Handbook of green analytical chemistry

Handbook of Green Analytical Chemistry

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Handbook of Green Analytical Chemistry

Edited by

MIGUEL DE LA GUARDIA
Department of Analytical Chemistry, University of Valencia, Valencia, Spain
SALVADOR GARRIGUES
Department of Analytical Chemistry, University of Valencia, Valencia, Spain

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This edition first published 2012
© 2012 John Wiley & Sons, Ltd.
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Library of Congress Cataloging-in-Publication Data
Handbook of green analytical chemistry / edited by Miguel de la Guardia, Salvador Garrigues.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-97201-4 (cloth)
1. Environmental chemistry–Industrial applications–Handbooks, manuals, etc. 2. Environmental chemistry–Handbooks, manuals, etc.
I. Guardia, M. de la (Miguel de la) II. Garrigues, Salvador.
TD193.H35 2012
543–dc23
2011051666
A catalogue record for this book is available from the British Library.
Print ISBN: 9780470972014
Set in 10/12pt Times by SPi Publisher Services, Pondicherry, India

1

2012

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Contents
List of Contributors
Preface

xv
xix

Section I: Concepts

1

1 The Concept of Green Analytical Chemistry
Miguel de la Guardia and Salvador Garrigues

3

1.1 Green Analytical Chemistry in the frame of Green Chemistry
1.2 Green Analytical Chemistry versus Analytical Chemistry
1.3 The ethical compromise of sustainability
1.4 The business opportunities of clean methods

1.5 The attitudes of the scientific community
References

3
7
9
11
12
14

2 Education in Green Analytical Chemistry
Miguel de la Guardia and Salvador Garrigues

17

2.1 The structure of the Analytical Chemistry paradigm
2.2 The social perception of Analytical Chemistry
2.3 Teaching Analytical Chemistry
2.4 Teaching Green Analytical Chemistry
2.5 From the bench to the real world
2.6 Making sustainable professionals for the future
References

17
20
21
25
26
28
29

3 Green Analytical Laboratory Experiments
Suparna Dutta and Arabinda K. Das

31

3.1 Greening the university laboratories
3.2 Green laboratory experiments
3.2.1 Green methods for sample pretreatment
3.2.2 Green separation using liquid-liquid, solid-phase and solventless extractions
3.2.3 Green alternatives for chemical reactions
3.2.4 Green spectroscopy
3.3 The place of Green Analytical Chemistry in the future of our laboratories
References

31
33
33
37
42
45
52
52

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vi

Contents

4 Publishing in Green Analytical Chemistry
Salvador Garrigues and Miguel de la Guardia

55

4.1 A bibliometric study of the literature in Green Analytical Chemistry
4.2 Milestones of the literature on Green Analytical Chemistry
4.3 The need for powerful keywords
4.4 A new attitude of authors faced with green parameters
4.5 A proposal for editors and reviewers
4.6 The future starts now
References

56
57
61
62
64
65
66

Section II: The Analytical Process

67

5 Greening Sampling Techniques
José Luis Gómez Ariza and Tamara García Barrera

69

5.1 Greening analytical chemistry solutions for sampling
5.2 New green approaches to reduce problems related to sample losses, sample
contamination, transport and storage
5.2.1 Methods based on flow-through solid phase spectroscopy
5.2.2 Methods based on hollow-fiber GC/HPLC/CE
5.2.3 Methods based on the use of nanoparticles
5.3 Greening analytical in-line systems
5.4 In-field sampling
5.5 Environmentally friendly sample stabilization
5.6 Sampling for automatization
5.7 Future possibilities in green sampling
References

70
70
70
71
75
76
77
79
79
80
80

6 Direct Analysis of Samples
Sergio Armenta and Miguel de la Guardia

85

6.1 Remote environmental sensing
6.1.1 Synthetic Aperture Radar (SAR) images (satellite sensors)
6.1.2 Open-path spectroscopy
6.1.3 Field-portable analyzers
6.2 Process monitoring: in-line, on-line and at-line measurements
6.2.1 NIR spectroscopy
6.2.2 Raman spectroscopy
6.2.3 MIR spectroscopy
6.2.4 Imaging technology and image analysis
6.3 At-line non-destructive or quasi non-destructive measurements
6.3.1 Photoacoustic Spectroscopy (PAS)
6.3.2 Ambient Mass Spectrometry (MS)
6.3.3 Solid sampling plasma sources
6.3.4 Nuclear Magnetic Resonance (NMR)

85
86
86
90
91
92
92
93
93
94
94
95

95
96

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Contents

6.3.5 X-ray spectroscopy
6.3.6 Other surface analysis techniques
6.4 New challenges in direct analysis
References

vii

96
97
97
98

7 Green Analytical Chemistry Approaches in Sample Preparation
Marek Tobiszewski, Agata Mechlin´ska and Jacek Namies´ nik

103

7.1 About sample preparation
7.2 Miniaturized extraction techniques
7.2.1 Solid-phase extraction (SPE)

7.2.2 Solid-phase microextraction (SPME)
7.2.3 Stir-bar sorptive extraction (SBSE)
7.2.4 Liquid-liquid microextraction
7.2.5 Membrane extraction
7.2.6 Gas extraction
7.3 Alternative solvents
7.3.1 Analytical applications of ionic liquids
7.3.2 Supercritical fluid extraction
7.3.3 Subcritical water extraction
7.3.4 Fluorous phases
7.4 Assisted extractions
7.4.1 Microwave-assisted extraction
7.4.2 Ultrasound-assisted extraction
7.4.3 Pressurized liquid extraction
7.5 Final remarks
References

103
104
104
105
106
106
108
109
113
113
114
115
116

117
117
117
118
119
119

8 Green Sample Preparation with Non-Chromatographic Separation Techniques
María Dolores Luque de Castro and Miguel Alcaide Molina

