Handbook of Green Analytical Chemistry

The emerging field 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 significant developments in methodological and technological tools to prevent and reduce the deleterious effects of analytical activities; key strategies include recycling, replacement, reduction and detoxification of reagents and solvents.

The 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 field, 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.
• The 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.

This advanced handbook is a practical resource for experienced analytical chemists who are interested in implementing green approaches in their work.

Preface xix

Section I: Concepts 1

1 The Concept of Green Analytical Chemistry 3
Miguel 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 17
Miguel 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 31
Suparna 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

4 Publishing in Green Analytical Chemistry 55
Salvador 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 69
José 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 85
Sergio 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

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 103
Marek 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 125
María 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

8.4.4 Continuous filtration 143

8.5 A Green future for sample preparation 145

References 145

9 Capillary Electrophoresis 153
Mihkel 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 175
Chi-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 199
Martín 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

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 221
Antonio 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 245
José 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 261
Paloma 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

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 291
Mihkel 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 321
Luis 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 339
Alberto 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

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 389
Mariana 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 407
Edmondo 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

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 427
Tadashi 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 449
Mohammadreza 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

22 Environmental Analysis 475
Ricardo 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 505
Sergio 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

Miguel de la Guardia, Professor of Analytical Chemistry, Valencia University, Spain
Professor 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, Spain
Salvador Garrigues works in the research team with Prof. Miguel de la Guardia and has collaborated in more than 150 publications.