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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.
List of Contributors | p. xv |
Preface | p. xix |
Concepts | p. 1 |
The Concept of Green Analytical Chemistry | p. 3 |
Green Analytical Chemistry in the frame of Green Chemistry | p. 3 |
Green Analytical Chemistry versus Analytical Chemistry | p. 7 |
The ethical compromise of sustainability | p. 9 |
The business opportunities of clean methods | p. 11 |
The attitudes of the scientific community | p. 12 |
References | p. 14 |
Education in Green Analytical Chemistry | p. 17 |
The structure of the Analytical Chemistry paradigm | p. 17 |
The social perception of Analytical Chemistry | p. 20 |
Teaching Analytical Chemistry | p. 21 |
Teaching Green Analytical Chemistry | p. 25 |
From the bench to the real world | p. 26 |
Making sustainable professionals for the future | p. 28 |
References | p. 29 |
Green Analytical Laboratory Experiments | p. 31 |
Greening the university laboratories | p. 31 |
Green laboratory experiments | p. 33 |
Green methods for sample pretreatment | p. 33 |
Green separation using liquid-liquid, solid-phase and solventless extractions | p. 37 |
Green alternatives for chemical reactions | p. 42 |
Green spectroscopy | p. 45 |
The place of Green Analytical Chemistry in the future of our laboratories | p. 52 |
References | p. 52 |
Publishing in Green Analytical Chemistry | p. 55 |
A bibliometric study of the literature in Green Analytical Chemistry | p. 56 |
Milestones of the literature on Green Analytical Chemistry | p. 57 |
The need for powerful keywords | p. 61 |
A new attitude of authors faced with green parameters | p. 62 |
A proposal for editors and reviewers | p. 64 |
The future starts now | p. 65 |
References | p. 66 |
The Analytical Process | p. 67 |
Greening Sampling Techniques | p. 69 |
Greening analytical chemistry solutions for sampling | p. 70 |
New green approaches to reduce problems related to sample losses, sample contamination, transport and storage | p. 70 |
Methods based on flow-through solid phase spectroscopy | p. 70 |
Methods based on hollow-fiber GC/HPLC/CE | p. 71 |
Methods based on the use of nanoparticles | p. 75 |
Greening analytical in-line systems | p. 76 |
In-field sampling | p. 77 |
Environmentally friendly sample stabilization | p. 79 |
Sampling for automatization | p. 79 |
Future possibilities in green sampling | p. 80 |
References | p. 80 |
Direct Analysis of Samples | p. 85 |
Remote environmental sensing | p. 85 |
Synthetic Aperture Radar (SAR) images (satellite sensors) | p. 86 |
Open-path spectroscopy | p. 86 |
Field-portable analyzers | p. 90 |
Process monitoring: in-line, on-line and at-line measurements | p. 91 |
NIR spectroscopy | p. 92 |
Raman spectroscopy | p. 92 |
MIR spectroscopy | p. 93 |
Imaging technology and image analysis | p. 93 |
At-line non-destructive or quasi non-destructive measurements | p. 94 |
Photoacoustic Spectroscopy (PAS) | p. 94 |
Ambient Mass Spectrometry (MS) | p. 95 |
Solid sampling plasma sources | p. 95 |
Nuclear Magnetic Resonance (NMR) | p. 96 |
X-ray spectroscopy | p. 96 |
Other surface analysis techniques | p. 97 |
New challenges in direct analysis | p. 97 |
References | p. 98 |
Green Analytical Chemistry Approaches in Sample Preparation | p. 103 |
About sample preparation | p. 103 |
Miniaturized extraction techniques | p. 104 |
Solid-phase extraction (SPE) | p. 104 |
Solid-phase microextraction (SPME) | p. 105 |
Stir-bar sorptive extraction (SBSE) | p. 106 |
Liquid-liquid microextraction | p. 106 |
Membrane extraction | p. 108 |
Gas extraction | p. 109 |
Alternative solvents | p. 113 |
Analytical applications of ionic liquids | p. 113 |
Supercritical fluid extraction | p. 114 |
Subcritical water extraction | p. 115 |
Fluorous phases | p. 116 |
Assisted extractions | p. 117 |
Microwave-assisted extraction | p. 117 |