125

8.1 Sample preparation in the frame of the analytical process
8.2 Separation techniques involving a gas–liquid interface
8.2.1 Gas diffusion
8.2.2 Pervaporation
8.2.3 Membrane extraction with a sorbent interface
8.2.4 Distillation and microdistillation
8.2.5 Head-space separation
8.2.6 Hydride generation and cold-mercury vapour formation
8.3 Techniques involving a liquid–liquid interface
8.3.1 Dialysis and microdialysis
8.3.2 Liquid–liquid extraction
8.3.3 Single-drop microextraction
8.4 Techniques involving a liquid–solid interface
8.4.1 Solid-phase extraction
8.4.2 Solid-phase microextraction
8.4.3 Stir-bar sorptive extraction

125

127
127
127
130
131
131
133
133
133
134
137
139
139
141
142

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Contents

8.4.4 Continuous filtration
8.5 A Green future for sample preparation
References

143

145
145

9 Capillary Electrophoresis
Mihkel Kaljurand

153

9.1
9.2

153
155
155
156
159

The capillary electrophoresis separation techniques
Capillary electrophoresis among other liquid phase separation methods
9.2.1 Basic instrumentation for liquid phase separations
9.2.2 CE versus HPLC from the point of view of Green Analytical Chemistry
9.2.3 CE as a method of choice for portable instruments
9.2.4 World-to-chip interfacing and the quest for a ‘killer’ application
for LOC devices
9.2.5 Gradient elution moving boundary electrophoresis and
electrophoretic exclusion
9.3 Possible ways of surmounting the disadvantages of CE
9.4 Sample preparation in CE
9.5 Is capillary electrophoresis a green alternative?
References

163
165
167
168
169
170

10 Green Chromatography
Chi-Yu Lu

175

10.1 Greening liquid chromatography
10.2 Green solvents
10.2.1 Hydrophilic solvents
10.2.2 Ionic liquids
10.2.3 Supercritical Fluid Chromatography (SFC)
10.3 Green instruments
10.3.1 Microbore Liquid Chromatography (microbore LC)
10.3.2 Capillary Liquid Chromatography (capillary LC)
10.3.3 Nano Liquid Chromatography (nano LC)
10.3.4 How to transfer the LC condition from traditional LC to microbore LC,
capillary LC or nano LC
10.3.5 Homemade micro-scale analytical system
10.3.6 Ultra Performance Liquid Chromatography (UPLC)
References

175
176

176
177
177
178
179
180
181

11 Green Analytical Atomic Spectrometry
Martín Resano, Esperanza García-Ruiz and Miguel A. Belarra

199

11.1 Atomic spectrometry in the context of Green Analytical Chemistry
11.2 Improvements in sample pretreatment strategies
11.2.1 Specific improvements
11.2.2 Slurry methods
11.3 Direct solid sampling techniques

199
202
202
204
205

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183
184

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Contents

11.3.1
11.3.2
11.3.3

Basic operating principles of the techniques discussed
Sample requirements and pretreatment strategies
Analyte monitoring: The arrival of high-resolution continuum source atomic
absorption spectrometry
11.3.4 Calibration
11.3.5 Selected applications
11.4 Future for green analytical atomic spectrometry
References

ix

205
207
208
210
210
213
215

12 Solid Phase Molecular Spectroscopy
Antonio Molina-Díaz, Juan Francisco García-Reyes and Natividad Ramos-Martos

221

12.1 Solid phase molecular spectroscopy: an approach to Green Analytical Chemistry
12.2 Fundamentals of solid phase molecular spectroscopy
12.2.1 Solid phase absorption (spectrophotometric) procedures
12.2.2 Solid phase emission (fluorescence) procedures
12.3 Batch mode procedures
12.4 Flow mode procedures
12.4.1 Monitoring an intrinsic property
12.4.2 Monitoring derivative species
12.4.3 Recent flow-SPMS based approaches
12.5 Selected examples of application of solid phase molecular spectroscopy
12.6 The potential of flow solid phase envisaged from the point of view of
Green Analytical Chemistry
References

221
222
222
225
225
226
227
231
232
233

13 Derivative Techniques in Molecular Absorption, Fluorimetry and Liquid
Chromatography as Tools for Green Analytical Chemistry
José Manuel Cano Pavón, Amparo García de Torres, Catalina Bosch Ojeda,
Fuensanta Sánchez Rojas and Elisa I. Vereda Alonso

235
240

245

13.1 The derivative technique as a tool for Green Analytical Chemistry
13.1.1 Theoretical aspects
13.2 Derivative absorption spectrometry in the UV-visible region
13.2.1 Strategies to greener derivative spectrophotometry
13.3 Derivative fluorescence spectrometry
13.3.1 Derivative synchronous fluorescence spectrometry
13.4 Use of derivative signal techniques in liquid chromatography
References

245
246
247
248
250
251
254
255

14 Greening Electroanalytical Methods
Paloma Yáñez-Sedeño, José M. Pingarrón and Lucas Hernández

261

14.1 Towards a more environmentally friendly electroanalysis
14.2 Electrode materials
14.2.1 Alternatives to mercury electrodes
14.2.2 Nanomaterial-based electrodes
14.3 Solvents

261
262
262
268
270

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x

Contents

14.3.1 Ionic liquids
14.3.2 Supercritical fluids
14.4 Electrochemical detection in flowing solutions
14.4.1 Injection techniques
14.4.2 Miniaturized systems
14.5 Biosensors

14.5.1 Greening biosurface preparation
14.5.2 Direct electrochemical transfer of proteins
14.6 Future trends in green electroanalysis
References

