Handbook of green analytical chemistry

Handbook of Green Analytical Chemistry DelaGuardia_ffirs.indd i 2/1/2012 4:14:15 PM 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 DelaGuardia_ffirs.indd iii 2/1/2012 4:14:15 PM This edition first published 2012 © 2012 John Wiley & Sons, Ltd Registered Office John Wiley & Sons, Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988 All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic books Designations used by companies to distinguish their products are often claimed as trademarks All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners The publisher is not associated with any product or vendor mentioned in this book This publication is designed to provide accurate and authoritative information in regard to the subject matter covered It is sold on the understanding that the publisher is not engaged in rendering professional services If professional advice or other expert assistance is required, the services of a competent professional should be sought The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose This work is sold with the understanding that the publisher is not engaged in rendering professional services The advice and strategies contained herein may not be suitable for every situation In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read No warranty may be created or extended by any promotional statements for this work Neither the publisher nor the author shall be liable for any damages arising herefrom 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) Environmental chemistry–Industrial applications–Handbooks, manuals, etc 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 2012 DelaGuardia_ffirs.indd iv 2/1/2012 4:14:16 PM Contents List of Contributors Preface xv xix Section I: Concepts 1 The Concept of Green Analytical Chemistry Miguel de la Guardia and Salvador Garrigues 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 11 12 14 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 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 DelaGuardia_ftoc.indd v 2/3/2012 7:25:07 PM vi Contents 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 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 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 DelaGuardia_ftoc.indd vi 2/3/2012 7:25:07 PM 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 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 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 DelaGuardia_ftoc.indd vii 2/3/2012 7:25:07 PM viii Contents 8.4.4 Continuous filtration 8.5 A Green future for sample preparation References 143 145 145 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 DelaGuardia_ftoc.indd viii 182 183 184 185 2/3/2012 7:25:07 PM 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 đez-Sedo, 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 DelaGuardia_ftoc.indd ix 2/3/2012 7:25:07 PM 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 DelaGuardia_ftoc.indd x 2/3/2012 7:25:07 PM 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-Sỏnchez and Arben Merkoỗi 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 DelaGuardia_ftoc.indd xi 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 407 408 408 408 409 411 411 411 412 412 412 413 413 414 2/3/2012 7:25:07 PM 532 Index laser induced breakdown spectroscopy (LIBS), direct analysis, 90–1 open-path spectroscopy, 90–1 soil analysis, 489 leaching, energy savings, 300 LED, see light-emitting diode LIBS, see laser induced breakdown spectrometry light detection and ranging (LIDAR), direct analysis, 89–90 open-path spectroscopy, 89–90 light-emitting diode (LED), 184 energy savings, 301 flow analysis, 330 photometer based, 330 solid phase spectroscopy, 73 liquid chromatography, capillary liquid chromatography (capillary LC), 180–1 conversion, 182–3 derivative techniques, 254–5 green instruments, 178–84 green solvents, 175–8 high-temperature, 443 hollow-fibre, 71–5 homemade micro-scale, 183–4 hydrophilic solvents, 176–7 ionic liquids, 177 mass spectrometry, 413, 420, 443 microbore liquid chromatography (microbore LC), 179–80 nano liquid chromatography, 181–2 sampling techniques, 71–5 supercritical fluid chromatography (SFC), 177–8 ultra performance liquid chromatography (UPLC), 184–5 liquid-liquid extraction, liquid-liquid interface, 134–7 miniaturization, 360–1 non-chromatographic, 134–7 sample preparation, 134–7 separation techniques, 134–7 liquid-liquid interface, 133–9 dialysis, 133–4 liquid-liquid extraction, 134–7 microdialysis, 133–4 single-drop microextraction, 137–9 liquid-liquid-liquid microextraction (LLLME) configuration, 343 development, 6, miniaturization techniques, 343 sampling techniques, 74–5 DelaGuardia_bindex.indd 532 liquid-liquid microextraction, extraction techniques, 106–8 miniaturized, 106–8 sample preparation, 106–8 liquid phase microextraction (LPME) automation, 80 combined with capillary electrophoresis, 74, 168 gas chromatography, 74 liquid chromatography, 75 comparison, 479 contribution to energy saving, 308–9 development, 6, dynamic, 80 environmental analysis, 478 hollow fibre (HF-LPME), 479 HPLC, 75 membrane extraction, 108 sampling techniques, 74, 79–80 liquid phase separations, 155–67 capillary