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Handbook of Green
Analytical Chemistry
EDITORSMIGUEL DE LA GUARDIA
SALVADOR GARRIGUES
RED BOX RULES ARE FOR PROOF STAGE ONLY. DELETE BEFORE FINAL PRINTING.
Handbook of Green Analytical ChemistryEDITORSMIGUEL DE LA GUARDIA and SALVADOR GARRIGUES, Department of Analytical Chemistry, University of Valencia, Valencia, Spain
� e emerging � eld of green analytical chemistry is concerned with the development of analytical procedures that minimize consumption of hazardous reagents and solvents, and maximize safety for operators and the environment. In recent years there have been signi� cant developments in methodological and technological tools to prevent and reduce the deleterious e� ects of analytical activities; key strategies include recycling, replacement, reduction and detoxi� cation of reagents and solvents.� e Handbook of Green Analytical Chemistry provides a comprehensive overview of the present state and recent developments in green chemical analysis. A series of detailed chapters, written by international specialists in the � eld, discuss the fundamental principles of green analytical chemistry and present a catalogue of tools for developing environmentally friendly analytical techniques.Topics covered include:
• Concepts: Fundamental principles, education, laboratory experiments and publication in green analytical chemistry.
• � e Analytical Process: Green sampling techniques and sample preparation, direct analysis of samples, green methods for capillary electrophoresis, chromatography, atomic spectroscopy, solid phase molecular spectroscopy, derivative molecular spectroscopy and electroanalytical methods.
• Strategies: Energy saving, automation, miniaturization and photocatalytic treatment of laboratory wastes.
• Fields of Application: Green bioanalytical chemistry, biodiagnostics, environmental analysis and industrial analysis.
� is advanced handbook is a practical resource for experienced analytical chemists who are interested in implementing green approaches in their work.
EDITORSDE LA GUARDIA
GARRIGUES
Handbook of G
reen A
nalytical Chemistry
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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 GARRIGUESDepartment of Analytical Chemistry, University of Valencia, Valencia, Spain
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This edition first published 2012
© 2012 John Wiley & Sons, Ltd.
Registered OfficeJohn Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom
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The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and
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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 xv
Preface xix
Section I: Concepts 1
1 The Concept of Green Analytical Chemistry 3Miguel de la Guardia and Salvador Garrigues
1.1 Green Analytical Chemistry in the frame of Green Chemistry 3
1.2 Green Analytical Chemistry versus Analytical Chemistry 7
1.3 The ethical compromise of sustainability 9
1.4 The business opportunities of clean methods 11
1.5 The attitudes of the scientific community 12
References 14
2 Education in Green Analytical Chemistry 17Miguel de la Guardia and Salvador Garrigues
2.1 The structure of the Analytical Chemistry paradigm 17
2.2 The social perception of Analytical Chemistry 20
2.3 Teaching Analytical Chemistry 21
2.4 Teaching Green Analytical Chemistry 25
2.5 From the bench to the real world 26
2.6 Making sustainable professionals for the future 28
References 29
3 Green Analytical Laboratory Experiments 31Suparna Dutta and Arabinda K. Das
3.1 Greening the university laboratories 31
3.2 Green laboratory experiments 33
3.2.1 Green methods for sample pretreatment 33
3.2.2 Green separation using liquid-liquid, solid-phase and solventless extractions 37
3.2.3 Green alternatives for chemical reactions 42
3.2.4 Green spectroscopy 45
3.3 The place of Green Analytical Chemistry in the future of our laboratories 52
References 52
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4 Publishing in Green Analytical Chemistry 55Salvador Garrigues and Miguel de la Guardia
4.1 A bibliometric study of the literature in Green Analytical Chemistry 56
4.2 Milestones of the literature on Green Analytical Chemistry 57
4.3 The need for powerful keywords 61
4.4 A new attitude of authors faced with green parameters 62
4.5 A proposal for editors and reviewers 64
4.6 The future starts now 65
References 66
Section II: The Analytical Process 67
5 Greening Sampling Techniques 69José Luis Gómez Ariza and Tamara García Barrera
5.1 Greening analytical chemistry solutions for sampling 70
5.2 New green approaches to reduce problems related to sample losses, sample
contamination, transport and storage 70
