Handbook of Green Analytical Chemistry

List of Contributors xv
<p>Preface xix</p>
<p>Section I: Concepts 1</p>
<p>1 The Concept of Green Analytical Chemistry 3<br /> Miguel de la Guardia and Salvador Garrigues</p>
<p>1.1 Green Analytical Chemistry in the frame of Green Chemistry 3</p>
<p>1.2 Green Analytical Chemistry versus Analytical Chemistry 7</p>
<p>1.3 The ethical compromise of sustainability 9</p>
<p>1.4 The business opportunities of clean methods 11</p>
<p>1.5 The attitudes of the scientific community 12</p>
<p>References 14</p>
<p>2 Education in Green Analytical Chemistry 17<br /> Miguel de la Guardia and Salvador Garrigues</p>
<p>2.1 The structure of the Analytical Chemistry paradigm 17</p>
<p>2.2 The social perception of Analytical Chemistry 20</p>
<p>2.3 Teaching Analytical Chemistry 21</p>
<p>2.4 Teaching Green Analytical Chemistry 25</p>
<p>2.5 From the bench to the real world 26</p>
<p>2.6 Making sustainable professionals for the future 28</p>
<p>References 29</p>
<p>3 Green Analytical Laboratory Experiments 31<br /> Suparna Dutta and Arabinda K. Das</p>
<p>3.1 Greening the university laboratories 31</p>
<p>3.2 Green laboratory experiments 33</p>
<p>3.2.1 Green methods for sample pretreatment 33</p>
<p>3.2.2 Green separation using liquid–liquid, solid–phase and solventless extractions 37</p>
<p>3.2.3 Green alternatives for chemical reactions 42</p>
<p>3.2.4 Green spectroscopy 45</p>
<p>3.3 The place of Green Analytical Chemistry in the future of our laboratories 52</p>
<p>References 52</p>
<p>4 Publishing in Green Analytical Chemistry 55<br /> Salvador Garrigues and Miguel de la Guardia</p>
<p>4.1 A bibliometric study of the literature in Green Analytical Chemistry 56</p>
<p>4.2 Milestones of the literature on Green Analytical Chemistry 57</p>
<p>4.3 The need for powerful keywords 61</p>
<p>4.4 A new attitude of authors faced with green parameters 62</p>
<p>4.5 A proposal for editors and reviewers 64</p>
<p>4.6 The future starts now 65</p>
<p>References 66</p>
<p>Section II: The Analytical Process 67</p>
<p>5 Greening Sampling Techniques 69<br /> Jos&eacute; Luis G&oacute;mez Ariza and Tamara Garc&iacute;a Barrera</p>
<p>5.1 Greening analytical chemistry solutions for sampling 70</p>
<p>5.2 New green approaches to reduce problems related to sample losses, sample contamination, transport and storage 70</p>
<p>5.2.1 Methods based on flow–through solid phase spectroscopy 70</p>
<p>5.2.2 Methods based on hollow–fiber GC/HPLC/CE 71</p>
<p>5.2.3 Methods based on the use of nanoparticles 75</p>
<p>5.3 Greening analytical in–line systems 76</p>
<p>5.4 In–field sampling 77</p>
<p>5.5 Environmentally friendly sample stabilization 79</p>
<p>5.6 Sampling for automatization 79</p>
<p>5.7 Future possibilities in green sampling 80</p>
<p>References 80</p>
<p>6 Direct Analysis of Samples 85<br /> Sergio Armenta and Miguel de la Guardia</p>
<p>6.1 Remote environmental sensing 85</p>
<p>6.1.1 Synthetic Aperture Radar (SAR) images (satellite sensors) 86</p>
<p>6.1.2 Open–path spectroscopy 86</p>
<p>6.1.3 Field–portable analyzers 90</p>