electrophoresis, 155–67 liquid-solid interface, 139–45 continuous filtration, 143–5, 144 solid-phase extraction, 139–41 solid-phase microextraction, 141–2, 142 stir-bar sorptive extraction, 142–3 lithography, 397 photolithography, 397 soft, 397 LLLME, see liquid-liquid-liquid microextraction losses, sample, 70–6 sampling techniques, 70–6 LOV, see lab-on-valve LPME, see liquid phase microextraction MAE, see microwave-assisted extraction MALDI, see matrix-assisted laser-desorption ionization MAME, see microwave-assisted micellar extraction MASE, see membrane assisted solvent extraction mass spectrometry, ambient, 95 applications, 486–7, 489–91, 493–4 at-line, 95 calibration, 210 capillary electrophoresis, 180 direct analysis, 95 effluent control, 513 elemental analysis, 199 environmental analysis, 479 gases, 496 2/2/2012 4:40:27 PM Index glow discharge, 95, 205, 206, 488–9 HPLC, 154, 487, 492 ICP, 35, 513 industrial analysis, 513 laser ablation, 205, 488, 489 liquid chromatography, 413, 420, 443 MALDI, 302 miniaturization, 354 multielement, 211 nano liquid chromatography, 181 particulates, 497 secondary-ion, 97 slurry methods, 205 soil, 487 solid sampling, 95, 205, 206 trace metals, 481 water analysis, 486 matrix-assisted laser-desorption ionization (MALDI), 113, 302, 362 mass spectrometry, 302 matrix isopotential, 253–4 derivative techniques, 253–4 fluorescence spectrometry, 253–4 synchronous fluorescence spectrometry, 253–4 matrix-solid phase dispersion (MSPD), miniaturization, 350–1 medical analysis, chemometrics, 454–5 infrared spectroscopy, 453–7 membrane assisted solvent extraction (MASE), 110, 479 environmental analysis, 479 extraction techniques, 108–9, 109 membrane extraction, 108–9, 109 miniaturized, 108–9, 109 sample preparation, 108–9, 109 membrane-based extraction, 69–70, 306 non-chromatographic techniques, 128 separation techniques, 127 units, 128 membrane extraction, 108–9, 130 applications, 109, 110 assisted solvent, 108 electro, 308–9 gas–liquid interface, 130 hollow-fibre, 132 liquid-liquid, 344 membrane assisted solvent extraction, 108–9, 109 membrane extraction with sorbent interface, 108, 109 DelaGuardia_bindex.indd 533 533 microporous liquid-liquid, 108, 109, 479 non-chromatographic, 130 sample preparation, 108–9, 130 sample treatment, 306 separation techniques, 130 sorbent interface, 108, 130, 479 supported liquid, 108, 109, 479 membrane extraction with sorbent interface (MESI), 110, 130, 479 extraction techniques, 108, 109 membrane extraction, 108, 109 miniaturized, 108, 109 sample preparation, 108, 109 mercury, clean extraction, 37–8 screening, 212, 213 soil analysis, 212, 213 species, 37–8 MESI, see membrane extraction with sorbent interface metal nanoparticles, electroanalytical methods, 269–70 metals, 35–7 contamination, 70 pressurized liquid extraction, 35–7 soil analysis, 70 methodologies, screening, 32, 202, 212–3, 294 method greenness, 64, 158, 312–13 microbore liquid chromatography (microbore LC), green instruments, 179–804 liquid chromatography, 179–80 microchip, capillary electrophoresis, 363 derivatization, 373 filtration, 365 solid phase extraction, 364 microdialysis, 133–4 liquid–liquid interface, 133–4 non-chromatographic, 133–4 sample preparation, 133–4 separation techniques, 133–4 microdistillation, 131, 131–2 gas–liquid interface, 131, 131–2 non-chromatographic, 131, 131–2 sample preparation, 131, 131–2 separation techniques, 131, 131–2 microextraction, dispersive liquid-liquid, derivative techniques, 250 environmental analysis, 479 miniaturization, 345 2/2/2012 4:40:27 PM 534 Index microextraction (cont’d) liquid-liquid-liquid configuration, 343 development, 6, miniaturization techniques, 343 sampling techniques, 74–5 liquid phase, automation, 80 combined with capillary electrophoresys, 74, 168 gas chromatography, 74 liquid chromatography, 75 comparison, 479 contribution to energy saving, 308–9 development, 6, dynamic, 80 environmental analysis, 478 hollow fibre (HF-LPME), 479 membrane extraction, 108 sampling techniques, 74, 79–80 single-drop, applications, 343, 487 capillary electrophoresis, 168, 169 characteristics, 342 development, 6, direct immersion, 106–7, 137–9, 342, 343–4 dynamic, 344 electrothermal atomic absorption spectrometry, 139 headspace (HS-SDME), 106, 107, 137–9, 344, 479 ionic liquid, 138–9 liquid-liquid interface, 137–9 liquid-liquid microextraction, 106 modes, 138 non-chromatographic separations, 137–9 sample preparation, 137–9 sample treatment, 308 sampling automatization, 79 separation techniques, 137–9 set-up, 107 solid phase, 348–9 environmental analysis, 478 extraction techniques, 105–6 liquid–solid interface, 141–2, 142 miniaturized, 105–6 non-chromatographic, 141–2, 142 sample preparation, 105–6, 141–2, 142 separation techniques, 141–2, 142 stir bar sorptive extraction, extraction techniques, 106 liquid-solid interface, 142–3 DelaGuardia_bindex.indd 534 miniaturized, 106, 349–50 non-chromatographic, 142–3 sample preparation, 106, 142–3 separation techniques, 142–3 microfluidic, chip, 366 platforms, 353–78 microfluidic device/s, capillary electrophoresis, 164, 164 chip fabrication, 399 miniaturization, 365 sample preparation, 373, 377 sensor, 310 microfluidic platforms, 353–78 derivatization schemes, 