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Advanced Environmental Analysis

Applications of Nanomaterials, Volume 1
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RSC Detection Science Series

Editor-in-Chief
Professor Michael Thompson, University of Toronto, Canada
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Titles in the Series:

1: Sensor Technology in Neuroscience
2: Detection Challenges in Clinical Diagnostics
3: Advanced Synthetic Materials in Detection Science
4: Principles and Practice of Analytical Techniques in Geosciences
5: Microfluidics in Detection Science: Lab-on-a-chip Technologies
6: Electrochemical Strategies in Detection Science
7: Peroxynitrite Detection in Biological Media: Challenges and Advances
8: Biological Fluid-Surface Interactions in Detection and Medical Devices
9: Advanced Environmental Analysis: Applications of Nanomaterials, Volume 1

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Advanced Environmental
Analysis
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Applications of Nanomaterials, Volume 1

Edited by

Chaudhery Mustansar Hussain

New Jersey Institute of Technology, Newark, NJ, USA
Email: [email protected]

and

Boris Kharisov
Universidad Autonoma de Nuevo Leon, Monterrey, Mexico
Email: [email protected]
Published on 08 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782623625-FP001 View Online

RSC Detection Science Series No. 9

Print ISBN: 978-1-78262-144-7

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ISSN: 2052-3068

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Published on 08 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782623625-FP005

Preface

Environmental analysis has become a topic of considerable importance

these days. It is not only significant to environmentalists but also to
regulators, decision makers, surveillance agencies and the organizations
assessing the impact of pollutants on the environment, and it has evolved
as a true discipline throughout the world. In recent years, there has been a
rapid union of nanotechnology and analytical sciences. This convergence,
although highly interdisciplinary in nature, has been brought about by new
technologies that have led to application-specific devices, for example lab-
on-a chip. The high demand for advanced comprehensive understanding
and awareness of more accurate and precise measurement tools for pollut-
ants and their characterization dictate the terms and conditions for this con-
vergence. The reduction in size from bulk to micro- and nano-scale promises
high sensitivity, high speed, increased selectivity and increased device lifetime
for new devices. Instruments with more sensitivity are required today to analyze
ultra-trace levels of environmental pollutants, pathogens in water, and low
vapor pressure energetic materials in air.
The objective of this book is to provide an overview of new developments
for a variety of environmental analytical techniques. Every effort has been
made to include the state-of-the-art to show improvements in environmental
analytical techniques and processes due to nanomaterials in the book.
Additionally, special attention is paid to those approaches that are green and
reduce the cost of the analysis, process both in terms of chemicals and time
consumption. In the end the legal, economical and toxicity aspects of nano-
materials are also presented in detail.
To put all of the shared knowledge into perspective, add a touch of reality
to the concepts, and to cover extensive expansion of the applications of nano-
materials in the environmental analysis field, the book is divided into two
volumes and each volume has subdivisions of several sections. Moreover, to

RSC Detection Science Series No. 9

Advanced Environmental Analysis: Applications of Nanomaterials, Volume 1
Edited by Chaudhery Mustansar Hussain and Boris Kharisov
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org