271
273
274
274
276
278
278
281
282
282

Section III: Strategies

289

15 Energy Savings in Analytical Chemistry
Mihkel Koel

291

15.1 Energy consumption in analytical methods
15.2 Economy and saving energy in laboratory practice
15.2.1 Good housekeeping, control and maintenance
15.3 Alternative sources of energy for processes
15.3.1 Using microwaves in place of thermal heating

15.3.2 Using ultrasound in sample treatment
15.3.3 Light as a source of energy
15.4 Using alternative solvents for energy savings
15.4.1 Advantages of ionic liquids
15.4.2 Using subcritical and supercritical fluids
15.5 Efficient laboratory equipment
15.5.1 Trends in sample treatment
15.6 Effects of automation and micronization on energy consumption
15.6.1 Miniaturization in sample treatment
15.6.2 Using sensors
15.7 Assessment of energy efficiency
References

291
294
295
296
297
299
301
302
303
303
305
306
307
308
310
312
316

16 Green Analytical Chemistry and Flow Injection Methodologies
Luis Dante Martínez, Soledad Cerutti and Raúl Andrés Gil

321

16.1 Progress of automated techniques for Green Analytical Chemistry
16.2 Flow injection analysis
16.3 Sequential injection analysis
16.4 Lab-on-valve
16.5 Multicommutation
16.6 Conclusions and remarks
References

321
322
325
327
328
334
334

17 Miniaturization
Alberto Escarpa, Miguel Ángel López and Lourdes Ramos

339

17.1 Current needs and pitfalls in sample preparation
17.2 Non-integrated approaches for miniaturized sample preparation

340
341

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Contents

xi

17.2.1 Gaseous and liquid samples
17.2.2 Solid samples
17.3 Integrated approaches for sample preparation on microfluidic platforms
17.3.1 Microfluidic platforms in sample preparation process
17.3.2 The isolation of analyte from the sample matrix: filtering approaches
17.3.3 The isolation of analytes from the sample matrix: extraction approaches
17.3.4 Preconcentration approaches using electrokinetics
17.3.5 Derivatization schemes on microfluidic platforms
17.3.6 Sample preparation in cell analysis
17.4 Final remarks
References

341
350
353
353
356
360

365
372
373
378
379

18 Micro- and Nanomaterials Based Detection Systems Applied in
Lab-on-a-Chip Technology
Mariana Medina-Sánchez and Arben Merkoçi

389

18.1 Micro- and nanotechnology in Green Analytical Chemistry
18.2 Nanomaterials-based (bio)sensors
18.2.1 Optical nano(bio)sensors
18.2.2 Electrochemical nano(bio)sensors
18.2.3 Other detection principles
18.3 Lab-on-a-chip (LOC) technology
18.3.1 Miniaturization and nano-/microfluidics
18.3.2 Micro- and nanofabrication techniques
18.4 LOC applications
18.4.1 LOCs with optical detections
18.4.2 LOCs with electrochemical detectors
18.4.3 LOCs with other detections
18.5 Conclusions and future perspectives
References

389
390
391

393
395
396
396
397
398
398
398
399
400
401

19 Photocatalytic Treatment of Laboratory Wastes Containing
Hazardous Organic Compounds
Edmondo Pramauro, Alessandra Bianco Prevot and Debora Fabbri

407

19.1
19.2
19.3
19.4
19.5

19.6
19.7
19.8

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Photocatalysis
Fundamentals of the photocatalytic process
Limits of the photocatalytic treatment
Usual photocatalytic procedure in laboratory practice
19.4.1 Solar detoxification of laboratory waste
Influence of experimental parameters
19.5.1 Dissolved oxygen
19.5.2 pH
19.5.3 Catalyst concentration
19.5.4 Degradation kinetics
Additives reducing the e−/h+ recombination
Analytical control of the photocatalytic treatment
Examples of possible applications of photocatalysis to the treatment of laboratory wastes
19.8.1 Percolates containing soluble aromatic contaminants

407
408
408
408
409
411
411
411
412
412
412
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Contents

19.8.2 Photocatalytic destruction of aromatic amine residues in aqueous wastes
19.8.3 Degradation of aqueous wastes containing pesticides residue
19.8.4 The peculiar behaviour of triazine herbicides
19.8.5 Treatment of aqueous wastes containing organic solvent residues
19.8.6 Treatment of surfactant-containing aqueous wastes
19.8.7 Degradation of aqueous solutions of azo-dyes
19.8.8 Treatment of laboratory waste containing pharmaceuticals
19.9 Continuous monitoring of photocatalytic treatment
References

414
415
416
416
416
419
419
420
420

Section IV: Fields of Application

425

20 Green Bioanalytical Chemistry
Tadashi Nishio and Hideko Kanazawa

427

20.1
20.2
20.3

427
428

The analytical techniques in bioanalysis
Environmental-responsive polymers
Preparation of a polymer-modified surface for the stationary phase
of environmental-responsive chromatography
20.4 Temperature-responsive chromatography for green analytical methods
20.5 Biological analysis by temperature-responsive chromatography
20.5.1 Analysis of propofol in plasma using water as a mobile phase
20.5.2 Contraceptive drugs analysis using temperature gradient chromatography
20.6 Affinity chromatography for green bioseparation
20.7 Separation of biologically active molecules by the green chromatographic method
20.8 Protein separation by an aqueous chromatographic system
20.9 Ice chromatography
20.10 High-temperature liquid chromatography
20.11 Ionic liquids
20.12 The future in green bioanalysis
References

430
432
432
434
435
436
438
441
442
443
443
444
444

21 Infrared Spectroscopy in Biodiagnostics: A Green Analytical Approach
Mohammadreza Khanmohammadi and Amir Bagheri Garmarudi