Ultrasound-assisted extraction | p. 117 |
Pressurized liquid extraction | p. 118 |
Final remarks | p. 119 |
References | p. 119 |
Green Sample Preparation with Non-Chromatographic Separation Techniques5 | p. 12 |
Sample preparation in the frame of the analytical process | p. 125 |
Separation techniques involving a gasâÇôliquid interface | p. 127 |
Gas diffusion | p. 127 |
Pervaporation | p. 127 |
Membrane extraction with a sorbent interface | p. 130 |
Distillation and microdistillation | p. 131 |
Head-space separation | p. 131 |
Hydride generation and cold-mercury vapour formation | p. 133 |
Techniques involving a liquidâÇôliquid interface | p. 133 |
Dialysis and microdialysis | p. 133 |
LiquidâÇôliquid extraction | p. 134 |
Single-drop microextraction | p. 137 |
Techniques involving a liquidâÇôsolid interface | p. 139 |
Solid-phase extraction | p. 139 |
Solid-phase microextraction | p. 141 |
Stir-bar sorptive extraction | p. 142 |
Continuous filtration | p. 143 |
A Green future for sample preparation | p. 145 |
References | p. 145 |
Capillary Electrophoresis | p. 153 |
The capillary electrophoresis separation techniques | p. 153 |
Capillary electrophoresis among other liquid phase separation methods | p. 155 |
Basic instrumentation for liquid phase separations | p. 155 |
CE versus HPLC from the point of view of Green Analytical Chemistry | p. 156 |
CE as a method of choice for portable instruments | p. 159 |
World-to-chip interfacing and the quest for a âÇ killerâÇÖ application for LOC devices | p. 163 |
Gradient elution moving boundary electrophoresis and electrophoretic exclusion | p. 165 |
Possible ways of surmounting the disadvantages of CE | p. 167 |
Sample preparation in CE | p. 168 |
Is capillary electrophoresis a green alternative? | p. 169 |
References | p. 170 |
Green Chromatography | p. 175 |
Greening liquid chromatography | p. 175 |
Green solvents | p. 176 |
Hydrophilic solvents | p. 176 |
Ionic liquids | p. 177 |
Supercritical Fluid Chromatography (SFC) | p. 177 |
Green instruments | p. 178 |
Microbore Liquid Chromatography (microbore LC) | p. 179 |
Capillary Liquid Chromatography (capillary LC) | p. 180 |
Nano Liquid Chromatography (nano LC) | p. 181 |
How to transfer the LC condition from traditional LC to microbore LC, capillary LC or nano LC | p. 182 |
Homemade micro-scale analytical system | p. 183 |
Ultra Performance Liquid Chromatography (UPLC) | p. 184 |
References | p. 185 |
Green Analytical Atomic Spectrometry | p. 199 |
Atomic spectrometry in the context of Green Analytical Chemistry | p. 199 |
Improvements in sample pretreatment strategies | p. 202 |
Specific improvements | p. 202 |
Slurry methods | p. 204 |
Direct solid sampling techniques | p. 205 |
Basic operating principles of the techniques discussed | p. 205 |
Sample requirements and pretreatment strategies | p. 207 |
Analyte monitoring: The arrival of high-resolution continuum source atomic absorption spectrometry | p. 208 |
Calibration | p. 210 |
Selected applications | p. 210 |
Future for green analytical atomic spectrometry | p. 213 |
References | p. 215 |
Solid Phase Molecular Spectroscopy | p. 221 |
Solid phase molecular spectroscopy: an approach to Green Analytical Chemistry | p. 221 |
Fundamentals of solid phase molecular spectroscopy | p. 222 |
Solid phase absorption (spectrophotometric) procedures | p. 222 |
Solid phase emission (fluorescence) procedures | p. 225 |
Batch mode procedures | p. 225 |
Flow mode procedures | p. 226 |
Monitoring an intrinsic property | p. 227 |
Monitoring derivative species | p. 231 |
Recent flow-SPMS based approaches | p. 232 |
Selected examples of application of solid phase molecular spectroscopy | p. 233 |
The potential of flow solid phase envisaged from the point of view of Green Analytical Chemistry | p. 235 |
References | p. 240 |