v
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vi Preface
maintain coherence in the flow of knowledge, these sections are patterned
in a continuous manner in both volumes. As a result, sections one to four are
contained in the first volume, whereas sections five to ten are provided in the
second volume.
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In Volume One, the first section talks about the perspective of analytical
sciences in relation to nanotechnology, synthetic techniques for nanomate-
rials, different unique properties of nanomaterials and a detailed descrip-
tion of the mechanisms of adsorption on nanomaterials. The second section
encompasses the recent advances in sample preparation and extraction
techniques for organic and inorganic pollutants with nanomaterials. The
third section is all about new developments in separation techniques with a
focus on applications of nanomaterials for chromatography and membrane
technology. The fourth section incorporates spectroscopic techniques using
nanomaterials, especially surface-enhanced Raman scattering (SERS), for
detection of environmental pollutants.
In Volume Two, the fifth section describes new trends in environmental anal-
ysis, i.e., applications of magnetic nanomaterials, nano-sensors, composite
materials and nano-bio sensors, like nanozymes. The sixth section talks
about the applications of nanomaterials for water treatment and purifica-
tion techniques. The effects of nanomaterials on the environment and the
ecosystem in terms of their toxicity, safety regulations and economic issues
are depicted in the seventh section. Section eight discusses the monitoring
and analysis of nanomaterials, whereas section nine is about the future of
environmental analysis in light of new developments in science and tech-
nology. In the last section, the editors provide concluding remarks about the
application of nanomaterials for environmental analysis.
The selection of these sections in both volumes is based on the most recent
research, teaching, the practical experience of editors and the philosophy
that environmental analysis is moving towards its next generation. The con-
tributing authors are selected from a wide cross-section around the world.
The diversity of authors for each chapter and their disciplinary backgrounds
reveal the interdisciplinary emphasis of this book. Thanks to the multidisci-
plinary nature of this book, the reader can enjoy a lot of knowledge in one
place.
The anticipated audience is scientists, researchers, consultants, regula-
tors and engineers. Moreover, graduate students will find this book to be
very useful in their research and understanding of advances in environmen-
tal analysis techniques and beyond. The book is also intended to provide
more experienced researchers with a condensed summary of the influence of
nanotechnology on analytical techniques and excellent up-to-date references
that will prove useful in their future endeavors. The editors and contributors
are lead scientists and researchers in academia and industry in their subject
areas. On behalf of the Royal Society of Chemistry, we are very thankful to
all contributors for their special and hard work in the making of this book.
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Contents

Section I: Introduction-Perspective of Analytical Sciences,

Properties, Mechanism of Adsorption on Nanomaterials

Chapter 1 Perspective on Analytical Sciences and Nanotechnology  3

Deepali Sharma, Suvardhan Kanchi, Krishna Bisetty and
Venkatasubba Naidu Nuthalapati

1.1 Introduction  3
1.1.1 Nanotechnology  4
1.1.2 Analytical Sciences  6
1.2 Facets of Analytical Nanoscience and
Nanotechnology  9
1.2.1 Instrumentation  10
1.3 Nanoparticles  15
1.3.1 Metal Nanoparticles  15
1.3.2 Metal Oxide Nanoparticles  17
1.3.3 Quantum Dots  18
1.3.4 Carbon Allotropes  19
1.3.5 Molecularly Imprinted Polymeric Nanoparticles  21
1.4 Analytical Applications of Nanostructured Materials  21
1.4.1 Nano Drug Delivery Application  22
1.4.2 Energy Application  23
1.4.3 Environmental Applications  24
1.4.4 Electronic Applications  25
1.4.5 Food Industry Applications  27
1.5 Biomimetics  28
1.5.1 Nanobiosensors  29
1.6 Limitations of Nanotechnology in Analytical
Sciences  30

RSC Detection Science Series No. 9

Advanced Environmental Analysis: Applications of Nanomaterials, Volume 1
Edited by Chaudhery Mustansar Hussain and Boris Kharisov
© The Royal Society of Chemistry 2017
Published by the Royal Society of Chemistry, www.rsc.org

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viii Contents
1.7 Conclusions  31
References  31

Chapter 2 Novel Synthetic Techniques for Nanomaterials  35

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Jesús Prado-Gonjal, Romain Heuguet, Sylvain Marinel,

Emilio Morán and Rainer Schmidt

2.1 Introduction  35
2.2 Experimental  38
2.2.1 Synthetic Aspects  38
2.2.2 Structural and Microstructural
Characterization  39
2.2.3 BET Analysis  40
2.2.4 Impedance Spectroscopy  40
2.3 Results  41
2.3.1 Structural Characterization  41
2.3.2 Microstructural Characterization  41
2.3.3 BET Surface Area Analysis  45
2.3.4 Ionic Conductivity Measurements by
Impedance Spectroscopy  46
2.4 Conclusions  55
Acknowledgements  56
References  56