449

21.1
21.2
21.3

449
451
453
455
457
457
457

459
460
465
468
470

Infrared spectroscopy capabilities
Infrared spectroscopy of bio-active chemicals in a bio-system
Medical analysis of body fluids by infrared spectroscopy
21.3.1 Blood and its extracts
21.3.2 Urine
21.3.3 Other body fluids
21.4 Diagnosis in tissue samples via IR spectroscopic analysis
21.4.1 Main spectral characteristics
21.4.2 The role of data processing
21.4.3 Cancer diagnosis by FTIR spectrometry
21.5 New trends in infrared spectroscopy assisted biodiagnostics
References

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Contents

xiii

22 Environmental Analysis
Ricardo Erthal Santelli, Marcos Almeida Bezerra, Julio Carlos Afonso,

Maria de Fátima Batista de Carvalho, Eliane Padua Oliveira and Aline Soares Freire

475

22.1 Pollution and its control
22.2 Steps of an environmental analysis
22.2.1 Sample collection
22.2.2 Sample preparation
22.2.3 Analysis
22.3 Green environmental analysis for water, wastewater and effluent
22.3.1 Major mineral constituents
22.3.2 Trace metal ions
22.3.3 Organic pollutants
22.4 Green environmental analysis applied for solid samples
22.4.1 Soil
22.4.2 Sediments
22.4.3 Wastes
22.5 Green environmental analysis applied for atmospheric samples
22.5.1 Gases
22.5.2 Particulates
References

475
476
476
476
479
480
480
481

483
485
485
488
492
496
496
497
497

23 Green Industrial Analysis
Sergio Armenta and Miguel de la Guardia

505

23.1 Greening industrial practices for safety and cost reasons
23.2 The quality control of raw materials and end products
23.3 Process control
23.4 Effluent control
23.5 Working atmosphere control
23.6 The future starts now
References

505
506
510
511
514
515
515

Index

519

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List of Contributors
Julio Carlos Afonso Departamento de Química Analítica, Universidade Federal do Rio de Janeiro, Cidade
Universitária, Rio de Janeiro, Brazil
Elisa I. Vereda Alonso Department of Analytical Chemistry, University of Málaga, Málaga, Spain
José Luis Gómez Ariza Departamento de Química y Ciencia de los Materiales ‘Profesor José Carlos
Vílchez Martín’, Universidad de Huelva, Huelva, Spain
Sergio Armenta Department of Analytical Chemistry, University of Valencia, Valencia, Spain
Tamara García Barrera Departamento de Química y Ciencia de los Materiales ’Profesor José Carlos
Vílchez Martín’, Universidad de Huelva, Huelva, Spain
Maria de Fátima Batista de Carvalho Centro de Pesquisa e Desenvolvimento, Cidade Universitária,
Rio de Janeiro, Brazil
Miguel A. Belarra Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain
Marcos Almeida Bezerra Departamento de Química e Exatas, Universidade Estadual do Sudoeste da
Bahia, Jequié, Brazil
Soledad Cerutti Instituto de Química de San Luis, Universidad Nacional de San Luis-CONICET, San
Luis, Argentina
Arabinda K. Das Department of Chemistry, University of Burdwan, Burdwan, West Bengal, India
Suparna Dutta Sonamukhi Girls’ High School, Bankura, West Bengal, India
Alberto Escarpa
Madrid, Spain

Department of Analytical Chemistry and Chemical Engineering, University of Alcala,

Debora Fabbri Department of Analytical Chemistry, V. Pietro Giuria 5, Torino, Italy
Aline Soares Freire Departmento de Química Analítica, Universidade Federal do Rio de Janeiro, Rio de
Janeiro, Brazil

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xvi

List of Contributors

Juan Francisco García-Reyes Analytical Chemistry Research Group, Department of Physical and
Analytical Chemistry, University of Jaén, Jaén, Spain
Esperanza García-Ruiz Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain
Amir Bagheri Garmarudi Chemistry Department, Faculty of Science, Imam Khomeini International
University, Qazvin, Iran
Salvador Garrigues Department of Analytical Chemistry, University of Valencia, Valencia, Spain
Raúl Andrés Gil
Argentina

Instituto de Química de San Luis, Universidad Nacional de San Luis-CONICET, San Luis,

Miguel de la Guardia Department of Analytical Chemistry, University of Valencia, Valencia, Spain
Lucas Hernández
Madrid, Spain

Department of Analytical and Instrumental Analysis, Universidad Autónoma de Madrid,

Mihkel Kaljurand Institute of Chemistry, Faculty of Science, Tallinn University of Technology, Tallinn,
Estonia
Hideko Kanazawa

Faculty of Pharmacy, Keio University, Tokyo, Japan

Mohammadreza Khanmohammadi
International University, Qazvin, Iran

Chemistry Department, Faculty of Science, Imam Khomeini

Mihkel Koel Institute of Chemistry, Faculty of Science, Tallinn University of Technology, Tallinn, Estonia
Miguel Ángel López Department of Analytical Chemistry and Chemical Engineering, Faculty of
Chemistry, University of Alcala, Madrid, Spain
Chi-Yu Lu

Department of Biochemistry, Kaohsiung Medical University, Kaohsiung, Taiwan

María Dolores Luque de Castro
Spain

Department of Analytical Chemistry, Campus of Rabanales, Córdoba,

Luis Dante Martínez Instituto de Química de San Luis, Universidad Nacional de San Luis-CONICET,
San Luis, Argentina
Agata Mechlin´ska Department of Analytical Chemistry, Chemical Faculty, Gdansk University of
Technology (GUT), Gdansk, Poland

Mariana Medina-Sánchez Nanobioelectronics and Biosensors Group, Institut Català de Nanotecnologia:
Universitat Autónoma de Barcelona, Bellaterra, Barcelona, Spain
Arben Merkoçi Nanobioelectronics and Biosensors Group, Institute Català de Nanotechnologia & ICREA,
Barcelona, Spain