<p>6.2 Process monitoring: in–line, on–line and at–line measurements 91</p>
<p>6.2.1 NIR spectroscopy 92</p>
<p>6.2.2 Raman spectroscopy 92</p>
<p>6.2.3 MIR spectroscopy 93</p>
<p>6.2.4 Imaging technology and image analysis 93</p>
<p>6.3 At–line non–destructive or quasi non–destructive measurements 94</p>
<p>6.3.1 Photoacoustic Spectroscopy (PAS) 94</p>
<p>6.3.2 Ambient Mass Spectrometry (MS) 95</p>
<p>6.3.3 Solid sampling plasma sources 95</p>
<p>6.3.4 Nuclear Magnetic Resonance (NMR) 96</p>
<p>6.3.5 X–ray spectroscopy 96</p>
<p>6.3.6 Other surface analysis techniques 97</p>
<p>6.4 New challenges in direct analysis 97</p>
<p>References 98</p>
<p>7 Green Analytical Chemistry Approaches in Sample Preparation 103<br /> Marek Tobiszewski, Agata Mechlinska and Jacek Namiesnik</p>
<p>7.1 About sample preparation 103</p>
<p>7.2 Miniaturized extraction techniques 104</p>
<p>7.2.1 Solid–phase extraction (SPE) 104</p>
<p>7.2.2 Solid–phase microextraction (SPME) 105</p>
<p>7.2.3 Stir–bar sorptive extraction (SBSE) 106</p>
<p>7.2.4 Liquid–liquid microextraction 106</p>
<p>7.2.5 Membrane extraction 108</p>
<p>7.2.6 Gas extraction 109</p>
<p>7.3 Alternative solvents 113</p>
<p>7.3.1 Analytical applications of ionic liquids 113</p>
<p>7.3.2 Supercritical fluid extraction 114</p>
<p>7.3.3 Subcritical water extraction 115</p>
<p>7.3.4 Fluorous phases 116</p>
<p>7.4 Assisted extractions 117</p>
<p>7.4.1 Microwave–assisted extraction 117</p>
<p>7.4.2 Ultrasound–assisted extraction 117</p>
<p>7.4.3 Pressurized liquid extraction 118</p>
<p>7.5 Final remarks 119</p>
<p>References 119</p>
<p>8 Green Sample Preparation with Non–Chromatographic Separation Techniques 125<br /> Mar&iacute;a Dolores Luque de Castro and Miguel Alcaide Molina</p>
<p>8.1 Sample preparation in the frame of the analytical process 125</p>
<p>8.2 Separation techniques involving a gas liquid interface 127</p>
<p>8.2.1 Gas diffusion 127</p>
<p>8.2.2 Pervaporation 127</p>
<p>8.2.3 Membrane extraction with a sorbent interface 130</p>
<p>8.2.4 Distillation and microdistillation 131</p>
<p>8.2.5 Head–space separation 131</p>
<p>8.2.6 Hydride generation and cold–mercury vapour formation 133</p>
<p>8.3 Techniques involving a liquid liquid interface 133</p>
<p>8.3.1 Dialysis and microdialysis 133</p>
<p>8.3.2 Liquid liquid extraction 134</p>
<p>8.3.3 Single–drop microextraction 137</p>
<p>8.4 Techniques involving a liquid solid interface 139</p>
<p>8.4.1 Solid–phase extraction 139</p>
<p>8.4.2 Solid–phase microextraction 141</p>
<p>8.4.3 Stir–bar sorptive extraction 142</p>
<p>8.4.4 Continuous filtration 143</p>
<p>8.5 A Green future for sample preparation 145</p>
<p>References 145</p>
<p>9 Capillary Electrophoresis 153<br /> Mihkel Kaljurand</p>
<p>9.1 The capillary electrophoresis separation techniques 153</p>
<p>9.2 Capillary electrophoresis among other liquid phase separation methods 155</p>
<p>9.2.1 Basic instrumentation for liquid phase separations 155</p>
<p>9.2.2 CE versus HPLC from the point of view of Green Analytical Chemistry 156</p>
<p>9.2.3 CE as a method of choice for portable instruments 159</p>
