Handbook of Green Analytical Chemistry

Miguel de la Guardia, Professor of Analytical Chemistry, Valencia University, SpainProfessor de la Guardia's research is focused on the automation of analytical methods through multicommutation, sample preparation procedures, chemometrics, development of green analytical methods and development of portable spectrometers. He is a member of the editorial board of Spectroscopy Letters, Ciencia and J. Braz. Chem. Soc., and he was a member of the advisory board of Analytica Chimica Acta from 1995 to 2000. In addition, he is a government consultant for Portugal, Italy, Argentina and China for the evaluation of research proposals and grants. Professor de la Guardia prepared a special issue on Green Spectroscopy in Spectroscopy Letters in 2009, and he is in the process of preparing a special issue on Green Analytical Chemistry for of TrAC which is due to publish in March 2010.Salvador Garrigues, Professor of Analytical Chemistry, Valencia University, SpainSalvador Garrigues works in the research team with Prof. Miguel de la Guardia and has collaborated in more than 150 publications.

• List of Contributors xv Preface xixSection I: Concepts 11 The Concept of Green Analytical Chemistry 3Miguel de la Guardia and Salvador Garrigues1.1 Green Analytical Chemistry in the frame of Green Chemistry 31.2 Green Analytical Chemistry versus Analytical Chemistry 71.3 The ethical compromise of sustainability 91.4 The business opportunities of clean methods 111.5 The attitudes of the scientific community 12References 142 Education in Green Analytical Chemistry 17Miguel de la Guardia and Salvador Garrigues2.1 The structure of the Analytical Chemistry paradigm 172.2 The social perception of Analytical Chemistry 202.3 Teaching Analytical Chemistry 212.4 Teaching Green Analytical Chemistry 252.5 From the bench to the real world 262.6 Making sustainable professionals for the future 28References 293 Green Analytical Laboratory Experiments 31Suparna Dutta and Arabinda K. Das3.1 Greening the university laboratories 313.2 Green laboratory experiments 333.2.1 Green methods for sample pretreatment 333.2.2 Green separation using liquid-liquid, solid-phase and solventless extractions 373.2.3 Green alternatives for chemical reactions 423.2.4 Green spectroscopy 453.3 The place of Green Analytical Chemistry in the future of our laboratories 52References 524 Publishing in Green Analytical Chemistry 55Salvador Garrigues and Miguel de la Guardia4.1 A bibliometric study of the literature in Green Analytical Chemistry 564.2 Milestones of the literature on Green Analytical Chemistry 574.3 The need for powerful keywords 614.4 A new attitude of authors faced with green parameters 624.5 A proposal for editors and reviewers 644.6 The future starts now 65References 66Section II: The Analytical Process 675 Greening Sampling Techniques 69José Luis Gómez Ariza and Tamara García Barrera5.1 Greening analytical chemistry solutions for sampling 705.2 New green approaches to reduce problems related to sample losses, sample contamination, transport and storage 705.2.1 Methods based on flow-through solid phase spectroscopy 705.2.2 Methods based on hollow-fiber GC/HPLC/CE 715.2.3 Methods based on the use of nanoparticles 755.3 Greening analytical in-line systems 765.4 In-field sampling 775.5 Environmentally friendly sample stabilization 795.6 Sampling for automatization 795.7 Future possibilities in green sampling 80References 806 Direct Analysis of Samples 85Sergio Armenta and Miguel de la Guardia6.1 Remote environmental sensing 856.1.1 Synthetic Aperture Radar (SAR) images (satellite sensors) 866.1.2 Open-path spectroscopy 866.1.3 Field-portable analyzers 906.2 Process monitoring: in-line, on-line and at-line measurements 916.2.1 NIR spectroscopy 926.2.2 Raman spectroscopy 926.2.3 MIR spectroscopy 936.2.4 Imaging technology and image analysis 936.3 At-line non-destructive or quasi non-destructive measurements 946.3.1 Photoacoustic Spectroscopy (PAS) 946.3.2 Ambient Mass Spectrometry (MS) 956.3.3 Solid sampling plasma sources 956.3.4 Nuclear Magnetic Resonance (NMR) 966.3.5 X-ray spectroscopy 966.3.6 Other surface analysis techniques 976.4 New challenges in direct analysis 97References 987 