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List of Contributors xvii

Miguel Alcaide Molina Department of Analytical Chemistry, University of Córdoba, Córdoba, Spain
Antonio Molina-Díaz Analytical Chemistry Research Group, Department of Physical and Analytical
Chemistry, University of Jaén, Jaén, Spain
Jacek Namies´ nik Department of Analytical Chemistry, Chemical Faculty, Gdansk University of
Technology (GUT), Gdansk, Poland
Tadashi Nishio Faculty of Pharmacy, Keio University, Tokyo, Japan
Catalina Bosch Ojeda Department of Analytical Chemistry, University of Málaga, Málaga, Spain
Eliane Padua Oliveira Departamento de Geoquímica, Universidade Federal Fluminense, Niterói, Brazil
José Manuel Cano Pavón Department of Analytical Chemistry, University of Málaga, Málaga, Spain
José M. Pingarrón Department of Analytical Chemistry, Faculty of Chemistry, University Complutense
of Madrid, Madrid, Spain
Edmondo Pramauro Department of Analytical Chemistry, V. Pietro Giuria 5, Torino, Italy
Alessandra Bianco Prevot Department of Analytical Chemistry, V. Pietro Giuria 5, Torino, Italy
Lourdes Ramos Department of Instrumental Analysis and Environmental Chemistry, Institute of Organic
Chemistry, CSIC, Madrid, Spain
Natividad Ramos-Martos Analytical Chemistry Research Group, Department of Physical and Analytical
Chemistry, University of Jaén, Jaén, Spain
Martín Resano Department of Analytical Chemistry, University of Zaragoza, Zaragoza, Spain

Fuensanta Sánchez Rojas Department of Analytical Chemistry, University of Málaga, Málaga, Spain
Ricardo Erthal Santelli Departamento de Química Analítica, Universidade Federal do Rio de Janeiro, Rio
de Janeiro, Brazil
Marek Tobiszewski Department of Analytical Chemistry, Chemical Faculty, Gdansk University of
Technology (GUT), Gdansk, Poland
Amparo García de Torres Department of Analytical Chemistry, University of Málaga, Málaga, Spain
Paloma Yáñez-Sedeño Department of Analytical Chemistry, Faculty of Chemistry, University
Complutense of Madrid, Madrid, Spain

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Preface
Now it is time to move from the general principles to the practice. The efforts made by the analytical chemistry
and chemistry community opinion during the 2011 International Year of the Chemistry have been focused on
demonstrating to the public that our discipline is not the reason for the environmental damage and the health
problems that have emerged from our developed societies. On the contrary, chemistry is one of the main
reasons to extend the human life and to improve its quality level and the best tool to solve the environmental
problems created in the past by uncorrect use of the available technologies. So, it is a happy coincidence that
in recent months the first books especially devoted to Green Analytical Chemistry have been published and
also that important journals like Trends in Analytical Chemistry have devoted special issues to the topic of
Green Analytical Chemistry.
The handbook, which the reader has in hand, is an attempt to advance the ethics and practical objectives of
Green Analytical Chemistry. The book has been possible due to the invitation of Wiley-Blackwell editors but
also because of the critical mass of research teams who have contributed to establish a series of methodological
and technological tools to prevent and reduce the deleterious effects of our analytical activities.
As a main difference to previously published texts, the readers will find in this book a deep and complete
perspective of the Green Analytical Chemistry as a matter of facts guided by the most fundamental principles

and also a catalogue of tools for greening the work on chemical analysis.
The structure of the text covers a fundamental part, a series of proposals for greening the different steps of
the analytical process and some final chapters focused on different fields of applications.
In the fundamental part, the main idea has been to move from historical and theoretical considerations to
proposals for authors, editors, and users of the analytical laboratories to move from the old practices, which
take into consideration only the method figures of merit, to a new frame in which the side environmental and
operator risk effects could pay an important role. However, the most important part of the handbook is the
series of detailed chapters, written by specialists in each field, which have made a literature survey on efforts
to avoid reagent consumption and waste generation and can provide to the reader many practical tools to do
environmentally friendly analytical tasks and to take advantage of the economical opportunities that are
offered by Green Analytical Chemistry.
In the different application fields considered in this text, the reader will identify that Green Analytical
Chemistry can operate in all contexts; from the industrial to the sanitary and not only in environmental
applications, thus contributing once again, to move from the theory to the practice.
For the aforementioned reasons, editors and authors are convinced of the necessity of this book and the fact
that a prestigious analytical journal like Analytical and Bioanalytical Chemistry is preparing a special issue
on Green Analytical Methods for 2012 confirms that this is a good opportunity to incorporate to our everyday
work the main ideas and tools of Green Analytical Chemistry and to do it, we hope that this handbook will be
the reference book.