Chapter 3 Fractal Properties of Nanoparticle Aggregation  58

Jianchao Cai, Yiwen Ju, Xiangyun Hu and Boming Yu

3.1 Introduction of Nanoparticle and Fractal Geometry  58

3.2 Fractal Model for Thermal Conductivity of Nanofluids  62
3.3 Fractal Aggregation of Nanoparticles  66
3.4 Fractal Analysis of Yield Stress Property of
Nanoparticle Aggregation  69
3.5 Conclusions  70
Acknowledgements  71
References  71

Chapter 4 Removal of Pollutants from the Environment

Using Sorbents and Nanocatalysts  74
H. R. Aghabozorg and S. Sadegh Hassani

4.1 Introduction  74
4.2 Removal of Sulfur Compounds from Fuels  75
4.3 Elimination of Heavy Metals from Wastewater  80
4.4 Separation of the Dangerous Radionuclides
from Liquid Nuclear Wastes  83
4.5 Conclusion  84
References  84
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Contents ix
Chapter 5 Mechanism of Adsorption on Nanomaterials  90
Rani Bushra, Anees Ahmed and Mohammad Shahadat

5.1 Introduction  90
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5.2 Adsorption Mechanism  92

5.2.1 Adsorption Isotherms  92
5.2.2 Adsorption Kinetics and Thermodynamics  94
5.2.3 Adsorption of Pollutants by Nanoparticles  96
5.2.4 Adsorption of Pollutants by CNTs  99
5.2.5 Adsorption of Pollutants by Dendritic
Nanopolymers  103
5.3 Future Prospects  104
5.4 Conclusion  105
References  105

Chapter 6 Adsorption and Desorption on Nanostructured

Materials  112
Rohama Gill, Quratulain Nadeem and
Mohamed Bououdina

6.1 Introduction  112

6.2 Carbonaceous Nanomaterials as Nanoadsorbents  116
6.2.1 Carbon Nanotubes as Nanoadsorbents  116
6.2.2 Carbon Nanosheets as Nanoadsorbents  118
6.3 Magnetic Nanomaterials as Nanoadsorbents  119
6.4 Metal Oxide Nanoparticles as Adsorbents  122
6.5 Metallic Nanomaterials as Adsorbents  124
6.6 Clays as Nanoadsorbents  125
6.6.1 Nanoclays as Adsorbents for Dyes  126
6.6.2 Nanoclays as Adsorbents for Phenols  127
6.6.3 Nanoclays as Adsorbents for Heavy Metals  128
6.6.4 Nanoclays as Adsorbents for Gases  129
6.7 Silicon-Based Nanomaterials as Nanoadsorbents  131
6.7.1 Silicon-Based Nanoparticles as Nanoadsorbents  131
6.7.2 Silicon-Based Nanotubes as Nanoadsorbents  131
6.7.3 Silicon-Based Nanosheets as Nanoadsorbents  132
6.8 Polymer-Based Nanoadsorbents  132
6.9 Conclusion  133
Acknowledgements  134
References  134

Chapter 7 Nanomaterials for Heavy Metal Removal  139

S. Azzaza, R. Thinesh Kumar, J. Judith Vijaya and
M. Bououdina

7.1 Introduction  139

7.2 Sources of Heavy Metal in the Environment  140
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x Contents
7.3 Nanotechnology for Environment Remediation  140
7.4 Types of Adsorbents  142
7.4.1 Carbon-Based Nanomaterials  142
7.4.2 Metal-Based Nanomaterials  146
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7.4.3 Nanosized Metal Oxides  150

7.4.4 Other Oxides  159
7.5 Conclusion  160
References  161

Chapter 8 Adsorption Selectivity of Boron Nitride Nanostructures

Designed for Environmental Protection  167
Levan Chkhartishvili, Lina Sartinska and Tsiuri Ramishvili