372–3 microtechnology, 389 proteomic, 374, 376 sample preparation, 353–6 sampling techniques, 78 micromaterials lab-on-a-chip, 389 micronization, energy savings, 307–12 microporous membrane liquid-liquid extraction (MMLLE), applications, 110 environmental analysis, 479 extraction techniques, 108, 109 membrane extraction, 108, 109 miniaturized, 108, 109 sample preparation, 108, 109 scheme, 109 micro-scale, derivative techniques, 248–9 HPLC, 155 microspectroscopy, IR, 449 micro-TAS, see micro-total analytical systems micro-total analytical systems (μ-TAS), advantages, 396 capillary electrophoresis, 164 development, electroanalytical methods, 276 energy saving, 309 lab-on-valve, 327, 396 microfluidic, 353–5 microwave-assisted digestion, 35 dissolution, 34–5, 36 drying, 299 extraction, 117, 477, 488, 489–93 GF-AAS, 203 2/2/2012 4:40:27 PM Index methodologies, 21 micellar extraction (MAME), 419 oxidation, 47, 48 sample preparation, 117, 297 solvent extraction (MAE), 6, 41, 298 environmental analysis, 477 miniaturization, 352 solvent free extraction, 42 microwave heating, 297–9 accelerated extraction, 297–8 assisted adsorption, 299 assisted desorption, 299 assisted digestion, 298–9 drying, 299 microwaves, atomic spectrometry, 203 GF-AAS, 203 sample pretreatment strategies, 203 mid infrared, at-line measurements, 93 direct analysis, 93 in-line, 93 on-line, 93 process monitoring, 93 milestones, chemometrics, 57 green analytical chemistry, 6, 19, 57–61, 60 publishing, 6, 57–61, 60 miniaturization, 339–87 cell analysis, 373–8 current needs, 340–1 derivatization schemes, 354–5, 372–3 dispersive liquid-liquid microextraction, 345 electrokinetics preconcentation, 365–72 energy saving, 308–10 extraction approaches, 360–5 filtering approaches, 356–65 flow focusing, 371–2 flow restrictions, 357–8 hollow fibre-protected microextraction, 344–5 integrated approaches, 353–78 liquid/liquid extraction, 360–1 mass spectrometry, 354 matrix-solid phase dispersion, 350–1 microextraction, 344 microfluidic platforms, 353–78 nanochannels, 372 non-integrated approaches, 341–52 particle filtering, 357–8 particle retention, 357–8 DelaGuardia_bindex.indd 535 535 preconcentration approaches, 365–72 proteomic, 362, 374, 376 sample preparation, 341–52 sample treatment, 308–10 screening, 347 soil analysis, 346 solid phase extraction, 345–8 solid phase microextraction, 348–9 solvent-based extraction techniques, 341–4 stir bar sorptive extraction, 349–50 thermal desorption-based techniques, 341 miniaturized extraction, 104–13 gas extraction, 109–13, 110 headspace analysis in a dynamic system, 112 liquid-liquid microextraction, 106–8 membrane assisted solvent extraction (MASE), 108–9, 109 membrane extraction, 108–9, 110 membrane extraction with sorbent interface (MESI), 108, 109 microporous membrane liquid-liquid extraction (MMLLE), 108, 109 sample preparation, 104–13 solid-phase extraction (SPE), 104–5, 105 solid-phase microextraction (SPME), 105–6 static headspace sampling, 111–12 stir-bar sorptive extraction (SBSE), 106 supported liquid membrane (SLM), 108, 109 thin-layer headspace extraction, 113 miniaturized systems, electroanalytical methods, 276–8 MIP, see molecular imprinted polymer MIR, see mid infrared, see also infrared spectroscopy MIR spectroscopy, at-line measurements, 93 attenuated total reflectance, 93 direct analysis, 93 in-line, 93 on-line, 93 process monitoring, 93 MMLLE, see microporous membrane liquid-liquid extraction modified electrode, 267, 274, 282 moisture analysis, 86 molecular absorption, derivative techniques, 245–59 molecularly imprinted polymer (MIP), 229, 483, 488, 490 soil analysis, 491 2/2/2012 4:40:28 PM 536 Index monitoring, atomic spectrometry, 208–10 attenuated total reflectance, 92 derivative species, 231–2 direct sampling, 208–10 flow injection, 229–31 flow modes, 227–31 HPLC, 413 multianalyte, 230 multicommutated, 231 photocatalytic treatment, 420 sequential determinations, 230–1 simultaneous determinations, 230 solid phase molecular spectroscopy, 227–31 solid sampling, 208–10 therapeutic drug, 432–435 monolithic, ion exchange concentrator, 366 monosegmented flow analysis (MSFA), 265, 275, 275 MSFA, see monosegmented flow analysis multi-analyte, 230 flow through, 229, 233 mass spectrometry, 211 monitoring, 230 multicommuted, 231 optosensors, 228, 230 procedures, 230 simultaneous, 312 solid phase spectroscopy, 228, 229 vitamins, 232 multicommutated procedures, flow injection methodologies, 328–9 monitoring, 231 solid phase molecular spectroscopy, 231 multicommutation applications, 330, 333 development, 4, flow analysis, 322, 328–34, 329, 331 flow injection, 328–34, 329 regular, 331 sampling, 79 set-up, 331 solid phase spectroscopy, 71, 73, 227, 231 vibrational spectroscopy, 330 multielement mass spectrometry, 211 multiparametric screening, 11 multipumping, 330, 334 multiresidue screening, 312 multisyringe, 330 burette, 330 DelaGuardia_bindex.indd 536 piston pump, 330 solid phase spectroscopy, 232–3 multisyringe flow injection analysis (MSFIA), 330 multivariate statistical, 254 derivative techniques, 254 fluorescence spectrometry, 254 synchronous fluorescence spectrometry, 254 nano(bio)sensors, stripping voltammetry, 394 nanochannels, 372 nanocomposite, 270, 394 