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xx

Preface

We would like to express our thanks to the personnel of Wiley-Blackwell who have offered all the time

their support, specially Sarah Hall and Sarah Tilley for their help to make this book possible, and Lynette
James for her diligent and careful work on editing the final version. Obviously, also the generosity, patience
and good work of all the authors are acknowledged. Many of these authors are old friends with whom we
have collaborated on many occasions in the past and who have influenced our research. On other occasions,
like in the case of Mihkel Kaljurand, Mihkel Koel and Jacek Namies´ nik, they are excellent specialists in the
field but we do not have any previous relationship with them. However, their generous acceptance to
participate in this project has been of great value to sum the efforts for greening our analytical work and has
contributed to improve the handbook. On the other hand, we are totally convinced that this book is also the
starting point for future cooperation in a new analytical chemistry built to improve both the fundamental and
green parameters of the methods and to increase the amount of information obtained from samples with the
minimum consumption of reagents and solvents, and the maximum safety for operators and the environment.
Miguel de la Guardia and Salvador Garrigues
Valencia, September 2011

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Section I
Concepts

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1
The Concept of Green Analytical Chemistry
Miguel de la Guardia and Salvador Garrigues

Department of Analytical Chemistry, University of Valencia, Valencia, Spain

1.1

Green Analytical Chemistry in the frame of Green Chemistry

Three years ago, when we published our review paper on Green Analytical Chemistry [1] it was clear that, at
this time, Green Chemistry was a well established paradigm well supported by more than 50 published books,
an increasing number of research teams who influenced the scientific literature and involved the editions of
special journals like Green Chemistry or Green Chemistry Letters and Reviews. However, there was a big
contrast between the situation of green catalyst development and the scarce use of the term Green Analytical
Chemistry in the literature. In spite of the fact that many studies from 1995 [2–5] were focused on the
objective of reducing the analytical wastes and making the methods environmentally friendly and sustainable
there was little conscience in the analytical community about the use of green or sustainable terms to define
their work.
Fortunately, the efforts of research teams like those of Jacek Namie´snick in Poland [6–9] and Mihkel Koel
and Mihkel Kaljurand in Estonia [10–11] have contributed to establish the main principles and strategies
which support the green practices in analytical chemistry and, because of that, the publication of the books
of Koel and Kaljuran [12] in 2010, de la Guardia and Armenta [13] in 2011, and that of de la Guardia and
Garrigues [14] in 2011 evidenced that nowadays Green Analytical Chemistry is becoming a movement which
can modify our perspective and practices in the analytical field in future years.
A simple idea could be to consider Green Analytical Chemistry as a part of the whole green chemistry idea, in
the same way that someone could consider that analytical chemistry is the part of chemistry devoted to development
and analysis. However, it is evident that analytical chemistry itself is not a part, but all chemistry, observed from
an analytical viewpoint which consists of searching for the differences between atoms, molecules and chemical
structures. Ahead of considering the links between the elements of the periodic table or evaluating the molecules
from the presence of a functional groups, analytical chemistry focuses on the differences between atoms and

Handbook of Green Analytical Chemistry, First Edition. Edited by Miguel de la Guardia and Salvador Garrigues.
© 2012 John Wiley & Sons, Ltd. Published 2012 by John Wiley & Sons, Ltd.

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4

Handbook of Green Analytical Chemistry
Remote sensing & direct measurement of untreated samples
Green
Analytical Chemistry
strategies

Replacement of toxic reagents
Miniaturization of procedures & instrumentation
Automation
On-line treatment of analytical wastes

Green Chemistry principles
1.
2.
3.
4.

Prevent waste
Maximize atom economy
Design less hazardous chemical synthesis
Design safer chemicals and products

5.
6.
7.
8.
9.

Use safer solvents & reaction conditions
Increase energy efficiency
Use renewable feedstock
Avoid chemical derivatives
Use of catalyst
10. Design for degradation
11. Analysis in real time to prevent pollution
12. Minimize the potential accidents

Figure 1.1 The Green Analytical Chemistry strategies in the frame of the Green Chemistry principles.

molecules which are apparently similar and thus there are many specificities of Green Analytical Chemistry
which must be evaluated in order to be able to provide a clear orientation for greening the analytical tasks.
As Paul Anastas has established in his abundant literature on Green Chemistry [15–21], the idea to replace
hazardous substances with less polluting ones or, if possible, innocuous products, and the prevention of waste
products in origin together with the restricted use of the prime matters and energy can be summarized in
12 principles (see Figure 1.1). These principles focus on prevention more than on remediation of pollution
effects of chemicals and provide guidelines for improving the synthesis methods through the use of renewable
raw materials, the maximization of the final product in terms of total mass, the reduction of energy consumption
and the search for the reduction of chemical toxicity of involved compounds, also improving the use of
catalytic reagents instead of stoichiometric ones. In the aforementioned principles there is a direct reference
to the analytical methodologies and the need that they must be improved to allow real time and in-process
monitoring and control prior to the formation of hazardous substances.
However, the analytical work also involves the use of reagents and solvents, employs energy as well as data

and results, and it generates waste. So, some of the Anasta’s principles can be easily translated to the analytical
field as those concerning the replacement of toxic reagents, energy saving, the reduction of reagents consumed
and waste generation. However, there are several specific strategies of the analytical work which are of
tremendous importance for greening our practices. As has been indicated in the scheme of Figure 1.1, remote
sensing and direct measurements of untreated samples are the greenest methodologies which we can imagine
and, because of that, the development of portable instruments and an instrumentation able to provide remote
sample measurements without the use of reagents and solvents, will be a primary task in the future.
Additionally, as is shown in Figure 1.2, all the developments in chemometrics will improve the multiparametric
capabilities of the aforementioned instruments in order to provide as much information as possible with a
reduced consumption of reagents and based on few measurements.

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The Concept of Green Analytical Chemistry

5

Greening strategies
•
•
•
•

Enhances the information obtained from the analytical signals
Provides multiparametric data
Removes the need for specific methods for determining each parameter
Improves the capability of remote sensing methodology

Chemometrics

Automation

•
•
•
•

Reduces reagents consumed
Deletes cleaning steps
Reduces waste generation
Favours on-line waste treatment

Miniaturization

• Reduces reagents and sample consumed
• Reduces waste generation
• Minimizes risks for operators

Figure 1.2 The main tools for greening the analytical method.