Green Analytical Chemistry Approaches in Sample Preparation 103Marek Tobiszewski, Agata Mechlinska and Jacek Namiesnik7.1 About sample preparation 1037.2 Miniaturized extraction techniques 1047.2.1 Solid-phase extraction (SPE) 1047.2.2 Solid-phase microextraction (SPME) 1057.2.3 Stir-bar sorptive extraction (SBSE) 1067.2.4 Liquid-liquid microextraction 1067.2.5 Membrane extraction 1087.2.6 Gas extraction 1097.3 Alternative solvents 1137.3.1 Analytical applications of ionic liquids 1137.3.2 Supercritical fluid extraction 1147.3.3 Subcritical water extraction 1157.3.4 Fluorous phases 1167.4 Assisted extractions 1177.4.1 Microwave-assisted extraction 1177.4.2 Ultrasound-assisted extraction 1177.4.3 Pressurized liquid extraction 1187.5 Final remarks 119References 1198 Green Sample Preparation with Non-Chromatographic Separation Techniques 125María Dolores Luque de Castro and Miguel Alcaide Molina8.1 Sample preparation in the frame of the analytical process 1258.2 Separation techniques involving a gas–liquid interface 1278.2.1 Gas diffusion 1278.2.2 Pervaporation 1278.2.3 Membrane extraction with a sorbent interface 1308.2.4 Distillation and microdistillation 1318.2.5 Head-space separation 1318.2.6 Hydride generation and cold-mercury vapour formation 1338.3 Techniques involving a liquid–liquid interface 1338.3.1 Dialysis and microdialysis 1338.3.2 Liquid–liquid extraction 1348.3.3 Single-drop microextraction 1378.4 Techniques involving a liquid–solid interface 1398.4.1 Solid-phase extraction 1398.4.2 Solid-phase microextraction 1418.4.3 Stir-bar sorptive extraction 1428.4.4 Continuous filtration 1438.5 A Green future for sample preparation 145References 1459 Capillary Electrophoresis 153Mihkel Kaljurand9.1 The capillary electrophoresis separation techniques 1539.2 Capillary electrophoresis among other liquid phase separation methods 1559.2.1 Basic instrumentation for liquid phase separations 1559.2.2 CE versus HPLC from the point of view of Green Analytical Chemistry 1569.2.3 CE as a method of choice for portable instruments 1599.2.4 World-to-chip interfacing and the quest for a ‘killer’ application for LOC devices 1639.2.5 Gradient elution moving boundary electrophoresis and electrophoretic exclusion 1659.3 Possible ways of surmounting the disadvantages of CE 1679.4 Sample preparation in CE 1689.5 Is capillary electrophoresis a green alternative? 169References 17010 Green Chromatography 175Chi-Yu Lu10.1 Greening liquid chromatography 17510.2 Green solvents 17610.2.1 Hydrophilic solvents 17610.2.2 Ionic liquids 17710.2.3 Supercritical Fluid Chromatography (SFC) 17710.3 Green instruments 17810.3.1 Microbore Liquid Chromatography (microbore LC) 17910.3.2 Capillary Liquid Chromatography (capillary LC) 18010.3.3 Nano Liquid Chromatography (nano LC) 18110.3.4 How to transfer the LC condition from traditional LC to microbore LC, capillary LC or nano LC 18210.3.5 Homemade micro-scale analytical system 18310.3.6 Ultra Performance Liquid Chromatography (UPLC) 184References 18511 Green Analytical Atomic Spectrometry 199Martín Resano, Esperanza García-Ruiz and Miguel A. Belarra11.1 Atomic spectrometry in the context of Green Analytical Chemistry 19911.2 Improvements in sample pretreatment strategies 20211.2.1 Specific improvements 20211.2.2 Slurry methods 20411.3 Direct solid sampling techniques 20511.3.1 Basic operating principles of the techniques discussed 20511.3.2 Sample requirements and pretreatment strategies 20711.3.3 Analyte monitoring: The arrival of high-resolution continuum source atomic absorption spectrometry 20811.3.4 Calibration 21011.3.5 Selected applications 21011.4 Future for green analytical atomic spectrometry 213References 21512 Solid Phase Molecular Spectroscopy 221Antonio Molina-Díaz, Juan Francisco García-Reyes and Natividad Ramos-Martos12.1 Solid phase molecular spectroscopy: an approach to Green Analytical Chemistry 22112.2 Fundamentals of solid phase molecular spectroscopy 22212.2.1 Solid phase absorption (spectrophotometric) procedures 22212.2.2 Solid phase emission (fluorescence) procedures 22512.3 Batch mode procedures 22512.4 Flow mode procedures 22612.4.1 Monitoring an intrinsic property 22712.4.2 Monitoring derivative species 23112.4.3 Recent flow-SPMS