5.2.1 Methods based on flow-through solid phase spectroscopy 70
5.2.2 Methods based on hollow-fiber GC/HPLC/CE 71
5.2.3 Methods based on the use of nanoparticles 75
5.3 Greening analytical in-line systems 76
5.4 In-field sampling 77
5.5 Environmentally friendly sample stabilization 79
5.6 Sampling for automatization 79
5.7 Future possibilities in green sampling 80
References 80
6 Direct Analysis of Samples 85Sergio Armenta and Miguel de la Guardia
6.1 Remote environmental sensing 85
6.1.1 Synthetic Aperture Radar (SAR) images (satellite sensors) 86
6.1.2 Open-path spectroscopy 86
6.1.3 Field-portable analyzers 90
6.2 Process monitoring: in-line, on-line and at-line measurements 91
6.2.1 NIR spectroscopy 92
6.2.2 Raman spectroscopy 92
6.2.3 MIR spectroscopy 93
6.2.4 Imaging technology and image analysis 93
6.3 At-line non-destructive or quasi non-destructive measurements 94
6.3.1 Photoacoustic Spectroscopy (PAS) 94
6.3.2 Ambient Mass Spectrometry (MS) 95
6.3.3 Solid sampling plasma sources 95
6.3.4 Nuclear Magnetic Resonance (NMR) 96
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6.3.5 X-ray spectroscopy 96
6.3.6 Other surface analysis techniques 97
6.4 New challenges in direct analysis 97
References 98
7 Green Analytical Chemistry Approaches in Sample Preparation 103Marek Tobiszewski, Agata Mechlinska and Jacek Namiesnik
7.1 About sample preparation 103
7.2 Miniaturized extraction techniques 104
7.2.1 Solid-phase extraction (SPE) 104
7.2.2 Solid-phase microextraction (SPME) 105
7.2.3 Stir-bar sorptive extraction (SBSE) 106
7.2.4 Liquid-liquid microextraction 106
7.2.5 Membrane extraction 108
7.2.6 Gas extraction 109
7.3 Alternative solvents 113
7.3.1 Analytical applications of ionic liquids 113
7.3.2 Supercritical fluid extraction 114
7.3.3 Subcritical water extraction 115
7.3.4 Fluorous phases 116
7.4 Assisted extractions 117
7.4.1 Microwave-assisted extraction 117
7.4.2 Ultrasound-assisted extraction 117
7.4.3 Pressurized liquid extraction 118
7.5 Final remarks 119
References 119
8 Green Sample Preparation with Non-Chromatographic Separation Techniques 125María Dolores Luque de Castro and Miguel Alcaide Molina
8.1 Sample preparation in the frame of the analytical process 125
8.2 Separation techniques involving a gas–liquid interface 127
8.2.1 Gas diffusion 127
8.2.2 Pervaporation 127
8.2.3 Membrane extraction with a sorbent interface 130
8.2.4 Distillation and microdistillation 131
8.2.5 Head-space separation 131
8.2.6 Hydride generation and cold-mercury vapour formation 133
8.3 Techniques involving a liquid–liquid interface 133
8.3.1 Dialysis and microdialysis 133
8.3.2 Liquid–liquid extraction 134
8.3.3 Single-drop microextraction 137
8.4 Techniques involving a liquid–solid interface 139
8.4.1 Solid-phase extraction 139
8.4.2 Solid-phase microextraction 141
8.4.3 Stir-bar sorptive extraction 142
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8.4.4 Continuous filtration 143
8.5 A Green future for sample preparation 145
References 145
9 Capillary Electrophoresis 153Mihkel Kaljurand
9.1 The capillary electrophoresis separation techniques 153
9.2 Capillary electrophoresis among other liquid phase separation methods 155
9.2.1 Basic instrumentation for liquid phase separations 155
9.2.2 CE versus HPLC from the point of view of Green Analytical Chemistry 156
9.2.3 CE as a method of choice for portable instruments 159
9.2.4 World-to-chip interfacing and the quest for a ‘killer’ application
for LOC devices 163
9.2.5 Gradient elution moving boundary electrophoresis and
electrophoretic exclusion 165
9.3 Possible ways of surmounting the disadvantages of CE 167
9.4 Sample preparation in CE 168
9.5 Is capillary electrophoresis a green alternative? 169
References 170
10 Green Chromatography 175Chi-Yu Lu
10.1 Greening liquid chromatography 175
10.2 Green solvents 176
10.2.1 Hydrophilic solvents 176
10.2.2 Ionic liquids 177
10.2.3 Supercritical Fluid Chromatography (SFC) 177
10.3 Green instruments 178
10.3.1 Microbore Liquid Chromatography (microbore LC) 179
10.3.2 Capillary Liquid Chromatography (capillary LC) 180
10.3.3 Nano Liquid Chromatography (nano LC) 181
10.3.4 How to transfer the LC condition from traditional LC to microbore LC,
capillary LC or nano LC 182
10.3.5 Homemade micro-scale analytical system 183
10.3.6 Ultra Performance Liquid Chromatography (UPLC) 184
References 185
11 Green Analytical Atomic Spectrometry 199Martín Resano, Esperanza García-Ruiz and Miguel A. Belarra
11.1 Atomic spectrometry in the context of Green Analytical Chemistry 199
11.2 Improvements in sample pretreatment strategies 202
11.2.1 Specific improvements 202
11.2.2 Slurry methods 204
11.3 Direct solid sampling techniques 205
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11.3.1 Basic operating principles of the techniques discussed 205