Miniaturization of processes and instruments will be also a key factor for the dramatic reduction of
consumables and energy and many efforts have also been made in the literature to downsize the pretreatment
and measurement steps, based on the development of microextraction technologies and micrototal analysis in
order to move from gram and millilitre scales to micro- and nanoscales. So, it is clear that the strong reduction
of reagents and solvents involved in miniaturization processes is welcome from the environmental point of
view, but attention must be paid to the lack of representativity which can affect analytical results based on
reduced amounts of bulk samples and thus, extra efforts must be made in order to avoid the potential

drawbacks of using small amounts of samples.
Automation was a revolution in analytical chemistry in the mid1970s and the development of flow injection
(FIA) [22], sequential injection analysis (SIA) [23] and multicommutation [24] provided essential tools for
improving, at the same time, the main analytical figures of merit of the methods and their green parameters,
based on scaling down the amount of reagents and sample employed and the use of pure solutions which are only
mixed when necessary. That reduces drastically the reagents consumed and waste generated. An additional
advantage offered by the automation in the analytical work is to avoid the cleaning of the glassware employed
in former times in batch analysis, which also contributes to remove or minimize the use of solvents and detergents.
However, the fast, self-cleaning and reagent saving mechanized and automatized methods of analysis
also produce waste, which in many cases are toxic residues containing small amounts of pollutant
substances present in standards, employed reagents or injected samples. Because of that, the on-line
treatment of analytical wastes has been emerged as an important contribution of Green Analytical
Chemistry in order to move from the old practices, which do not take into account the deleterious
environmental side effects of the analytical practices, to a new sustainable paradigm [5]. It is, from our
point of view, a highly interesting contribution from the practical and also from the theoretical perspective,
because it clearly shows that for deleting the pollution effects of chemicals an additional chemical effort

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Year

1980

1985

1990

2005

Lab-on-valve (LOV)
J. Ruzicka.

2010

Stir bar sorptive extraction (SBSE)
E. Baltussen, P. Sandra, F. David and C. Cramers.

2000

First precedent of multicommutation flow systems.
B.F. Reis, M.F. Giné, E.A.G. Zagatto, J.L.F.C. Lima and R.A. Lapa.

1995

Figure 1.3 Milestones in the development of Green Analytical Chemistry methods and strategies.

Molecularly imprinted solid phase extraction (MISPE).
B. Sellergren.

Solid phase microextraction (SPME)
C.L. Arthur and J.B. Pawliszyn.

Microwave-assisted solvent extraction (MAE)

K. Ganzler, A. Salgo, K. Valko.

Microwave ovens for sample digestion.
A. Abusamra, J.S. Morris and S.R. Koirtyohann.

1975

Liquid phase microextraction (LPME) and Single drop microextraction (SDME).
H.H. Liu and P.K. Dasgupta.

Flow injection analysis (FIA)
J. Ruzicka and E.H. Hansen.

Liquid-liquid-liquid microextraction (LLLME)
M. Ma and F.F. Cantwell.

Nano LC.
M.A. Moseley, L.J. Deterding, K.B. Tomer and J.W. Jorgenson.

Solid phase spectrophotometry (SPS)
K. Yoshimura, H. Waki and S. Ohashi.

Cloud point extraction (CPE)
H. Tanaka.

Micro total analytical system (μTAS)
A. Manz, N. Graber and H.M. Widmer.

Supercritical fluid extraction (SFE)
and supercritical fluid chromatography (SFC).

K. Sugiyama, M. Saito, T. Hondo and M. Senda.

Sequential injection analysis (SIA)
J. Ruzicka and G.D. Marshall.

Green Analytical Chemistry developments


The Concept of Green Analytical Chemistry

7

is desirable. So it offers a clear example that chemistry is not only one of the reasons of the environmental
pollution problems but also an important part of their solution.
The on-line reuse or recycling of solvents used in chromatography, flow or sequential analysis, the on-line
decontamination of pollutant compounds through chemical oxidation, thermo or photodegradation, together
with the use of biodegration systems and, in the case of pollutant mineral elements, their passivation and on-line
removal, can be integrated in the whole analytical protocol. So, this strategy could provide clean methodologies
which can improve the green parameters of a method without sacrificing any of its figures of merit.
In short, as is clearly shown in the scheme of Figure 1.2, the main tools available today for greening the
analytical methods concern chemometrics, automation and miniaturization. From those, a drastic reduction
of reagent consumption and waste generation can be made improving also the main analytical parameters.
On looking through the analytical work in the last 40 years (see Figure 1.3) it can be seen that the efforts
made for greening the methods came from the objective to reduce the cost of analysis, to improve their speed
and also to downsize the scale of work. We could mention, in addition to the development of FIA [22], SIA
[23] and multicommutation [24], the use of microwave energy for sample digestion [25] and analyte extraction
[26], developments in extraction techniques using solid phase and especially including a reduction of working
scale in the case of solid phase microextraction (SPME) [27], the use of stir bar sorptive extraction (SBSE)
[28], and measurements on solid phase spectrometry (SPS) [29]. Molecularly imprinted solid-phase extraction
(MISPE) [30] has contributed to enhancing the selectivity of extraction techniques while reducing the amount

of reagents employed.
From the initial contribution of cloud point techniques [31] liquid phase extraction also has been enhanced
by reducing the volume of solvent required through the development of liquid phase microextraction (LPME)
and single drop microextraction (SDME) [32,33], also including liquid-liquid-liquid microextraction
(LLLME) [34,35]. The use of supercritical fluid extraction for both analytical and chromatographic separations
was an important step in the development of new analytical applications [36], as well as the possibility of
working at the nanoscale in liquid chromatography [37,38]. Finally, the proposal of miniaturized total
chemical-analysis systems based sensors [39] or the development of lab-on-valve as a universal microflow
analyser [40] are other examples of contributions to the development of today’s analytical chemistry.

