field.
Key words: green analytical chemistry, basic principles, perspectives in Bulgaria, review.

This article is dedicated to the memory of Professor Dr. Nikolay Jordanov on the occasion of his 90 th anniversary.

components. First, it addresses the problem of


SUSTAINABLE DEVELOPMENT AND GREEN efficient utilisation of raw materials and
CHEMISTRY concomitant elimination of waste. Second, it deals
In 1987 the World Commission on Environment with the health, safety and environmental issues
and Development defined sustainable development associated with the manufacture, use and disposal
as a form of development that meets the needs of or re-use of chemicals. The activities in the area of
the present generation without compromising the green chemistry should meet two goals [1]:
ability of future generations to meet their own x teaching of basic aspects of environmental
needs [1]. One of the major goals of sustainability science at all levels of education, resulting in the
is to maintain an optimal balance between increases production of specialists, capable of handling and
in manufacturing output, and a clean and safe solving existing and potential environmental
environment. In the 1990s the concept of green problems;
chemistry emerged with the aim of minimizing the x creating a fresh approach to typical chemical
environmental impact of chemical activities. In activities, leading to the environmentally more
their book Green chemistry published in 1998 friendly use of facilities.
[2], P. Anastas and R. Warner defined the
principles to which a chemical procedure should GREEN ANALYTICAL CHEMISTRY
correspond in order to be recognized as An important part of the green chemistry
environmentally friendly. These include reduction philosophy is the need to develop and adopt green
of reagent and solvent usage, minimization of solid, analytical techniques and procedures. Analytical
liquid and gaseous materials, produced by the chemistry takes a special place in the green
processes involved, reduction of energy and water chemistry concept. It is aimed to detect and
consumption. Environmentally friendly (green) quantitatively determine various substances by
chemistry has received widespread interest in the means of methods which often use harmful
past two decades due to its ability to harness reagents. As a result, the analysis itself may
chemical innovation to meet economic and become a source of pollution. Analytical chemistry
environmental goals simultaneously [37]. is considered to be a small-scale activity, but this is
Green chemistry embodies two main not always true in the case of controlling and

* To whom all correspondence should be sent:


e-mail: eliva@svr.igic.bas.bg 2012 Bulgarian Academy of Sciences, Union of Chemists in Bulgaria 5
E. H. Ivanova et al.:Green analytical chemistry and its perspectives in Bulgaria

monitoring laboratories with a large number of runs issue was dedicated to green analytical techniques
performed. The use of instrumental methods instead in the spectrometric analysis of environmental and
of wet chemistry; the miniaturization and biological samples [11], simple alternatives for
automation are the new trends of analytical sample pretreatment and analyte determination
chemistry, making this branch of chemistry more [12], alternative solid sample pretreatment methods
sustainable [8]. The determination of a broad in green analytical atomic spectrometry [13], a.o.
spectrum of analytes at low concentrations (ppb, The most common method of sample
even ppt) in samples of complex matrix introduction in atomic spectrometry is via a
composition has been facilitated by the introduction solution despite the fact that the large volume of
of a new generation of highly sensitive analytical solvent compared to the analyte may present
devices and by the development of new sample problems to the atom cell: decrease in temperature,
preparation procedures. The main features of green increase in the time of atomization, etc. The use of
analytical chemistry are [9]: a thermospray sample introduction system is a way
x elimination or significant reduction of reagents, to remove or considerably reduce the solvent in a
especially toxic substances and organic solvents solution prior to its delivery to the atom cell. This
from the analytical procedures; can minimize potential interferences and improve
x reduced emissions of vapors and gases, as well the accuracy and precision of the analysis, as well
as liquid and solid wastes, generated in the as reduce the amount of waste [14,15].
analytical laboratories; Solid sampling spectroscopy strongly
x reduced labor, energy and water consumption contributes to the development of green analytical
of the analytical procedures; chemistry methodologies. Direct solid sampling
x reduced time between sampling and obtaining methods of atomic spectrometry are particularly
of the desired information about the sample. useful for the analysis of materials that need
x The challenges to the introduction of sophisticated and time-consuming decomposition.
sustainable development (green) principles to Only several milligrams of the sample are
analytical laboratories are related to: consumed; contamination and loss hazards are
x preferable use of direct methods of analysis; brought to the minimum, no reagents are needed
x simplification, intensification and acceleration and there are no wastes. A number of direct solid
of the sample preparation procedures; sampling methods of atomic spectrometry are
developed and optimized for the trace and
x miniaturization, integration and automation of
microtrace analysis in various matrices like
the analytical systems;
industrial materials, plants, plastics, foods, etc. [16
x assessment of the environmental impact of the
23]. Slurry sampling is another highly efficient
analytical procedures.
green approach of atomic spectrometry, applicable
The challenges are magnified when trace
to the trace element analysis in solid samples by
analysis and particularly microtrace analysis is
flame AAS, electrothermal AAS, total reflection X-
concerned.
ray fluorescence spectrometry (TXRF) and other
Methods of analysis spectroanalytical techniques [2431].
The development of direct instrumental methods There are several benefits of using field analysis
is a general trend in analytical chemistry resulting to reduce environmental impact. Along with better
in time saving and waste reduction. Optimization of efficiency and financial profile, field techniques
instrumental methods is often related to a decrease allow for analysis and data collection to be
in sample volume needed for analysis. In some conducted on-site. As an example the field portable
cases, there is a choice of direct techniques of X-ray fluorescence (XRF) facilities for analysis of
analysis which may be defined as green processes, environmental samples may be mentioned [32, 33].
especially when the method is automated and uses a Energy dispersive XRF has found application as a
minimal amount of sample. field analysis method for the determination of trace
Presently, spectroscopic methods dominate the and microtrace element contents in a large variety
area of green analytical chemistry [10]. A special of samples like objects of arts, industrial materials,
issue of Spectroscopy letters appeared in 2009 as an as well as for in-vivo measurements [3438].
attempt to put green spectroscopy in the first line of
the objectives of the spectroscopy community. The

6
E. H. Ivanova et al.:Green analytical chemistry and its perspectives in Bulgaria

Sample preparation methods methods, if the use of toxic reagents cannot be


avoided, the involved amounts should be
Direct methods of analysis are although
minimized. This approach also has the advantage of
preferable, but not always available, particularly in
reducing operational costs, including those spent on
the case of microtrace analysis in samples of
waste treatment and disposal [24]. Promoting clean
complex matrix composition. In these cases sample
methodologies in environmental remediation is the
preparation procedures are unavoidable. Sample
best way to address future challenges [68].
preparation has three main functions [39]: (i)
The use of organic solvents in separation and
digestion/dissolution of the sample; (ii)
preconcentration methods is the main source of
preconcentration of the analytes; and (iii)
organic waste. The search for alternative solvents is
separation of the analytes from the matrix
an important step in making an analysis greener
components.
and environmentally friendlier. Moreover,
The choice of a separation/preconcentration
alternative solvents like supercritical fluids and
procedure depends on the particular analytical task
ionic liquids are even more attractive due to the
method of analysis, type of analytes and matrix,
possibility of varying their properties like
required level of sensitivity, accuracy and precision
solubility, polarity or volatility. Using supercritical
of the analysis, loss/contamination hazards. Some
fluids instead of organic solvents is becoming
of the most popular separation/preconcentration
popular for most liquid-liquid extractions,
techniques are liquid-liquid extraction,
especially when supercritical water or CO2 are used
precipitation/co-precipitation and solid phase
as solvents [8,69]. The application of ionic liquids
extraction. These techniques are continuously
is intensifying in many areas of analytical
improved and new techniques are introduced by the
chemistry, particularly in chromatography [70]. The
demand for faster, more cost-effective and
non-volatility and good solvating properties,
environmentally friendlier analytical methods. For
together with a large range of spectral transparency
example, a simple and efficient sample preparation
make them suitable solvents for spectroscopic
procedure was proposed for the flame or
measurements as well [8].
electrothermal AAS determination of trace
During the last two decades cloud point
elements in nails and hair by sample solubilization
extraction has become a versatile and simple
with aqueous tetraalkylammonium hydroxide [40].
alternative to liquid-liquid extraction. In this
Both existing methods and new procedures were
method the organic solvents are replaced with non-
improved by miniaturization and integration to
ionic surfactants [71,72]. Some recent examples for
provide higher sample throughput and/or
the use of cloud point extraction for the
unattended operation using minicolumns, coiled or
preconcentration of metal ions prior to their
knotted reactors, most often in flow injection
spectrometric determination are given in [73-79].
performance [4157]. A modern way of increasing
the selectivity of the separation/preconcentration Green analytical chemistry in Bulgaria
process is the solid-phase extraction using
The analytical laboratories in Bulgaria are
molecularly imprinted or ion imprinted polymers
presently in a process of renovating their
[5861]. The hyphenation (integration) of
methodologies and adapting them to the European
separation and detection, as well as the
norms. This renovation is based on the green
incorporation of microwave or ultrasonic treatment
chemistry concept, recognized as one of the main
considerably contributes to increase the efficiency
tools for reducing environmental pollution. In
and environmental safety of the methods, e.g. [62
Bulgaria, however, this process is at the initial
67].
stage. Nevertheless, some of the methods for trace
element analysis by atomic spectrometry (XRF,
ASSESSMENT OF THE ENVIRONMENTAL
AAS, ICP-OES, ICP-MS), published by Bulgarian
IMPACT AND WASTE MANAGEMENT
scientists, are essentially green analytical methods,
Nowadays, in the development of new analytical e.g., [44, 8093].
procedures, the amount and toxicity of the wastes Recently, two projects in the area of green
are as important as any other analytical feature. analytical chemistry were funded by the National
Miniaturization and automation are explored as Science Fund of Bulgaria. According to the first
approaches for waste minimization. As stated in the one, the GAMA Green Analytical Methods
priority order for establishing of cleaner analytical Academic Centre was created at the University of

7
E. H. Ivanova et al.:Green analytical chemistry and its perspectives in Bulgaria

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(2008).


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Open Access
Austin Journal of Analytical and
Pharmaceutical Chemistry

Special Article - Green Chemistry

Green Analytical Chemistry in Teaching Laboratory:


Spectrophotometric Determination of Fe Ions with Using
Green Tea to Demonstrate the Principles of Sequential
Injection Analysis
Martinovic Bevanda A1*, Tali S1 and Ivankovic A2
Abstract
1
Department of Chemistry, Faculty of Science and
Education, University of Mostar, Bosnia and Herzegovina An interesting, simple and an inexpensive experiment that can be
2
Faculty of Agronomy and Food Technology, University of successfully applied in student laboratory for the course of green analytical
Mostar, Bosnia and Herzegovina chemistry was proposed. The students have goal to design SIA method through
*Corresponding author: Martinovic Bevanda Anita, experiments optimization and finally take advantage of this method in the
Faculty of Science and Education, University of Mostar, analysis of real samples. Optimization procedures of SIA system are suggested
Bosnia and Herzegovina and the achieved results presented. The proposed method, based on reaction
between green tea polyphenols and Fe ions, can allowed the determination
Received: April 28, 2015; Accepted: May 28, 2015; of Fe ions in the concentration range of 410-5 to 410-4 mol/L with sample
Published: May 29, 2015 throughput 122 h-1. The formed stable complex has the absorption maximum at
= 570 nm. This optimized method was successfully applied to the determination
of Fe ions in laboratory samples and pharmaceuticals.
Keywords: Green analytical chemistry; Sequential injection analysis;
Teaching experiment; Green tea extracts; Natural reagents; Spectrophotometry

Introduction The detector should be equipped to accept a solution in flow (eg. flow
cell for spectrophotometry). Let us mention only the basic advantages
The achievements of green chemistry in the years since it provided by SIA: less waste due to a decrease in the consumption
emerged as a cohesive field in the early 1990s has been remarkable.
of the solution of reagents and samples, complete automation and
It is important to recognize the scientific breakthroughs that have
control using software, a simple adaptation to different methods
been made through excellent research as well as through the other
without significant changes of manifold.
elements of education, industrial engagement, and outreach that are
required to provide the broader structure needed to drive the field [1]. In addition, green analytical methodology implies a combination
of flow techniques and reagents from nature, as a green reagents.
The timeframe of green chemistry implies that it is a green area;
however the principles of green chemistry, suggested by Anastas and A symbiotic relationship exists between research and teaching
Warner [2], are well known to the scientific community in the field of aspects of any academic discipline. The next generation of researchers
chemistry. One editorial of this journal [3] is dealing with principles learn their trade in the undergraduate classroom and modern
of green analytical chemistry. Different aspects of green chemistry teaching practices are shaped by current research trends [5].
idea have their foundation in sustainable development and in some
There are numerous possibilities to use natural plant [6-8] extracts
present and future goals of all aspects of human activity.
as a tool in chemical analysis or in education chemical analysis. Several
The ideas of a green chemistry should become part of chemists advantages arises from these approach: many plants to choose, low
and chemical engineers training from the very start. Students of cost or no cost at all, renewable source, simple extraction, less ethical
chemistry programs at university should be guided to develop a conflict, extended teaching/learning topics can be covered [6].
deep consciousness of the importance of sustainability strategies in
chemistry research and industry, and also to develop knowledge and Interestingly, Cucurbira pepo L extracts can be used at optimized
skills to operate them [4]. experimental condition for the synthesis of gold nanoparticles [9].
Also, the group of scientists has proposed educational experiment for
In a special way the application of sequential injection analysis preparation of gold nanoparticles using the extract of black tea leaves
(SIA) can enhance green chemistry experiment or any other [10].
experiment and it can make it greener.
It is obviously from the available literature that very few research
The main components of manifold SIA were injection pump and groups explore the potential of application of plant extracts in
selection valve with ports for support of all solutions involved in the analytical chemistry and in educational chemistry.
analysis. The main characteristic of SIA is the sequential aspiration
of the determined small volumes of solutions to a holding coil and Recently Pinyou and co-workers [11] have developed a new
then flow reversal for the propulsion of reaction zone to the detector. analytical method for determination of iron ions using flow injection

Austin J Anal Pharm Chem - Volume 2 Issue 3 - 2015 Citation: Martinovic Bevanda A, Tali S and Ivankovic A. Green Analytical Chemistry in Teaching Laboratory:
ISSN : 2381-8913 | www.austinpublishinggroup.com Spectrophotometric Determination of Fe Ions with Using Green Tea to Demonstrate the Principles of Sequential
Bevanda et al. All rights are reserved Injection Analysis. Austin J Anal Pharm Chem. 2015;2(3): 1043.
Martinovic Bevanda A Austin Publishing Group

Table 1: The SIA protocol sequence. GTE-green tea extract.


Operation Valve port Volume, L Flow rate,L/min
Stacking of zones:
GTE aspiration 1 300 3500
Sample/standard aspiration 2-9 350 3500
Measurement of absorbance:
Dispense to detector 10 4000 3500

computer and using UVmini-1240 data manager software and


plug-in memory card with kinetics program both from Shimadzu
(Shimadzu, Kyoto, Japan). M6-LHS -M6 Liquid Handling Software
(Valco Instruments, Houston, Texas, USA) has been used for writing
Figure 1: Sequential injection system. A-Siringe pump, B-Selection valve,
C-holding coil, D-reaction coil; S-UV-Vis Spectrophotometer with flow cell (V sequences of analysis and for the pump and the valve control. All used
= 80 L), W- waste. tubing were PTFE tubing of 1/16 OD and 0.75 mm ID supplied by
VICI (Valco Instruments, Houston, Texas, USA)
analysis and natural reagent extracted from green tea. It seemed
interesting to apply and adjust this experiment for teaching analytical Recommended procedure for optimization SIA system
chemistry in our undergraduate laboratory. The SIA system with Before beginning of the analysis, all reagents and samples/
spectrophotometric detector in combination with the extract of green standards must be aspirated in holding coli (HC), and washed from
tea as natural chromogenic reagents was used for determination HC dispensing carrier with flow reversal. This is necessary for filling
of Fe (III) and Fe (II). This green analytical method is based on all flow lines.
formation of Fe-polyphenol complex that was monitored at 570 nm.
The optimization experiments were performed following
The suggested experiment can be divided in two experimental parts.
sequences that had been written using the software (mentioned
The first one is the optimization of the SIA system. The second one
above) M6-LHS.
is the application of the optimized method in the analysis of the real
samples. For the successful work in laboratory it is important to get Briefly described steps to be taken during the optimization
familiar with all the principles earlier, that the experiment is based on procedure are:
and the cooperation of students with their instructor.
Valve position 1: At a selected flow the injection pump aspirates
Experimental some volume of the green tea extract into the holding coil.
Reagents and chemicals Valve positions 2-9: At a selected flow the injection pump
Standard solutions, 100 mL each of 0.1 M Fe(II) and Fe(III) were aspirates the solution of the standard Fe ions into the holding coil.
prepared by dissolving 3.9214 g Fe(NH4)2(SO4)26H2O and 4.8219 Valve position 10 (detector line): With flow reversal the pump
g Fe(NH4)(SO4)212H2O, respectively, in deionized (DI) water dispense 5 mL of the carrier solution (acetate buffer, pH = 4.8) and
containing 1 % (v/v) concentrated H2SO4. Green tea is purchased during this process it drives reagent and standard zones from the
from local stores. Extract (GTE) suspension was prepared with 4.0 g holding to the reaction coil and subsequently to detector.
green tea from tea bags, in 150 mL acetate buffer (0.2 M, pH = 4.8)
[11]. The suspension was shaken for 20 min. Then, the suspension After optimization experiments, obtained results can be used for
was filtered and diluted to a volume of 500 mL with acetate buffer determination of Fe ions in real samples. In Table 1 are presented the
(pH= 4.8). The extract was prepared daily. SIA protocol sequence (steps of analyses, injection volume and flow
rate) that can be applied for analysis of real samples.
Sample solutions preparation. Twenty tablets were accurately
weighed and ground. A portion of powder was weighted and mixed Results and Discussion
with DI water, concentrated HCl, then was boiled and it was allowed The well-known principles of established green method were used
to cool down to room temperature and diluted to 1000 mL with water. as a starting material for the optimization of SIA system. This teaching
The mixture was filtered. The aliquot of the filtrate was transfered to experiment has so popular story about green tea polyphenols that can
a 25 mL volumetric flask. Hydrogen peroxide (0.3 mL) was added, to attract the interest of students for analytical chemistry experiment for
ensure the complete oxidation of Fe(II) to Fe(III). development and optimization of SIA system. The obtained results
Aparatus will certainly be inspiring for the discussion upon completing the
The system for sequential injection analysis is illustrated in Figure experiment.
1. It was constructed from syringe pump M6-Pump VICI (Valco Optimization of the SIA system
Instruments, Houston, Texas, USA), a 10-port electrically actuated Before laboratory experiments and during discussions with their
selection valve C25- 3180EMH Cheminert (Valco Instruments, instructors students are made familiar with the well-known principles
Houston, Texas, USA), a Shimadzu UV mini-1240 (Shimadzu, described previously (preparation of the green tea extract, influence
Kyoto, Japan) UV-Vis spectrophotometer equipped with a flow of possible interferences, reagent stability) [5]. Moreover, students
cell (Hellma, Mllheim, Germany) of 80 L internal volume and 10 have to become familiar with different application possibilities and
mm optical path. Spectrophotometric data acquisition and control principles, which the system for the sequential injection analysis is
of measurement were achieved by coupling detector with personal based on.