Derivative Techniques in Molecular Absorption, Fluorimetry and Liquid Chromatography as Tools for Green Analytical Chemistry | p. 245 |
The derivative technique as a tool for Green Analytical Chemistry | p. 245 |
Theoretical aspects | p. 246 |
Derivative absorption spectrometry in the UV-visible region | p. 247 |
Strategies to greener derivative spectrophotometry | p. 248 |
Derivative fluorescence spectrometry | p. 250 |
Derivative synchronous fluorescence spectrometry | p. 251 |
Use of derivative signal techniques in liquid chromatography | p. 254 |
References | p. 255 |
Greening Electroanalytical Methods | p. 261 |
Towards a more environmentally friendly electroanalysis | p. 261 |
Electrode materials | p. 262 |
Alternatives to mercury electrodes | p. 262 |
Nanomaterial-based electrodes | p. 268 |
Solvents | p. 270 |
Ionic liquids | p. 271 |
Supercritical fluids | p. 273 |
Electrochemical detection in flowing solutions | p. 274 |
Injection techniques | p. 274 |
Miniaturized systems | p. 276 |
Biosensors | p. 278 |
Greening biosurface preparation | p. 278 |
Direct electrochemical transfer of proteins | p. 281 |
Future trends in green electroanalysis | p. 282 |
References | p. 282 |
Strategies | p. 289 |
Energy Savings in Analytical Chemistry | p. 291 |
Energy consumption in analytical methods | p. 291 |
Economy and saving energy in laboratory practice | p. 294 |
Good housekeeping, control and maintenance | p. 295 |
Alternative sources of energy for processes | p. 296 |
Using microwaves in place of thermal heating | p. 297 |
Using ultrasound in sample treatment | p. 299 |
Light as a source of energy | p. 301 |
Using alternative solvents for energy savings | p. 302 |
Advantages of ionic liquids | p. 303 |
Using subcritical and supercritical fluids | p. 303 |
Efficient laboratory equipment | p. 305 |
Trends in sample treatment | p. 306 |
Effects of automation and micronization on energy consumption | p. 307 |
Miniaturization in sample treatment | p. 308 |
Using sensors | p. 310 |
Assessment of energy efficiency | p. 312 |
References | p. 316 |
Green Analytical Chemistry and Flow Injection Methodologies | p. 321 |
Progress of automated techniques for Green Analytical Chemistry | p. 321 |
Flow injection analysis | p. 322 |
Sequential injection analysis | p. 325 |
Lab-on-valve | p. 327 |
Multicommutation | p. 328 |
Conclusions and remarks | p. 334 |
References | p. 334 |
Miniaturization | p. 339 |
Current needs and pitfalls in sample preparation | p. 340 |
Non-integrated approaches for miniaturized sample preparation | p. 341 |
Gaseous and liquid samples | p. 341 |
Solid samples | p. 350 |
Integrated approaches for sample preparation on microfluidic platforms | p. 353 |
Microfluidic platforms in sample preparation process | p. 353 |
The isolation of analyte from the sample matrix: filtering approaches | p. 356 |
The isolation of analytes from the sample matrix: extraction approaches | p. 360 |
Preconcentration approaches using electrokinetics | p. 365 |
Derivatization schemes on microfluidic platforms | p. 372 |
Sample preparation in cell analysis | p. 373 |
Final remarks | p. 378 |
References | p. 379 |
Micro- and Nanomaterials Based Detection Systems Applied in Lab-on-a-Chip Technology | p. 389 |
Micro- and nanotechnology in Green Analytical Chemistry | p. 389 |
Nanomaterials-based (bio)sensors | p. 390 |
Optical nano(bio)sensors | p. 391 |
Electrochemical nano(bio)sensors | p. 393 |
Other detection principles | p. 395 |
Lab-on-a-chip (LOC) technology | p. 396 |
Miniaturization and nano-/microfluidics | p. 396 |
Micro- and nanofabrication techniques | p. 397 |
LOC applications | p. 398 |
LOCs with optical detections | p. 398 |
LOCs with electrochemical detectors | p. 398 |
LOCs with other detections | p. 399 |
Conclusions and future perspectives | p. 400 |
References | p. 401 |
Photocatalytic Treatment of Laboratory Wastes Containing Hazardous Organic Compounds | p. 407 |