nano HPLC, 157 nano liquid chromatography (nano LC), green instruments, 181–2 liquid chromatography, 181–2 mass spectrometry, 181 proteomic, 181–2 nanomaterials, 389–405 biosensors, 390–6 lab-on-a-chip, 389 nanoparticles, HPLC, 70, 75 metal, 269–70 sample, 75–6 sample manipulation, 75–6 sampling techniques, 75–6 nanotubes, 142, 389–91, 396 atomic spectrometry, 204 sample pretreatment strategies, 204 nanowires, 399 silicon, 399 national environmental methods index (NEMI), 63 energy efficiency, 313 pictogram, 63 near infrared spectroscopy (NIR), at-line measurements, 92 direct analysis, 92 in-line, 92 on-line, 92 process monitoring, 92 NEMI, see national environmental methods index new approaches, sample, 70–6 sampling techniques, 70–6 NIR, see near infrared spectroscopy NMR, see nuclear magnetic resonance non-chromatographic separations, lab-on-valve, 127 non-coherent light sources, 86–8 2/2/2012 4:40:28 PM Index non-destructive measurements, ambient mass spectrometry, 95 direct analysis, 94–7 nuclear magnetic resonance (NMR), 96 photoacoustic spectroscopy (PAS), 94 plasma sources, 95–6 solid sampling, 95–6 surface analysis techniques, 97 X-ray spectroscopy, 96–7 non-integrated approaches, miniaturization, 341–52 nuclear magnetic resonance (NMR), at-line measurements, 96 calibration, 462 direct analysis, 96 energy consumption, 305 urine, 457 on-line analysis, 76, 352, 515 analyzer, 340, 512 ATR spectroscopy, 93 capillary electrophoresis, 129 clean-up, 306 decontamination, 7, 9, 9, 32, 50, 492 derivatización, 231, 372 determinations, 9, 52, 324 dilution, 326 direct analysis, 91–4 electroanalytical, 282 hydrolysis, 49 image analysis, 93–4 imaging technology, 93–4 infrared spectroscopy, 93 liquid-liquid extraction, 326 measurements, 91–4, 134, 513 membrane extraction, 70, 130 microdialysis, 75 minicolumn, 229–30 monitoring, 228, 275, 420, 513 NIR spectroscopy, 92 photoreactor, 230 preconcentration, 365 pressurized hot water, 494 process control, 510 proteomic, 362 Raman spectroscopy, 92–3 Reactions, 354 recovery, 27–8, 324 recycling, 14, 12 sampling, 78, 118 DelaGuardia_bindex.indd 537 537 sensors, 513 separation, 48, 229 solid phase extraction, 104, 307, 325, 346–8, 352, 484 supported liquid membrane, 108 systems, 476 thermal desorption, 341 treatment, 326 wastes treatment, 4–5, 5, 10, 11, 25–6, 27, 63, 65, 333 on-line reactions, optosensors, 232 solid phase molecular spectroscopy, 232 open-path infrared, 86, 87 spectroscopy, 86 technologies, 86 open-path spectroscopy, coherent light sources, 86–8 differential absorption LIDAR (DIAL), 89–90 direct analysis, 86–90 FTIR, 86–8 laser induced breakdown (LIBS), 90–1 light detection and ranging (LIDAR), 89–90 non-coherent light sources, 86–8 stand-off Raman, 88 UV differential optical absorption (DOAS), 88 optosensors, applications, 233 chemiluminicence, 232 flow through, 227, 229, 231 fluorimetric, 233, 234 immobilization, 232 monitoring, 231 multicommutated, 71 multi-analyte, 230 on-line reaction, 232, 236 reactive immobilization, 232, 236 renewable surface, 233 sampling techniques, 71 simultaneous determination, 231 single-analyte, 229, 232–3 solid phase spectroscopy, 70–1, 227, 232–3, 236 UV, 235–6 organic pollutants, environmental analysis, 483, 486–7 outlier detection, infrared spectroscopy, 460–2 particle, filtering, 357–8 retention, 357–8 2/2/2012 4:40:28 PM 538 Index particulates, analysis, 497 environmental analysis, 497 mass spectrometry, 497 stripping voltammetry, 497 passivation, electrode, 300 methodologies, 63 wastes, PAT, see process analytical technology PBT, see persistent, bioaccumulative and toxic PDMS, see polydimethylsiloxane persistent, bioaccumulative and toxic (PBT), 63, 63 pervaporation, 127–30, 129 gas–liquid interface, 127–30, 129 non-chromatographic, 127–30, 129 sample preparation, 127–30, 129 separation techniques, 127–30, 129 pesticides, degradation, 415–6 residues, 415–6 screening, 347, 486 pharmaceuticals, degradation, 419–20 photoacoustic spectroscopy (PAS), at-line measurements, 94 direct analysis, 94 photocatalysis, 407–24 additives reducing, 412–13 catalyst concentration, 412 degradation kinetics, 412 dissolved oxygen, 411 experimental parameters, 411–12 fundamentals, 407–8 process, 408, 409 photocatalytic degradation, 411, 413, 415, 417, 419–20 photocatalytic treatment, 407–20 analytical control, 413 batch mode, 408 continuous monitoring, 420 laboratory wastes, 407–24 solar detoxification, 409–11 photochemical reactor, 410 photolithography, 397 photometer based, light-emitting diode, 330 PHWE see pressurized hot water extraction POC, see point of care point-of-care, capillary electrophoresis, 159–61, 167 instruments, 167, 310 DelaGuardia_bindex.indd 538 microtechnology, 389 portable instruments, 159 sensors, 310 pollution, control, 302, 475–6 soil analysis, 160, 513 polyaniline nanotubes (PANINT), 279, 281 polydimethylsiloxane (PDMS), 349 chip fabrication, 397 hollow-fibre, 71 immobilized membrane, 276 lab-on-valve, 328 membrane extraction, 108 microchannel, 368 microfluidics, 399 stir bar sorptive extraction, 106, 143 polymer(s), analysis, 207, 211 coating, 106 environmental-responsive, 428–9 molecular imprinted (MIPs), 346 polymer-modified surface, preparation, 430–1, 431 polymerization