based approaches 23212.5 Selected examples of application of solid phase molecular spectroscopy 23312.6 The potential of flow solid phase envisaged from the point of view of Green Analytical Chemistry 235References 24013 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 Alonso13.1 The derivative technique as a tool for Green Analytical Chemistry 24513.1.1 Theoretical aspects 24613.2 Derivative absorption spectrometry in the UV-visible region 24713.2.1 Strategies to greener derivative spectrophotometry 24813.3 Derivative fluorescence spectrometry 25013.3.1 Derivative synchronous fluorescence spectrometry 25113.4 Use of derivative signal techniques in liquid chromatography 254References 25514 Greening Electroanalytical Methods 261Paloma Yáñez-Sedeño, José M. Pingarrón and Lucas Hernández14.1 Towards a more environmentally friendly electroanalysis 26114.2 Electrode materials 26214.2.1 Alternatives to mercury electrodes 26214.2.2 Nanomaterial-based electrodes 26814.3 Solvents 27014.3.1 Ionic liquids 27114.3.2 Supercritical fluids 27314.4 Electrochemical detection in flowing solutions 27414.4.1 Injection techniques 27414.4.2 Miniaturized systems 27614.5 Biosensors 27814.5.1 Greening biosurface preparation 27814.5.2 Direct electrochemical transfer of proteins 28114.6 Future trends in green electroanalysis 282References 282Section III: Strategies 28915 Energy Savings in Analytical Chemistry 291Mihkel Koel15.1 Energy consumption in analytical methods 29115.2 Economy and saving energy in laboratory practice 29415.2.1 Good housekeeping, control and maintenance 29515.3 Alternative sources of energy for processes 29615.3.1 Using microwaves in place of thermal heating 29715.3.2 Using ultrasound in sample treatment 29915.3.3 Light as a source of energy 30115.4 Using alternative solvents for energy savings 30215.4.1 Advantages of ionic liquids 30315.4.2 Using subcritical and supercritical fluids 30315.5 Efficient laboratory equipment 30515.5.1 Trends in sample treatment 30615.6 Effects of automation and micronization on energy consumption 30715.6.1 Miniaturization in sample treatment 30815.6.2 Using sensors 31015.7 Assessment of energy efficiency 312References 31616 Green Analytical Chemistry and Flow Injection Methodologies 321Luis Dante Martínez, Soledad Cerutti and Raúl Andrés Gil16.1 Progress of automated techniques for Green Analytical Chemistry 32116.2 Flow injection analysis 32216.3 Sequential injection analysis 32516.4 Lab-on-valve 32716.5 Multicommutation 32816.6 Conclusions and remarks 334References 33417 Miniaturization 339Alberto Escarpa, Miguel Ángel López and Lourdes Ramos17.1 Current needs and pitfalls in sample preparation 34017.2 Non-integrated approaches for miniaturized sample preparation 34117.2.1 Gaseous and liquid samples 34117.2.2 Solid samples 35017.3 Integrated approaches for sample preparation on microfluidic platforms 35317.3.1 Microfluidic platforms in sample preparation process 35317.3.2 The isolation of analyte from the sample matrix: filtering approaches 35617.3.3 The isolation of analytes from the sample matrix: extraction approaches 36017.3.4 Preconcentration approaches using electrokinetics 36517.3.5 Derivatization schemes on microfluidic platforms 37217.3.6 Sample preparation in cell analysis 37317.4 Final remarks 378References 37918 Micro- and Nanomaterials Based Detection Systems Applied in Lab-on-a-Chip Technology 389Mariana Medina-Sánchez and Arben Merkoçi18.1 Micro- and nanotechnology in Green Analytical Chemistry 38918.2 Nanomaterials-based (bio)sensors 39018.2.1 Optical nano(bio)sensors 39118.2.2 Electrochemical nano(bio)sensors 39318.2.3 Other detection principles 39518.3 Lab-on-a-chip (LOC) technology 39618.3.1 Miniaturization and nano-/microfluidics 39618.3.2 Micro- and nanofabrication techniques 39718.4 LOC applications 39818.4.1 LOCs with optical detections 39818.4.2 LOCs with electrochemical detectors 39818.4.3 LOCs with other detections 39918.5 Conclusions and future perspectives 400References 40119 Photocatalytic Treatment of Laboratory Wastes Containing Hazardous Organic Compounds 407Edmondo Pramauro, Alessandra Bianco Prevot and Debora Fabbri19.1 Photocatalysis 40719.2 Fundamentals of the photocatalytic process 40819.3 Limits of