Photocatalysis | p. 407 |
Fundamentals of the photocatalytic process | p. 408 |
Limits of the photocatalytic treatment | p. 408 |
Usual photocatalytic procedure in laboratory practice | p. 408 |
Solar detoxification of laboratory waste | p. 409 |
Influence of experimental parameters | p. 411 |
Dissolved oxygen | p. 411 |
pH | p. 411 |
Catalyst concentration | p. 412 |
Degradation kinetics | p. 412 |
Additives reducing the eâêÆ/h+ recombination | p. 412 |
Analytical control of the photocatalytic treatment | p. 413 |
Examples of possible applications of photocatalysis to the treatment of laboratory wastes | p. 413 |
Percolates containing soluble aromatic contaminants | p. 414 |
Photocatalytic destruction of aromatic amine residues in aqueous wastes | p. 414 |
Degradation of aqueous wastes containing pesticides residue | p. 415 |
The peculiar behaviour of triazine herbicides | p. 416 |
Treatment of aqueous wastes containing organic solvent residues | p. 416 |
Treatment of surfactant-containing aqueous wastes | p. 416 |
Degradation of aqueous solutions of azo-dyes | p. 419 |
Treatment of laboratory waste containing pharmaceuticals | p. 419 |
Continuous monitoring of photocatalytic treatment | p. 420 |
References | p. 420 |
Fields of Application | p. 425 |
Green Bioanalytical Chemistry | p. 427 |
The analytical techniques in bioanalysis | p. 427 |
Environmental-responsive polymers | p. 428 |
Preparation of a polymer-modified surface for the stationary phase of environmental-responsive chromatography | p. 430 |
Temperature-responsive chromatography for green analytical methods | p. 432 |
Biological analysis by temperature-responsive chromatography | p. 432 |
Analysis of propofol in plasma using water as a mobile phase | p. 434 |
Contraceptive drugs analysis using temperature gradient chromatography | p. 435 |
Affinity chromatography for green bioseparation | p. 436 |
Separation of biologically active molecules by the green chromatographic method | p. 438 |
Protein separation by an aqueous chromatographic system | p. 441 |
Ice chromatography | p. 442 |
High-temperature liquid chromatography | p. 443 |
Ionic liquids | p. 443 |
The future in green bioanalysis | p. 444 |
References | p. 444 |
Infrared Spectroscopy in Biodiagnostics: A Green Analytical Approach | p. 449 |
Infrared spectroscopy capabilities | p. 449 |
Infrared spectroscopy of bio-active chemicals in a bio-system | p. 451 |
Medical analysis of body fluids by infrared spectroscopy | p. 453 |
Blood and its extracts | p. 455 |
Urine | p. 457 |
Other body fluids | p. 457 |
Diagnosis in tissue samples via IR spectroscopic analysis | p. 457 |
Main spectral characteristics | p. 459 |
The role of data processing | p. 460 |
Cancer diagnosis by FTIR spectrometry | p. 465 |
New trends in infrared spectroscopy assisted biodiagnostics | p. 468 |
References | p. 470 |
Environmental Analysis | p. 475 |
Pollution and its control | p. 475 |
Steps of an environmental analysis | p. 476 |
Sample collection | p. 476 |
Sample preparation | p. 476 |
Analysis | p. 479 |
Green environmental analysis for water, wastewater and effluent | p. 480 |
Major mineral constituents | p. 480 |
Trace metal ions | p. 481 |
Organic pollutants | p. 483 |
Green environmental analysis applied for solid samples | p. 485 |
Soil | p. 485 |
Sediments | p. 488 |
Wastes | p. 492 |
Green environmental analysis applied for atmospheric samples | p. 496 |
Gases | p. 496 |
Particulates | p. 497 |
References | p. 497 |
Green Industrial Analysis | p. 505 |
Greening industrial practices for safety and cost reasons | p. 505 |
The quality control of raw materials and end products | p. 506 |
Process control | p. 510 |
Effluent control | p. 511 |
Working atmosphere control | p. 514 |
The future starts now | p. 515 |
References | p. 515 |
Index | p. 519 |
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