based prototyping, 397 portable, analysers, 90–1 capillary electrophoresis, 155, 159–68, 162–3 gas chromatograph, 74, 160 instruments, 4, 11, 57, 350, 513, 514 NIR spectrometer, 91 real-time field, 307 soil analysis, 70, 490 XRF instrument, 69–70, 490 portable analyzers, direct analysis, 90–1 electrochemical, 90 ion mobility spectrometry (IMS), 90–1 soil analysis, 70, 490 spectroscopy, 91 portable instruments, capillary electrophoresis, 159–63, 162–3 point-of-care, 159 preconcentration approaches, atomic spectrometry, 204 electrophoresis, 367 flow focussing, 371–2 miniaturization, 365–72 sample pretreatment strategies, 204 velocity changes, 366–71 preservatives, sample stabilization, 79 sampling, 78 2/2/2012 4:40:28 PM Index solid phase microextraction, 141 wood, 341 pressurized hot water extraction (PHWE), assisted extraction, 478 energy saving, 307 environmental analysis, 478 metals, 35 sample treatment, 307 solvent trapping, 478 pressurized liquid extraction (PLE), assisted extractions, 118 atomic spectrometry, 203 energy saving, 307 environmental analysis, 477 extraction techniques, 118 metals, 35–7 sample preparation, 118, 203 sample pretreatment strategies, 203 pressurized solvent extraction (PSE), 477 energy consumption, 305, 307 environmental analysis, 477 sample preparation, 118 soil analysis, 488 waste analysis, 419 process analytical technology (PAT), 510 process control, 87, 90, 92, 294, 311, 325, 512 attenuated total reflectance, 511 HPLC, 510 industrial analysis, 510–1 process monitoring, direct analysis, 91–94 image analysis, 93–4 imaging technology, 93–4 MIR spectroscopy, 93 NIR spectroscopy, 92 Raman spectroscopy, 92–3 propofol analysis, 434, 435 protein(s), analysis, 184, 376, 390 biosensors, 390 characterization, 154, 159 chips, 281, 359 electroanalytical methods, 281–2 green fluorescent protein, 371, 493 infrared, 451–2, 455–6, 459 microbore LC, 180–1 nanomaterials, 394 NIR, 92 preconcentration, 359, 362 separation, 376, 441–2 urine, 457 proteomic, DelaGuardia_bindex.indd 539 539 cell analysis, 374 microfluidic platforms, 374, 376 miniaturization, 362, 374, 376 nano liquid chromatography, 181–2 on-line, 362 sample preparation, 362, 374, 376 solid phase extraction, 362 PSE, see pressurized solvent extraction publications, 60, 65 green analytical chemistry, 60, 65 publishing, 55–66 authors, 59 bibliometric, 56–7 books, 22–3 diffusion channels, 56 editors, 64–5 future, 65–6 green analytical chemistry, 55–66 green parameters, 62–4 green pictograms, 63 journals, 13, 58–9 keywords, 57, 61–2, 62 milestones, 6, 57–61, 60 reviewers, 64–5 purge and trap, 110, 112, 112 quality control, 11, 154, 225, 248, 324 HPLC, 508 industrial analysis, 506–10 screening, 507–8 soil analysis, 76 quasi non-destructive measurements, ambient mass spectrometry, 95 direct analysis, 94–7 nuclear magnetic resonance (NMR), 96 photoacoustic spectroscopy (PAS), 94 plasma sources, 95–6 solid sampling, 95–6 surface analysis techniques, 97 X-ray spectroscopy, 96–7 radiofrequency glow discharge, 96, 207 Raman instruments, 88 Raman scattering, 93 Raman spectroscopy, 199, 507, 511 at-line measurements, 92–3 atmospheric analysis, 497 blister analysis, 93 bottles analysis, 93 direct analysis, 92–3 in-line, 92–3 on-line, 92–3 2/2/2012 4:40:28 PM 540 Index Raman spectroscopy (cont’d ) process monitoring, 92–3 solid phase molecular, 229 stand-off, 88, 89 surface enhanced (SERS), 98 raw materials, 496, 512 industrial analysis, 506–10, 506–7 screening, 507–8 REACH, 10, 25, 505 reactive immobilization, 232 optosensors, 232 solid phase molecular spectroscopy, 232 remote environmental sensing 85–91 remote sampling, 93 remote sensing, direct analysis, 85–91 effluent control, 512, 513, 514 environmental, 85–6 green analytical strategies, 4–5, 9–10, 57 portable instruments, 12 satellite, 86 soil analysis, 86 strategies, 86 reversed-phase HPLC, 158, 443, 508 room temperature ionic liquids (RTILs), 202, 478 RP-HPLC, see reversed-phase HPLC RTILs, see room temperature ionic liquids SAE see sonication assisted extraction saliva analysis, attenuated total reflectance, 457 sample, collection, 476 contamination, 70–6 losses, 70–6 transport, 70–6 stabilization, 79 storage, 70–6 sample preparation, alternative solvents, 113–17 analytical process, 125–7 assisted extractions, 117–18 capillary electrophoresis, 168–9 environmental analysis, 476–9 gas extraction, 109–13, 110 gas-liquid interface, 127–33 gaseous samples, 341–50 GF-AAS, 104 liquid-liquid interface, 133–9 liquid-liquid microextraction, 106–8 liquid samples, 341–50 DelaGuardia_bindex.indd 540 liquid-solid interface, 139–45 membrane extraction, 108–9 microfluidic platforms, 353–6 miniaturization, 341–52 miniaturized extraction techniques, 104–13 non-chromatographic, 125–51 pressurized solvent extraction, 118 proteomic, 362, 374, 376 separation techniques, 125–51 solid-phase extraction (SPE), 104–5, 105 solid-phase microextraction (SPME), 105–6 solid samples, 350–3 stir-bar sorptive extraction (SBSE), 106 trends, 145 sample pretreatment, 202–6 atomic spectrometry, 202–6 biosorption of uranium, 38–40 clean extraction, 37–8 cloud point extraction, 204 electrothermal atomic absorption spectrometry, 202 enzymatic approaches, 203–4 extraction with