<p>9.2.4 World–to–chip interfacing and the quest for a killer application for LOC devices 163</p>
<p>9.2.5 Gradient elution moving boundary electrophoresis and electrophoretic exclusion 165</p>
<p>9.3 Possible ways of surmounting the disadvantages of CE 167</p>
<p>9.4 Sample preparation in CE 168</p>
<p>9.5 Is capillary electrophoresis a green alternative? 169</p>
<p>References 170</p>
<p>10 Green Chromatography 175<br /> Chi–Yu Lu</p>
<p>10.1 Greening liquid chromatography 175</p>
<p>10.2 Green solvents 176</p>
<p>10.2.1 Hydrophilic solvents 176</p>
<p>10.2.2 Ionic liquids 177</p>
<p>10.2.3 Supercritical Fluid Chromatography (SFC) 177</p>
<p>10.3 Green instruments 178</p>
<p>10.3.1 Microbore Liquid Chromatography (microbore LC) 179</p>
<p>10.3.2 Capillary Liquid Chromatography (capillary LC) 180</p>
<p>10.3.3 Nano Liquid Chromatography (nano LC) 181</p>
<p>10.3.4 How to transfer the LC condition from traditional LC to microbore LC, capillary LC or nano LC 182</p>
<p>10.3.5 Homemade micro–scale analytical system 183</p>
<p>10.3.6 Ultra Performance Liquid Chromatography (UPLC) 184</p>
<p>References 185</p>
<p>11 Green Analytical Atomic Spectrometry 199<br /> Mart&iacute;n Resano, Esperanza Garc&iacute;a–Ruiz and Miguel A. Belarra</p>
<p>11.1 Atomic spectrometry in the context of Green Analytical Chemistry 199</p>
<p>11.2 Improvements in sample pretreatment strategies 202</p>
<p>11.2.1 Specific improvements 202</p>
<p>11.2.2 Slurry methods 204</p>
<p>11.3 Direct solid sampling techniques 205</p>
<p>11.3.1 Basic operating principles of the techniques discussed 205</p>
<p>11.3.2 Sample requirements and pretreatment strategies 207</p>
<p>11.3.3 Analyte monitoring: The arrival of high–resolution continuum source atomic absorption spectrometry 208</p>
<p>11.3.4 Calibration 210</p>
<p>11.3.5 Selected applications 210</p>
<p>11.4 Future for green analytical atomic spectrometry 213</p>
<p>References 215</p>
<p>12 Solid Phase Molecular Spectroscopy 221<br /> Antonio Molina–D&iacute;az, Juan Francisco Garc&iacute;a–Reyes and Natividad Ramos–Martos</p>
<p>12.1 Solid phase molecular spectroscopy: an approach to Green Analytical Chemistry 221</p>
<p>12.2 Fundamentals of solid phase molecular spectroscopy 222</p>
<p>12.2.1 Solid phase absorption (spectrophotometric) procedures 222</p>
<p>12.2.2 Solid phase emission (fluorescence) procedures 225</p>
<p>12.3 Batch mode procedures 225</p>
<p>12.4 Flow mode procedures 226</p>
<p>12.4.1 Monitoring an intrinsic property 227</p>
<p>12.4.2 Monitoring derivative species 231</p>
<p>12.4.3 Recent flow–SPMS based approaches 232</p>
<p>12.5 Selected examples of application of solid phase molecular spectroscopy 233</p>
<p>12.6 The potential of flow solid phase envisaged from the point of view of Green Analytical Chemistry 235</p>
<p>References 240</p>
<p>13 Derivative Techniques in Molecular Absorption, Fluorimetry and Liquid Chromatography as Tools for Green Analytical Chemistry 245<br /> Jos&eacute; Manuel Cano Pav&oacute;n, Amparo Garc&iacute;a de Torres, Catalina Bosch Ojeda, Fuensanta S&aacute;nchez Rojas and Elisa I. Vereda Alonso</p>