11.3.2 Sample requirements and pretreatment strategies 207
11.3.3 Analyte monitoring: The arrival of high-resolution continuum source atomic
absorption spectrometry 208
11.3.4 Calibration 210
11.3.5 Selected applications 210
11.4 Future for green analytical atomic spectrometry 213
References 215
12 Solid Phase Molecular Spectroscopy 221Antonio Molina-Díaz, Juan Francisco García-Reyes and Natividad Ramos-Martos
12.1 Solid phase molecular spectroscopy: an approach to Green Analytical Chemistry 221
12.2 Fundamentals of solid phase molecular spectroscopy 222
12.2.1 Solid phase absorption (spectrophotometric) procedures 222
12.2.2 Solid phase emission (fluorescence) procedures 225
12.3 Batch mode procedures 225
12.4 Flow mode procedures 226
12.4.1 Monitoring an intrinsic property 227
12.4.2 Monitoring derivative species 231
12.4.3 Recent flow-SPMS based approaches 232
12.5 Selected examples of application of solid phase molecular spectroscopy 233
12.6 The potential of flow solid phase envisaged from the point of view of
Green Analytical Chemistry 235
References 240
13 Derivative Techniques in Molecular Absorption, Fluorimetry and Liquid Chromatography as Tools for Green Analytical Chemistry 245José Manuel Cano Pavón, Amparo García de Torres, Catalina Bosch Ojeda, Fuensanta Sánchez Rojas and Elisa I. Vereda Alonso
13.1 The derivative technique as a tool for Green Analytical Chemistry 245
13.1.1 Theoretical aspects 246
13.2 Derivative absorption spectrometry in the UV-visible region 247
13.2.1 Strategies to greener derivative spectrophotometry 248
13.3 Derivative fluorescence spectrometry 250
13.3.1 Derivative synchronous fluorescence spectrometry 251
13.4 Use of derivative signal techniques in liquid chromatography 254
References 255
14 Greening Electroanalytical Methods 261Paloma Yáñez-Sedeño, José M. Pingarrón and Lucas Hernández
14.1 Towards a more environmentally friendly electroanalysis 261
14.2 Electrode materials 262
14.2.1 Alternatives to mercury electrodes 262
14.2.2 Nanomaterial-based electrodes 268
14.3 Solvents 270
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14.3.1 Ionic liquids 271
14.3.2 Supercritical fluids 273
14.4 Electrochemical detection in flowing solutions 274
14.4.1 Injection techniques 274
14.4.2 Miniaturized systems 276
14.5 Biosensors 278
14.5.1 Greening biosurface preparation 278
14.5.2 Direct electrochemical transfer of proteins 281
14.6 Future trends in green electroanalysis 282
References 282
Section III: Strategies 289
15 Energy Savings in Analytical Chemistry 291Mihkel Koel
15.1 Energy consumption in analytical methods 291
15.2 Economy and saving energy in laboratory practice 294
15.2.1 Good housekeeping, control and maintenance 295
15.3 Alternative sources of energy for processes 296
15.3.1 Using microwaves in place of thermal heating 297
15.3.2 Using ultrasound in sample treatment 299
15.3.3 Light as a source of energy 301
15.4 Using alternative solvents for energy savings 302
15.4.1 Advantages of ionic liquids 303
15.4.2 Using subcritical and supercritical fluids 303
15.5 Efficient laboratory equipment 305
15.5.1 Trends in sample treatment 306
15.6 Effects of automation and micronization on energy consumption 307
15.6.1 Miniaturization in sample treatment 308
15.6.2 Using sensors 310
15.7 Assessment of energy efficiency 312
References 316
16 Green Analytical Chemistry and Flow Injection Methodologies 321Luis Dante Martínez, Soledad Cerutti and Raúl Andrés Gil
16.1 Progress of automated techniques for Green Analytical Chemistry 321
16.2 Flow injection analysis 322
16.3 Sequential injection analysis 325
16.4 Lab-on-valve 327
16.5 Multicommutation 328
16.6 Conclusions and remarks 334
References 334
17 Miniaturization 339Alberto Escarpa, Miguel Ángel López and Lourdes Ramos
17.1 Current needs and pitfalls in sample preparation 340
17.2 Non-integrated approaches for miniaturized sample preparation 341
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17.2.1 Gaseous and liquid samples 341
17.2.2 Solid samples 350
17.3 Integrated approaches for sample preparation on microfluidic platforms 353
17.3.1 Microfluidic platforms in sample preparation process 353
17.3.2 The isolation of analyte from the sample matrix: filtering approaches 356
17.3.3 The isolation of analytes from the sample matrix: extraction approaches 360
17.3.4 Preconcentration approaches using electrokinetics 365
17.3.5 Derivatization schemes on microfluidic platforms 372
17.3.6 Sample preparation in cell analysis 373
17.4 Final remarks 378
References 379
18 Micro- and Nanomaterials Based Detection Systems Applied in Lab-on-a-Chip Technology 389Mariana Medina-Sánchez and Arben Merkoçi
18.1 Micro- and nanotechnology in Green Analytical Chemistry 389
18.2 Nanomaterials-based (bio)sensors 390
18.2.1 Optical nano(bio)sensors 391