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Martinovic Bevanda A Austin Publishing Group

Table 2: The parameters optimized by the teaching experiment and values that
are chosen as optimal.
Parameter /Optimization range Suitable condition

Volume of GTE, 200-400 L a,b,c,e 300 L

Volume of standard Fe , 80-400 L a,b,d,e


350 L
Holding coil, 50-200 cm a,b,c,d,e 200 cm
Reaction coil, 50-200 cm a,b,c,d,e 50 cm
Flow rate, 2000-5000 L/min a,c,d,e, 3500 L/min
Experimental condition: a. c{Fe(III)} = 110 M; b. Flow rate: 2000 L/min;
-4

c. V(Fe(III)) = 100 L; d. V (GTE) = 300 L; e. Volume of flow cell: 80 L.

expected to get the concentration gradients (peaks) with narrower


bases by increasing the flow-rate. Likewise, the height of peak is also
increased by increasing the flow-rate. The optimal one is the flow-rate
at which the maximal absorbance is recorded. Also, it can observe
the reduction of the recorded absorbance in flows-rate greater than
the optimal one. The recomended tested flow-rates range for this
optimization experiments is 2000-5000 L/min
The characteristic of the SIA system is the holding-coil in which
Figure 2: In holding coil. GTE-green tea extract. the sample and reagent zones disperse. The flow direction is changed
in the holding-coil, the mixing of zones is more successful, but
System for sequential injection analysis (SIA) shown in Figure 1 dispersion is also increased. The holding coil with a optimal length
was used for the optimization experiment and for the determination of gave the optimal result, implying: accommodation of the stacks of the
iron ions with the green tea extracts (GTE). This spectrophotometric sample and the reagent zone, initial dispersion, stable base line due to
method was based on the reaction of the formation of stable complex an uncontaminated carrier. The formation of complex is practically
between Fe ion and polyphenols from green tea extract. The advantage instantaneous, and higher peaks can be obtained with a shorter coil
of SIA was injection of certain volume of analyte (Fe ions) and reagent length due to less dispersion. At optimization of the holding-coil
(GTE) in the holding coil at a selected flow. Zone of iron solution was length the compromise between the reaction kinetics and dispersion
injected next to the zone of the solution of GTE. Zone dispersions has to be entirely achieved, which results in the maximal recorded
begin from the moment of injection solution of reagents and analyte absorbance and increases the method sensitivity. Generally, at
in the holding coil (Figure 2). Flow reverse, oriented towards the optimal length of the holding coil the concentration gradients with
detector, promote mixing (zone dispersion) of sample and reagent narrower bases were recorded. A longer reaction coil can increased
zone, increasing amounts of formed complex which absorbs at the residence time of the complex, while increasing the dispersion
the wavelength of = 570 nm. The optimization of variables that and decreasing the peak heights. The holding and reaction coils
significantly affect the SIA system included: the injection volumes, length can be tested over the range of 50.0 200.0 cm.
carrier flow-rate, holding coil and reaction coil lengths.
In the optimization process of the SIA system it is important to
The SIA method sensitivity is determined by dispersion degree consider the influence of the internal diameter of the tubes in which
of the reagent and sample zones under the flow conditions. The the flow is in progress, the shape of the holding coil, and the whole
influence of the injected volumes on method sensitivity can be tested length of the system. The internal diameter of the tubules, which the
in determining Fe ions in solutions at the concentration, c {Fe (III)} used SIA system is composed of, is adjusted to the dimensions of the
= 1 10-4 mol / L. During the measurement different volumes of valves and injection pump and it is = 0.75 mm. In order to reduce
reagent solutions (GTE) and analyte were injected. Under the flow dispersion even more, the holding coil can be spirally coiled around
conditions these zones disperse, get mixed and amount of the formed a solid base of a specific diameter, = 10.0 mm. The total length of
complex increase. Furthermore, by increasing the volume of reagents the tube system determines, as well, the total volume of the carrier
and analyte, the amount of species mutually reacting is also increased, solution, needed for enabling the flow of the overlapping zone by
which results in greater amount of the formed complex and greater the means of the system through the detector. The properly chosen
recorded absorbance. However, at a specific combination of volumes volume of the carrier solution, flowing through the flow system
a considerable dilution can be expected as a consequence of dispersion between the two sequences enables the quality of the system rinsing,
and the concentration of the absorbing species is decreased in the differentiation of signals of the two measurements, the return to the
overlapping zone and proportionally the measured absorbance is baseline, and determining the next sample without the contribution
decreased as well. The volumes of Fe ions solutions in range of 80-400 of analyte remained from the previous measurement.
L and volumes of GTE solution in range of 200-400 L can be tested.
In table 2 is presented an overview of the parameters optimized
Flow-rate can control dispersion proces, enhance sensitivity of by the teaching experiment and of values that are chosen as optimal.
methods and sample throughput. At higher flow-rates the dispersions After the optimization of the SIA system it is important to get the
of reagent and sample zones decrease, which is manifested by the good method sensitivity, to decrease dispersion and to improve the
change of the shape of the concentration gradient (peak). It is measurement dynamics.

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Martinovic Bevanda A Austin Publishing Group

Table 3: Linear regression equation and figures of merit for Fe (II).


Linear regression equation R2 LDR, mol/L Detection limit, mol/L Determination limit, mol/L

A=652.09c(Fe(II)) + 0.0183 0.9992 4 10 - 4 10


-5 -4
5.2910 -6
1.7610-5

Table 4: Results obtained for determination of Fe(II) in pharmaceuticals n = 3. of analytical chemistry in under graduate studies and also in quality
Sample Labeled amount, mg Determinated SD, mg Recovery, % control laboratory for determination of Fe ions in pharmaceuticals.
Heferol 115 112.70 0.005 98.00 The applied method meets basic principles of green chemistry.
Retafer 100 96.08 0.003 96.08 References
1. Anastas Paul T, Beach Evan S. Green chemistry: the emergence of a
Analytical application of the optimized SIA system transformative framework, Green Chem Lett Rev. 2007; 1: 9-24.

The high of the concentration gradient (signal) is changed by 2. P T Anastas, J C Warner. Green Chemistry: Theory and Practice, Oxford
changing the concentration of Fe ions, that is, the recorded absorbance University Press, New York (1998).
is increased by increasing the concentration. The obtained piks have 3. Samanidou Victoria F. Pharmaceutical Analysis from a Green Perspective.
to be sharp and repeatable. Under the optimal conditions the linear Austin J Anal Pharm Chem. 2014; 1: 1016.
dynamic range of concentrations is obtained, in which Fe (III) ions 4. Eilks I, Rauch F. Sustainable development and green chemistry in chemistry
can be determined by the application of the SIA system: 4 10-5 education. Chem Educ Res Pract. 2012; 13: 5758.
mol/L to 4 10-4 mol/L. The optimized SIA system allows sample 5. Andraos J and Dicks Andrew P. Green chemistry teaching in higher education:
throughput of 122 h-1. a review of effective practices. Chem Educ Res Pract. 2012; 13: 69-79.

The equation of the calibration line, R2 and the limits of detection 6. Kradtap Hartwell S. Exploring the potential for using inexpensive natural
reagents extracted from plants to teach chemical analysis. Chem Educ Res
and determination are presented in the table 3. Pract. 2012; 13: 135146.
The method is tested in the pharmaceutics analysis. Regarding the 7. Grudpan K, Kradtap Hartwell S, Lapanantnoppakhun S and McKelvie I. The
fact that pharmaceuticals contain Fe (II) ions, the amount of 0.3 mL case for the use of unrefined natural reagents in analytical chemistryA
H2O2 was added into the working solution of the sample, in order for green chemical perspective. Anal Methods. 2010; 2: 16511661.

Fe (II) to oxidize into Fe (III). 8. Grudpan K, Kradtap Hartwell S, Wongwilai W, Grudpan S and
Lapanantnoppakhun S. Exploiting green analytical procedures for acidity
The results of the analysis of the two commercially available and iron assays employing flowanalysis with simple natural reagent extracts.
pharmaceuticals are given in the table 4. Talanta. 2011; 84: 13961400.

9. Insain P, Khonyoung S, Sooksamiti P, Lapanantnoppakhun S, Jakmunee


Conclusion J, Grudpan K, et al. Green Analytical Methodology Using Indian Almond
(Terminalia Catappa L.) Leaf Extract for Determination of Aluminum Ion in
The process of the SIA system optimization, aiming at determining
Waste Water from Ceramic Factories. Anal. Sci. 2013; 29: 655-659.
Fe ions by the application of the natural reagent, is suggested in this
paper. The development of flow based technique such as SIA provides 10. Sharma R K, Gulati S, and Mehta S. Preparation of Gold Nanoparticles Using
Tea: A Green Chemistry Experiment. J. Chem. Educ. 2012; 89: 13161318.
a new opportunity for the development of green analytical chemistry
methods. This method offers good analytical characteristics due to 11. Pinyou P, Kradtap Hartwell S, Jakmunee J, Lapanantnoppakhun S, Grudpan
K. Flow injection determination of iron ions with green tea extracts as a
their simplicity, high analytical frequency and capacity to reduce natural chromogenic reagent. Anal Sci. 2010; 26: 619-623.
reagent consumption when compared with FIA or batch procedure.
This method is interesting, inexpensive and suitable for the courses

Austin J Anal Pharm Chem - Volume 2 Issue 3 - 2015 Citation: Martinovic Bevanda A, Tali S and Ivankovic A. Green Analytical Chemistry in Teaching Laboratory:
ISSN : 2381-8913 | www.austinpublishinggroup.com Spectrophotometric Determination of Fe Ions with Using Green Tea to Demonstrate the Principles of Sequential
Bevanda et al. All rights are reserved Injection Analysis. Austin J Anal Pharm Chem. 2015;2(3): 1043.

Submit your Manuscript | www.austinpublishinggroup.com Austin J Anal Pharm Chem 2(3): id1043 (2015) - Page - 04
Trends in Analytical Chemistry, Vol. 27, No. 6, 2008 Trends

Green Analytical Chemistry


S. Armenta, S. Garrigues, M. de la Guardia

We discuss the origins and the fundamentals of Green Analytical Chemistry and to collect residues to avoid contami-
(GAC), based on the literature published about clean, environmentally- nation of water and discharge with urban
friendly or GAC methods. We pay special attention to the strategies and the wastes. However, there is evidence of a
tools available to make sample-pretreatment and analytical methods greener. real problem the great quantity of toxic
We consider that the main principles are to replace toxic reagents, to residues which creates difficulties in
miniaturize and to automate methods, making it possible to reduce drama- their management.
tically the amounts of reagents consumed and wastes generated, so reducing With this background, Green Analytical
or avoiding side effects of analytical methods. We also consider on-line Chemistry (GAC) started as a search for
decontamination or passivation of wastes to be of special interest in making practical alternatives to the off-line treat-
analytical chemistry sustainable. ment of wastes and residues in order to
2008 Elsevier Ltd. All rights reserved. replace polluting methodologies with
clean ones.
Keywords: Automation; Clean analytical chemistry; Decontamination; Environmentally-
In this review, we provide a picture of
friendly method; Green analytical chemistry; Miniaturization; Passivation; Sample
the origin, the state-of-the-art and the
pretreatment; Toxic reagent; Waste
future prospects of GAC based on the most
1. Introduction relevant, representative scientific refer-
S. Armenta, S. Garrigues, ences found in the Chemical Abstracts
M. de la Guardia*
For analytical methodologies, develop- Service (CAS), the US National Library of
Department of Analytical
Chemistry, Research Building, ment and validation include optimization Medicine and the Science Citation Index
University of Valencia, 50th of some critical analytical parameters (SCI) database of the Institute for Scientific
Dr. Moliner St., E-46100 (e.g., accuracy, sensitivity, reproducibility, Information (ISI), Philadelphia, PA, USA.
Burjassot, Valencia, Spain
simplicity, cost effectiveness, flexibility and
speed). However, other aspects concerning
operator safety and environmental impact 2. Origin of the concept
of analytical methods are not commonly
considered. Because of that, a paradoxical In 1987 in Paris during Euroanalysis VI,
situation emerged during the 1990s, due Malissa presented his ideas about changes
to the side effects of analytical methodol- in paradigms in analytical chemistry [1].
ogies developed to analyze different kinds The dissertation based on the different
of sample, including environmental steps covered by the chemistry in history,
samples that generate a large amount of included the concept of the ecological
chemical waste, resulting in a great envi- paradigm being imposed at the end of the
ronmental and human impact. In some twentieth century. These ideas were in
circumstances, the chemicals employed for good agreement with the conclusions of
analysis were even more toxic than the the Pimentel report, published in the USA
species being determined. in 1985 [2], about the impact of chemistry
Taking into account current public on the health of the Earth. Ten years later,
concern on environmental matters, envi- The Analyst journal of the Royal Society of
ronmental analytical studies and the Chemistry in the UK proposed the topic of
consequent use of toxic reagents and sol- Environmental Analytical Chemistry as a
vents have increased to a point at which model of analytical practices in an inte-
they became unsustainable to continue grated approach to analytical chemistry
without an environmentally friendly per- that also consider the environmental side
spective. effects of analytical practices [3].
*
The need for carefully checking of the Green Chemistry is the use of chemis-
Corresponding author.
Tel./Fax: +34 96 35 44 838;
side effects of chemistry in general and try techniques and methodologies that
E-mail: analytical chemistry in particular has reduce or eliminate the use or generation
miguel.delaguardia@uv.es moved laboratories to control wastes and of feedstocks, products, by-products,

0165-9936/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2008.05.003 497
Trends Trends in Analytical Chemistry, Vol. 27, No. 6, 2008

solvents, reagents, etc. that are hazardous to human i) reduction of the amount of solvents required in
health or the environment [4]. In short, it is the use of sample pre-treatment;
chemistry for pollution prevention. The same philosophy ii) reduction in the amount and the toxicity of solvents
and ideas on Green Chemistry are those previously and reagents employed in the measurement step,
developed in analytical laboratories (GAC). especially by automation and miniaturization; and,
Although the analytical community has been envi- iii) development of alternative direct analytical meth-
ronmentally sensitive for a long time and the idea of odologies not requiring solvents or reagents.
improving analytical methods by reducing consumption Fig. 2 shows GAC milestones in the period 1970
of solvents and reagents pre-dates the theoretical devel- 2007. There is a difference between the conceptual
opments, the first descriptions of GAC methods (or clean milestones and the tools suitable for making methods
analytical methods) appeared in 1995 [3,5,6]. However, greener. In this sense, it is interesting to note that the
in the light of these new ideas, previous developments in concepts of GAC and Green Chemistry were established
both sample pretreatment and measurement methods in the 1990s but the tools arose from developments in
were incorporated into the new integrated approach to the 1970s, indicating that experimental advances
analytical chemistry [7]. pre-dated theoretical ones.
The scientific references found in the CAS and SCI To reduce the amount of solvent required for sample
database, relating to GAC (also called clean analytical pretreatment, the application of microwave energy for
chemistry or environmentally-friendly analytical sample digestion was first proposed in 1975 in the
methods) have been growing significantly in recent pioneering study of Abu-Samra et al. [8]. However,
years. Fig. 1 shows that the literature on this topic has organic analytes were isolated from diverse sample
grown exponentially since the 1990s and two clear matrices in the mid-1980s. Compared to traditional
changes can be identified in the rate of scientific litera- convective heating sample-preparation methods,
ture production at the end of the twentieth century and microwave-assisted extraction (MAE) saves solvent,
in this new century with 4 papers per year published and is rapid and efficient from the point of view of
before 2000, 11 papers a year from 2000 to 2005, and energy use.
22 papers a year since 2005. This change in the rate of An alternative to MAE is supercritical fluid extraction
publication on GAC methods is related to the increasing (SFE), based on extracting analytes by a fluid in super-
concern of the scientific community about the environ- critical conditions. SFE emerged in the mid-1980s to
mental impact of their activity. overcome difficulties of solid-sample extraction and the
use of supercritical CO2 avoided the side effects of organic
solvents. However, despite the promising features of SFE,
3. Milestones in Green Analytical Chemistry it has not fulfilled the expectations of researchers in
chemical analysis [9].
The adverse environmental impact of analytical Pressurized fluid extraction (PFE) is similar to Soxhlet
methodologies has been reduced in three different ways: extraction, except that the solvents are used near their
supercritical region, where high temperatures produce
high solubility and high diffusion rates of solutes in the
solvent, while the high pressure, in keeping the solvent
140
below its boiling point, enables high penetration of the
Cumulated number of papers

120 solvent in the sample. PFE provides high extraction


100 efficiency with low solvent volumes (1540 ml) and a
80 short extraction time (1520 min). PFE is also known
60
as accelerated solvent extraction (ASE), which was
first developed by Dionex in 1996 [10] and validated on
40
a commercially-available, automated extraction system.
20 Solid-phase extraction (SPE) is an important method-
0 ology to avoid the use of large amounts of organic sol-
1993 1995 1997 1999 2001 2003 2005 2007
vents in preconcentration and extraction steps. It has
Year
been used mainly for trace enrichment of water samples
Figure 1. Evolution of the scientific literature about Green with many advantages over liquid-liquid extraction
Analytical Methods (obtained from the Chemical Abstracts Service (LLE), such as:
(CAS), the US National Library of Medicine and the Science
i) reduction in the amounts of solvents used;
Citation Index (SCI) database of the Institute for Scientific
Information (ISI), Philadelphia, PA, USA), using the subjects ii) extractions unhindered by emulsion formation;
Green Analytical Chemistry, clean analytical chemistry or iii) high extraction efficiency; and,
environmentally-friendly analytical methods. iv) ease of automation.

498 http://www.elsevier.com/locate/trac
Trends in Analytical Chemistry, Vol. 27, No. 6, 2008 Trends

Figure 2. Milestones of both Green Analytical Chemistry concepts and greener methodologies.

