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1 OXFORD Nanotechnology Applications for Clean Water Solutions for Improving Water Quality Second Edition Edited by Anita Street US Department of Energy Richard Sustich Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign Jeremiah Duncan Department of Atmospheric Science and Chemistry, Plymouth State University Nora Savage Office of Research and Development, US Environmental Protection Agency Foreword by George Gray ELSEVIER AMSTERDAM BOSTON HEIDELBERG LONDON NEW YORK PARIS SAN DIEGO SAN FRANCISCO SINGAPORE SYDNEY TOKYO w William Andrew is an imprinl of" lilscvicr

2 List of Contributors Foreword Preface Acknowledgment Introduction xxi xxxi xxxiii xxx v xxxvii PART 1 CONTAMINANT SENSING TECHNOLOGIES CHAPTER 1 Sensors Based on Carbon Nanotube Arrays and Graphene for Water Monitoring Introduction CNT-based electrochemical sensors Various methods for preparation of CNT-based sensors Fabrication of aligned CNT NEA Applications of CNT-based sensors for metal ion monitoring Graphene-based sensors Graphene-based electrochemical sensors Graphene sensors for pesticides Graphene sensors for other pollutants Conclusions and future work 15 Acknowledgments 16 References 16 CHAPTER 2 Advanced Nanosensors for Environmental Monitoring Introduction Nanostructured sensing materials developed Incorporation of metal nanoparticles in photopolymerized organic conducting polymers Nanostructured PAA membranes as novel electrode materials Chemical sensor arrays and pattern recognition Data processing, pattern recognition, and support vector machines Integration of sensor array with chromatographic systems 32 iii

3 iv Contents 2.4 Biosensing applications of nanostructured materials Biosensors for polychlorinated biphenyls Endocrine disrupting chemicals, chlorinated organics, and other analytes Multiarray electrochemical sensors for monitoring pathogenic bacteria, cell viability, and antibiotic susceptibility Conclusions and future perspectives 41 Acknowledgments 41 References 42 CHAPTER 3 Electrochemical Biosensors Based on Nanomaterials for Detection of Pesticides and Explosives Introduction Nanomaterials-based biosensors for pesticides Biosensor based on AChE Biosensor based on ChO/AChE bienzyme Biosensor based on LBL assembly of AChE on CNT Biosensor based on OPH NP-based electrochemical immunoassay of TNT The principle of NP-based TNT sensor The analytical performance of TNT sensor Conclusions 60 Acknowledgments 60 References 61 CHAPTER 4 Dye Nanoparticle-Coated Test Strips for Detection of ppb-level Ions in Water Introduction Fundamental concept of dye nanoparticle-coated test strip Structural features of dye nanoparticle-coated test strip Simple yet versatile fabrication methods of DNTSs Detection characteristics with DNTS The strategy to produce a suitable DNTS for a target ion Detection of harmful ions in water with DNTSs PAN nanofiber DNTS for Zn(II) detection Dithizone nanofiber DNTS for Hg(II) detection Conclusions and future perspectives 71 Acknowledgments 71 References 71

4 v CHAPTER 5 Functional Nucleic Acid-Directed Assembly of Nanomaterials and Their Applications as Colorimetric and Fluorescent Sensors for Trace Contaminants in Water Detection of trace contaminants in water Functional nucleic acids for molecular recognition In vitro selection of functional nucleic acids that are selective for a broad range of target analytes Analytes or contaminants recognized selectively by functional nucleic acids Functional nucleic acid-directed assembly of nanomaterials for sensing contaminants Fluorescent sensors Colorimetric sensors Simultaneous multiplexed detection using quantum dots and gold nanoparticles Sensors on solid supports Dipsticks Incorporation of sensors into devices Other sensing schemes utilizing electrochemistry and magnetic resonance imaging Conclusions and future perspective 87 Acknowledgments 87 References 88 PART 2 SEPARATION TECHNOLOGIES CHAPTER 6 Nanostructured Membranes for Water Purification Introduction Conducting PAA membranes PAA membranes for nanofillration of ENPs Application of PAA membranes for absolute disinfection of drinking water Conclusions 102 Acknowledgments 103 References 104

5 vi Contents CHAPTER 7 Advances in Nanostructured Membranes for Water Desalination Introduction Desalination technologies HO State of the art in RO HO State of the art in MD Nanostructured membranes Nanozeolite membranes Clay nanocomposite membranes CNT membranes Application of nanostructured membranes CNT membranes in RO CNT membranes in MD Commercial efforts to date Future challenge of energy-efficient CNT membranes for desalination 120 Acknowledgments 120 References 120 CHAPTER 8 Nanostructured Titanium Oxide Film- and Membrane-Based Photocatalysis for Water Treatment Ti02 photocatalysis and challenges 123 8:2 Sol gel synthesis of porous Ti02: surfactant self-assembling Immobilization of TiOz in the form of films and membranes Activation of Ti02 under visible light irradiation Selective decomposition of target contaminants Versatile environmental applications Suggestions and implications 129 Acknowledgments 130 References 130 CHAPTER 9 Nanotechnology-Based Membranes for Water Purification Introduction Zeolite-coated ceramic membranes Inorganic organic TFN membranes 137