8.1 Introduction  167

8.2 Experimental  171
8.2.1 Auger Spectra  171
8.2.2 Raman Spectra  174
8.3 Theorizing  176
8.3.1 Surface Reconstruction  177
8.3.2 Particle Morphology  180
8.3.3 Near-Surface Electric Field  181
8.4 Estimates  186
8.4.1 Ions  186
8.4.2 Polar Molecules  187
8.4.3 Nonpolar Molecules  188
8.5 Conclusions  190
References  191

Chapter 9 Environmental Applications of Iron-Containing

Nanomaterials: Synthetic Routes, Structures,
Compositions and Properties  193
Víctor Manuel Jiménez-Pérez, Oxana V. Kharissova and
Blanca M. Muñoz Flores

9.1 Introduction  193

9.1.1 Nanomaterials  194
9.1.2 General Data of Nanomaterials
Containing Iron  194
9.2 Syntheses  197
9.2.1 Classic Routes  198
9.2.2 Green Synthesis  198
9.3 Remediation  204
9.3.1 Organic Compounds  204
9.3.2 Metals  206
9.4 Disinfection  209
9.5 Toxicity and Risks of Application of
Iron Nanomaterials  210
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Contents xi
9.6 Conclusion  214
References  215

Section II: Sample Preparation and Extraction Techniques

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with Nanomaterials

Chapter 10 Sample Preparation and Extraction Techniques

Using Nanomaterials  223
Mostafa Khajeh, Kamran Dastafkan, Mousa Bohlooli and
Mansour Ghaffari-Moghaddam

10.1 Important Aspects Prior to Quantitative

Determination in Environmental Analysis  223
10.2 Advanced Adsorption by Nanomaterials  233
10.2.1 Nanometric Scale  233
10.2.2 Interaction Mechanisms  236
10.2.3 Behavior of Nanomaterials in Analytical Media  244
10.3 Nanoadsorbents  246
10.3.1 Metallic Nanoparticles  247
10.3.2 Carbonaceous Nanomaterials  251
10.3.3 Siliceous Nanomaterials  260
10.3.4 Nanofibers  262
10.3.5 Polymer Nanomaterials  267
10.3.6 Nanoclays  272
References  274

Chapter 11 Nanomaterials in Extraction Techniques  284

Krystyna Pyrzynska

11.1 Introduction  284

11.2 Nanoparticles Used in Environmental Analysis  285
11.2.1 Metallic Nanoparticles  287
11.2.2 Carbon Nanotubes  289
11.2.3 Graphene  291
11.3 Applications of Nanoparticles in Sorptive
Extraction Techniques  293
11.3.1 Solid-Phase Extraction  294
11.3.2 Solid-Phase Microextraction  296
11.4 Conclusions  300
References  300

Chapter 12 Pretreatment Processes for the Analysis of Organic

Pollutants with Nanomaterials  306
Amirhassan Amiri

12.1 Introduction  306

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xii Contents
12.2 Role of Nanomaterials in the Sample
Treatment Step  307
12.3 Nanoparticles as Support  307
12.3.1 Non-Magnetic  307
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12.3.2 Magnetic  308

12.4 Nanomaterials as Sorbent Materials  311
12.4.1 Molecularly Imprinted Polymers (MIP)  312
12.4.2 Carbon-Based Nanomaterials  313
12.4.3 Nanofiber-Based Sorbents  337
12.4.4 Metal–Organic Framework Materials  341
12.4.5 Metallic Nanoparticles  344
12.5 Nanomaterials as Pseudo-Stationary Phase  347
12.5.1 Nanoparticles in Liquid–Liquid
Extraction (LLE)  347
12.5.2 Nanoparticles in Liquid-Phase
Microextraction  348
References  348

Section III: Separation Techniques with Nanomaterials

(Chromatography and Membranes Applications of
Nanomaterials)

Chapter 13 Separation Techniques with Nanomaterials:

Chromatography and Membrane Applications of
Nanomaterials  357
Elizabeth Guihen

13.1 Fundamentals and Theory of Nanomaterials in

Separation Science  357
13.1.1 Concepts and Theory of Nanomaterials in
Chemical Analysis  358
13.2 Applications of Nanomaterials in
Environmental Analysis  364
13.2.1 Carbon-Based Nanomaterials in
Environmental Analysis  364
13.2.2 Gold Nanoparticles in Environmental
Analysis  367
13.2.3 Magnetic Nanoparticles in Environmental
Analysis  368
13.2.4 Quantum Dots in Environmental
Analysis  372
13.2.5 Graphene Nanoparticles in Environmental
Analysis  372
13.3 Conclusions and Future Direction  375
References  375
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Contents xiii
Chapter 14 Advanced Environmental Engineering Separation
Processes, Environmental Analysis and Application
of Nanotechnology: A Far-Reaching Review  377
Sukanchan Palit
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14.1 Introduction  377

14.2 Vision of the Present Treatise  378
14.2.1 Purpose and Aim of the Present Study  379
14.3 Global Ecological Balance, Provision of Clean Drinking
Water and the Progress of Human Civilization  379
14.3.1 Environmental Engineering Science: A New
Beginning and Future Perspective  380
14.3.2 Water Process Engineering, Environmental
Separation Processes and the Vision of
Tomorrow  381
14.3.3 Water Quality: Scientific Perspectives  381
14.4 A Review of Important and Relevant Technologies
for Wastewater Treatment and Oxidation
Technologies: A Vision for the Future  383
14.4.1 The Vision of Scientific Endeavour in the
Field of Advanced Oxidation Processes:
A Deep Introspection  384
14.4.2 Use and Immense Importance of Selected
Advanced Oxidation Processes for
Wastewater Treatment  384
14.4.3 Wastewater Treatment by a Visionary
Combination of Advanced Oxidation Processes
and Conventional Biological Systems  385
14.4.4 Ozonation: The Next Generation
Environmental Engineering Technique  387
14.4.5 Contribution of Membrane Separation
Processes in the Advancement of Science  387
14.5 Advanced Oxidation Processes: Vision, Current
Status and Visionary Prospects  387
14.5.1 A Review of Photochemical Processes in
Wastewater Treatment  388
14.5.2 An Introspection into Treatment of Textile
Wastewater by Advanced Oxidation
Processes: A Critical Overview  389
14.6 Recent Scientific Endeavour in the Field of
Non-Conventional Environmental Engineering
Separation Processes  390
14.6.1 Recent Scientific Pursuits in the Field of
Membrane Separation Processes and Other
Environmental Engineering Separation
Processes  398
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xiv Contents
14.6.2 Recent Scientific Endeavour in the Field
of Ozonation of Industrial Wastewater  401
14.7 Milestones in the Research of Advanced Oxidation
Processes  404
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14.7.1 Milestones and Unparalleled Achievements

in Environmental Engineering Separation
Processes  404
14.8 Global Drinking Water Crisis and Application of
Membrane Separation Processes  404
14.8.1 Industrial Wastewater Treatment and the
Application of Novel Separation Processes:
A Definitive Vision for the Future  405
14.8.2 Doctrine of Environmental Engineering
Separation Processes and the World of
Indomitable Challenges  405
14.9 Scientific Cognizance, Visionary Future of
Environmental Pollution Control and
Environmental Analysis  406
14.9.1 Visionary Environmental Analysis and
the Progress of Science Ahead  406
14.10 Application of Nanotechnology in Environmental
Engineering and the Vision for the Future  406
14.10.1 Nanofiltration, Application of Membrane
Separation Processes and the Visionary
Domain of Environmental Analysis  407
14.11 Fouling: Difficulties and Plausible Solutions  407
14.12 Advanced Environmental Analysis and Recent
Scientific Research Thrust Areas  407
14.13 Future Perspectives of Application of Novel
Separation Processes and the Visionary
Frontier Ahead  408
14.13.1 Challenges, Difficulties and Barriers to
Environmental Sustainability and
Ecological Balance  408
14.13.2 Environmental Sustainability and the
Future of Science and Technology  409
14.13.3 Challenges, Barriers and Vision in the
Application of Environmental Separation
Processes  409
14.14 Environmental Analysis and Its Application to
Relevant Environmental Separation Processes  409
14.15 Future Targets, Future Vision and the March of
Science and Engineering  410
14.15.1 A Deep Introspection and the Road
Towards the Future  410
14.15.2 Challenges in Advanced Oxidation Processes
and Membrane Separation Processes  410
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Contents xv
14.15.3 Challenges in the Research Areas of
Environmental Engineering Separation
Processes and the Relevant Domain of
Advanced Environmental Analysis  411
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14.15.4 Successful Sustainable Development and