The development of solid-phase microextraction microextraction (SDME) and liquid-liquid-liquid micro-


(SPME) by Belardi and Pawliszyn in 1989 [11] was also extraction (LLLME). SDME was developed in 1996 by Liu
of great importance in greening analytical sample and Dasgupta [13] and is based on the suspension of a
preparation. It is based on the sorption of analytes di- microdrop of a water-immiscible organic solvent in an
rectly from the samples or in headspace vials by a thin aqueous donor solution. LLLME, which is based on
film of an extracting phase immobilized over the surface liquid-liquid extraction and a back-extraction, was first
of a fused-silica fiber. The extracts can be desorbed developed by Ma and Cantwell in 1998 [14].
thermally or using solvents. Cloud-point extraction (CPE) provides another alter-
Another solid-phase alternative to using organic sol- native for greener sample pretreatments. It is based on
vents is stir-bar sorptive extraction (SBSE), which is cloud-point and phase-separation phenomena observed
based on the interaction of analytes with a coating of in surfactant aqueous solutions, which favor miscibility
polydimethylsiloxane (PDMS) deposited on a magnetic and separation of surfactant micelles and water as a
rod. It was developed in 1999 by Baltussen et al. [12]. function of temperature. The CPE technique was intro-
The stir bar can be desorbed with a small volume of a duced by Watanabe and Tanaka to preconcentrate metal
suitable solvent, but, for volatile and semi-volatile com- ions from aqueous samples [15]. Subsequently, the scope
pounds, on-line thermal desorption provides a very of CPE has been extended to extraction of proteins,
sensitive approach that avoids using organic solvents. enzymes and organic environmental pollutants.
SBSE uses a thicker polymeric layer than that employed The development of modified surfaces to be used as
in SPME, resulting in a high enrichment factor. SPE units is also of interest in GAC. Molecularly-
Liquid-phase microextraction (LPME) is an emerging imprinted polymers (MIPs) are capable of recognizing
technique that employs a small volume of solvent. The specific molecules with a sorption capacity dependent on
two main methodologies that have evolved from solvent the properties and the template concentration of the
microextraction in recent years have been single-drop surrounding medium. MIPs have been exploited in a

http://www.elsevier.com/locate/trac 499
Trends Trends in Analytical Chemistry, Vol. 27, No. 6, 2008

number of applications, including separation of materi- scaled by reducing the size of the chromatographic
als, antibody mimics and recognition elements in bio- column (capillary high-performance LC, HPLC), the
sensors. Molecularly-imprinted SPE (MISPE), based on particle size of the stationary phase (ultra performance
surface modifications by immobilizing the chelating liquid chromatography, UPLC) or integrating the whole
agents on the appropriate support, has been employed system on a chip.
for metal-ion preconcentration. The ability of mass spectrometry (MS) to extract
Concerning the measurement step, greener analytical chemical fingerprints from trace levels of analyte is
procedures are inherent to automated flow-based meth- invaluable and its combination with GC, LC and induc-
odologies, due to their capability of reducing reagent and tively coupled plasma (ICP) have provided routine tools
solvent consumption and also to the possibility of to enable simultaneous detection and characterization of
incorporating decontamination of wastes on-line [7]. a wide range of analytes in very complex matrices.
From the first paper published by Ruzicka and Hansen The evolution of the available instrumentation and
on flow-injection analysis (FIA) in 1974 [16], the mathematical data treatments (chemometrics) has
development of flow-analysis-based techniques seems a allowed the development of solvent-free methodologies
search to minimize reagent consumption. based on direct measurements on solid or liquid samples
The evolution of flow systems comprises the use of without any chemical sample pre-treatment. Examples of
solid-phase reagents, and especially immobilized re- methodologies based on direct measurement and che-
agents in solid-phase spectrophotometry (SPS), which mometric data treatment are applications of vibrational
Yoshimura et al. introduced in 1976 [17]. In SPS, the spectrometric-based techniques (near infrared (NIR),
solid support is placed inside the flow cell and analyte mid-infrared (mid-IR) or Raman spectrometry), fluores-
retention, preconcentration and detection are performed cence, UV-Vis spectroscopy and nuclear magnetic reso-
simultaneously, increasing the sensitivity and the selec- nance (NMR). The main advantage of these methods is
tivity of the analytical procedures and reducing the to avoid sample pre-treatment, thus reducing the use of
reagents consumed. solvents and reagents, and also the time of analysis.
Sequential-injection analysis (SIA) is a robust alter-
native to classical flow injection (FI) that allows imple-
mentation of different flow methodologies without 4. Greener sample pretreatments
modification of the manifold [18]. The main advantages
of SIA over FIA are the dramatic reduction in the The public concern over protecting the environment has
amounts of solvent and reagents consumed, simplicity induced chemists to look for new sample-preparation
and reduction of wastes. techniques that could reduce the adverse environmental
One of the recent approaches in flow systems is mul- impact of organic solvents [22].
ticommutation. This technique involves use of discrete Table 1 summarizes the characteristics of the main
commutation devices (e.g., three-way solenoid valves or sample-treatment methods developed to avoid or to
minipumps) to build up dynamic manifolds that can be reduce use of organic solvents, as selected from papers
reconfigured by software [19]. This approach increases identified in the literature as describing clean, green or
the versatility of FIA systems because each analytical environmentally friendly methods.
step can be implemented independently. Usually, one Microwave-assisted extraction (MAE) has been applied
commutation device is employed to manage each solu- to the extraction of organic compounds from very dif-
tion, so only the reagent volume required is introduced ferent types of matrix. It employs less organic solvent
into the system for sample processing. and a shorter extraction time than traditional extraction
All current procedures could become environmentally methods. In a comparative study by Pastor et al. [36], it
friendly by reducing the amounts of reagents consumed was evident that MAE reduced extraction time by a
and it can easily be achieved by downscaling the man- factor of 20 and organic solvent consumtion by a factor
ifold components and arranging them in a single device. of 10, as compared with the Soxhlet extraction, and
This concept is known as the micro-total analytical reduced solvent consumtion by a factor of 15 and
system (l-TAS), which involves arranging all steps of extraction time by a factor of 3, compared with ultra-
sample processing in a single device of a few square sound-assisted extraction (UAE).
centimeters [20]. MAE has been proposed for GAC extraction of atra-
Micro FIA (l-FIA) systems, which exploit micro- zine, simazine and prometryne from synthetic-soil
electronic techniques to integrate pumps, mixing and samples, using water and some organic solvents [23].
reaction chambers as well as detectors in a single Triazines could be efficiently extracted with 30-ml water
chip provide the so-called lab-on-valve (LOV) concept, as they provide a cheap, safe, environmentally-friendly
proposed by Ruzicka [21]. alternative to organic solvents.
Classical techniques (e.g., liquid chromatography (LC) MAE can be used together with a micellar system to
and capillary electrophoresis (CE)) have been down- extract organic compounds from soils. This method was

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Table 1. Some green alternatives, obtained from papers in which one of the objectives was to make analytical methods greener

Extraction method Analyte Matrix Solvent Amount solvent Ref.


per sample
MAE Triazines Soils Water 30 mL [23]
Phenols Soil POLE:water (5:95) 8 mL [24]

SFE Pesticide residues Plants CO2 // n-hexane 1 mL [25]


Pesticide residues Strawberries CO2// acetone 10 mL [26]
ASE Estrogens Soils Acetone n.c. [27]
Carotenoids Food Methanol/ethyl acetate/light petroleum n.c. [28]

SPME Phenols Water Acetonitrile:water (70:30) 70lL [29]


VOC Snow Thermal desorption [30]

SBSE Pesticide residues Juice Thermal desorption [31]

SDME Aniline derivatives Water Extrc. benzyl alcoholethyl acetate, 80:20 Extrc.: 150lL [32]
Retroextrc.: HCl (pH2) Retroextrc.:1lL

LLLME Phenoxy herbicides Bovine milk DS: sample + HCl (0.5 M) AS: 7lL [33]
OS: 1-octanol
AS: 0.1 M NaOH
Aniline derivatives Water DS: sample + NaOH (pH13) AS: 3lL [32]
OS: benzyl alcoholethyl acetate, 80:20
AS: HCl (pH2)

MASE Pesticide residues Juice DS: sample + NaCl (saturated) AS:800lL [31]
AS: cyclohexane

Micelle mediated extraction Trichlorfon Cabbage SDS 0.01 M 200 mL [34]

Modifications of surfaces Cu Water HCl 0.1N 10 mL [35]

MAE, Microwave-assisted extraction; SFE, Supercritical fluid extraction; SPME, Solid-phase microextraction; SBSE, Stir-bar sorptive extraction;
SDME, Single-drop microextraction; LLLME, Liquid-liquid-liquid microextraction; MASE, Membrane-assisted solvent extraction; PHB, Poly(3-
hydroxy)butyrate; VOC, Volatile organic compounds; POLE, Polyoxyethylene 10 lauryl ether; DS, Donor solvent; OS, Organic solvent; AS,
Acceptor solvent; SDS, Sodium dodecyl sulfate.

used for the analysis of phenols in soils and provided a pletely. SFE has been employed in extraction of pesticide
viable, greener alternative by replacing organics with residues from plants [25] and fruits [26].
surfactants [24]. In the same way, accelerated solvent extraction (ASE),
The main advantages of MAE are: also known as pressurized solvent extraction (PSE),
i) short extraction time; pressurized fluid extraction (PFE), pressurized liquid
ii) reduction in the amount of sample required; extraction (PLE) and solvolytic extraction, is a solid
iii) high sample throughput; liquid extraction process performed at high temperatures
iv) reduced cost; and, (50200 C) and high pressures (1015 MPa). ASE is a
v) great safety, since it does not require the use of haz- form of PSE similar to SFE, although, in ASE, the extrac-
ardous materials and can be contained in closed tion is carried out under pressure to maintain the solvent
reactors. in its liquid state at high temperature, but always below
SFE also offers an attractive alternative to overcome its critical condition. Although the solvent used in ASE is
the unfavourable effect of non-polar organic solvents usually organic, pressurized hot water can also be used.
employed in extracting non-polar compounds. The main Nowadays, ASE is considered a potentially, attractive,
advantages of SFE are: alternative technique for extracting organic compounds
i) it can achieve high concentrations; from environmental or biological matrices [27] and for
ii) it is quantitative; food applications [28], its main advantages over tradi-
iii) it is fast; tional extraction methods being dramatic decreases in the
iv) it is simple; and, amount of solvent used and the extraction time.
v) it is selective. In SPME, sorbent-coated silica fibers are used to
SFE is also an environmentally-friendly analytical extract analytes from aqueous or gaseous samples. After
methodology that can be automated easily and com- extraction, the fibers can be desorbed by using small

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amounts of organic solvents or transferring thermally micellar phase and the original water phase is achieved
the fiber directly into the injection port of a GC. Based on as a function of temperature and the presence of some
the first approach, seven phenols were extracted from salts. The use of surfactants to increase the solubility of
water using oxidized multi-walled carbon nanotubes for organic compounds in water has been succesfully com-
extraction and 70 lL of acetonitrile:water (70:30) for bined with SPE to extract pesticides from vegetables [34].
elution [29]. However, SPME with thermal desorption Beyond sample-preparation methods previously com-
has been used for the analysis of snow samples by GC mented upon, derivatization of surface molecules is a
[30], avoiding completely the use of organic solvents. valuable tool in making sample treatment greener.
SBSE is not as popular a technique as SPME, but it has Molecular imprinting has become a powerful method for
been used as a green alternative for extracting pesticide preparing robust materials that can recognize specific
residues in sugarcane [31]. chemical species. However, applications as real alterna-
LPME is essentially miniaturised liquidliquid extrac- tives or complements to biomolecules are limited to some
tion, in which the analyte moves between the bulk extent by inherent shortcomings (e.g., non-specificity
aqueous phase and a very small volume of organic sol- and low affinity of binding sites [37]).
vent. Recent developments use a single droplet of sol- However, chelating solid phases can be made by
vent, suspended at the tip of a needle and exposed to the immobilizing chelating agents on appropriate supports.
sample solution (SDME), and they have been employed This methodology has been succesfully applied to
for extracting aniline derivatives from water samples in a extracting trace-metal ions from water samples [35].
two-step procedure [32].
By using membrane-based devices, different ideas have
been developed to extract and preconcentrate different 5. Green analytical methodologies
tipes of analytes, avoiding or reducing the amount of
organic solvents. Investigation of GAC methodologies encompasses a
In LLLME, a thin film of organic solvent is immobilized number of strategies to minimize or to eliminate the use
in the pores of a polypropylene hollow fiber placed on the of toxic substances and the generation of wastes. The
exterior of the hollow fiber carrying the donor aqueous main focus has been the development of new routes to
phase. The pH of sample is adjusted to neutralize the minimize the amounts of side products and to replace
target compound and the internal channel of the fiber toxic solvents [38].
acts as the acceptor aqueous phase, with a pH adjusted
to ionize the target compounds. With stirring, neutral 5.1. Screening methodologies
compounds in the donor phase are extracted into the It is clear that one of the aims of the GAC is to reduce the
organic film on the fiber and then back extracted into the number of samples to be analyzed by classical, non-
acceptor phase inside the fiber. This technique has been environmentally friendly methodologies and also to re-
used in extracting herbicides from milk [33] and aniline duce the waste generated as a result. However, this
derivatives from water samples [32]. reduction in the number of samples for analysis should
Another membrane-based approach is called sup- be done in a safe, controlled way. It can be achieved by
ported-liquid-membrane extraction (SLME) or mem- using the so-called screening methods that involve
brane-assisted solvent extraction (MASE). In this case, procedures to indicate whether target analytes are
separation occurs when compounds are transported to a present above or below a threshold but also comprise
greater extent than others from a donor phase through those that provide fast acquisition of semi-quantitative
the membrane into an acceptor phase. For non-porous data about all components of a sample.
membranes, the efficiency of the transport of compounds In general, screening methods tend to to be qualita-
depends to a large extent on the partition coefficient tive, involving little or no sample treatment, and the
between the different parts of the extraction system, so response is used for immediate decision-making, with
good selectivity can be achieved by choosing appropriate confirmation requiring a conventional alternative. Put
membrane material and organic acceptor phases. This plainly, a screening method is a simple measurement
technique has been used for green extraction of pesticide that provides a yes/no response, avoiding the need to
residues from juice [31] using only 800 ll of organic process a large number of samples so as to limit complex
solvent. sample treatments of conventional techniques to those
CPE offers advantages: samples with positive responses.
i) it is inexpensive; It is important to note the great efforts made by the
ii) good concentration efficiency; scientific community in this direction in recent years. In
iii) low environmental toxicity; and, this respect, it is interesting to mention immunoassays
iv) safety. (IAs), which were first developed for monitoring insulin
Surfactants can dissolve organic compounds en- in blood in 1960 [39] and are now usually employed in
trapped in the micellar phase. Complete separation of the clinical chemistry to determine hormones, drugs and

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viruses in biological samples [40,41]. Enzyme-linked ployed only one reagent (HClO4) and avoided interfer-
immunosorbent assay (ELISA) is the most common IA ences of humic acid, NO2 , PO34 , Cl , SO24 and Fe3+. The
technique employed. The main advantages of those same principle was applied in the SIA determination of
biology-based analytical-screening techniques is the phosphate in urine [46]. The interferences of Ca, due to
complete replacement of organic solvents by aqueous the crystallisation of calcium phosphate, were avoided
media and the consequent reduction of toxic wastes. using a cation-exchange resin.
As well as so-called rapid colorimetric tests employed As can be seen in Table 2, there is great interest in
to determine the presence of some inorganic compounds, replacing organic solvents as the mobile phase in HPLC.
we should mention the different analytical techniques Solvent-free HPLC methods have been proposed for the
commonly employed for rapid analysis of elemental determination of dyes in foods [47]. In this case, organic
composition of samples: solvents were substituted by surfactants as mobile phase.
 X-ray fluorescence, which provides excellent qualita- Acified water, without organic solvent, was employed
tive or semi-quantitative data without any pre- as the mobile phase in separation and quantification of
treatment; UV filters in cosmetics by using cyclodextrins as organic
 inductively coupled plasma atomic emission spec- modifiers [48], and for separation of steroids, amino
trometry (ICP-AES) and inductively coupled plasma acids and proteins using thermo-responsive copolymers
mass spectrometry (ICP-MS), which are the most sen- as the stationary phase [49].
sitive, selective techniques for multi-elemental deter- Chlorophyl, extracted from pea leaves, has been pro-
mination of several components in the same sample; posed as a natural fluorometric reagent for the deter-
 mass spectrometry (MS), which offers good advanta- mination of Hg, based on quenching fluorescence in the
ges for selective determination of compounds and presence of Hg2+ [50].
sensitive determination of organic pollutants, Replacement of Hg-based electrodes has been a hot
providing fast sequential information on multiple topic in GAC method development of stripping voltam-
compounds with high level of sensitivity; and, metry. Table 2 shows the different electrode materials
 ion-mobility spectrometry (IMS), which is usually proposed.
used for screening explosives at airports and detection Bismuth thin films, deposited in situ on a copper
of compounds from pyrolysis, detecting chemicals for substrate, have been proposed for monitoring Cd, Pb, Co,
the military industry, including warfare agents, and Ni [51]. Moreover differential pulse voltammetry (DPV)
monitoring stack-gas emissions in industry [42]. and adsorptive stripping voltammetry (AdSV) at a
modified silver solid amalgam electrode (m-AgSAE) have
5.2. Replacement of toxic reagents been employed for the determination of trace amounts of
As can be seen in Table 2, the use of flow-based proce- genotoxic substances [52].
dures has contributed to achieving greener analytical The use of vapour-phase generation with Fourier
methods, by automation and miniaturization, but also transform infrared (FT-IR) spectroscopy provided a green
by replacing toxic reagents by non-contaminating alternative for ethanol determination in mouthwashes
reagents (see Fig. 3a)). [53]. Without pre-treatment, 2 lL of samples were
Guava leaf extract has been used as an alternative injected inside a reactor heated at 70 C, and the vapour
natural reagent for the FI determination of Fe [43] phase generated was transported to the FTIR spectro-
without the need for further purification. meter using carrier flow of nitrogen. The proposed
The use of SPE in combination with FIA systems has procedure is a simple, fast, environmentally-friendly
been proposed as a way of replacing toxic reagents. A alternative, which avoids using reagents and chlorinated
time-based, multi-syringe FI (MSFI) approach was organic solvents commonly used for this determination.
developed for automating disk-based sorbent extraction
of nitro-substituted phenol isomers followed by on-line 5.3. Minimization of wastes
simultaneous determination of individual species by The substitution of all toxic reagents employed in
diode-array spectrophotometry [44]. The method chemical analysis is not easy, so reduction of
involved on-line enrichment of target analytes and the amounts employed should be also considered
removal of potentially-interfering matrix components. (see Fig. 3b)). In this sense, multicommutation has the
The nitrophenol isomers were eluted with an alkaline advantages of minimizing both reagent consumption
solution and the UV-vis spectra were recorded. Decon- and waste generation. In this approach, micro-volumes
volution of strongly-overlapping spectra was done using of samples and reagents are sequentially inserted into
multivariate regression models. the reaction coil of a single line manifold, providing a
A GAC procedure was developed for nitrate determi- simple system, suitable mixing conditions, and easy
nation in natural waters based on direct spectrophoto- optimization of the sample/reagent ratio, and avoiding
metric measurements [45], using an FIA system with an excessive use of reagents. Multicommuted flow systems
anion-exchange column. The proposed method em- can be designed with solenoid micro-pumps that can

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Trends
Table 2. Some green analytical methods proposed in the literature

Green strategy Flow method Analyte Reagent Green aspects Ref.


http://www.elsevier.com/locate/trac

Replacement of FIA - UV Fe Guava leaf extract Use of Guava extract as colorimetric reagent [43]
toxic reagents Multi-syringe FIA - UV Nitro-substituted - Flow-through disk-based system organic solvent [44]
phenols extraction
FIA - UV Nitrate HClO4 Use of SPE to avoid interferences [45]
SIA - UV Phosphate Use of SPE to avoid interferences [46]
HPLC Colorants Triton X-100 Use Triton X-100 as mobile phase and to modify [47]
the C18 column
HPLC UV filters EthOH-water-acetic acid Use cyclodextrin as mobile phase modifier [48]
hydroxypropyl-b-cyclodextrin
HPLC Steroids, amino acids Aqueous mobile phase Use of thermo-responsive copolymers as [49]
and proteins stationary phases
Fluorimetry Hg(II) Clorophylla Use of Chlorophyll as reagent [50]
Anodic and Cathodic Cd, Pb, Co, Ni Bismuth film electrode Replacement of Mercury-based electrodes [51]
stripping voltammetry
Adsorptive stripping 3-nitrofluoranthene Silver Solid Amalgam Electrodes Replacement of Mercury-based electrodes [52]
voltammetry
VP-FTIR Ethanol VP-FTIR avoids the use of chlorinated solvents [53]

Minimization of Multicomm. - UV Cyclamate NaNO2/KI Solenoid micropumps [54]


reagents and Multicomm. - UV Carbaryl PAP Solenoid valves [55]
wastes Multicomm.-HG-AFS Hg Solenoid valves [56]
Multicomm. - FTIR Benzene CHCl3 Solenoid valves [57]
FIA-FTIR Malathion CHCl3 Closed FIA manifold [58]
FIA-UV Chloride Hg(SCN)2/Fe(III) Hg(SCN)2 immobilized in epoxy resin [59]
FIA-Chemiluminescence Chlorpyrifos Luminol or periodate Controled reagents release from a solid phase [60]
Double line SIA-UV Cu, Fe, Mn, Zn 1,10-phenanthroline/ [61]

Trends in Analytical Chemistry, Vol. 27, No. 6, 2008


formaldoxime / zincon
FIA-SPS Fe(II) Acid and reducing agent SPS - reduce reagent consumption [62]
lFA - vis Cu(II) 2-carboxy-2-hydroxy-5- Micro fluidic manifold [63]
sulfoformazyl benzene
l UV assay Malondialdehyde Thiobarbituric acid and ethyl Micro extraction - UV [64]
acetate
Capillary HPLC Flavonoids Acetonitrile Reduction of the organic solvent volume to less [65]
than 1 mL per run
UPLC Lovastatin Acetonitrile Reduction of the organic solvent volume to less [66]
than 1.5 mL per run
LC-MS Drugs Acetonitrile Multicomponent (7) determination in only 8 min. [67]
and 4 mL per run
LC-MS Pesticides Methanol Multicomponent (10) determination in only [68]
10 min. and 3 mL per run
l CE-MS Drugs Acetonitrile/methanol Multicomponent (4) determination in only 1 min. [69]
l CE Phenolic compounds Micromachined capillary electrophoresis (CE) [70]
chip with a thick-film amperometric detector
NIR Pesticides Acetonitrile [71]
Trends in Analytical Chemistry, Vol. 27, No. 6, 2008 Trends

reproduce the micro-volumes of solutions dispensed,

spectrometry; PAP: p-aminophenol; MB: Methylene blue; FTIR: Fourier transform infrared; HIFU: High-intensity focused ultrasound; SPS: Solid phase spectrometry; NIR: Near infrared; PAS:
FIA: Flow injection analysis; UV: Ultraviolet; SPE: Solid phase extraction; SIA: Sequential injection analysis; lFA: micro Flow analysis; HG-AFS: Hydride generation-Atomic fluorescence
[72]

[73]

[75]
[76]
[77]
[78]
[79]
[80]
thus dowscaling the methods automated.
As can be seen in Table 2, multicommutation has
been employed in combination with spectrophotometry
for fast, clean determination of cyclamate [54]. The
Distillation unit - on-line recycling of the CHCl3

procedure exploits the reaction of cyclamate with nitrite


Cation exchange column to regenerate the

in acidic medium and the spectrophotometric determi-

Sample matrix reduce Hg ions to Hg(0).


nation of the excess of nitrite by iodometry. The method

Direct measurement solid pesticide


consumes only 3 mg KI and 1.3 lg NaNO2, generating
Direct measurement in glass vials
Direct measurement in glass vials
Direct measurement in glass vials
2.0 mL of effluent waste per determination.
reagent and retain toxic ions.