6 vii 9.4 Hybrid protein polymer biomimetic membranes Aligned CNT membranes Self-assembled block copolymer membranes Graphene-based membranes Conclusions 148 References 149 CHAPTER 10 Multifunctional Nanomaterial-Enabled Membranes for Water Treatment Introduction Nanostructured membranes with functional nanoparticles Overview of recent progress in the development of multifunctional membranes Porous polymer nanocomposile membranes: structural aspects Example: effect of filler incorporation route on the structure and biocidal properties of polysulfone-silver nanocomposite membranes of different porosities Example: Self-cleaning membrane for ozonation ultrafiltration hybrid process Potential future research directions 166 Acknowledgments 166 References 166 CHAPTER 11 Nanofluidic Carbon Nanotube Membranes: Applications for Water Purification and Desalination Introduction: carbon nanotube membrane technology for water purification Basic structure and properties of carbon nanotubes Water transport in carbon nanotube pores: an MD simulation view Water inside carbon nanotubes Carbon nanotubes as biological channel analogs Fabrication of carbon nanotube membranes Polymeric/CNT membranes Silicon nitride CNT membranes CNT polymer network fabrication 180

7 viii Contents 11.5 Experimental observations of water transport in double-wall and multi-wall carbon nanolube membranes Nanofiltration properties of carbon nanotube membranes Size exclusion experiments in the 1 10 nm size range Ion exclusion in carbon nanotube membranes Altering transport selectivity by membrane functionalization Is energy-efficient desalination and water purification with carbon nanotube membranes possible and practical? 184 Acknowledgments 186 References 186 CHAPTER 12 Design of Advanced Membranes and Substrates for Water Purification and Desalination Overview Novel method to make a continuous micro-mesopore membrane with tailored surface chemistry for use in nanofiltration Deposition of polyelectrolyte complex films under pressure and from organic solvents Solvent resistant hydrolyzed polyacrylonitrile membranes Polyimides membranes for nanofiltration Conclusions 197 References 197 CHAPTER 13 Customization and Multistage Nanofiltration Applications for Potable Water, Treatment, and Reuse Potable water Nanofiltration membranes as a water treatment solution Nanofiltration of freshwater sources Nanofiltration for seawater desalination Water treatment and reuse Nanofiltration for wastewater treatment and reuse 205 Reference 207

8 ix CHAPTER 14 Commercialization of Nanotechnology for Removal of Heavy Metals in Drinking Water Issues that need to be addressed General approaches Specific technology used by CCT and results Synthesis and characterization of materials Metal binding tests Moving technology to the next phase 224 References 225 CHAPTER 15 Water Treatment by Dendrimer-Enhanced Filtration: Principles and Applications Introduction Dendrimers as recyclable ligands for cations Dendrimers as recyclable ligands for anions Dendrimer-enhanced filtration: overview and applications Summary and outlook 238 Acknowledgments 238 References 239 CHAPTER 16 Detection and Extraction of Pesticides from Drinking Water Using Nanotechnologies Introduction The need for nanomaterials and nanotechnology Earlier efforts for pesticide removal Surface adsorption Biological degradation Membrane filtration Nanomaterials-based chemistry: recent approaches Homogeneous versus heterogeneous chemistry Variety of nanosystems Pesticide removal from drinking water: a case study Noble metal nanoparticle-based mineralization of pesticides Detection of ultralow pesticide contamination in water Technology to product: a snapshot view Future directions Summary 266

9 x Contents References 267 Further reading 269 CHAPTER 17 Nanomaterials-Enhanced Electrically Switched Ion Exchange Process for Water Treatment Introduction Principle of the electrically switched ion exchange technology Nanomaterials-enhanced electrically switched ion exchange for removal of radioactive cesium Nanomaterials-enhanced electrically switched ion exchange for removal of chromate and perchlorate Conclusions 279 Acknowledgments 280 References 280 PART 3 TRANSFORMATION TECHNOLOGIES CHAPTER 18 Nanometallic Particles for Oligodynamic Microbial Disinfection Introduction Economic impact of modern disinfection systems Health impact of water disinfection shortfalls Modern disinfection systems Nanometallic particles in alternative disinfection systems Silver nanoparticles Synthesis Utility Conclusions 293 References 293 CHAPTER 19 Nanostructured Visible-Light Photocatalysts for Water Purification Visible-light photocatalysis with titanium oxides Sol gel fabrication of nitrogen-doped titanium oxide nanoparticle photocatalysts Metal-ion-modified nitrogen-doped titanium oxide photocatalysts 304