18.2.2 Electrochemical nano(bio)sensors 393
18.2.3 Other detection principles 395
18.3 Lab-on-a-chip (LOC) technology 396
18.3.1 Miniaturization and nano-/microfluidics 396
18.3.2 Micro- and nanofabrication techniques 397
18.4 LOC applications 398
18.4.1 LOCs with optical detections 398
18.4.2 LOCs with electrochemical detectors 398
18.4.3 LOCs with other detections 399
18.5 Conclusions and future perspectives 400
References 401
19 Photocatalytic Treatment of Laboratory Wastes Containing Hazardous Organic Compounds 407Edmondo Pramauro, Alessandra Bianco Prevot and Debora Fabbri
19.1 Photocatalysis 407
19.2 Fundamentals of the photocatalytic process 408
19.3 Limits of the photocatalytic treatment 408
19.4 Usual photocatalytic procedure in laboratory practice 408
19.4.1 Solar detoxification of laboratory waste 409
19.5 Influence of experimental parameters 411
19.5.1 Dissolved oxygen 411
19.5.2 pH 411
19.5.3 Catalyst concentration 412
19.5.4 Degradation kinetics 412
19.6 Additives reducing the e−/h+ recombination 412
19.7 Analytical control of the photocatalytic treatment 413
19.8 Examples of possible applications of photocatalysis to the treatment of laboratory wastes 413
19.8.1 Percolates containing soluble aromatic contaminants 414
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19.8.2 Photocatalytic destruction of aromatic amine residues in aqueous wastes 414
19.8.3 Degradation of aqueous wastes containing pesticides residue 415
19.8.4 The peculiar behaviour of triazine herbicides 416
19.8.5 Treatment of aqueous wastes containing organic solvent residues 416
19.8.6 Treatment of surfactant-containing aqueous wastes 416
19.8.7 Degradation of aqueous solutions of azo-dyes 419
19.8.8 Treatment of laboratory waste containing pharmaceuticals 419
19.9 Continuous monitoring of photocatalytic treatment 420
References 420
Section IV: Fields of Application 425
20 Green Bioanalytical Chemistry 427Tadashi Nishio and Hideko Kanazawa
20.1 The analytical techniques in bioanalysis 427
20.2 Environmental-responsive polymers 428
20.3 Preparation of a polymer-modified surface for the stationary phase
of environmental-responsive chromatography 430
20.4 Temperature-responsive chromatography for green analytical methods 432
20.5 Biological analysis by temperature-responsive chromatography 432
20.5.1 Analysis of propofol in plasma using water as a mobile phase 434
20.5.2 Contraceptive drugs analysis using temperature gradient chromatography 435
20.6 Affinity chromatography for green bioseparation 436
20.7 Separation of biologically active molecules by the green chromatographic method 438
20.8 Protein separation by an aqueous chromatographic system 441
20.9 Ice chromatography 442
20.10 High-temperature liquid chromatography 443
20.11 Ionic liquids 443
20.12 The future in green bioanalysis 444
References 444
21 Infrared Spectroscopy in Biodiagnostics: A Green Analytical Approach 449Mohammadreza Khanmohammadi and Amir Bagheri Garmarudi
21.1 Infrared spectroscopy capabilities 449
21.2 Infrared spectroscopy of bio-active chemicals in a bio-system 451
21.3 Medical analysis of body fluids by infrared spectroscopy 453
21.3.1 Blood and its extracts 455
21.3.2 Urine 457
21.3.3 Other body fluids 457
21.4 Diagnosis in tissue samples via IR spectroscopic analysis 457
21.4.1 Main spectral characteristics 459
21.4.2 The role of data processing 460
21.4.3 Cancer diagnosis by FTIR spectrometry 465
21.5 New trends in infrared spectroscopy assisted biodiagnostics 468
References 470
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22 Environmental Analysis 475Ricardo Erthal Santelli, Marcos Almeida Bezerra, Julio Carlos Afonso, Maria de Fátima Batista de Carvalho, Eliane Padua Oliveira and Aline Soares Freire
22.1 Pollution and its control 475
22.2 Steps of an environmental analysis 476
22.2.1 Sample collection 476
22.2.2 Sample preparation 476
22.2.3 Analysis 479
22.3 Green environmental analysis for water, wastewater and effluent 480
22.3.1 Major mineral constituents 480
22.3.2 Trace metal ions 481
22.3.3 Organic pollutants 483
22.4 Green environmental analysis applied for solid samples 485
22.4.1 Soil 485
22.4.2 Sediments 488
22.4.3 Wastes 492
22.5 Green environmental analysis applied for atmospheric samples 496
22.5.1 Gases 496
22.5.2 Particulates 497
References 497
23 Green Industrial Analysis 505Sergio Armenta and Miguel de la Guardia
23.1 Greening industrial practices for safety and cost reasons 505
23.2 The quality control of raw materials and end products 506
23.3 Process control 510
23.4 Effluent control 511
23.5 Working atmosphere control 514
23.6 The future starts now 515
References 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 Department of Analytical Chemistry and Chemical Engineering, University of Alcala,
Madrid, Spain