<p>13.1 The derivative technique as a tool for Green Analytical Chemistry 245</p>
<p>13.1.1 Theoretical aspects 246</p>
<p>13.2 Derivative absorption spectrometry in the UV–visible region 247</p>
<p>13.2.1 Strategies to greener derivative spectrophotometry 248</p>
<p>13.3 Derivative fluorescence spectrometry 250</p>
<p>13.3.1 Derivative synchronous fluorescence spectrometry 251</p>
<p>13.4 Use of derivative signal techniques in liquid chromatography 254</p>
<p>References 255</p>
<p>14 Greening Electroanalytical Methods 261<br /> Paloma Y&aacute;&ntilde;ez–Sede&ntilde;o, Jos&eacute; M. Pingarr&oacute;n and Lucas Hern&aacute;ndez</p>
<p>14.1 Towards a more environmentally friendly electroanalysis 261</p>
<p>14.2 Electrode materials 262</p>
<p>14.2.1 Alternatives to mercury electrodes 262</p>
<p>14.2.2 Nanomaterial–based electrodes 268</p>
<p>14.3 Solvents 270</p>
<p>14.3.1 Ionic liquids 271</p>
<p>14.3.2 Supercritical fluids 273</p>
<p>14.4 Electrochemical detection in flowing solutions 274</p>
<p>14.4.1 Injection techniques 274</p>
<p>14.4.2 Miniaturized systems 276</p>
<p>14.5 Biosensors 278</p>
<p>14.5.1 Greening biosurface preparation 278</p>
<p>14.5.2 Direct electrochemical transfer of proteins 281</p>
<p>14.6 Future trends in green electroanalysis 282</p>
<p>References 282</p>
<p>Section III: Strategies 289</p>
<p>15 Energy Savings in Analytical Chemistry 291<br /> Mihkel Koel</p>
<p>15.1 Energy consumption in analytical methods 291</p>
<p>15.2 Economy and saving energy in laboratory practice 294</p>
<p>15.2.1 Good housekeeping, control and maintenance 295</p>
<p>15.3 Alternative sources of energy for processes 296</p>
<p>15.3.1 Using microwaves in place of thermal heating 297</p>
<p>15.3.2 Using ultrasound in sample treatment 299</p>
<p>15.3.3 Light as a source of energy 301</p>
<p>15.4 Using alternative solvents for energy savings 302</p>
<p>15.4.1 Advantages of ionic liquids 303</p>
<p>15.4.2 Using subcritical and supercritical fluids 303</p>
<p>15.5 Efficient laboratory equipment 305</p>
<p>15.5.1 Trends in sample treatment 306</p>
<p>15.6 Effects of automation and micronization on energy consumption 307</p>
<p>15.6.1 Miniaturization in sample treatment 308</p>
<p>15.6.2 Using sensors 310</p>
<p>15.7 Assessment of energy efficiency 312</p>
<p>References 316</p>
<p>16 Green Analytical Chemistry and Flow Injection Methodologies 321<br /> Luis Dante Mart&iacute;nez, Soledad Cerutti and Ra&uacute;l Andr&eacute;s Gil</p>
<p>16.1 Progress of automated techniques for Green Analytical Chemistry 321</p>
<p>16.2 Flow injection analysis 322</p>
<p>16.3 Sequential injection analysis 325</p>
<p>16.4 Lab–on–valve 327</p>
<p>16.5 Multicommutation 328</p>
<p>16.6 Conclusions and remarks 334</p>
<p>References 334</p>
<p>17 Miniaturization 339<br /> Alberto Escarpa, Miguel &Aacute;ngel L&oacute;pez and Lourdes Ramos</p>
<p>17.1 Current needs and pitfalls in sample preparation 340</p>
<p>17.2 Non–integrated approaches for miniaturized sample preparation 341</p>
<p>17.2.1 Gaseous and liquid samples 341</p>