nanotubes, 204 green speciation, 40–1 liquid-liquid extractions, 37–42 mercury species, 37–8 metals, 35–7 microwave-assisted dissolution, 34–5 microwaves, 203 preconcentration with nanotubes, 204 pressurized liquid extraction, 35–7, 203 sediments, 207 separations, 37–42 slurry methods, 204–5 solid-phase extractions, 37–42 solventless extractions, 37–42 ultrasound-assisted leaching, 33–4 ultrasounds, 203 sample stabilization, carbon dioxide, 79 sample treatment, energy saving, 306–7 miniaturization, 308–10 trends, 306–7 ultrasound, 299–301 sampling, active, 514 analytical process, 86, 201, 355 attenuated total reflectance, 511 automated, 76, 79–80 containers, 70 dialysis, 134 2/2/2012 4:40:28 PM Index direct solid, 205–6, 206, 206, 210–13, 214 environmental, 77, 476 extraction techniques, 111–12 for, capillary electrophoresis, 160–2, 163 MIR spectroscopy, 93, 455, 468 NIR spectroscopy, 92 frequency, 51, 72–3, 77, 323, 327, 332, 482–3 gas extraction, 111–12 greening techniques, 69–83 headspace, 106, 111–12, 131–2, 342 in-field, 9, 77–8, 80, 294, 321 in-situ, 476 in vivo, 77 membrane devices, 326 miniaturized, 111–12 on-line, 118 passive, 106, 514 probes, 315, 511 problems, 93 remote, 93 rolling stir bar, 77 sample preparation, 111–12 sediments, 476 slurry, 34, 129, 204–5, 489 soil analysis, 70, 76, 476 solid, 201–2, 489 solid-phase microextraction, 105 solutions for greening, 70 static headspace, 111–12 techniques, 69–83, 202, 205–13, 206, 206 valves, 410, 411 sampling techniques, automatization, 79–80 contamination, 70–6 electrothermal atomic absorption spectrometry, 80 flow-through, 70–1, 72–3 hollow-fibre, 71–5 in-field, 77–8 in-line, 76–7 losses, 70–6 microfluidic platforms, 78 nanoparticles, 75–6 new approaches, 70–6 solid phase spectroscopy, 70–1, 72–3 stabilization, 79 storage, 70–6 transport, 70–6 trends, 80 satellite sensors, 86 SBSE, see stir bar sorptive extraction DelaGuardia_bindex.indd 541 541 screen-printed electrodes, 76, 266, 275 sensor for DNA, 279 techniques, 266, 379, 397 technology, 397 screening, atomic spectrometry, 212 bioactive compounds, 443 capillary electrophoresis, 159 chemical, 294 chemical residues, 308 direct analysis, 214 electroanalytical methods, 281 environmental, 308 explosives, 91 GF-AAS, 214 HTLC, 443 ion mobility spectrometry, 91 industrial analysis, 507–8 mercury, 212, 213 methodologies, 32 methods, 202, 212–13, 294 miniaturization, 347 multiparametric methods, 11 multi residue, 312 pesticides, 347, 486 quality control, 507–8 raw materials, 507–8 schemes, 213 seawater, 486 soils, 212, 213, 214 solid sampling, 202 solid phase microextraction, 349 stir bar sorptive extraction, 486 X-ray fluorescence, 508 SDME, see single-drop microextraction seawater screening, 486 secondary ion mass spectrometry (SIMS), 97 surface analysis, 97 sediments, accelerated extraction, 300 applications, 489–90, 493 capillary electrophoresis, 166 environmental analysis, 488–92 marine, 299 sample collection, 476 sample pretreatment, 207 slurries, 346 solid phase extraction, 346 supercritical fluid extraction, 114 ultrasonic leaching, 300 vacuum drying, 299 2/2/2012 4:40:28 PM 542 Index sensors, applications, 233 chemiluminicence, 232 flow through, 227, 229, 231 fluorimetric, 233, 234 immobilization, 232 monitoring, 231 multi-analyte, 230 multicommutated, 71 on-line reaction, 232, 236 reactive immobilization, 232, 236 renewable surface, 233 sampling techniques, 71 satellite, 86 screen-printed, 76, 266, 275 simultaneous determination, 231 single-analyte, 229, 232–3 solid phase spectroscopy, 70–1, 227, 232–3, 236 UV, 235–6 separation techniques, capillary electrophoresis, 153–5 cold-mercury vapour, 133 continuous filtration, 143–5, 144 dialysis, 133–4 distillation, 131 gas diffusion, 127 gas-liquid interface, 127–33 head-space separation, 131–2 hydride generation, 133 liquid-liquid extraction, 134–7 liquid-liquid interface, 133–9 liquid-solid interface, 139–45 membrane extraction, 130 microdialysis, 133–4 microdistillation, 131, 131–2 pervaporation, 127–30, 129 single-drop microextraction, 137–9 solid-phase extraction, 139–41 solid-phase microextraction, 141–2, 142 stir-bar sorptive extraction, 142–3 sequential determinations, monitoring, 230–1 solid phase molecular spectroscopy, 230–1 sequential injection analysis (SIA), bead injection, 328 flow injection methodologies, 325–7, 325 lab-on-valve, 328 solid phase molecular spectroscopy, 232–3, 235 SFC, see supercritical fluid chromatography SFE, see supercritical fluid extraction SIMS, see Secondary ion mass spectrometry DelaGuardia_bindex.indd 542 simultaneous determinations, monitoring, 230 solid phase molecular spectroscopy, 230 single-drop microextraction (SDME), 137–9 applications, 343, 487 capillary electrophoresis, 168, 169 characteristics, 342 development, 6, direct immersion, 106–7, 137–9, 342, 343–4 dynamic, 344 electrothermal atomic absorption spectrometry, 139 headspace (HS-SDME), 106, 107, 137–9, 344, 479 ionic liquid, 138–9 liquid-liquid interface, 137–9 liquid-liquid microextraction, 106 modes, 138 non-chromatographic separations, 137–9 sample preparation, 137–9 sample treatment, 308 sampling automatization, 79 separation techniques, 137–9 set-up, 107 SLME, see supported liquid membrane