Multicommutation has been applied for Hg determi-


Direct measurement oil nation in milk by hydride generation atomic fluores-
cence spectrometry (HG-AFS) [55]. The method
dramatically reduces reagent consumption (by a factor
of 4) and effluent generation, and it also improves lab-
oratory productivity by increasing sample throughput.
PAP/ KIO4

An FT-IR multicommutation method was developed to


[56]

determine benzene in motor fuels [56]. The method


permitted direct determination of benzene without any
pre-treatment of samples. Advantages of the method
were a solvent consumption of 1.2 ml per determination
and an analytical throughput of 81 samples per hour.
Deactivation heavy metals -

Photoacoustic spectroscopy; PI-CVG-AFS: Photo induced-cold vapor generation-Atomic fluorescence spectrometry.

Analytical characteristics of multicommutation have


been compared with those obtained by classical FIA and
SIA, in improving the automated spectrophotometric
matrix of Fe(OH)3

determination of carbaryl with p-aminophenol (PAP)


UV radiation

[57]. Multicommutation provided a limit of detection


Formetanate
Arsenazo III

(LOD) comparable to that obtained using FIA and lower


than that found by SIA, but generating a total waste
volume per sample of 1.7 ml, which was comparable to

that found in SIA and 6 times lower than that obtained


by classical FIA. This comparative study showed that
SIA is the best strategy for reducing reagent consump-
Propyphenazone and

tion but multicommutation provides a faster, more


sensitive alternative to SIA.
Peroxyde value

A closed FIA system was developped to extract mala-


Sweeteners
FIA-UV/vis

Mancozeb

thion from pesticide formulations with 2 ml CHCl3 prior


Pesticides
Iprodione
caffeine

to the determination of the pesticide by FTIR [58].


Lead

[74]

The retention of reagents in solid supports was pro-


Hg

posed for the determination of chloride in natural waters


by reaction with Hg(SCN)2 immobilized in an epoxy-
resin bead [59] and for the chemiluminescence deter-
Detoxification TiO2 and

Sample matrix-assisted

mination of chlorpyrifos in fruit based on immobilizing


Cyclic FIA UV/vis

decontamination of

luminol or periodate on an anion-exchange column


[60].
UV radiation

PI-CVG-AFS

SIA permits great reduction in the volumes of waste,


FT-Raman
FT-Raman
FIA-FTIR

and several metal ions were determined in waters using


wastes

a double-line sequential injection spectrophotometric


PAS
NIR
NIR
Hg

system [61]. The proposed configuration added sample


and chromogenic reagents as merging zones. The
methodology was applied to the spectrophotometric
methodologies

determination of copper, iron, manganese, and zinc in


Multicomm.-

Reagent-free
Recovery of

samples of diverse origin.


HG-AFS
reagents

On-line

SPS simultaneously reduces the volumes of reagents


used and improves analytical selectivity and sensitivity.
It concentrates the analyte in situ due to its accumulation in

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a) Replacement of toxic reagents b) Minimization of wastes


Determination of Fe using Guava leaf extracts by UV Determination of chloride in waters by UV
Peristaltic pump Guava Leaf Solid phase reactor
retained in a
Reagent solution column Regeneration
reservoir Injector commutator
solution
Sample injection
valve
Waste
Sample
Injection
Reaction coil loop
Waste Sample and
reagent solutions Peristaltic pump Reaction coil

UV-vis detector
UV-vis detector

c) Recovery of reagents
Determination of Pb in gasoline by UV Determination of propyphenazone and caffeine in
pharmaceuticals by FTIR
Peristaltic pump Reaction coil Peristaltic pump
Reagent solution
reservoir

Sample injection Sample injection


valve valve

Magnetic Ion exchange


stirrer column

UV-vis detector
IR detector

Solvent
reservoir
Distillation unit

d) On-line decontamination of wastes


Determination of formetanate in waters by UV
Peristaltic pump
Reaction coil
Reaction coil

Sample
injection
valve UV lamp =254 nm
Clean waste
Reagent
solution reservoirs
Photo assisted
degradation coil

UV-vis detector

TiO2
Peristaltic pump Dry air
Determination of Hg in milk by AFS

Argon
Gas Liquid
Peristaltic pump separation
Reaction coil unit CV-AFS

Reaction Clean waste


coil

Reagent Fe (III)
solution reservoirs
NaOH
Peristaltic pump Magnetic stirrer

Figure 3. Basic components of characteristic manifolds designed to: (a) replace toxic reagents, (b) minimize wastes, (c) recover reagents, and (d)
decontaminate wastes on-line.

a small volume of the solid support, thus resulting in FI-SPS was proposed for iron determination [62].
better sensitivity and lower LODs in comparison with Iron(II) is reversibly retained on 1-(2-thiazolylazo)-
measurements made in solution. 2-naphthol immobilized on C18-bonded silica, yielding

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a brown complex. The metal ion is eluted as iron(II) with Furthermore, the use of MS detectors in combination
a small volume of a dilute-acid solution without with chromatography is of paramount importance in
removing the immobilized reagent, which can be used new applications, as they improve detection sensitivity
for at least 100 determinations. The proposed procedure by 101000 times and so reduce the amount of sample
reduced effluent generation (3.6 mL per determination) needed [81]. As a direct consequence, the decrease in
and consumed micro amounts of reagents. mobile phases used has greatly reduced the amounts of
Waste generation can also be minimized by reducing waste produced. One of the major breakthroughs has
the size of manifolds developed. A clear example was the been the development of new MS interfaces, especially
micro-flow system comprising a planar glass chip with a atmospheric pressure ionization (API) sources, such as
PDMS top plate fitted with a fiber-optic probe, employed electrospray ionization (ESI) and atmospheric pressure
as optical sensor, for monitoring Cu(II) [63]. chemical ionization (APCI), which have simplified the
By miniaturizing the manifold, a micro-extraction- compatibility between the separation step working in the
spectrophotometric assay developed for the determina- liquid phase and the MS detector working in the gas
tion of malonaldehyde (MDA) in blood after formation of phase.
MDA-thiobarbituric acid (TBA) adduct [64] reduced the Moreover, in many cases, MS detectors have replaced
volumes of sample and waste. In this case, the volume of the classical detectors, reducing the number of systems
serum sample required was 20 lL and the total volume required for a single analysis and at the same time
of aqueous phase was 420 lL. avoiding some of the chromatographic toxic gases
Fast-response miniaturized systems with negligible typically used.
waste production are particularly promising for meeting Another advantage of combining HPLC or GC with MS
the requirements of GAC, so the concept of miniaturizing is simultaneous screening, identification, confirmation
separation and detection systems has an important role and quantitative multi-component determinations in a
to play. single run, in this way, reducing the time of analysis and
Capillary HPLC is based on decreasing the size of the waste generated. This shows the great potential for
packed HPLC columns in the capillary range, where HPLC-tandem MS (HPLC-MS2) methods, where direct
column ID is 100500 lm and flow rates are 0.4 injection of samples or sample extracts is often feasible,
100 lL/min, It improves the speed and the mass sensi- removing sample treatment and solvent consumption.
tivity of a separation. HPLC-MS has led to major breakthroughs in quanti-
Improvement in mass sensitivity achieved with capil- tative bioanalysis since the 1990s, due to its inherent
lary HPLC is perhaps the most understandable advan- specificity, sensitivity, and speed. In the past few years,
tage of the technique for the same size of injection, a increased use of LC-MS in various analytical fields,
300-lm capillary format offers sensitivity 235 times including forensic [67] and clinical toxicology [68], has
greater than a column with an ID of 4.6 mm. been spectacular, so it is now competing with GC-MS for
Three major additional advantages of capillary HPLC the status of being the Number One analytical technique
over traditional HPLC are faster column equilibration, in toxicology. This is due not only to its technological
smaller solvent volumes and lower back-pressures (e.g., advantages but also to its reduced cost.
using a 0.3 50-mm capillary column, a run for a However, samples from biological matrices are not
small-molecule separation will take 5 min at 10 lL/min, usually directly compatible with LC-MS2 analyses, as
using 60 lL of solvent with a pre-wash and a post-wash they require pre-treatment, so we need to mention the
[65]). on-line combination of SPE and chromatography [82], in
Similarly, by using a small particle size in the sta- which the solid phase is packed in columns that are
tionary phase of an HPLC system, speed and peak normally much shorter than analytical columns. In
capacity (number of peaks resolved per unit time in these SPE systems, the analyte is retained, pre-concen-
gradient separations) can be improved significantly (i.e. trated and separated from impurities and weakly re-
ultra-performance LC (UPLC)). Technical improvements tained compounds in the SPE column, to be later eluted
in stationary-phase particles (<2 lm) and instrument inside the chromatographic column by switching a
technology (capable of resisting the high pressure gen- valve. Sometimes, the flush-back technique is also
erated and with a detection system providing an appro- used; that involves changing the direction of flow
priate sampling rate) have allowed columns to be through the SPE column to minimize band broadening.
shortened in line with particle size without loss of reso- By using SPE coupled to HPLC, sample handling is
lution. In addition, the increase in sensitivity with UPLC reduced and sample treatment is completely automated.
should be 23 times greater than with HPLC, depending The major advantage of on-line SPE over off-line
on the detection technique [66]. A typical conversion of extraction is that the sample-preparation step is
a method from HPLC to UPLC could reduce analysis time embedded in the chromatographic separation so elimi-
from several minutes to 30 s, and also reduce the nating most of the sample-preparation time traditionally
amounts of solvent consumed and waste generated. performed at the bench.

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Coming back to the concept of miniaturized separation A useful way of recovering reagents on-line is to
and detection systems, at present, on-chip separations incorporate a cation exchange mini-column after a flow-
are dominated by CE and other electrophoretic methods. through cell. In this way, the main reagent can be
However, as l-TAS, develops, there is growing demand regenerated on-line and heavy-metal ions can be re-
for additional modes of separation, especially chro- moved from the waste, thus reducing both reagent
matographic, in order to improve handling of increas- consumption and waste generation [72]. The method
ingly complex samples [83]. involves spectrophotometric determination of Pb with
For CE microchips injecting small sample volumes, chromogenic reagent arsenazo (III), accumulation of Pb
highly-efficient separations can be achieved within just onto the cationic exchanger, and subsequent regenera-
one-tenth of the time required for capillary-based elec- tion of the arsenazo (III), which makes the system
trophoresis, while also reducing the volumes of residues reversible and the reagent reusable.
generated. However, the low sample capacity of the CE In FT-IR determination of propyphenazone and caf-
microchips requires sensitive detectors, so, currently, feine in pharmaceuticals, incorporating a distillation
most CE microchips are coupled to MS [69]. unit after the measurement cell provides on-line recy-
An example of this kind of analytical system was cling of CHCl3, which is used as carrier and solvent, thus
employed for separating and detecting toxic phenolic reducing both cost and side effects of laboratory waste
compounds, based on coupling of a micromachined CE [73]. The system developed permits a dramatic reduction
chip with a thick-film amperometric detector [70]. The of reagent consumption, and makes sampling and
integrated microsystem offered rapid (4 min) simulta- cleaning of the measurement cell easy and fast.
neous measurement of seven priority chlorophenolic
pollutants. 5.5. On-line decontamination of wastes
A promising alternative to CE is electrochromato- As described above in the context of GAC, special
graphy (EC), a technique that includes features of both emphasis should be placed on assessing the environ-
electrophoresis and LC, so there are in the literature mental impact of new methods in addition to traditional
several excellent reviews covering the broad area of goals (e.g., accuracy, precision, sensitivity, and LODs). In
separations in l-TAS [84] and also specific discussions 1994, different flow methods proposed involved an
on chip EC [85]. additional effort to detoxify wastes generated. Basically,
However, NIR can be used for pesticide determina- on-line treatment of waste involves adding a decon-
tions, reducing the volumes of waste generated [71]. The tamination step after analytical measurement to obtain
methodologies described above were based on pesticide clean waste (Fig. 3d).
extraction with acetonitrile and subsequent measure- In 1999, to detoxify wastes on-line, it was suggested
ment of transmittance. Reagent consumption was using:
clearly reduced (1 ml acetonitrile) and samples can be i) thermal degradation;
stored in the glass vials for later analysis. ii) oxidative detoxification;
Other analytical techniques that could be consid- iii) photodegradation; and,
ered GAC methods, due to their simultaneous screen- iv) biodegradation [7].
ing, identification, confirmation and quantitative Some of these strategies have yet to be applied to
multi-component determinations in a single run specific methods.
with little or no sample preparation, are ICP-AES and A detoxification step based on in-line TiO2-catalyzed
ICP-MS. photodegradation reduces the toxicity of wastes. It has
been applied for the determination of formetanate in
5.4. Recovery of reagents waters [74] using their reaction with p-aminophenol
The recovery of reagents provides a satisfactory way to (PAP). After the measurement step, the analytical waste
cut down on the side effects of analytical methods, as it is was merged with a TiO2 (anatase)-catalyst slurry and
an important step towards achieving zero emissions in then detoxified by on-line UV irradiation. After that, the
research. catalyst can be recovered through flocculation and
Laboratory wastes are not dscarded directly into the reused.
environment but are treated off-line. However, this Metal ions are non-degradable pollutants, so it is
practice increases the running costs of analytical impossible to decontaminate metal wastes. However, it is
laboratories and creates a problem through the possible to passivate wastes containing heavy metals and
accumulation of toxic residues. A green alternative to to reduce greatly the volume of waste (e.g., in the
waste storage is therefore on-line recovery of solvents determination of Hg in milk by AFS [56]). The analytical
and toxic or expensive reagents. Fig. 3 shows the basic waste was merged with NaOH and that solution was
components of ways described in the literature to re- mixed with a solution of Fe(III), which precipitates
duce consumption of reagents by using solid reagents Fe(OH)3 and co-precipitates Hg, thus contributing to
(Fig. 3B) and to recover solvents on-line (Fig. 3C). deactivation of traces of Hg and other heavy metals

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Trends in Analytical Chemistry, Vol. 27, No. 6, 2008 Trends

present in samples and standards, reducing the toxic benefits, so we would like to propose for these methods
wastes from several liters to less than 1 g of an hydroxide the term Sustainable Analytical Procedures (SAPs).
mixture with a high content of Fe. The growth and evolution of chemometrics has shown
that spectroscopic methods could be the best way to-
5.6. Reagent-free methodologies wards GAC. However, the development of new methods
Methods based on direct measurements of untreated of sample preparation, which reduces dramatically the
samples can be the best options to make analytical amounts of reagent and organic solvents, also improves
determinations greener. the characteristics of other methodologies, which cannot
FT-Raman spectrometry has been used as a reagent- be applied directly to the samples as electrochemical and
free methodology. The quantitative determination of chromatographic methoids can.
different analytes performed directly on the sample, solid The progress of flow methodologies has contributed to
or liquid, using standard glass vials as sample cells, GAC, but we are convinced that their potential has not
eliminates reagent consumption and avoids waste gen- yet been exploited fully.
eration, also reducing the need for sample handling and Multipumping flow systems have proved to be a cost-
the contact of the operator with potentially toxic sub- effective, valuable alternative to fully automated ana-
stances. This technique has been used for the determi- lytical methods for pharmaceutical, food, environmental,
nation of iprodione in solid-pesticide formulations [75] agroindustrial and large-scale routine clinical analysis.
and for the analysis of sweetener formulations [76]. Moreover, they are fast, precise and accurate, and
The evolution of chemometrics has supported devel- require less operator intervention or maintenance than
opment of solvent-free methodologies based on mathe- classical FIA.
matical treatment of signals obtained by direct Miniaturization is one way to avoid side effects of
measurements on untreated solid or liquid samples. analytical methods, and has been the subject of a sig-
Partial least squares NIR (PLS-NIR) provides a direct nificant number of research efforts. In this respect,
procedure for pesticide determination in formulations combination of modern analytical techniques with
[77]. NIR spectroscopy using transmittance measure- breakthroughs in microelectronics and miniaturization
ments, in combination with chemometrics, has proved to allows development of powerful analytical devices for
be a powerful tool for the determination of the peroxide effective control of processes and pollution. Combining
index in edible oil using PLS calibration without the need miniaturization in analytical systems with advances in
to use solvents or derivatization reagents [78]. chemometrics is very important. Of course, development
Another example of solvent-free methodology is based and improvement of new components for instrumenta-
on photoacoustic-Fourier-transform infrared-spectros- tion is critical in GAC.
copy (PAS-FT-IR), which was applied to determine Using examples, we have illustrated the power and the
Mancozeb in agrochemicals [79]. The method involved versatility of modern analytical systems and their po-
direct measurement of the transmittance spectra of solid tential for minimizing the consumption of hazardous
samples substances and the amounts of waste generated during
Other reagent-free methodologies proposed in the lit- assays.
erature include photo-induced mercury cold/chemical Commercialization, together with acceptance by
vapor generation (PI-CVG), which uses sample matrix as quality-control laboratories and industrial plants, should
a reductant. It was proposed for atomic fluorescence gear up GAC methods to the large scale needed for
detection of trace mercury in wine or liquor samples environmental and industrial applications. This trans-
[80]. The new method is based on the reduction of formation is also required in the context of education in
mercury by wine ethanol irradiated with UV light. The chemistry. Replacement of old experimental practices by
standard-addition method was used for real sample attractive procedures exploiting available instrumenta-
analysis to achieve the reagent-free goal. tion will result in the immediate reduction of wastes as
Direct measurement of the elemental composition of well as developing the environmental conscience essen-
samples through energy dispersion X-ray fluorescence tial for our students in the future.
(ED-XRF) is not called a green methodology. However, it Our final conclusion deals with the principles and
is clear that these measurements involve no sample philosophical fundamentals of the search for green
treatment and can be done without creating wastes. methods. Many of the methodologies that have con-
tributed to GAC were developed before the introduction
of concepts such as ecological paradigms (1987), envi-
ronmentally-friendly analytical chemistry (1994) and
6. Conclusions Green Chemistry (1999). But, it has been in the light of
these ideas that laboratories have taken into consider-
The use of GAC methods has proved to be a smart ation practical aspects (e.g., the toxicity of reagents
strategy to provide both environmental and economic employed, the amounts of reagents consumed, the

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Trends Trends in Analytical Chemistry, Vol. 27, No. 6, 2008

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Pure Appl. Chem., Vol. 85, No. 12, pp. 22172229, 2013.
http://dx.doi.org/10.1351/PAC-CON-13-02-05
2013 IUPAC, Publication date (Web): 1 September 2013

Sustainable analytical chemistrymore than


just being green*
Charlotta Turner

Department of Chemistry, Centre for Analysis and Synthesis, Lund University,


P.O. Box 124, SE-221 00 Lund, Sweden

Abstract: This review article describes analytical chemistry beyond green chemistry and all
efforts that contribute to a more sustainable development. A background is given on sustain-
able development and green chemistry. Examples of greening strategies for sample prepa-
ration, chromatography, and detection are given. Thereafter, the review discusses how and
why a method or a solvent could be claimed as being green. Green metrics for analytical
chemistry is discussed, including the environment, health, and safety (EHS) index and life
cycle assessment (LCA). The choice of solvent and the criteria for a solvent being green is
also discussed. Finally, sustainable analytical chemistry is described by considering the three
important legs so as to obtain sustainable developmenteconomic feasibility, societal rel-
evance, and environmental soundness. Hopefully, the review article will stimulate some new
perspectives on the difference between greenness and sustainability in analytical chemistry.