<p>17.2.2 Solid samples 350</p>
<p>17.3 Integrated approaches for sample preparation on microfluidic platforms 353</p>
<p>17.3.1 Microfluidic platforms in sample preparation process 353</p>
<p>17.3.2 The isolation of analyte from the sample matrix: filtering approaches 356</p>
<p>17.3.3 The isolation of analytes from the sample matrix: extraction approaches 360</p>
<p>17.3.4 Preconcentration approaches using electrokinetics 365</p>
<p>17.3.5 Derivatization schemes on microfluidic platforms 372</p>
<p>17.3.6 Sample preparation in cell analysis 373</p>
<p>17.4 Final remarks 378</p>
<p>References 379</p>
<p>18 Micro– and Nanomaterials Based Detection Systems Applied in Lab–on–a–Chip Technology 389<br /> Mariana Medina–S&aacute;nchez and Arben Merko&ccedil;i</p>
<p>18.1 Micro– and nanotechnology in Green Analytical Chemistry 389</p>
<p>18.2 Nanomaterials–based (bio)sensors 390</p>
<p>18.2.1 Optical nano(bio)sensors 391</p>
<p>18.2.2 Electrochemical nano(bio)sensors 393</p>
<p>18.2.3 Other detection principles 395</p>
<p>18.3 Lab–on–a–chip (LOC) technology 396</p>
<p>18.3.1 Miniaturization and nano–/microfluidics 396</p>
<p>18.3.2 Micro– and nanofabrication techniques 397</p>
<p>18.4 LOC applications 398</p>
<p>18.4.1 LOCs with optical detections 398</p>
<p>18.4.2 LOCs with electrochemical detectors 398</p>
<p>18.4.3 LOCs with other detections 399</p>
<p>18.5 Conclusions and future perspectives 400</p>
<p>References 401</p>
<p>19 Photocatalytic Treatment of Laboratory Wastes Containing Hazardous Organic Compounds 407<br /> Edmondo Pramauro, Alessandra Bianco Prevot and Debora Fabbri</p>
<p>19.1 Photocatalysis 407</p>
<p>19.2 Fundamentals of the photocatalytic process 408</p>
<p>19.3 Limits of the photocatalytic treatment 408</p>
<p>19.4 Usual photocatalytic procedure in laboratory practice 408</p>
<p>19.4.1 Solar detoxification of laboratory waste 409</p>
<p>19.5 Influence of experimental parameters 411</p>
<p>19.5.1 Dissolved oxygen 411</p>
<p>19.5.2 pH 411</p>
<p>19.5.3 Catalyst concentration 412</p>
<p>19.5.4 Degradation kinetics 412</p>
<p>19.6 Additives reducing the e /h+ recombination 412</p>
<p>19.7 Analytical control of the photocatalytic treatment 413</p>
<p>19.8 Examples of possible applications of photocatalysis to the treatment of laboratory wastes 413</p>
<p>19.8.1 Percolates containing soluble aromatic contaminants 414</p>
<p>19.8.2 Photocatalytic destruction of aromatic amine residues in aqueous wastes 414</p>
<p>19.8.3 Degradation of aqueous wastes containing pesticides residue 415</p>
<p>19.8.4 The peculiar behaviour of triazine herbicides 416</p>
<p>19.8.5 Treatment of aqueous wastes containing organic solvent residues 416</p>
<p>19.8.6 Treatment of surfactant–containing aqueous wastes 416</p>
<p>19.8.7 Degradation of aqueous solutions of azo–dyes 419</p>
<p>19.8.8 Treatment of laboratory waste containing pharmaceuticals 419</p>
<p>19.9 Continuous monitoring of photocatalytic treatment 420</p>
<p>References 420</p>
<p>Section IV: Fields of Application 425</p>
<p>20 Green Bioanalytical Chemistry 427<br /> Tadashi Nishio and Hideko Kanazawa</p>