1.2

Green Analytical Chemistry versus Analytical Chemistry

We can understand that the environmental pollution is the matter of concern for all those who live and work
on this planet but what value does Green Analytical Chemistry add to the essential importance of analytical
chemistry? To answer this question we must think about the main aspects of the analytical methods and the
challenges for the future.
On considering the essential aspects of the analytical work (see Figure 1.4), the analytical parameters
emerge as the key factors to be considered. Accuracy, traceability, sensitivity, selectivity and precision are the
essential and basic figures of merit which must be assured in order to provide to the industries, consumers and
policy makers the appropriate tools to do their determinations. However, all the aforementioned parameters
do not take into consideration the safety of operators or the environmental effects of the use of the analytical
methods. Additional practical parameters, which must be also considered concern speed, cost and safety of
the determinations which are called practical parameters but can affect also basic parameters such as precision,
by increasing the number of replicate analyses based on their relative low cost and speed. So, at the end, an
increase of practical parameters can reduce the standard deviation of determinations by increasing the number
of analyses in the same sample and enhancing the analytical methodology in terms of precision.
Taking into consideration the objectives of Green Analytical Chemistry it could be enough to add to the
aforementioned figures of merit the so called green parameters which involve the evaluation and quantification

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8

Handbook of Green Analytical Chemistry
Analytical figures
of merit
Improved operators & environment safety

Applied

Safety

Speed
Basic

Reduced cost through miniaturization

Cost
Green
Analytical
Precision
Chemistry
Selectivity

objectives

Improved precision through automation
Improved selectivity through incorporation
of kinietic aspects
Maintenance of sensitivity

Sensitivity
Essential

Improved speed by avoiding pretreatments

Improved traceability by reducing steps

Tracebility

Maintenance of accuracy

Accuracy
+ added care on

Green parameters
of the method

• Toxicity or dangerous nature of reagents & wastes
• Amount of reagents & solvents used
• Energy consumed
• Volume of waste generated

Figure 1.4 Objectives of Green Analytical Chemistry in the frame of the analytical figures of merit.

of: (1) the toxicity or dangerous nature of reagents and solvents employed, (2) the volume of reagents and
solvents employed, (3) the energy consumed, and (4) the amount of waste generated.
In short, when we consider the Green Analytical Chemistry in the frame of Analytical Chemistry we must
think that the basic idea is to preserve the main objectives and to try to improve the analytical figures of merit
but at the same time, to add an extra effort to take into account the replacement of toxic reagents, to avoid or
at least, to reduce the amount of reagents and solvents employed to do the analytical determinations, to
evaluate and reduce the energy consumed and to avoid or minimize the volume of waste.
So, the Green Analytical Chemistry does not try to renounce to any one of the progress in method
development but adds a compromise with the preservation of the environment, and, as it can be seen in the
scheme of Figure 1.4, the main strategies involved in greening the analytical methods can also improve the
traditional figures of merit. Because of that, there is no conflict between the work made in the past and that
suggested for the future. Green Analytical Chemistry just adds an extra ethical value in front of environmental
protection and thus, we can see the evolution of the analytical methodologies from the classical analytical
chemistry to the green as a change of mentality and practices more drastic than modification of principles. In
fact, Green Analytical Chemistry will continue to be an effort projected on the whole chemistry field to search
for the best way to improve our knowledge on the composition and properties of all type of samples in order
to provide a correct answer to any kind of problems in chemical terms.
When we look at the different steps of the so called analytical procedure and we consider sampling to
sample preservation, sample transport and sample preparation to analyte preconcentration and analyte
separation and determination, the translation from classical analytical chemistry to the green involves an

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The Concept of Green Analytical Chemistry

Sampling
Sample transport

Sample preservation
Sample preparation

Analytical
Chemistry

Analyte
preconcentration
Analyte
separation

Determination

New

9

Avoided or simplified through in-situ or on-line determinations
Avoided or simplified taking into account reagents toxicity
Avoided or simplified by incorporating in-field sampling strategies
From hard to soft

Green Analytical
Chemistry
From liquid-liquid to solid phase extraction

From complex clean up to simplified clean up

From multistep to non-invasive and remote sensing

Analysis

From single determination to total information

Wastes

From disposal to on-line detoxification

Figure 1.5 The evaluation of methodologies from classical Analytical Chemistry to Green Analytical Chemistry.

effort to avoid as many as possible steps, especially those concerning the movement of samples from their
original environment to the laboratory, together with an evolution of our mentality from the hard methods of
sample digestion or analyte extraction to the soft ones, involving a strong reduction of energy and reagents
consumed. In many cases the aforementioned changes offer a simplification of matrix problems and opens
exciting possibilities for the characterization of the specific chemical forms existing originally in the samples
thus, also improving the main analytical parameters. As Figure 1.5 shows, additional efforts in greening the
methods involve a transition from high reagent volume strategies like liquid-liquid extraction to microextraction
ones and to solid phase extraction; and a general evolution from complex and multistep strategies to simplified
alternatives and to non-invasive and remote sensing measurements. In short, the basic idea is to move from
single determinations to methodologies providing total information from a reduced number of analytical
measurements. Additionally, a new aspect to be included in our consideration of the analytical process is the
waste generation and its treatment and, in this aspect, the change in mentality must move from disposal to
on-line detoxification of residues generated though analytical measurements.

1.3 The ethical compromise of sustainability
Sustainability is a new concept emerged from the consideration of sustainable development [41] to describe an
economy in equilibrium with basic ecological support systems [42]. So, this idea to recover the equilibrium
between the man and the biosphere after many years of disordered technical development has not taken into
consideration the environmental impact of human activities or all the risks involved of such activities in the long
term, can explain new values established from the conscience about the limits of the development [43] and the

need of the restoration of environmental equilibrium in order to assure the continuity of our life for the future

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