Keywords: green analytical chemistry; sample preparation; solvents; supercritical fluids; sus-
tainable chemistry; sustainable development.

INTRODUCTION
Analytical chemistry plays an important role in the sustainable development of the planet. This is true
not only for the monitoring of pollutants in the environment, but also for the development of more sus-
tainable processes, as well as for supporting important areas such as improved uses of renewable mate-
rials and biorefinery solutions. Certainly, analytical methodologies should first of all hold high quality,
such as being accurate, precise, and sensitive; and secondly, the method itself should be as environ-
mentally sustainable as possible. However, the aim of this review article is to expand the current know-
ledge and thoughts about green chemistry, especially green analytical chemistry, to the more compre-
hensive field of analytical chemistry for a sustainable development, or sustainable analytical
chemistry.
In this article, the authors personal views on the role of analytical chemistry from a sustainable
development perspective will be discussed taking cognisance of the significant work already achieved
in the field. The review is certainly far from being a complete coverage of the subject, but rather con-
tains snapshots of key contributions that the author has come across during the last several years.
Initially, a background on sustainable development and the current important questions in the
green chemistry field will be given. Then green chemistry will be discussed, including the development
of analytical chemistry in the area, as well as some useful tools that could be employed to assess the

*Pure Appl. Chem. 85, 21452248 (2013). A collection of invited papers based on presentations at the African Network of
Analytical Chemists (SEANAC) 4th Analytical Chemistry Conference, Maputo, Mozambique, 811 July 2012.

2217
2218 C. TURNER

greenness of a process. Thereafter, the paper will focus on sustainable analytical chemistry and con-
clude with some suggestions for future research.

SUSTAINABLE DEVELOPMENT
Sustainable development is a concept that was established in 1987 by the World Commission on
Environment and Development (WCED) through the well-known report Our Common Future [1],
chaired by Norways prime minister at the time, Gro Harlem Brundtland. However, the awareness of
pollution and environmental issues was raised long before then. For example, the unwrapping of the
Minamata disaster in Japan 1956, where methyl mercury was released from a chemical company for
over 20 years, resulting in the death of around 2000 people and severe neurological diseases in more
than 10 000 victims [2]. Perhaps most of us remember the start of environmental awareness from the
1962 book by Rachel Carson, Silent Spring, now published as a 40th anniversary edition [3]. Carsons
alarming observations were about the death of millions of birds due to environmental pollution, mainly
pesticides such as DDT. During that time, industry dealt with air pollution by building taller chimneys,
although obviously this would only protect the most nearby environment.
The second industrial revolution, during the second half of the 19th century, with innovations such
as the steam engine and the combustion engine, resulted in a dramatic increase in the combustion of
coal. In addition, the petroleum industry, starting in 1859 with the first oil well in Pennsylvania in North
America, certainly was the start of our current oil-dependency, or fossil fuel-based economy.
In 1972, for the first time the United Nations (UN) gathered to discuss pollution and environ-
mental challenges, which resulted in the report by Maurice Strong, which was also published in book
form: Only One Earth: The Care and Maintenance of a Small Planet [4]. During this UN meeting, 113
countries were represented and the UN Environment Program (UNEP) was founded. Twenty years later,
the UN Conference on Environment and Development (the Earth Summit) was held in Rio de Janeiro,
Brazil. 172 countries participated, and several documents were published as a result. The documents
include, for example, the Rio Declaration, Agenda 21, the Statement of Forest Principles, the UN
Framework Convention on Climate Change (UNFCCC), and the UN Convention on Biological
Diversity. The year after, in 1993, the International Organization for Standardization (ISO) formed the
Technical Committee 207 on environmental management. ISO/TC 207 is the umbrella committee
under which the ISO 14000 series of environmental management standards are being developed. These
include, for instance, environmental management systems (EMS); environmental labeling (EL); life
cycle assessment (LCA); and greenhouse gas management and related activities. These documents and
their implications are important milestones in the work towards a more sustainable future.
In 1997, the Kyoto protocol was composed by the UNFCCC, with the aim to reduce greenhouse
gases to fight global warming. Currently, 191 states have signed the agreement that went into force as
of 2005. The only country that did not sign is the United States of America. Canada has since renounced
the protocol.
Recently, in 2012, the UN again arranged a conference on sustainable development in Rio de
Janeiro, Brazil. The meeting was popularly called Rio 20+ since 20 years have passed after the quite
successful 1992 meeting. From a political point of view, the Rio 20+ meeting was not a success as only
a rather vague document, titled The Future We Want, came out from the meeting [5]. However, several
working groups had put extensive work into defining and elaborating around seven important focus
areas:
1. Jobs: There are currently 190 million unemployed people.
2. Energy: There is a need to get away from oil-dependency.
3. Cities: The main challenges are congestion, pollution, housing, and transportation.
4. Food: There are 925 million hungry people today and many more expected in the future.
5. Water: Scarcity, poor quality, and inadequate sanitation will affect one in four people by 2050.

2013, IUPAC Pure Appl. Chem., Vol. 85, No. 12, pp. 22172229, 2013
Sustainable analytical chemistry 2219

6. Oceans: Increasing temperature, decreasing pH, and pollution of our oceans affects drinking
water, weather, climate, coastlines, food, and ambient air.
7. Disasters: Earthquakes, floods, droughts, hurricanes, and tsunamis are all devastating.
These focus areas are perhaps far from analytical chemistry, but as will be discussed further,
chemistry and analytical chemistry are important factors for several of these areas.

GREEN CHEMISTRY
A literature search using the topic words green chemistry in Web of Knowledge, 2012-12-26, gave
8641 hits, of which one of the most cited (617 times) was published by Anastas and Kirchhoff in 2002
[6]. Paul Anastas is one of the key persons who first came up with the concept of green chemistry, which
is about the design of chemical products and processes that reduce or eliminate the use and generation
of hazardous substances [7]. Green chemistry includes both chemicals of immediate hazardous con-
cerns and more global issues such as climate change, energy production, availability of clean water,
food production, and the presence or spread of compounds of environmental concern. Green chemistry
is simply a compilation of 12 principles that serve as a guideline to create more environmentally benign
products and processes [6].
Green chemistry is about atom economy, energy efficiency, and avoiding the use of toxic sub-
stances. One obvious concern is the number of synthesis steps required to produce a chemical. In Jessop
et al. [8], it was discussed how much energy was required and the release of CO2 in the manufacturing
of different solvents. The number of synthesis steps certainly affects the outcome, for instance, tetra-
hydrofuran (THF) costs about five times more in energy (MJ/kg) to manufacture than ethanol. In the
same publication, it was also made clear that ionic liquids often require 2030 synthesis steps, while
hexane and CO2 are available without any synthesis step (only purification/separation).
There are several excellent review articles describing the use of supercritical CO2 (scCO2) as a
solvent in catalytic reactions [9], enzymatic reactions [10], extraction and fractionation [11], as well as
processing of materials [12]. scCO2 is certainly less toxic than hexane, but there are also other green
solvent options, such as polyethylene glycol (PEG [13]), d-limonene [14], ethanol, and, of course,
water. Some of the most enthusiastic researchers, and also pioneers in this field, are Roger A. Sheldon
and Martyn Poliakoff, as they have further developed the principles of green chemistry. For instance,
Poliakoff and coauthors described the 13 principles of green chemistry and engineering for a greener
Africa [15], which are as follows:
G Greener Africa
R Regard for all life and human health
E Energy from the sun
E Ensure degradability and no hazards
N New ideas and different thinking
E Engineer for simplicity and practicality
R Recycle whenever possible
A Appropriate materials for functions
F Fewer auxiliary substances and solvents
R Reactions using catalysts
I Indigenous renewable feedstock
C Cleaner air and water
A Avoid the mistakes of others
Roger Sheldon has contributed strongly to the field of green chemistry through his work on the
E-factor [16] and green solvents [17], which will be discussed further in the following sections. There
is a lot more to say about green chemistry, but the reader is instead referred to any of the most recent

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2220 C. TURNER

review articles on this subject, for instance, the one by Anastas and Eghbali [18] or in the special issue
on green chemistry [Chem. Soc. Rev. Feb. 21, issue 4, 14051608 (2012)].

GREEN ANALYTICAL CHEMISTRY


To the best of my knowledge, it is Paul Anastas who first mentioned green analytical chemistry in a
review article from 1999 [19]. However, analytical chemistry has been used since the 1960s to monitor
pollutants from environmental and food samples. Analytical methodologies have continuously been
improved by better accuracy, sensitivity, and precision. In addition, improvements have been done in
terms of reducing the use of solvents in sample preparation and miniaturization of columns, however,
not always mentioning the concept of green analytical chemistry. Green analytical chemistry is not
about monitoring of environmental pollutants, but rather greening of methodologies. From the
12 principles, 7 principles of green analytical chemistry can be extracted:
1. Prevent or reduce the formation of waste, for instance, by using smaller inner diameter columns
in chromatography.
2. Use less toxic/environmentally burdensome chemicals and solvents.
3. Design energy-efficient analytical systems and methodologies.
4. Avoid the use of chemical catalysts, derivatization reagents, and other auxiliary substances.
5. Catalysis is better than stoichiometric reactions.
6. In situ analysis is better than off-line analysis.
7. Use safer chemistry to prevent accidents such as explosions and fires.
There are several review articles [2022] as well as a few books [23,24] describing the area of
green analytical chemistry. For instance, Armenta et al. [20] described the time-line and concepts for
many of the analytical techniques identified as being green, including microwave-assisted extraction
(MAE), supercritical fluid extraction (SFE), pressurized liquid extraction (PLE), solid-phase micro-
extraction (SPME), stir-bar sorptive extraction (SBSE), single-drop microextraction (SDME), and
liquidliquidliquid microextraction (LLLME), among others. The focus has been on sample prepara-
tion, since this part of the analytical chain is well recognized as the least green, mainly due to the large
consumption of solvents.

Greening sample preparation


In sample preparation, the solvent issue is obviously a main concern, and there are a large number of
publications describing alternative extraction methods using pressurized hot (subcritical) water [25] and
scCO2 [26] as solvents. In some publications, different green extraction techniques have been compared
[27]. In our own work, we have demonstrated that subcritical water enables a faster and greener alter-
native with equal accuracy compared to conventional solvent extraction, for the determination of
flavonoids and anthocyanins in onion [28,29] and red cabbage [30]. In the case of quercetin in onion,
we have conducted an LCA to examine the environmental impact of a novel method using hot water
and thermostable -glucosidase for the extraction and hydrolysis of quercetin glucosides in onion. The
new method was compared to a conventional method based on the combined extraction and hydrolysis
with aqueous methanol containing hydrochloric acid [29]. Figure 1 demonstrates the environmental
impact of the two methods, as calculated in terms of primary energy consumption and CO2 equivalents
in the respective processes. The newly developed method clearly has less environmental impact.
Another sample preparation technique worth mentioning is SPME, which is based on the use of
a sorptive fiber instead of an organic solvent. This fiber is immersed in the aqueous sample containing
the target analytes. The technique was introduced by Janusz Pawliszyn in 1990 [31] and has grown and

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Sustainable analytical chemistry 2221

Fig. 1 LCA of a developed method based on pressurized hot water extraction at 120 C and -glucosidase catalyzed
hydrolysis at 95 C. Primary energy consumption (left) and global warming potential expressed as CO2 equivalents.
Figure modified from [29].

developed continuously since then [32]. There are now many different examples of sorptive extraction
techniques that avoid or minimize the use of solvent. One such technique is molecularly imprinted
solid-phase extraction (MISPE) [33], which is a more selective technique than SPME, and the princi-
ple of operation is more similar to solid-phase extraction. Briefly, a polymer is synthesized with a tem-
plate molecule present, creating specific binding sites for the molecule. Even though in theory such a
sorbent should be highly specific, it usually offers nonspecific binding as well, making the technique
selective rather than specific. The challenge ahead is to make greener molecular imprinted polymers
(MIPs) that could be easily cleaned and reused a large number of times.

Greening chromatography
There are several publications dealing with greening of chromatography, by using smaller separation
systems [34], or greener solvents such as water [35,36]. In addition, older separation techniques such
as gas chromatography (GC) and capillary electrophoresis (CE) are in fact quite green techniques, and
when such techniques are applicable and practical to use, they are beneficial from a green chemistry
point of view. However, not all compounds and complex sample matrices can be processed by CE or
GC. Clearly, miniaturization is one way to go, and there is a lot of interesting novel research in
microfluidics and lab-on-a-chip applications [37].
Another recent trend is that supercritical fluid chromatography (SFC) has been revived, and
instrumentation is now available in both analytical and preparative scale from several vendors. Figure 2
shows that after 1990 there was a dip in terms of relative record count, comparing SFC with chro-
matography. However, SFC did not disappear completely and is now expected to get another upswing.
What is different compared to the 1990s, is that there is less concern of whether the mobile phase is a
supercritical fluid or not. Pressure, temperature, and co-solvent amount is optimized without consider-
ing the phase transfer into a liquid domain of the phase diagram. However, it has been shown that even
though large volume-concentration of methanol is added to the pressurized CO2, efficient chromatog-
raphy is obtained with nice peak shapes. It is important to realize that the pressure needs to be high
enough to avoid phase splitting into gas and liquid [38], unless this is desired, of course. The gain com-
pared to conventional high-performance liquid chromatography (HPLC) is the speed and the lower vol-
umes of organic solvents needed. Perhaps the biggest gains are found in applications where usually
quite strong nonpolar organic solvents are used, such as those used in normal phase chromatography of
lipids (e.g., dichloromethane).

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2222 C. TURNER

Fig. 2 Relative record count in percentage, using the topic SFC divided by chromatography, Web-of-Science
2014-04-25.

The use of pressurized hot (subcritical) water as a mobile phase in chromatography was pioneered
by Roger Smith in 1996 [39]. Since then, there have been more than 400 published papers on the sub-
ject, including a recent review article that describes not only subcritical water chromatography but also
ultrahigh pressure liquid chromatography and micro/nano-scale chromatography [36]. In one particu-
larly interesting publication, pressurized CO2 was added as a modifier to the subcritical water, in order
to reduce the polarity of the solvent [40]. Results showed that the introduction of CO2 at pressures of
around 160 atm and temperature of 100 C enabled Gaussian peak shape of 1-octanol and elution from
a poly(styrene-divinylbenzene) column within 4 min. When water at 100 C without the addition of
CO2 instead was used as a mobile phase, the peak was not eluting even after several hours. Similarly,
benzene, toluene, ethylbenzene, and p-xylene gave retention times of less than 5 min when using
160 atm and 100 C, compared to using only subcritical water at 200 C when only benzene was elut-
ing, after 30 min, see Fig. 3. However, it is unclear what the retention mechanism was, since CO2 and

Fig. 3 Comparison of conventional subcritical water chromatography at 200 C (dashed line) and CO2/water
chromatography at 160 atm and 100 C (solid line). Reprinted with permission from ref. [40]. Copyright 2008,
Elsevier.

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Sustainable analytical chemistry 2223

water at those conditions are immiscible, giving carbonated water in equilibrium with a dense (CO2)
gas phase containing small amounts of water.

Greening detection
In terms of detection in analytical chemistry, most of the greening efforts have been focused on in situ
analytical techniques, mainly different spectroscopic techniques [41]. From a green chemistry point of
view, in situ analysis is beneficial because it allows for real-time assessment of a process, allowing for
direct monitoring of the production of hazardous or non-safe substances. In situ analysis also avoids
extra handling steps that usually lead to larger usage of chemicals and energy. An example of such a
technique is Raman spectroscopy [42], which has been combined with microfluidic separation [43]. A
clear advantage of Raman spectroscopy is the possibility to use it for in situ analysis in high-pressure
fluid systems, since the laser beam reaches inside a fairly thick sapphire glass window [44]. For
instance, we have demonstrated the feasibility of using Raman spectroscopy for solubility determina-
tion in scCO2 [45]. Raman spectroscopy showed a great potential for use as an in situ monitoring detec-
tor, in processes, for surface analysis and for in vivo analysis in biological systems [46,47].

What makes it green?


Many of the publications already cited are well written when it comes to describing the different strate-
gies in green analytical chemistry, however, the motivation around why a certain technique or method
could be claimed as being green is rather weak. Often, common sense is sufficient, such as it is certainly
better to use less solvent than more in an extraction step. However, the replacement of a quite toxic sol-
vent with a less toxic one is perhaps not as clear, especially since different quantities of solvents are
needed to achieve the same result. One of our approaches has been to replace hexane with hot ethanol
in the extraction of carotenoids from carrot [48]. Our calculations showed that for the extraction of 1 g
of -carotene, 1.4 kg of ethanol at 60 C was needed as a solvent, while approximately only 90 g of THF
at ambient temperature was needed to achieve the same extraction, based on solubility data [49]. Hence,
although THF was a significantly more toxic solvent, to both humans and the environment when com-
pared to ethanol, a much smaller amount was needed due to the higher solubility of carotenoids in THF.
Clearly, there are many factors to take into consideration when greening analytical methods.
Such factors include the amount of waste produced; toxicity and environmental burden of all chemicals
used, waste generated; energy and electricity used in the analytical process, as well as in the production
of the chemicals; and the safety of the analytical method. Analytical methods are not easily compared,
taking all these factors into consideration. What is indisputably necessary in order to enable a compar-
ison of different analytical methods is to use a defined functional unit, to which all methods can relate.
Such a functional unit should preferably be one analytical result, taking the whole analytical chain
into consideration, from sample preparation to data analysis. This means, for instance, that the volume
of organic solvent used in method A could be compared to the volume of solvent used in method B, per
analytical result. A functional unit enables a more holistic sustainable perspective, as described in more
detail in the following sections.

SUSTAINABLE ANALYTICAL CHEMISTRY


It is becoming generally accepted that in order to claim the sustainability of a process or product, hard-
core data on true environmental impact is needed. Hence, in order to fully assess the greenness of an
analytical method, the environmental impact should be calculated based on input data that is as good as
possible. There are several green chemistry metric tools to be used for calculation of environmental
impact, including carbon footprint [50]; atom economy [51]; environmental E-factor [52]; environment,
health, and safety (EHS) index [53]; and LCA [54,55]. Most of the green chemistry metrics was adapted

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2224 C. TURNER

for classical green chemistry (i.e., chemical synthesis), however, these tools can still be used for the
assessment of the greenness of the chemicals and solvents used in the analytical method.