<p>20.1 The analytical techniques in bioanalysis 427</p>
<p>20.2 Environmental–responsive polymers 428</p>
<p>20.3 Preparation of a polymer–modified surface for the stationary phase of environmental–responsive chromatography 430</p>
<p>20.4 Temperature–responsive chromatography for green analytical methods 432</p>
<p>20.5 Biological analysis by temperature–responsive chromatography 432</p>
<p>20.5.1 Analysis of propofol in plasma using water as a mobile phase 434</p>
<p>20.5.2 Contraceptive drugs analysis using temperature gradient chromatography 435</p>
<p>20.6 Affinity chromatography for green bioseparation 436</p>
<p>20.7 Separation of biologically active molecules by the green chromatographic method 438</p>
<p>20.8 Protein separation by an aqueous chromatographic system 441</p>
<p>20.9 Ice chromatography 442</p>
<p>20.10 High–temperature liquid chromatography 443</p>
<p>20.11 Ionic liquids 443</p>
<p>20.12 The future in green bioanalysis 444</p>
<p>References 444</p>
<p>21 Infrared Spectroscopy in Biodiagnostics: A Green Analytical Approach 449<br /> Mohammadreza Khanmohammadi and Amir Bagheri Garmarudi</p>
<p>21.1 Infrared spectroscopy capabilities 449</p>
<p>21.2 Infrared spectroscopy of bio–active chemicals in a bio–system 451</p>
<p>21.3 Medical analysis of body fluids by infrared spectroscopy 453</p>
<p>21.3.1 Blood and its extracts 455</p>
<p>21.3.2 Urine 457</p>
<p>21.3.3 Other body fluids 457</p>
<p>21.4 Diagnosis in tissue samples via IR spectroscopic analysis 457</p>
<p>21.4.1 Main spectral characteristics 459</p>
<p>21.4.2 The role of data processing 460</p>
<p>21.4.3 Cancer diagnosis by FTIR spectrometry 465</p>
<p>21.5 New trends in infrared spectroscopy assisted biodiagnostics 468</p>
<p>References 470</p>
<p>22 Environmental Analysis 475<br /> Ricardo Erthal Santelli, Marcos Almeida Bezerra, Julio Carlos Afonso, Maria de F&aacute;tima Batista de Carvalho, Eliane Padua Oliveira and Aline Soares Freire</p>
<p>22.1 Pollution and its control 475</p>
<p>22.2 Steps of an environmental analysis 476</p>
<p>22.2.1 Sample collection 476</p>
<p>22.2.2 Sample preparation 476</p>
<p>22.2.3 Analysis 479</p>
<p>22.3 Green environmental analysis for water, wastewater and effluent 480</p>
<p>22.3.1 Major mineral constituents 480</p>
<p>22.3.2 Trace metal ions 481</p>
<p>22.3.3 Organic pollutants 483</p>
<p>22.4 Green environmental analysis applied for solid samples 485</p>
<p>22.4.1 Soil 485</p>
<p>22.4.2 Sediments 488</p>
<p>22.4.3 Wastes 492</p>
<p>22.5 Green environmental analysis applied for atmospheric samples 496</p>
<p>22.5.1 Gases 496</p>
<p>22.5.2 Particulates 497</p>
<p>References 497</p>
<p>23 Green Industrial Analysis 505<br /> Sergio Armenta and Miguel de la Guardia</p>
<p>23.1 Greening industrial practices for safety and cost reasons 505</p>
<p>23.2 The quality control of raw materials and end products 506</p>
<p>23.3 Process control 510</p>
<p>23.4 Effluent control 511</p>
<p>23.5 Working atmosphere control 514</p>
<p>23.6 The future starts now 515</p>
<p>References 515</p>
<p>Index 519</p>