the photocatalytic treatment 40819.4 Usual photocatalytic procedure in laboratory practice 40819.4.1 Solar detoxification of laboratory waste 40919.5 Influence of experimental parameters 41119.5.1 Dissolved oxygen 41119.5.2 pH 41119.5.3 Catalyst concentration 41219.5.4 Degradation kinetics 41219.6 Additives reducing the e−/h+ recombination 41219.7 Analytical control of the photocatalytic treatment 41319.8 Examples of possible applications of photocatalysis to the treatment of laboratory wastes 41319.8.1 Percolates containing soluble aromatic contaminants 41419.8.2 Photocatalytic destruction of aromatic amine residues in aqueous wastes 41419.8.3 Degradation of aqueous wastes containing pesticides residue 41519.8.4 The peculiar behaviour of triazine herbicides 41619.8.5 Treatment of aqueous wastes containing organic solvent residues 41619.8.6 Treatment of surfactant-containing aqueous wastes 41619.8.7 Degradation of aqueous solutions of azo-dyes 41919.8.8 Treatment of laboratory waste containing pharmaceuticals 41919.9 Continuous monitoring of photocatalytic treatment 420References 420Section IV: Fields of Application 42520 Green Bioanalytical Chemistry 427Tadashi Nishio and Hideko Kanazawa20.1 The analytical techniques in bioanalysis 42720.2 Environmental-responsive polymers 42820.3 Preparation of a polymer-modified surface for the stationary phase of environmental-responsive chromatography 43020.4 Temperature-responsive chromatography for green analytical methods 43220.5 Biological analysis by temperature-responsive chromatography 43220.5.1 Analysis of propofol in plasma using water as a mobile phase 43420.5.2 Contraceptive drugs analysis using temperature gradient chromatography 43520.6 Affinity chromatography for green bioseparation 43620.7 Separation of biologically active molecules by the green chromatographic method 43820.8 Protein separation by an aqueous chromatographic system 44120.9 Ice chromatography 44220.10 High-temperature liquid chromatography 44320.11 Ionic liquids 44320.12 The future in green bioanalysis 444References 44421 Infrared Spectroscopy in Biodiagnostics: A Green Analytical Approach 449Mohammadreza Khanmohammadi and Amir Bagheri Garmarudi21.1 Infrared spectroscopy capabilities 44921.2 Infrared spectroscopy of bio-active chemicals in a bio-system 45121.3 Medical analysis of body fluids by infrared spectroscopy 45321.3.1 Blood and its extracts 45521.3.2 Urine 45721.3.3 Other body fluids 45721.4 Diagnosis in tissue samples via IR spectroscopic analysis 45721.4.1 Main spectral characteristics 45921.4.2 The role of data processing 46021.4.3 Cancer diagnosis by FTIR spectrometry 46521.5 New trends in infrared spectroscopy assisted biodiagnostics 468References 47022 Environmental Analysis 475Ricardo Erthal Santelli, Marcos Almeida Bezerra, Julio Carlos Afonso, Maria de Fátima Batista de Carvalho, Eliane Padua Oliveira and Aline Soares Freire22.1 Pollution and its control 47522.2 Steps of an environmental analysis 47622.2.1 Sample collection 47622.2.2 Sample preparation 47622.2.3 Analysis 47922.3 Green environmental analysis for water, wastewater and effluent 48022.3.1 Major mineral constituents 48022.3.2 Trace metal ions 48122.3.3 Organic pollutants 48322.4 Green environmental analysis applied for solid samples 48522.4.1 Soil 48522.4.2 Sediments 48822.4.3 Wastes 49222.5 Green environmental analysis applied for atmospheric samples 49622.5.1 Gases 49622.5.2 Particulates 497References 49723 Green Industrial Analysis 505Sergio Armenta and Miguel de la Guardia23.1 Greening industrial practices for safety and cost reasons 50523.2 The quality control of raw materials and end products 50623.3 Process control 51023.4 Effluent control 51123.5 Working atmosphere control 51423.6 The future starts now 515References 515Index 519

“In conclusion, this is an interesting book for a reader who wants to expand their views on the topic, being edited by two of the most prolific contributors in the field, and carrying contributions from worldwide renowned groups on the subject. All aspects of the analytical process are covered, from sampling to waste management, while keeping an eye on the practical deployment of the method.”  (Green Processing and Synthesis, 1 August 2012)