Green metrics
In analytical chemistry, green metrics is rarely used. There are a few exceptions however. In Gaber et
al. [56], an environmental assessment tool (EAT) was developed for HPLC methods using EHS data.
The new software tool is called HPLC-EAT. HPLC-EAT was compared to another free software called
the Eco-solvent tool for LCA of waste disposal options of distillation or incineration [57,58]. Such tools
are valuable when choosing and developing analytical methods, in this case, regarding the selection of
solvents for HPLC methods. In a similar study, an analytical method volume intensity (AMVI) green
metrics tool for HPLC methods was developed, simply based on the total solvent consumption per chro-
matographic peak of interest [59]. In this case, no value was put on what type of solvent was used, but
rather just the volume.
There is a national environmental methods index (NEMI) developed by U.S. government agen-
cies and private sector organizations and companies in the United States. Current contributions by gov-
ernment agencies include the U.S. Environmental Protection Agency, the U.S. Geological Survey, and
the U.S. Department of Energy [22]. The NEMI takes into account PBT (persistent, bioaccumulative,
toxic, as defined by the EPAs toxic release inventory, TRI); hazardous (as listed on the TRI); cor-
rosive (pH during analysis is <2 or >12); and waste (the amount of waste generated in one analysis
is >50 g). More than 800 analytical methods have been evaluated. The NEMI is a start, but a clear weak-
ness is that it only considers the method as such and, for instance, not the energy demand for the man-
ufacturing of the chemicals used. Similarly, physical, environmental, and health hazards data from the
Globally Harmonized System of Classification and Labeling of Chemicals (GHS) have been used to
create an analytical eco-scale system, utilizing penalty points for steps in the analytical method that
does not comply with ideal green analysis [60]. Maximum obtainable points are 100, and any scor-
ing above 75 is said to be green analysis. Again, a problem is the arbitrary scoring system, being at best
semi-quantitative, which is also recognized by the authors.
The most powerful environmental assessment method is LCA, since this tool takes into account
the total environmental impact from cradle to grave (e.g., the production of solvents, transportation,
usage, and finally disposal of the solvent). There is only one example of an analytical chemistry study
where LCA has been applied (in addition to the HPLC-EAT example above) for the comparison of
preparative SFC to preparative HPLC [61]. In that study, depending on how the system boundaries were
set, preparative HPLC required 26 % more resources than the preparative SFC separation due to its
inherent higher use of organic solvents (process level boundary), while the opposite was true when
using a larger overall industrial system boundary, due to the production of liquid CO2 and the use of
electricity for heating and cooling. For the critical mind, the results from an LCA strongly depend on
the assumptions being made, in this case, one assumption was that liquid CO2 was being produced with
no other purpose, rather than being taken as a byproduct, for instance, from biogas production.

The case of greener solvents


One of the most difficult aspects to consider when comparing different analytical methods is the choice
of solvent, both in sample preparation and in chromatography. First of all, as mentioned earlier, the sol-
vent properties determine the solubility of the analytes as well as the selectivity of the process. Hence,
a greener solvent could be worse because of the larger volumes required. There has been a lot of effort
describing and classifying organic solvents. The easiest classification is based on the simplest inter-
molecular interactionspolar protic, polar aprotic, and nonpolar solvents. A similar classification is
based on solvatochromic parameters [62], which contain the three KamletTaft parameters , , and *,
which quantify hydrogen-bond donating ability (acidity), hydrogen-bond accepting ability (basicity)

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Sustainable analytical chemistry 2225

and polarity/polarizability, respectively. In Jessop et al. [62], solvatochromic data was published for 83
molecular solvents, 18 switchable solvents, and 187 ionic liquids that were cited in the green chemistry
literature. In a related study by Jessop et al. [8], it was demonstrated by using the KamletTaft param-
eters that there is a lack of appropriate green replacements for amines, hexamethylphosphoramide
(HMPA), halogenated solvents, and aromatic solvents. In the same study [8], certain solvents were
described as being green, including the Pfizer green list solvents (water, methanol, ethanol, 2-propanol,
1-propanol, 1-butanol, t-butanol, heptane, ethyl acetate, isopropyl acetate, acetone, and methyl ethyl
ketone), two carbonate solvents (diethylcarbonate and propylene carbonate), two liquid polymers
[poly(ethylene glycol) and poly(propylene glycol], several CO2-expanded solvents, scCO2, subcritical
water, and several biomass-derived organic solvents (-valerolactone, 2-methyltetrahydrofuran, glyc-
erol, glycerol ethers, ethyl lactate, and cyclopentyl methyl ether). Ionic liquids were not included
because of the generally large number of synthesis steps required to produce them.
A central question would be which solvents are actually green. Inherently, green metrics is needed
to determine the greenness of a solvent. This was also pointed out by Jessop et al. [8], and some green
metrics methods were suggested, such as calculation of the energy to manufacture the solvent; calcula-
tion of the cumulative energy demand from a life-cycle perspective; and assessment of the impact on
health and the environment. An important aspect is whether it is beneficial from an energy point of view
to incinerate the solvent after using it, or if it is worth it to recycle and reuse the solvent [58]. In Capello
et al. [63], 26 organic solvents were examined in terms of their environmental impact from cradle (man-
ufacturing) to grave (incineration alternatively distillation). LCA as well as EHS indexes were used to
score the solvents, and the results showed that simple alcohols (methanol, ethanol) and alkanes (hep-
tane, hexane) were environmentally preferable solvents from an LCA perspective, whereas the use of
dioxane, acetonitrile, acids, formaldehyde, and THF would be less sustainable. When EHS aspects are
also considered, methanol, ethanol, and methyl acetate seemed to be the preferred solvents, see Fig. 4
[63].

Fig. 4 Environmental assessment of 26 organic solvents using both EHS index and cumulative energy demand from
manufacturing to waste handling. Reprinted with permission from [63]. Copyright 2007, Royal Society of
Chemistry.

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2226 C. TURNER

It should be noted, however, that the study by Capello et al. [63] assumed that all solvents are
manufactured from the petrochemical industry, although this is not always true for ethanol and
methanol, for instance. In addition, water and pressurized CO2 were not at all considered in the study.
How could this information be of interest to analytical chemists? A first thought could be that it
is difficult to choose among organic solvents. One solvent that is more toxic than another one could be
easier to evaporate, thereby consuming less energy. Such considerations would also depend on the gen-
eral safety in the lab. Are there fume hoods? How is organic solvent waste handled? What is most
importantcumulative energy demand or health aspects?

From green metrics to sustainability


It is well known that for a development to be truly sustainable, all three areas of environment, economy,
and society need to be considered. So far, mainly the environmental aspects have been discussed, since
they are the dominant ones in the green metrics tools. What could it imply to do sustainable analytical
chemistry? Let us consider also economic and societal aspects.
For analytical chemistry to be economically sustainable, the methods should be cost-efficient,
which often means high-throughput and fully automated systems. Portable devices that can be taken to
the field for measurements at the source can be a cost-efficient alternative since sampling and trans-
portation is minimal [64]. However, cost-efficient portable instruments do not always fulfil the expec-
tations in terms of selectivity and limit of detection of the methodology.
Societal relevance implies that analytical chemistry should be developed in areas where there is
a significant societal importance, including the creation of new job opportunities; energy efficiency and
use of renewable resources; minimization of pollution in cities; food supply and security; water qual-
ity; oceans health; and prevention of devastating situations after natural disasters. Hence, for analyt-
ical chemistry to be sustainable for society, research efforts should go in those directions. This could
imply anything from determining environmental effects of novel materials (e.g., nanoparticles in marine
environments) or in situ assessment of reactions in biorefinery processes. Most of such relevant research
questions require multi-disciplinary efforts, including natural science, social science, engineering, eco-
nomics, and law. There are certainly examples of projects in analytical chemistry that deal with ques-
tions of less importance to the society. For sure, a crucial determinant here is the funding agency to
select among research proposals in a sound and sustainable way. Again, this requires multi-disciplinary
expertise, which in some cases can be a challenge.
Finally, analytical chemistry should be environmentally sound, which has already been discussed
regarding waste minimization through, for instance, miniaturization; green solvents or solventless
methods; energy efficiency; avoiding the use of auxiliary chemicals; preventing accidents through safer
methods; and further developing in situ and in-field analysis techniques.
Another aspect to point out is that often larger-scale processes are developed from smaller-scale
ones, hence it is important that although analytical methods are small-scale, they are sometimes taken
to industry where the environmental impacts will be larger.

SUGGESTIONS FOR THE FUTURE


Future challenges in sustainable analytical chemistry are firstly to apply green metrics such as LCA and
EHS to analytical methodologies, to assure a development towards environmental sustainability.
Publication opportunities in this area are wide open, and this should be a trigger for researchers.
Secondly, it is important that analytical chemistry continues to take the lead in research questions
of importance to the global society. It will be more and more important to be involved in interdiscipli-
nary research projects. Such efforts facilitate thinking outside the box, which is indispensable for
advancement in many of the large challenges we are facing.

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Sustainable analytical chemistry 2227

Thirdly, some of those large challenges ahead of us, for instance, the transfer from fossil fuel-
based economy to a bio-based economy, will require specific efforts in analytical method development.
Another challenge to mention is the one of drug residues in the environment, in which research has
shown that hormone-disrupting compounds are more toxic at extremely low concentrations than at rel-
atively higher concentrations. This puts higher demands on the analytical methods. To tackle large chal-
lenges like these, and at the same time consider the greening of the methods, is probably the most chal-
lenging aspect of them all.
Finally, analytical chemistry must be recognized for being a crucial discipline of chemistry, point-
ing at the fact that analytical chemistry is not just a simple tool for other chemists to use, but a contin-
uously developing research area with large implications for the future good.

ACKNOWLEDGMENTS
The Swedish Foundation for International Cooperation in Research and Higher Education (STINT,
YR2009-7015), the Swedish Research Council Formas (229-2009-1527), and the Swedish Research
Council (VR, 2010-333) are greatly acknowledged for financial support.

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Trends in Analytical chemistry 50 (2013) 7884

Contents lists available at SciVerse ScienceDirect

Trends in Analytical chemistry


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

Review

The 12 principles of green analytical chemistry and the SIGNIFICANCE mnemonic


of green analytical practices
Agnieszka Gauszka a, Zdzisaw Migaszewski a, Jacek Namiesnik b,
a
Geochemistry and the Environment Div., Institute of Chemistry, Jan Kochanowski University, 15G Swietokrzyska St., 25-406 Kielce, Poland
b
sk University of Technology (GUT), 11/12 G. Narutowicz St., 80-233 Gdan
Department of Analytical Chemistry, Chemical Faculty, Gdan sk, Poland

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

Keywords: The current rapid development of green analytical chemistry (GAC) requires clear, concise guidelines in
Energy reduction the form of GAC principles that will be helpful in greening laboratory practices. The existing principles of
Green analytical chemistry (GAC)
green chemistry and green engineering need revision for their use in GAC because they do not fully meet
Green chemistry principles
the needs of analytical chemistry.
Miniaturized methods
Minimization of analytical waste In this article we propose a set of 12 principles consisting of known concepts (i.e. reduction in the use of
Natural reagent reagents and energy, and elimination of waste, risk and hazard) together with some new ideas (i.e. the
Risk reduction use of natural reagents), which will be important for the future of GAC.
Safe reagent 2013 Elsevier Ltd. All rights reserved.
Waste reduction
12 principles of green analytical chemistry
(GAC)

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2. The 12 principles of GAC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3. The key components of green analysis a backbone of GAC principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.1. Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.2. Methods and instruments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.3. Reagents and safety of the operator. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.4. Analytical wastes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

1. Introduction Green analytical chemistry (GAC) emerged from green chemis-


try in 2000 [2]. This relatively new area of activity within green
The idea of green chemistry has its roots in sustainable chemistry concerns the role of analytical chemists in making labo-
development. The rst activities undertaken by chemists for sus- ratory practices more environmentally friendly, and it has gained a
tainability were focused mostly on industrial-scale processes and great deal of interest among chemists [35]. Aside from the
products, as clearly postulated in the most widely known deni- development in instrumentation and methodologies, which are
tion of green chemistry proposed by Anastas [1]. The beginnings necessary for improvements in the quality of chemical analyses, ef-
of green chemistry were dominated by the subject of green organic forts are being made to reduce the negative impact of chemical
synthesis in different branches of the chemical industry, especially analyses on the environment and to enable implementation of sus-
the pharmaceutical industry. tainable development principles to analytical laboratories. In this
context, GAC should be recognized as a stimulant to the progress
of analytical chemistry. The most important challenge to the future
of this discipline is to reach a compromise between the increasing
Corresponding author. Tel.: +48 58 347 10 10; Fax: +48 58 347 26 94. quality of the results and the improving environmental friendliness
E-mail address: chemanal@pg.gda.pl (J. Namiesnik).

0165-9936/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.trac.2013.04.010
A. Gauszka et al. / Trends in Analytical chemistry 50 (2013) 7884 79

of analytical methods. Guidelines that provide the framework for chemistry and green engineering IMPROVEMENTS PRODUC-
GAC are needed to meet this challenge. TIVELY [8,9].
In 1998 Anastas and Warner [6] formulated the 12 principles of
green chemistry. Designed to meet the needs of synthetic chemis- 3. The key components of green analysis a backbone of GAC
try, only some of these principles can directly be applied to analyt- principles
ical chemistry. The principles that nd such application for both
synthetic and analytical purposes are: Modern analytical chemistry offers many techniques and
instruments for determination of a given analyte in different sam-
(i) prevention of waste (principle number 1); ples. The key goals to be achieved in greening analytical methods
(ii) safer solvents and auxiliaries (principle number 5); are:
(iii) design for energy efciency (principle number 6); and,
(iv) reduction of derivatization (principle number 8). (1) elimination or reduction of the use of chemical substances
(solvents, reagents, preservatives, additives for pH adjust-
Efforts were also made to nd analytical consequences of the 12 ment and others);
principles of green chemistry [7], but at least one of the 12 princi- (2) minimization of energy consumption;
ples the maximization of atom economy (principle number 2) (3) proper management of analytical waste; and,
is inadequate for analytical chemistry. There are also important (4) increased safety for the operator.
concepts in GAC that have not been included in the 12 principles
proposed by Anastas and Warner [6]. Considering this, we suggest Most of these issues require reductions (e.g., sample number,
that the 12 principles of green chemistry should be revised to nd reagents, energy, waste, risk and hazard) [10].
full application in analytical chemistry. In our proposal, we used One of the drawbacks of greening laboratory practices is the
four of the principles provided by Anastas and Warner [6] and sup- need for compromise between the performance parameters and
plemented them with eight new principles that nd their impor- GAC requirements. Most of the guidelines for analytical chemists
tant application to GAC. proposed in our 12 principles may cause the decrease of perfor-
mance parameters such as accuracy, precision, sensitivity (Table 1).
The reliability of analytical methods may easily be questioned in
minimizing sample size, applying direct methods and miniaturiz-
2. The 12 principles of GAC
ing instruments. However, rapid technological development and
knowledge about existing problems will lead to improvements in
In our approach, the 12 principles of GAC are as follows:
green analytical methods. Sometimes, these problems can be
solved in simple ways (e.g., modifying in-situ measurements to im-
1. Direct analytical techniques should be applied to avoid
prove calibration by running standards between samples) [11].
sample treatment.
Chemical analysis is a complex process consisting of several
2. Minimal sample size and minimal number of samples are
steps, for which green alternatives can be employed. It is important
goals.
to evaluate each of the processes and the operations that are com-
3. In situ measurements should be performed.
ponents of analytical methodology for their agreement with the
4. Integration of analytical processes and operations saves
principles of green chemistry. In our recent paper [12], we
energy and reduces the use of reagents.
introduced such a green analytical evaluation tool an analytical
5. Automated and miniaturized methods should be selected.
Eco-Scale which will be helpful for nding and improving the
6. Derivatization should be avoided.
weakest link in the method.
7. Generation of a large volume of analytical waste should be
Despite the diversities of analytical methods and analytes
avoided and proper management of analytical waste should
determined, a sample and an operator take part in every analysis.
be provided.
Most of the methods also require the use of at least one reagent
8. Multi-analyte or multi-parameter methods are preferred
and produce analytical waste. Although chemical analysis is a pro-
versus methods using one analyte at a time.
cess comprising several steps inuencing each other, we nd six is-
9. The use of energy should be minimized.
sues critical for GAC principles (Fig. 2). Table 2 compares less green
10. Reagents obtained from renewable source should be preferred.
techniques used for determination of the same analyte in the same
11. Toxic reagents should be eliminated or replaced.
matrix with their greener alternatives. This comparison, based on
12. The safety of the operator should be increased.
different analytical applications (environmental, food, pharmaceu-
tical, industrial and biomedical) has some practical implications for
We also propose the mnemonic SIGNIFICANCE (Fig. 1) following
the use of green techniques. Most of recently introduced green
the idea of the mnemonic of the condensed 24 principles of green
analytical procedures [14,16,22,26,30] are characterized by not
only environmental friendliness, but also relatively high sensitiv-
ity, low cost of analysis, lower energy consumption, simplicity
and efciency in using time. Thus, it is very likely that some tradi-
tional methods will soon be replaced by these new green
techniques.

3.1. Sampling

Except for the use of direct analytical techniques, every analysis


begins with sampling. According to the second principle of GAC,
the number and the size of samples should be minimal. This prin-
ciple has special importance in environmental sample analysis be-
Fig. 1. The principles of green analytical chemistry expressed as the mnemonic cause the sampling strategy can easily be modied. Two
SIGNIFICANCE. approaches may be used to reduce the number of samples. The rst
80 A. Gauszka et al. / Trends in Analytical chemistry 50 (2013) 7884

Table 1
Practical consequences of GAC principles for selected parameters of analytical process.

STEPS IN ANALYSIS PARAMETERS OF THE ANALYTICAL PROCESS


Representativeness Accuracy Precision Selectivity Sensitivity Detectability
Sampling
Minimal sample size
Minimal sample number 0 0 0 0 0
Sample treatment
Without derivatization 0
Minimal use of energy 0
Reagents from renewable source 0
Without toxic reagents 0
Safety for operator 0
Measurement
Direct
*
In-situ
Integrated operations and processes 0 0 0
Automation 0
Miniaturized instruments
Multi-analyte and multi-parameter 0 0 0 0 0 0
Minimal use of energy 0

NOTE: decrease; increase; 0 neutral effect.


*
method dependent

involves the use of non-invasive methods, such as different geo- 3.2. Methods and instruments
physical techniques (e.g., remote sensing, seismic and magnetic
surveys), [35], or instruments (e.g., portable XRF) [36,37] for eld Selection of the greenest method from all the methods meeting
screening, and selection of sampling sites for a detailed chemical the needs of the user (e.g., detection limits, and accuracy), which
study. The second is to use statistics for selection of sampling sites are available for a given analyte, is critical for GAC. This is why ve
to obtain maximum data for reliable interpretation of the results of the 12 GAC principles refer to the method. Ideally, direct, auto-
with a minimal sample number. A barbell cluster ANOVA design mated, miniaturized analytical techniques are the greenest option
may be given as an example [38]. (principles number 1, 3 and 5). Important also is integration of
Reduction of sample size can be obtained through the application analytical processes and operations (principle number 4) because
of miniaturized analytical methods [39] or alternative sample- such an approach makes it possible to obtain all information from
introduction systems (e.g., laser ablation of solid samples by LA- a single analysis. Integration of analytical systems is best exempli-
ICP-MS). Reductions in sample number and volume should be done ed by microdevices, in which different steps of chemical analysis
carefully with awareness of the possibility of losing sample repre- (e.g., mixing, reaction and separation) are performed. A good
sentativeness, especially in sampling heterogeneous materials. example of this approach is a successful application of integrated
microchip capillary electrophoresis-electrochemical detection for
simultaneous determination of trace amounts of metals (e.g., Pb,
Cd and Cu) in vegetable juices [40]. It was shown that this simple,
quick technique has high resolution and sensitivity, requires small
amounts of sample and reagents, and is competitive with tradi-
tional analytical techniques.
Moreover, in many cases, it is necessary to determine more than
one analyte or parameter in one sample. In this case, multi-analyte
or multi-parameter methods should be preferred (principle num-
ber 8). These methods are of special importance in environmental
monitoring, when more than one analyte should be determined,
for instance in determination of potentially toxic trace elements.
Instead of time-consuming and reagent-consuming techniques
(e.g., atomic absorption spectrometry), a multi-element technique
(e.g., inductively coupled plasma mass spectrometry) will be more
suitable. It is preferable to avoid derivatization and other addi-
tional steps in analysis (principle number 6) because they consume
reagents and generate waste. If derivatization cannot be avoided, it
may be integrated with other processes (e.g., ltration, and extrac-
tion) in a single system [41]. The use of remote sensing, portable
instruments and miniaturized systems are often considered the
greenest methodologies [4244]. Their advantages in the light of
GAC principles are summarized in Fig. 3.
Each analytical methodology is characterized by its own specic
requirements and problems. Thus, it is important to evaluate and
to improve the greenness of an analytical method or technique
and to focus on its least green aspect. In GAC literature, there are
good examples of reviews on green spectroscopy [45,46], green
Fig. 2. Important components of analytical procedures in the aspect of GAC. electrochemistry [44] and green chromatography [4750]. Some
A. Gauszka et al. / Trends in Analytical chemistry 50 (2013) 7884 81

Table 2
Examples of green alternatives to conventional methods in different elds of analytical chemistry.