extraction slurry, 300, 351, 363, 409, 412, 420 slurry methods, atomic spectrometry, 204–5 ICP-MS, 205 mass spectrometry, 205 sample pretreatment strategies, 204–5 soil analysis, 346, 349 slurry sampling, 34, 129, 204–5, 489 soil analysis accelerated solvent extraction, 488 analytical techniques, 489–91 applications, 489–91 capillary electrophoresis, 160 cloud point extraction, 491 effluent control, 513 electroanalytical methods, 263, 271 environmental analysis, 475–6, 485–8, 489–91 field analytical chemistry, 160 GF-AAS, 214, 489 ICP-MS, 487 industrial analysis, 513 ionic liquids, 271 laser ablation, 489 LIBS, 489 mass spectrometry, 487 mercury screening, 212, 213 metal contamination, 70 2/2/2012 4:40:28 PM Index miniaturization, 346 moisture, 86 molecularly imprinted polymers, 491 polluting, 160, 513 portable instruments, 70, 490 pressurized solvent extraction, 488 quality, 76 remote sensing, 86 sampling, 70, 76, 476 screening, 212, 213, 214 slurries, 346, 349 solid phase microextraction, 141, 349 supercritical fluid extraction, 114 X-ray fluorescence, 70, 490 solid phase exchanger, 44–5 green synthesis, 44–5 solid-phase extraction (SPE), environmental analysis, 478 extraction techniques, 104–5, 105 HPLC, 79, 307 lab-on-valve, 140 liquid–solid interface, 139–41 miniaturization, 345–8 miniaturized, 104–5, 105 non-chromatographic, 139–41 proteomic, 362 sample preparation, 104–5, 105, 139–41 screening, 349 sediments, 346 separation techniques, 139–41 soil analysis, 141, 349 solid phase microextraction (SPME), 348–9 environmental analysis, 478 extraction techniques, 105–6 HPLC, 79, 307 liquid–solid interface, 141–2, 142 miniaturized, 105–6 non-chromatographic, 141–2, 142 sample preparation, 105–6, 141–2, 142 screening, 349 separation techniques, 141–2, 142 soil analysis, 141, 349 solid phase molecular spectroscopy (SPMS), 221–44 absorption, 222–4 applications, 233–5, 237–8 batch mode, 222, 225–7, 239 bead injection, 232, 239 derivatizing reactions, 231–2 emission, 225 flow, 226–33, 228 flow injection, 229–31 DelaGuardia_bindex.indd 543 543 fluorescence, 225 fundamentals, 222–5 green analytical chemistry, 235–40 monitoring, 227–31 multianalyte, 230 multicommutated, 231 multisyringe flow injection analysis, 232–3 on-line reactions, 232 optosensors, 232, 236 reactive immobilization, 232 sequential determinations, 230–1 sequential injection analysis, 232–3, 235 simultaneous determinations, 230 spectrophotometric, 222–4 solid phase spectroscopy, flow-through, 70–1, 72–3 light-emitting diode, 73 multicommutation, 71, 73, 227, 231 multisyringe, 330 sample, 70–1, 72–3 sampling techniques, 69–83, 70–1, 72–3 solid sampling, analyte monitoring, 208–10 applications, 210–13, 214 atomic spectrometry, 205–13 calibration, 210 direct, 202 electrothermal atomic absorption spectrometry, 206 GF-AAS, 205, 206, 489 graphite furnace, 489 high-resolution continuum source, 208–10 ICP-MS, 205, 206 laser ablation, 95, 205 mass spectrometry, 95, 205, 206 plasma sources, 95–6 pretreatment strategies, 207 principles, 205–7 sample requirements, 207 screening, 202 techniques, 202, 205–13, 206, 206 solid sampling plasma sources, 95–6 at-line measurements, 95–6 direct analysis, 95–6 solvent(s), electroanalytical methods, 270–3 energy savings, 302–5 reduction, 158 replacement, 158 solvent-based extraction techniques, miniaturization, 341–4 2/2/2012 4:40:28 PM 544 Index solventfree extraction, 41–2 essential oils, 41–2 sonication, see also ultrasound-assisted, accelerated extraction, 300 applications, 72–3, 495 cell analysis, 374 environmental analysis, 477 miniaturization, 352 room temperature, 57 sediments, 495 sonication assisted extraction (SAE), 300, see also ultrasound-assisted extraction soxhlet extraction, 117–18, 298, 300, 307, 340, 477 SPE, see solid phase extraction speciation, clean extraction, 37–8 green, 40–1 mercury species, 37–8 solid phase exchanger, 40–1 vanadium, 40–1 spectrophotometric, derivative techniques, 248–50 solid phase molecular spectroscopy, 222–4 spectroscopy, bead injection, 333 direct analysis, 91 field-portable analyzers, 91 SPME, see solid phase microextraction square-wave anodic, stripping voltammetry, 263, 489 stabilization, sample, 79 sampling techniques, 79 stand-off Raman spectroscopy, 88 direct analysis, 88 open-path spectroscopy, 88 stir bar microextraction, see also stir bar sorptive extraction stir bar sorptive extraction (SBSE), extraction techniques, 106 liquid-solid interface, 142–3 miniaturized, 106, 349–50 non-chromatographic, 142–3 sample preparation, 106, 142–3 screening, 486 separation techniques, 142–3 storage, sample, 70–6 sampling techniques, 70–6 strengths-weaknesses-opportunities-threats (SWOT), diagrams, 27 DelaGuardia_bindex.indd 544 green analytical chemistry, 27 methodology, 26 stripping voltammetry, adsorptive, 263, 267 anodic, 263, 266 bath injection analysis, 276 electrodes, 263 environmental analysis, 497 heavy metals analysis, 266 lab-on-a-chip, 394 particulates analysis, 497 nano(bio)sensors, 394 square-wave anodic, 263, 489 subcritical fluids, energy savings, 303–5 subcritical water extraction (SWE) alternative solvents, 115 environmental analysis, 478 extraction techniques, 115 sample preparation, 115 supercritical fluid(s), carbon