Future Perspectives of Environmental
Separation Processes  411
14.16 Scientific Wisdom, Future of Separation Processes
and the Wide Road Ahead  411
14.16.1 Future Dimensions of Thoughts and
Scientific Cognizance in the Field of
Environmental Separation Processes
and Environmental Analysis  412
14.16.2 Environmental Engineering Science:
The Road Ahead and the Vision for the
Future  412
14.17 Conclusion  413
Acknowledgements  413
References  413

Chapter 15 Application of Nanomaterials in Membrane

Technology  417
Soumitra Kar and R. C. Bindal

15.1 Membrane Technology  417

15.1.1 Types of Membranes  419
15.1.2 Need for Nanocomposite Membranes  422
15.2 Synthesis and Characterisation of
Nanocomposite Membranes  423
15.2.1 Synthesis of Nanocomposites  425
15.2.2 Characterisation of Nanocomposites  430
15.3 Nanocomposite Membranes in Water Treatment  436
15.3.1 Conventional Nanocomposites  437
15.3.2 Thin Film Nanocomposites  439
15.3.3 Thin Film Composites with
Nanocomposite Substrate  440
15.4 Nanocomposite Membranes in Gas Separation  441
15.4.1 Mixed Matrix Membrane Materials  443
15.4.2 Effect of the Inorganic Dispersed Phase
on Membrane Properties  443
15.5 Challenges in Processing and Manufacturing
Nanocomposite Membranes  444
15.5.1 Challenges in the Fabrication of
Nanocomposite Membranes  445
15.5.2 Challenges in Scale-up and Integration  448
15.5.3 Health and Environmental Safety  449
References  450
 View Online

xvi Contents
Chapter 16 Nanocellulose: A Novel Support for Water Purification  456
Runcy Wilson, Jithin Joy, Gejo George and V. Anuraj

16.1 Introduction  456

Published on 08 November 2016 on http://pubs.rsc.org | doi:10.1039/9781782623625-FP007

16.2 Preparation of Nanocellulose  457

16.2.1 Classification of Nanocellulose Based on
Morphological Features  457
16.3 Nanocellulose for Water Purification  458
16.3.1 Heavy Metal Removal from Water  459
16.3.2 Oil Absorption from Water  465
16.3.3 Dye Removal from Water  472
16.4 Conclusions  473
References  473

Section IV: Spectroscopic Techniques with

Nanomaterials

Chapter 17 Detection of Environmental Pollutants by

Surface-Enhanced Raman Spectroscopy  479
Monica Potara, Cosmin Farcau, Ioan Botiz and
Simion Astilean

17.1 Introduction  479

17.2 Environmental Monitoring by SERS  482
17.2.1 Detection of Pesticides  482
17.2.2 Detection of Polycyclic Aromatic
Hydrocarbons  488
17.2.3 Detection of Heavy Metal Ions  494
17.3 Conclusions and Outlook  499
Acknowledgements  499
References  499

Chapter 18 Surface-Enhanced Raman Scattering with

Nanomaterials  504
M. Umadevi and A. Milton Franklin Benial

18.1 Introduction  504

18.2 Theory of SERS  505
18.2.1 Electromagnetic Enhancement Mechanism  505
18.2.2 Chemical Enhancement Mechanism  505
18.3 Selection Rules  506
18.3.1 Image Field Model  507
18.3.2 Electromagnetic Field Model  507
18.4 Metal Nanoparticles  508
18.5 Importance of SERS in Pollutant Detection  509
18.6 Sample Preparation  510
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