Less green alternative Greener alternative Refs.


Determination of lead in water
GF-AAS Stripping voltammetry [13,14]
Advantages Disadvantages Advantages Disadvantages
Selective, sensitive, Requires preconcentration, consumes Low detection limits, sensitive, simple, Possible interferences with other metals,
accurate reagents, produces wastes, time- and rapid, reliable, inexpensive, possible to needs monitoring of electrode stability
cost-consuming use in-situ
Determination of nitrate in tap water
HPLC Microchip electrophoresis [15,16]
Advantages Disadvantages Advantages Disadvantages
Rapid, small sample Poor repeatability, consumes reagents Small sample volume, reduced reagent Often poor reproducibility and sensitivity
volume, low cost, high and energy use, automated, rapid
sensitivity, accuracy
and selectivity
Determination of atrazine in water
Spectrophotometry Electrochemical biosensor [17,18]
Advantages Disadvantages Advantages Disadvantages
Simple, rapid, Consumes reagents, produces wastes, Rapid, high sensitivity, inexpensive and Poor stability and short life-time of
inexpensive poor sensitivity and selectivity simplied procedures enzymes, time-consuming preparation of
immuno-reagents
Determination of 17b-estradiol in water
GC-MS Electrochemical sensor [19,20]
Advantages Disadvantages Advantages Disadvantages
Selective, sensitive, Requires the use of toxic reagents, Simple and fast, low detection limit, Time-consuming preparation of immuno-
accurate, low produces wastes, needs heavy highly sensitive, portable, rapid, low reagents
detection limit laboratory workload, time-consuming energy consumption
Determination of bisphenol A in urban wastewater
GC-MS Electrochemical sensor [21,22]
Advantages Disadvantages Advantages Disadvantages
High selectivity and Multi-stage sample treatment, uses High sensitivity, and accuracy, good Sometimes poor reproducibility, in case of
sensitivity, accurate, toxic reagents and produces wastes, selectivity, in-situ measurement, rapid, traditional sensors determination of
low detection limit sometimes low reproducibility, requires low energy consumption, low cost bisphenol a is problematic because of the
derivatization poor response
Determination of Hg in soils
Spectrophotometry Solid sampling GF-AAS [23,24]
Advantages Disadvantages Advantages Disadvantages
Simple, rapid, Consumes reagents, produces wastes, Direct determination, cost-effective, Possible loss of analyte due to
inexpensive poor sensitivity and selectivity fast, reliable results for the purpose of volatilization
screening
Determination of total petroleum hydrocarbons in soils
GC-FID Hand-held FTIR [25,26]
Advantages Disadvantages Advantages Disadvantages
Low detection limits, Matrix effect, low resolution, time- In-situ measurements, no reagents High detection limit, mostly for screening
high-sensitivity to consuming, use of toxic reagents, consumed, fast, no need for sample purposes
abroad range of production of toxic wastes, destructive treatment, simple and cost-effective,
hydrocarbons, technique, non-destructive
economic
Determination of trace metals in alloys
F-AAS LA-ICP-MS [27,28]
Advantages Disadvantages Advantages Disadvantages
Simple, economic, Needs preconcentration, time- Non-destructive, small sample size, no Expensive, needs professional experience,
accurate, selective, consuming sample treatment, consumes need of sample treatment suffers from interferences
and sensitive reagents, produces toxic and corrosive
wastes
Determination of folic acid in pharmaceuticals
Spectrophotometry Electrochemical biosensor [29,30]
Advantages Disadvantages Advantages Disadvantages
Simple, rapid, High detection limit, instability of the Simple and inexpensive, requires small Poor sensitivity, time-consuming
inexpensive colored product formed, consumes amount of sample preparation of immuno-reagents
reagents and produces wastes
Determination of blood glucose
Spectrophotometry Biosensor [31,32]
Advantages Disadvantages Advantages Disadvantages
Simple and rapid, Uses toxic and corrosive reagents, Real-time analysis, small sample Poor accuracy, possible interferences,
economic produces wastes, high detection limit volume, economic possible errors from incorrect use

(continued on next page)


82 A. Gauszka et al. / Trends in Analytical chemistry 50 (2013) 7884

Table 2 (continued)

Less green alternative Greener alternative Refs.


Determination of mercury in wine
ET-AAS Atomic uorescence spectrometry [33,34]
Advantages Disadvantages Advantages Disadvantages
Accurate, simple and Time-consuming sample treatment, High sensitivity, simplicity, rapidness, Relatively high detection limit
precise consumes reagents, produces wastes cost-effectiveness, uses sample matrix
as a reductant, no sample treatment

NOTE: AAS, Atomic absorption spectrometry (GF, Graphite furnace, F, Flame, ET, Electrothermal); HPLC, High-performance liquid chromatography; GC-MS, Gas chroma-
tography with mass spectrometry; GC-FID, Gas chromatography with ame-ionization detector; FTIR, Fourier-transform infrared spectroscopy; LA-ICP-MS, Laser-ablation
inductively coupled plasma mass spectrometry.

friendly equivalents is an important trend in GAC (GAC principle


number 11). The majority of reagents to be replaced in analytical
procedures are organic solvents [55]. Ionic liquids and supercritical
uids are considered as alternative (green) solvents. Different ionic
liquids, mostly based on quaternary nitrogen cations, have found
wide application in chromatographic and electromigration tech-
niques, electrochemistry and spectroscopy [5658]. Except for
serving as alternative solvents for extractions [59], ionic liquids
can be used as stationary phases in gas chromatography [60].
Green alternatives for extraction with traditional solvents are
supercritical uid extraction (SFE) and a subcritical water extrac-
tion (SWE). Advantages of supercritical CO2 as an alternative sol-
vent made SFE one of the most popular sample-preparation
techniques in chromatography [61]. Application of supercritical
uids in chromatography resulted in the introduction of capillary
column supercritical uid chromatography (SFC) and packed col-
umn SFC [62].
One of the recent trends in GAC is the use of reagents obtained
from renewable sources in analysis (GAC principle number 10).
Plants, animals, microorganisms and their extracts may be used
as the pH and redox indicators, reagents for spectrophotometry,
Fig. 3. Advantages of portable instruments, remote sensing and miniaturized uorimetry or applied in biosensors [63]. Despite their limitations
systems in the context of GAC principles. in quantitative analysis, the green natural reagents may be used in
teaching analytical chemistry [64]. One of the priorities in sustain-
of the published GAC reviews are devoted to a specic step of ana-
able development is to reduce the use of non-renewable resources
lytical procedure (e.g., sample treatment) [51].
in favor of renewables. This should stimulate the progress of ana-
The instrument is directly linked to the method. In general, for the
lytical methods utilizing natural reagents.
purpose of GAC, instrumental methods are preferred, but there may
Safer (less toxic, natural) reagents contribute to increase the
also be some classical, wet chemistry methods that are as green as
safety of the operator (GAC principle number 12). However, reduc-
the instrumental ones (e.g., procedures for determination of Cu in
ing the risk for the operator is also ensured through the use of
a brass sample by titration, electrogravimetry and AAS Tables 3
automated instrumental methods, miniaturized systems, and on-
5 in [12]). The problem that still needs discussion in GAC is the large
line decontamination of analytical waste [3].
ecological footprint of the production and the maintenance of ana-
lytical instruments, which can be fully understood and ameliorated
3.4. Analytical wastes
through assessing the life-cycle of analytical instruments. Auto-
mated and miniaturized instruments reduce the amounts of re-
Analytical methods differ in the volume of waste produced.
agents consumed and waste generated (GAC principle number 7),
Greenest are methods that generate no waste or generate only a
increase the safety of the operator (GAC principle number 12) and fa-
small volume of waste (i.e. <50 mL(g)) [65]. In general, the more
vor proper waste treatment (GAC principle number 7) [52].
steps in an analytical procedure and the more reagents consumed,
The best example of miniaturization and integration of pro-
the higher the volume of analytical waste. Thus, reduction in the
cesses and operations (GAC principle numbers 4 and 5) is provided
use of reagents by the methods discussed above contributes to
by miniaturized total analysis systems (lTAS), in which sample
minimizing the production of waste.
treatment and measurement are located extremely close to each
Another important issue is ensuring the proper treatment of
other. First introduced in 1990 [53], these systems quickly became
analytical waste (GAC principle number 7). The toxicity of waste
very popular and found their applications mostly in clinical/bioan-
may be reduced through recycling, degradation and passivation
alytical and environmental laboratories [54]. Another clear advan-
of waste, preferably performed on-line [66].
tage of lTAS is the minimal sample and reagent volumes (between
pL and nL), which is favored for GAC (GAC principle number 2).
4. Conclusion

3.3. Reagents and safety of the operator Most analytical methods cannot be considered green and they
need certain improvements through eliminating toxic reagents,
Elimination or replacement of toxic, persistent reagents show- reducing the use of reagents and energy, and increasing operator
ing bioaccumulative properties with their more environmentally safety. Changes are needed in the whole analytical process, begin-
A. Gauszka et al. / Trends in Analytical chemistry 50 (2013) 7884 83

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TUTORIAL REVIEW www.rsc.org/csr | Chemical Society Reviews

Green analytical chemistrytheory and practice


Marek Tobiszewski,* Agata Mechlinska and Jacek Namies nik
Received 21st January 2010
First published as an Advance Article on the web 26th May 2010
DOI: 10.1039/b926439f

This tutorial review summarises the current state of green analytical chemistry with special
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emphasis on environmentally friendly sample preparation techniques. Green analytical chemistry


is a part of the sustainable development concept; its history and origins are described.
Miniaturisation of analytical devices and shortening the time elapsing between performing
analysis and obtaining reliable analytical results are important aspects of green analytical
chemistry. Solventless extraction techniques, the application of alternative solvents and assisted
extractions are considered to be the main approaches complying with green analytical chemistry
principles.

Introduction life. So, the starting point is focused on human beings, in


contrast to many ethical viewpoints on the environment. This
Sustainable development, like the earlier protection of the seems correct, since sustainable development demands certain
environment or ecology, has become a very popular term. limitations to human activities.2
Protection of the environment itself, however, is not a The above denition of sustainable development is also a
discipline with a long tradition. Contemporary environmental normative concept: it gives us standards (rules) upon which to
awareness probably stems from the famous U Thant Report, base judgments.2 Sustainable development concerns the
presented at the 23rd session of the United Nations in 1969. common area of three spheres: society, the market and the
Further tentative references to sustainable development can be environment (see Fig. 1).
found in the proceedings of the Stockholm conference in 1972. Among the factors inuencing a sustainable state, pride of
A clear formulation of the idea came to light in the 1980s. The place must go to manufacturing technologies, which in many
works of the United Nations Commission on Environment cases involve chemical activities at both the industrial and the
and Development, established in 1983, should also be laboratory scale. The crucial role of chemists is endorsed by
mentioned. This commission prepared the Brundtland Report, data in the OECD report on the rate of chemical production
published in Our Common Future. It is from this book that compared to the increase in the global human population
the well-known denition of sustainable development comes: (Fig. 2). These data also substantiate the hypothesis about the
a form of development that meets the needs of the present ongoing chemicalisation of the homosphere.3
without compromising the ability of future generations to We are becoming increasingly concerned about the state of
meet their own needs.1 Sustainable development is thus the environment. It would, therefore, be appropriate to
people-centred: it aims at improving the quality of human examine those activities of chemists and chemical engineers
that can signicantly inuence the state of the environment at
both the industrial and the laboratory scale.
Department of Analytical Chemistry, Chemical Faculty,
Gdansk University of Technology (GUT), Narutowicza 11/12 G., As a consequence of the ever-increasing quantities of
80-233 Gdansk, Poland. E-mail: marektobiszewski@wp.pl products and consumer goods needed in everyday life, the

Marek Tobiszewski MSc Agata Mechlinska MSc (born


(born 1984) obtained his 1982) graduated from the
MSc degree in 2008, after Gdansk University of Techno-
which he started his PhD logy with an MSc in analytical
studies at GUT. His research chemistry in 2008. She is
interests include environ- currently in her second year
mental analytical chemistry, of her postgraduate studies
sample preparation before (PhD). Her research interests
gas chromatographic analysis, include the isolation and deter-
and the environmental fate of mination of toxic congeners of
organic pollutants, in parti- polychlorinated biphenyls in
cular chlorinated solvents. environmental samples.

Marek Tobiszewski Agata Mechlinska

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c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 28692878 | 2869
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environmentally friendly, by making use of low waste


technologies and closed media cycles, and by recycling wastes
and by-products.4
The small-scale activities of chemists, such as laboratory
experiments, can also have a negative inuence on the
environment, e.g., through the uncontrolled disposal of
chemical wastes and spent reagents.
For all the above reasons the chemical community has been
developing dierent activities over a period of several years;
these may be considered on two planes:5
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- the teaching of basic aspects of environmental science at all


Fig. 1 Sustainable development as the common area of three spheres levels of education, resulting in the production of specialists
(economysocietyenvironment). capable of handling and solving existing and potential
environmental problems, and also in an increase of pro-
environmental awareness among the general public;
- an fresh approach to typical chemical activities, leading to
the environmentally more friendly use of facilities. In recent
times, this approach has been embraced on an ever larger
scale, and the term green chemistry has been coined to
describe it. Indeed, a new scientic journal has adopted
green chemistry for its name and is gradually becoming a
forum for the exchange of views and expertise among a
growing number of chemists.
A variety of terms are used to emphasise the possibility of
using chemical processes in environmentally friendly ways.
The most common ones are:
Fig. 2 Comparison of predicted changes in global population and
Green Chemistry
production of chemical goods at the global scale. Assumptions: the
Environmentally Benign Chemistry
production of chemical goods increases by 3% annually, the global
population increases at a rate of 0.77% per year.
Clean Chemistry
Atom Economy
label Homo technologicus has frequently been applied to Benign by Design Chemistry
contemporary humankind. This insatiable demand for various Ecological Chemistry
products is met by rapid developments in manufacturing Environmentally Friendly Chemistry
technology. These may exploit the environment and its Sustainable Chemistry
resources very wastefully; alternatively, they may be Ecochemistry
Much information is available on the principles of green
chemistry. They were rst explicitly stated as the 12 principles
of green chemistry in 1998 by Anastas and Warner.6 Another
Prof. Jacek Namiesnik (born paper (Winterton7) describes the principles for implementing
1949) obtained his PhD in green chemical syntheses on a technological scale.
1978, and has been a professor The two terms ecotechnology and ecological engineering
since 1996. Dean of the are also used in the literature, but often in diametrically
Chemical Faculty, GUT, from
opposing contexts.8 A special topic issue on green-sustainable
1996 to 2002 and since 2005.
Head of the Department of chemistry was published in 2007 in the IUPAC journal
Analytical Chemistry since Pure and Applied Chemistry.9 A special issue on this topic
1995. Chairman of the also appeared in the Review Chemistry Journal in that same
Committee on Analytical year.10
Chemistry Polish Academy of
Sciences (PAS) since 2005.
His major research interests
Green analytical chemistry
include the development of Environmental demands and ecotoxicological considerations
Jacek Namies nik new analytical procedures for call for action in two principal directions:11
determining trace and ultra-  the search for environmentally friendly technologies that
trace constituents in samples with complex matrix compositions,
are characterised by low, if not zero, emissions of pollutants;
the design and testing of customised analytical units and
measuring devices, and the production of new types of matrix-  the trend towards determining a broad spectrum of
free reference materials. Author and editor of 8 books, author analytes at low concentrations (ppb or even ppt) in samples
and co-author of over 300 papers and over 400 reports and with a complex matrix composition.
communications published in conference proceedings, and 10 The second approach has been facilitated by the intro-
patents. duction of a new generation of highly sensitive analytical

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c The Royal Society of Chemistry 2010
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devices and methods, and by the development of new sample procedures.15 Parameters like the EHS (Environmental
preparation procedures, that is, sample treatment prior to the HealthSafety) Indicator and CED (Cumulative Energy
nal determination stage. Demand) may be applied during such an assessment.
This line of action becomes particularly signicant in Fig. 3 illustrates schematically the dierences between the
modern environmental analysis, but these new detectors are terms frequently used to describe analytical activities. It is
insuciently sensitive to determine the majority of analytes in important to realise that these terms are not synonymous.
environmental samples.12 For this reason, it has become a Analytical chemistry and monitoring play important roles in
matter of urgency to optimise the stages and operations assessing the inuence of chemists on the environment.16
associated with sample preparation. There are already a vast number of analytical methods and
In this respect, sample preparation involves: techniques, and the number of determinations is increasing
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 isolating the analytes from the original matrix and moving very rapidly. By way of illustration, we may cite the more than
them to a recipient (secondary) matrix of simpler composition 3500 analytical procedures approved by the US Environ-
(analyte enrichment is optional); mental Protection Agency for the determination of more than
 releasing analytes, previously kept in a suitable trap, at the 4000 analytes in samples of dierent types of water, i.e.,
isolation and/or enrichment stage; surface water, drinking water and wastewater; and water is
 removing excess solvent, and drying, purifying and fraction- just one of the four elements of the environment. Now, since
ating the extracts. analytical activities can be carried out in environmentally
These steps are usually followed by chromatographic friendly or unfriendly ways, the development of green chemistry
techniques, which are routinely used to separate mixtures into as a whole will be at risk without the coexistence of green
individual chemical species prior to the nal determination. analytical chemistry, alternatively referred to by the terms clean
The operations involved in sample preparation are usually analytical chemistry and conscientious analytical methods.17
tedious and time-consuming and are dicult to automate. There are a number of literature reviews7,11,1824 discussing
Of special signicance to environmental analysis are sample dierent aspects of introducing the sustainable development
preparation methods in which liquid solvents are used in concept to analytical chemistry laboratories.
reduced amounts or even completely eliminated from the The aforementioned 12 principles of green chemistry may be
analytical procedure.13 Furthermore, the number of operations invoked to formulate the main features of green analytical
and processes involved in the sample preparation stage should chemistry. The following should be treated as top priorities:
be kept to a minimum.  the elimination (or at least, the signicant reduction) of
The isolation and/or preconcentration of analytes from reagents, particularly organic solvents, from analytical procedures;
samples with a complex matrix composition is a very important  reduced emissions of vapours and gases, as well as liquid
stage in trace and environmental analytical procedures. and solid wastes generated in analytical laboratories;
The work of analytical laboratories is closely scrutinised  the elimination of highly toxic and/or eco-toxic reagents
to minimise their negative impact on both the abiotic from analytical procedures (e.g., the substitution of benzene
environment and humans. We can talk about green analytical with other solvents);
chemistry.14 This is intended to develop tools for comparing  reduced labour and energy consumption of analytical
the environmental impacts of dierent analytical activities. procedures (per single analyte).
Life cycle assessment is one such tool: it can be applied not A further important parameter, characterising the analytical
only to industrial goods but also to a comparative assessment methods applied to obtain reliable information about the
of the environmental nuisance caused by individual chemicals, chemical composition of material objects and the processes
operations, analytical techniques and entire analytical taking place in them, is the time elapsing between the
collection of a representative sample and the desired informa-
tion becoming available. There are four ways of locating
analytical devices with respect to the material object to be
examined and the time elapsing between successive analytical
measurements (see Fig. 4).

Challenges in green analytical chemistry


The challenges to the introduction of sustainable development
principles to analytical laboratories are shown in Fig. 5.