dioxide, 114, 114, 273, 304, 488 electroanalytical methods, 273 energy savings, 303–5 supercritical fluid chromatography (SFC), green solvents, 177–8 liquid chromatography, 177–8 supercritical fluid extraction (SFE), alternative solvents, 114–15 environmental analysis, 477 extraction techniques, 114–15 sample preparation, 114–15 sediments, 114 supported liquid membrane (SLM), extraction techniques, 108, 109 membrane extraction, 108, 109 miniaturized, 108, 109 sample preparation, 108, 109 supported liquid membrane extraction (SLME), 108, 479 surface acoustic wave sensor (SAW), 395, 396 surface analysis, 97–8, 293 SWE, see subcritical water extraction SWOT, see strengths-weaknesses-opportunities-threats synchronous, derivative techniques, 251–4 fluorescence spectrometry, 251–4 synchronous fluorescence spectrometry, 251–4 constant-wavelength, 251–3 derivative techniques, 251–4 matrix isopotential, 253–4 2/2/2012 4:40:28 PM Index multivariate statistical, 254 variable-angle, 253 synthetic aperture radar (SAR), 86 TAS, see micro-total analytical systems teaching, analytical chemistry, 21–4 chemometrics, 25 green analytical chemistry, 25–6 temperature gradient chromatography, 435, 442 elution, 434 temperature gradient chromatography, see also temperature-responsive temperature gradient focusing (TGF), 371 temperature-responsive chromatography, 432 biological analysis, 432–3 contraceptive drugs analysis, 435–6, 436 propofol analysis, 434, 435 therapeutic drug monitoring, 432–5 thermal desorption-based techniques, miniaturization, 341 thin film, 74 thin-layer, extraction techniques, 113 gas extraction, 113 headspace extraction, 113 miniaturized, 113 sample preparation, 113 time of flight mass (TOF), 145, 362 tissue samples, infrared spectroscopy, 457–67 TOF, see time of flight mass toxic release inventory (TRI), 63, 64 trace metals, environmental analysis, 481, 484–5 GF-AAS, 481 ICP-MS, 481 mass spectrometry, 481 transport, sample, 70–6 sampling techniques, 70–6 trends, atomic spectrometry, 213 capillary electrophoresis, 169–70 sample preparation, 145 sampling techniques, 80 TRI, see toxic release inventory triad approach, 78 two-dimensional, attenuated total reflectance, 456 DelaGuardia_bindex.indd 545 545 UAE, see ultrasound-assisted extraction ultra performance liquid chromatography (UPLC), 158, 184–5 green instruments, 178–84 liquid chromatography, 175–6 ultrasonic bath, 33, 212 ultrasonic extraction, environmental analysis, 477 organic contaminants, 491 ultrasonic probe, 33, 117, 135–6, 305, 353 ultrasounds, atomic spectrometry, 203 sample pretreatment strategies, 203 ultrasound-assisted, atomic spectrometry, 203 biological materials, 33 cleaning, 118 extraction, 117–18, 137 filtration, 144, 145 leaching, 300 liquid-liquid extraction, 135, 136 organic pollutants, 487 sample preparation, 117–18 wastes, 492 ultrasound-assisted extraction (UAE), assisted extractions, 117–18 batch mode, 300 extraction techniques, 117–18 sample preparation, 117–18 ultrasound-assisted leaching, GF-AAS, 34 uranium, 38–40 biosorption, 38–40 urine, infrared spectroscopy, 457 nuclear magnetic resonance, 457 UV differential optical absorption spectroscopy (DOAS), 88 direct analysis, 88 open-path spectroscopy, 88 UV-visible, attenuated total reflectance, 511 derivative techniques, 247–50 internal standard, 45–7 vanadium speciation, 40–1 variable-angle, 253 derivative techniques, 253 fluorescence spectrometry, 253 synchronous fluorescence spectrometry, 253 velocity change, 366–71 2/2/2012 4:40:28 PM 546 Index wastewater, environmental analysis, 480–3 wastes, degradation, 415–16 environmental analysis, 492, 496 pressurized solvent extraction, 419 wastes treatment, aqueous wastes, 416–19 aromatic contaminants, 414 azo-dyes, 419 degradation, 415–16 examples, 413–19 organic solvent residues, 416 percolates, 414 pesticide residues, 415–16 pharmaceuticals, 419–20 photocatalytic destruction, 414–15 solar detoxification, 409–11 surfactant-containing, 416–19 triazine herbicides, 416 water analysis, environmental, 480–3 mass spectrometry, 486 working atmosphere, 506, 515 control, 514–15 DelaGuardia_bindex.indd 546 industrial analysis, 514 world-to-chip interfacing, capillary electrophoresis, 163–5 XPS, see also X-ray photoelectron spectrometry X-ray at-line measurements, 96–7 direct analysis, 96–7 energy consumption, 305 lithography, 397 screening, 508 soil analysis, 70, 490 X-ray fluorescence (XRF), 70, 78, 96 direct analysis, 96–7 microbeam, 97 portable instruments, 70, 490 raw material analysis, 507, 508 real time measurements, 78, 80 screening, 508 soil analysis, 70, 490 solid sample analysis, 488 X-ray photoelectron spectrometry (XPS), 97, 497 X-ray spectroscopy Auger emission spectroscopy, 96–7 XRF, see also X-ray fluorescence 2/2/2012 4:40:28 PM ... Publication of special issues of journals and books success of Green Chemistry Integration of Green Analytical Chemistry efforts in the frame of the Green Chemistry Figure 1.8 Attitudes of the scientific... TrAC – Trends in Analytical Chemistry Analytical and Bioanalytical Chemistry Environmental Friendly Analytical Chemistry Green Spectroscopy Green Analytical Chemistry Green Analytical Methods.. .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,