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 Instituto de Química de San Luis, Universidad Nacional de San Luis-CONICET, San Luis,
Argentina
Miguel de la Guardia Department of Analytical Chemistry, University of Valencia, Valencia, Spain
Lucas Hernández Department of Analytical and Instrumental Analysis, Universidad Autónoma de Madrid,
Madrid, Spain
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 Chemistry Department, Faculty of Science, Imam Khomeini
International University, Qazvin, Iran
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 Department of Analytical Chemistry, Campus of Rabanales, Córdoba,
Spain
Luis Dante Martínez Instituto de Química de San Luis, Universidad Nacional de San Luis-CONICET,
San Luis, Argentina
Agata Mechlinska 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 Namiesnik 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 Namiesnik, 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 IConcepts
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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.
1The 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 Namiesnick 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
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4 Handbook of Green Analytical Chemistry
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.
Green Chemistry principles
1. Prevent waste
2. Maximize atom economy
3. Design less hazardous chemical synthesis
4. Design safer chemicals and products
5. Use safer solvents & reaction conditions
6. Increase energy efficiency
7. Use renewable feedstock
8. Avoid chemical derivatives
9. Use of catalyst
Design for degradation
Analysis in real time to prevent pollution
Minimize the potential accidents
Remote sensing & direct measurement of untreated samples
Replacement of toxic reagents
Miniaturization of procedures & instrumentation
Automation
On-line treatment of analytical wastes
Green
Analytical Chemistry
strategies
10.
11.
12.
Figure 1.1 The Green Analytical Chemistry strategies in the frame of the Green Chemistry principles.
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The Concept of Green Analytical Chemistry 5
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
Figure 1.2 The main tools for greening the analytical method.
• 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
• Reduces reagents and sample consumed• Reduces waste generation• Minimizes risks for operators
• Reduces reagents consumed• Deletes cleaning steps• Reduces waste generation• Favours on-line waste treatment
Chemometrics
MiniaturizationAutomation
Greening strategies
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Liqu
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. Sai
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. Ho
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.L. A
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. Liu
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. Bal
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. San
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(CP
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.
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. Man
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. Det
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.W. J
org
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1975
1980
1985
1990
1995
2000
2005
2010
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(S
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J. R
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Figu
re 1
.3
Mile
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the
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f Gre
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met
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ies.
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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
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
Figure 1.4 Objectives of Green Analytical Chemistry in the frame of the analytical figures of merit.
Ess
entia
lB
asic
App
lied
Analytical figuresof merit
Safety
Cost
+ added care on
Improved operators & environment safety
Reduced cost through miniaturization
Improved speed by avoiding pretreatments
Improved precision through automation
Improved selectivity through incorporation of kinietic aspects
Maintenance of sensitivity
Improved traceability by reducing steps
Maintenance of accuracy
Green
Analytical
Chemistry
objectives
Green parametersof the method
• Toxicity or dangerous nature of reagents & wastes• Amount of reagents & solvents used• Energy consumed• Volume of waste generated
Speed
Precision
Selectivity
Sensitivity
Tracebility
Accuracy
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