Green sample preparation techniques


The literature data and observation of current trends in
analysis and monitoring indicate that progress has been
particularly rapid in the development of precisely those
methods and techniques ensuring compliance with green
Fig. 3 Schematic presentation of the dependencies among the terms analytical chemistry principles; solvent-free sample prepara-
often used to describe the analytical process. tion techniques are of special value.

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Fig. 4 The eect of locating an analytical device with respect to the object on the time delay in obtaining analytical information.

Fig. 5 Methodological challenges connected with the introduction of sustainable development principles to analytical chemistry laboratories.

Solid phase extraction (SPE) is a routine technique in and aqueous matrices has become popular in recent years.
sample preparation.25 Table 1 classies the dierent methodo- However, the low polarity of the membrane limits the number
logical versions of SPE. Some of them should be treated as of target compounds and renders the technique unsuitable for the
examples of the solventless approach to sample preparation. analysis of polar components.26 Although synthetic membranes
may be made of very dierent chemical compounds and may
display dierent properties, they can be classied as microporous
Membrane extraction
membranes, homogeneous membranes (also known as dense
The use of dierent membrane materials in various congura- membranes) made from metal, glass, polymer or liquid,
tions for the extraction of a broad range of analytes from gaseous ion-exchange membranes, and asymmetrical membranes.

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Table 1 Classication of solid phase extraction (SPE) techniques material; desorption or evaporation of the molecules on
the other side of the membrane to the receiving medium
No. Classication parameter Additional information
(carrier gas, absorbing solution, solid sorbent).
1. The origin of the sorbent  Natural In membrane-based processes, separation is the result of
- Activated carbon dierences in the transport rates of chemical species across the
 Synthetic
- Porous polymers interface. Transport through membranes is a non-equilibrium
2. The nature of the sorptive  Inorganic sorbents process in which ow can be related to the force that generated
material it. These forces are due mainly to:26
- Silica gel
- Aluminium oxide  Dierences in concentration. The International Union of
- Florisil Pure and Applied Chemistry (IUPAC) recommends the term
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 Organic sorbents dialysis for all processes caused by these forces. The
- Polyurethane foams (PUF) separated species may be gases or liquids.
- Porapacks (P, R, S, Q)
- Chromosorbs (101108)  Dierences in pressure. The three separation processes
- Tenax-TA through membranes in which transport is induced by the
- Tenax-GC application of pressure are microltration, ultraltration,
3. Surface development  Nonporous sorbents
 Porous sorbents
and reverse osmosis or hyperltration. They dier in the size
4. Pore diameter  Narrow pores of solutes retained by the membrane:
 Wide pores - between 0.1 and 1 nm in reverse osmosis
5. Sorbent grain size  Macrograins - between 1 and 104 nm in ultraltration
 Micrograins
 Nanograins - between 104 and 106 nm in microltration
6. Mode of extraction  Dynamic  Dierences in electrical potential. There are two processes
 Passive (passive dosimeters) based on the application of dierences in electrical potential:
 Denudation - electrodialysis. The system comprises a series of anionic
7. Geometric form of sorption  Tube lled with sorption
bed material bed and cationic exchange membranes arranged alternately
 Extraction discs between an anode and cathode. Electrodialysis can be used
 Denudation trap with both neutral and charged membranes;
 Extraction bres (SPME)
 Stir-bar sorptive extraction
- Donnan dialysis. This employs a charged membrane, but
(SBSE) no external potential dierence is applied. One of the two
 Sorbent added to medium solutions separated at the membrane has a lower concentra-
(dispersive extraction) tion of all species than the other one, giving rise to a ow of
8. Connection of sorption  O-line
system with measuring device one of the species (whose charge allows it to pass through the
 On-line membrane). In this way a dierence in potential is generated
9. Volume of medium passing  High-volume samplers (HVS) that must be compensated by the passage of ions from the
through sorbent
zone of lower concentration to that of higher concentration
 Low-volume samplers (LVS)
10. Release of sorbed analytes  Elution with organic solvent (against the gradient).
 Thermal desorption Overall, permeation is a function of the dissolution of the
 Elution with supercritical uid analyte in the membrane material, which means that the
11. Application of extraction in  Sample collection from medium
analytical procedures partition coecient of a given analyte between the donor
 Purication of extracts phase (sample matrix) and the membrane is a signicant
 Purication of laboratory media parameter limiting the mass transportation rate. Therefore,
(water, gases)
non-porous membranes are relatively non-selective. In
12. Physical phenomena  Adsorption
invoked at the analyte contrast, porous membranes are considered to be selective,
trapping stage the diameter of membrane pores being crucial for ensuring
 Interphase partition selective transport of analytes. However, not only diusion
 Exclusion
 Immunoanity itself but also dissolution in the membrane material plays a
role in analyte transportation.
Suitable membrane devices can be utilised directly, through
Semi-permeable porous and non-porous membranes are the contact of a gaseous or liquid sample with an appropriate
used to separate the components of gaseous and liquid polymer (silicone rubber or Teon) membrane, while the other
mixtures. These latter membranes were developed jointly by side of the membrane is ushed with a stream of suitable gas.
chemical engineers, materials scientists and polymer techno- The gas mixture produced in this way is directed straight to the
logists. They do not have pores in the conventional sense; measuring instrument. Solid or liquid samples can be analysed
their selectivity is based on dierences in the solubility and indirectly when the gaseous phase above the sample is in
diusion properties of the various components in a mixture. contact with the membrane. Membrane extraction can be
Separation is based on the dierent permeation of analytes carried out using suitable tubes (hollow bre membranes) or
through, e.g., a polymer or liquid membrane material. at lm membranes made of a semi-permeable material.27 The
This process can be divided into three stages: adsorption of rst attempts to adopt this approach date back to the 1980s.
molecules on the outer surface of the membrane; dissolution of A nitrogen stream is used as carrier gas for removing the
the adsorbed molecules and diusion through the membrane analytes from the outer surface of a at membrane in contact

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c The Royal Society of Chemistry 2010 Chem. Soc. Rev., 2010, 39, 28692878 | 2873
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with a liquid sample. The analytes are subsequently collected most likely to full the requirements of green chemistry,
on a sorbent bed and upon desorption are nally determined. particularly the former. It is non-ammable, readily accessible
Membrane techniques may be applied to the extraction of (from renewable feedstock or the power industry) and very
volatile analytes into a carrier gas stream from a sample of a cheap. Its critical parameters (Tk = 31.1 1C; Pk = 7.38 MPa)
particular volume in a container (static technique), and from are easily achievable, and because CO2 has a low heat of
the sample stream (dynamic technique).28 evaporation, its utilisation leads to energy savings. ScCO2 can
An extraction membrane can also serve as an inlet device. dissolve both nonpolar compounds and some polar ones
The classic example is a mass spectrometer equipped with a (e.g. methanol, acetone) at eciencies comparable with those
sampling interface in the form of a semi-permeable membrane. of halogenated solvents.29
In this case, introduction of volatile organic analytes to the Supercritical water, also used as a solvent, is non-
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mass spectrometer occurs through a polymer membrane ammable, widely accessible and cheap. It has low viscosity
(usually a silicone membrane), which is highly permeable to and diusivity, and can dissolve many polar compounds.
lipophilic organic compounds but is impermeable to water and Despite their many advantages, methods utilising super-
hydrophilic, polar and/or high-molecular weight compounds. critical uids are rarely used because they are technically
A membrane serving as an interface may be either at or complex: the extraction parameters have to be controlled with
tubular. precision as the solubility of compounds in a supercritical uid
is very sensitive to changes of pressure and temperature.30
Assisted analyte extraction
Ionic liquids
Microwave radiation
The search for new, environmentally friendly reaction media
This may be used for accelerating sample heating, sample
has drawn attention to ionic liquids (ILs), which have very
drying, determining water content (microwave moisture balance),
interesting and promising parameters.31 Ionic liquids are not
xing biological material samples, sample ashing and melting,
new to science: the rst oneethylammonium nitrate (EAN)
exciting analytes in plasma (MIP), increasing the rates of
(m.p. 14 1C)was synthesised by P. Walden. An interesting
chemical reactions, evaporating aqueous solutions, thermally
feature of ionic liquids is that properties like melting point or
stabilising wastes, heating chromatographic columns (in GC)
miscibility with organic solvents or water can be designed to
and extracting analytes (Microwave Assisted Extraction
meet chemists needs.32 ILs have other advantages, for example:
MAE). The almost routine utilisation of microwave radiation
 small amounts of wastes are generated (in production
in chemical laboratories has spawned the term Microwave
and use),
Enhanced Chemistry (MEC).
 they can be re-used many times,
Ultrasound  high reaction eciency and selectivity at room temperature,
 they can dissolve catalysts (particularly metal complexes),
According to the literature, ultrasound is used in the following
 they can dissolve both inorganic compounds (including
processes: sample mineralisation, sample dissolution, homo-
some minerals and carbon) and organics (from simple solvents
genisation, emulsion formation, ltration, chemical reactions
to polymers, wood and cellulose),
(derivatisation), reagent generation, glassware cleaning, sample
 thermal stability (their decomposition temperature is
degassing, ltration, and analyte extraction (Ultrasound
often 200250 1C),
Extraction USE).
 most are non-ammable and have a negligible vapour
Alternative media in laboratory practice pressure.
The properties of ILs make them interesting compounds for
Table 2 provides information on green media applicable in
many dierent applications: organic synthesis, catalysis,
analytical laboratories for dierent purposes.
biocatalysis, enzyme reactions, solvent extraction, electro-
Supercritical uids chemistry, electrolytes in batteries, electrolytes for dye-
synthesised solar cells, elements of polymer gel electrolytes,
Of the many potential supercritical uids, supercritical carbon in metal deposition, surfactant aggregate formation, high
dioxide (scCO2) and supercritical water (scH2O) are the ones surface tension materials and tissue preservation. They are
also used as the stationary phase in gas chromatography. The
Table 2 Green media used in analytical laboratories range, quality and rapidly increasing number of publications
Medium Area of utilisation in the past few decades are evidence enough that signicant
eorts are being made to utilise ILs in green chemistry.33
Supercritical uid Extraction agent
Mobile phase in Ionic liquids are not ideal, however. Their biggest disadvantage
chromatography at present is that they are produced only in small quantities, so
Ionic liquid Extraction agent they are expensive. In addition, ILs constitute a potential
Reaction medium threat to the aquatic environment (the imidazolium cation
Superheated water Extraction agent
(water in a subcritical state) has toxicological properties similar to those of dichloromethane
Inert gas Extraction agent or toluene). This threat stems from its low biodegradability, as
Mobile phase in gas well as the formation of new, even more toxic, ionic pairs with
chromatography
other organic ions present in the aquatic environment or the

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soil. Moreover, combustion of ILs produces toxic gases like F2 one capable of generating the pressure needed to force a liquid
or HF, which pollute the environment when released into it. through a very small channel. Producing a workable chromato-
Obtaining high purity ionic liquids is also problematic because graph on a chip will also require solutions to such problems as
of the presence of salts, colour or odour.34 making reproducible and stable stationary phases for packed
and open tubular columns, creating the pressure needed to
pump uids though the column at a constant ow rate,
Miniaturisation of analytical devices
accurately and reproducibly injecting sub-nanolitre volumes,
The search for faster and cheaper alternatives to laboratory- creating detection systems able to measure the very small
based analysis has been intensive, and throughout the 1980s quantities of analytes, and minimising dead volumes. Work
chemical sensors were seen by many as the way forward.35 on miniaturised chromatography is still in progress.42
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This approach is attractive because measurements can be The idea of the electronic tongue project is based on the
made quickly and easily. Though designed to measure a development of new types of poorly selective chemical sensors
specic analyte, sensors often do not handle interferents well displaying cross-sensitivity to multiple components in liquids,
and get contaminated quickly, so the potential originally and their application in an array.43 The electronic tongue
envisaged for them has not been realised. can be dened as an analytical instrument that includes an
In recent years, researchers have looked for solutions with array of non-selective chemical sensors with partial specicity
the advantages of sensors but also the versatility and reliability towards dierent solution components and an appropriate
of conventional instruments. At present, the most promising pattern recognition instrument capable of quantitative and
technology for achieving this involves carrying out chemical qualitative analysis.44
analysis on a very small scale by shrinking the standard In a recent development, separation techniques have been
laboratory techniques to t onto a chemical chip. This successfully integrated into the concept of the total chemical
process of miniaturisation has transformed electronics and analysis systemTAS.45 The combination of all sample
computing, and many see the potential for similar advances in handling and measurement steps into a single package
chemical analysis. Miniaturisation is set to produce a generation incorporating a high level of automation makes the TAS an
of analytical instruments that will be cheaper, faster and more ideal approach for the continuous monitoring of dierent types
exible, but no less ecient than the ones in use today. of analytes. TAS periodically transforms chemical information
The lab-on-a-chip concept is not new: the idea of making into electronic information.46 Sampling, sample transport, any
miniature separation columns goes back to the late 1970s necessary chemical reactions, separations and detection are all
when S. Terry and co-workers at Stanford University demon- performed automatically. Much of the sample pretreatment
strated a working GC on a silicon wafer.36 This pioneering serves to eliminate most interferents, so the detector or sensor
device included a column, injector and valves and was capable in a TAS does not need to be highly selective.
of separating a mixture of organics within ten seconds. The concept of miniaturised total chemical analysis system
Although the devices resolution was relatively poor, the extends this approach.47 A miniaturised TAS would be of
potential for improvement was obvious, and this paper benet since it could consist of several system elements, each
became a landmark in the lab-on-a-chip world. Nowadays, designed to protect the subsequent element of the downstream
GC-MS systems (e.g., analyser, ion traps, cylindrical ion traps, system from components of the sample matrix. Compared
quadrupole mass separators or time-of-ight (TOF) mass with utilising a sensor alone, the use of such a TAS system
spectrometers) have been miniaturised. The wafer-based should result in increased durability. At the same time, the
design enables large-scale production: all parts are fabricated performance required of any single component of the system
in a single piece of silicon, eliminating the need to align the could be less than that required of a sensor alone. Equally
units to each other. The vacuum requirements are signicantly intriguing, perhaps, is the fact that to the user, the system
relaxed and carrier gas consumption is reduced because of the would seem very much like a stand-alone sensor, but its
small size of the unit.37,38 performance would be under the users dynamic control. This
Even so, it was another decade before serious interest in would considerably improve the exibility of a m-TAS device,
microfabricated separation systems was revived, when A. Manz resulting in superior performance for chemical analysis
and co-workers at the Ciba-Geigy laboratories (Switzerland) compared to the stand-alone sensor approach. While such
proposed the miniaturised total analysis system or mTAS as devices may not always be able to compete with benchtop-
an alternative to chemical sensors for continuous monitoring.39 scale laboratory equipment in terms of sensitivity and selectivity,
To demonstrate how such systems could be built, Manzs integrated systems may prove superior in terms of speed of
group made capillary electrophoresis channels on glass chips analysis and production costs.
and showed that separation of two uorescent dyes could be Complete miniature modules aim to achieve:
achieved more quickly than was possible using a standard  total system size of the same order of magnitude as the
system.40 transducer;
Capillary electrophoresis is particularly suitable for  true on-chip referencing and multicomponent sensing by
microfabrication because no valves or pumps are needed to single-chip sensing-pad arrays;
propel the sample through the column. With chromatography,  low system complexity;
on the other hand, the need for pumps and valves remains and  minimal costs of (mass) production;
this presents signicant technical challenges.41 Although  ruggedness as a result of the built-in-alignment of sensor
microfabricated pumps are available, it is dicult to design parts;

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Table 3 Main trends in miniaturisation of analytical systems

Approach Examples
New types of sensors Supramolecular sensors
and biosensors
Systems of sensors Electronic nose
Electronic tongue
Microsystems m-Total analysis Systems
(m-TAS)
Lab-on-a-chip
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 standardised waveguides, sensing pads and schemes suitable


for a wide variety of applications.
The development of the electronic nose and the electronic
tongue was prompted by the desire to model, substitute and Fig. 6 The characteristics of test kits, the speed of analysis, complexity
enhance human olfactory and tasting abilities. The design of and sensitivity of equipment.
these devices is based on the biological principles of organising
sensor systemsarrays of non-specic chemical sensors with take the form of plates where the test eld is shielded by a plastic
subsequent image recognition by a neural network. Many cover or the tubes are packed with a support-coated reagent.
modern achievements in neural computing are widely applied  semi-dry tests. A semi-dry test is a test to which at least
in sensor science for the electronic nose and electronic one liquid reagent is added. Such a design is most often
tongue systems. Such systems can therefore be considered a dictated by chemical reasons, though it happens that techno-
specic branch of the development of articial intelligence logical requirements are the cause.
and/or a eld in the application of the electronic brain.  wet tests.
The history of the electronic nose as an intelligent Test methods have been developed for many analytes: metal
multisensor started in 1982, the term itself becoming widely ions, anions, dissolved oxygen and chlorine, hydrogen
accepted around 1990. Such noses usually provide a quanti- peroxide, ammonia, pesticides, nitrite, nitrate, petroleum
tative recognition of gas mixtures. Table 3 lists the main trends products (e.g., in water), sulfur dioxide, hydrogen sulde,
in the miniaturisation of analytical systems.48 ozone and many other gases (e.g., in air).36 Fig. 6 characterises
those test kits important from the green analytical chemistry
point of view.
Spot tests
In environmental and medical analysis (e.g., in a hospital)
Passive devices
there is a great demand for fast methods of obtaining analytical
information on material objects. Such information is one The use of passive samplers (dosimeters) is a modern approach
of the crucial elements upon which decisions are based.36 to the analysis of atmospheric, indoor and workplace air
Therefore, quick tests should be easy and simple to use, easily pollution. Simple in design and use, and relatively cheap,
available, of low unit cost, usable in self-measurement mode they do not require any power supply and facilitate the
(by patients), possibly for dierent objects (drinking water, simultaneous detection of vapours of many compounds.48
vegetables, fruit). Passive samplers are also often known as diusive samplers:
There is still a lot of ambiguity in the nomenclature relating they are capable of collecting samples of gas or vapour
to quick tests; dierent terms are used to denote the same pollutants from the atmosphere at rates controlled by physical
things, which can be a source of error or misunderstanding. processes like diusion through a static air layer or permeation
The terms quick test and rapid test usually refer to through a membrane, but which do not involve the active
types of tests with the following features in common: movement of air through the sampler. Compared with
 rapid measurement of a target parameter (concentration conventional pump samplers, passive samplers have the
of analyte, pH, etc.); advantages of not needing power sources or bulky and
 kits containing a complete set of reagents, vessels, and expensive pumps, being more acceptable for wearing as
possibly other equipment necessary for carrying out the analysis; personal dosimeters, and simplicity of operation.36
 the analysis can be performed in the eld. Passive samplers, therefore, oer the most attractive
Based on their principle of operation, there are three types alternative to active sampling techniques49 and are routinely
of tests commonly applied in laboratory practice:36 used to measure time-weighted average (TWA) exposure to
 dry tests. This test is based on an adsorptive material airborne pollutants. Moreover, their use to control workplace
saturated with a reagent mixture, which ensures the conditions airborne health hazards can substantially reduce the cost of
necessary for detecting and determining a target compound or analyses. Modern passive devices are similar in size, weight
ion. This eld testing material, as it is known, can be xed to a and convenience to the well-known radiation dosimeters. They
supporting material, usually made from some white plastic are especially important to health professionals like surgeons,
(PS, PUC, polyester), to produce a test strip. The dry test can dentists, nurses and veterinarians, who use them for deter-
be in a form appropriate to an automatic reectance reading mining exposure to waste anaesthetics. Personal charcoal tube
unit, i.e., in the form of a slide in Kodak tests. The same tests can (CT) samplers, active devices that run on battery-powered

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Fig. 7 Methodological approaches in green chemistry with special emphasis on the sample preparation step.

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11 J. Namies nik and W. Wardencki, J. High Resolut. Chromatogr.,
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14 L. H. Keith, L. U. Gron and J. L. Young, Chem. Rev., 2007, 107,
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