10 xi 19.4 Nanostructured nitrogen-doped titanium-oxide-based photocatalysts Environmental properties of nitrogen-doped titanium-oxidebased photocatalysts Conclusions and future directions 313 References 314 CHAPTER 20 Nanotechnology-Enabled Water Disinfection and Microbial Control: Merits and Limitations Introduction Current and potential applications Nanosilver Titanium oxide Fullerenes Combining current technologies with nanotechnology Outlook on the role of nanotechnology in microbial control: limitations and research needs 324 References 326 CHAPTER 21 Possible Applications of Fullerene Nanomaterials in Water Treatment and Reuse Introduction Chemistry of fullerene nanomaterials Applications of fullerene nanomaterials Membrane fabrication using fullerene nanomaterial s Oxidation of organic compounds Bacterial and viral inactivation Summary 336 Acknowledgements 337 References 337 CHAPTER 22 Heterogeneous Catalytic Reduction for Water Purification: Nanoscale Effects on Catalytic Activity, Selectivity, and Sustainability Introduction Catalytic hydrodehalogenation: iodinaled X-ray contrast media 340

11 22.3 Selective catalytic nitrate reduction Conclusions and prospects 346 References 347 CHAPTER 23 Enhanced Dechlorination of Trichloroethylene by Membrane-Supported Iron and Bimetallic Nanoparticles Introduction Nanoparticle formation Solution and emulsion techniques In situ formation of nanoparticles Addition of secondary metals Preserving zero-valence Polymers Composite material Water treatment Metal particle composition Absorption in support polymer Conclusions 365 References 366 CHAPTER 24 Synthesis of Nanostructured Bimetallic Particles in Polyligand-Functionalized Membranes for Remediation Applications Introduction Nanoparticle synthesis in functionalized membranes Polyvinylidene flouride membrane functionalization with polyacrylic acid Synthesis of fe-based bimetallic nanoparticles in polyacrylic acid layers Characterization of polyacrylic acid functionalized membranes Characterization of nanoparticles in membranes Chelation interaction between ferrous ions and polyacrylic acid Fe/Pd nanoparticle characterization Reactivity of membrane-based nanoparticles Catalytic hydrodechlorination of trichloroethylene 381

12 xiii Effect of dopant material and nanoparticle structure Catalytic hydrodechlorination of selected polychlorinated biphenyls Dechlorination efficiency of different polychlorinated biphenyls Catalytic activity as a function of palladium coating content Conclusions 390 Acknowledgments 391 References 391 CHAPTER 25 Magnesium-Based Corrosion Nano-Cells for Reductive Transformation of Contaminants Introduction Magnesium-based bimetallic systems Unique corrosion properties of magnesium Doping nanoscale palladium onto magnesium modified alcohol reduction route Role of nanosynthesis in assuaging palladium usage concerns from Challenges in nanoscaling magnesium Other environmental applications 401 Acknowledgments 401 References 402 PART 4 STABILIZATION TECHNOLOGIES CHAPTER 26 Multifunctional Materials Containing Nanoscale Zerovalent Iron in Carbon Microspheres for the Environmentally Benign Remediation of Chlorinated Hydrocarbons Introduction Materials synthesis Adsorption and reactivity studies Stability and transport characteristics Partitioning at TCE-water interfaces Summary 418 Acknowledgments 419 References 419

13 xiv Contents CHAPTER 27 Water Decontamination Using Iron and Iron Oxide Nanoparticles Introduction Synthesis and properties of iron and iron oxide nanoparticles Iron nanoparticles Iron oxide nanoparticles Removal of pollutants through sorption/dechlorination by iron/iron oxide nanoparticles Removal of arsenic in water Removal of chromium in water Removal of phosphates in water Removal of chloro-organics in water Removal of E. coli in Water Conclusions 438 References 438 CHAPTER 28 Nanotechnology for Contaminated Subsurface Remediation: Possibilities and Challenges Introduction Sources of groundwater contamination and remediation costs Remediation alternatives Contaminated site remediation via reactive nanomaterials Example of contaminated site remediation via reactive nanometals Summary 452 References 453 CHAPTER 29 Green Remediation of Hexavalent Chromium Using Naturally Derived Flavonoids and Engineered Nanoparticles Introduction Nanotechnologies for site remediation and wastewater treatment Bimetallic nanoparticles remediation approach Remediation of chromium using nanotechnology 463

14 xv Determination of Cr(VI) concentration Removal of Cr(VI) from complex aqueous media Naturally occurring flavonoids as reducing agents for hexavalent chromium Conclusions 469 Acknowledgments 469 References 470 CHAPTER 30 Physicochemistry of Polyelectrolyte Coatings That Increase Stability, Mobility, and Contaminant Specificity of Reactive Nanoparticles Used for Groundwater Remediation Challenges of using reactive nanomaterials for in situ groundwater remediation Polymeric surface modification/functionalization Definitions and materials Nanoparticle surface modification approaches Effect of surface modifiers on the mobility of nanomaterials in the subsurface Colloidal forces and Derjaguin Landau Verwey Overbeek theory Adsorbed layer characterization Contaminant targeting of polymeric functionalized nanoparticles Effect of surface modification/functionalization on contaminant degradation Remaining challenges and ongoing research and development opportunities 487 References 488 CHAPTER 31 Stabilization of Zero-Valent Iron Nanoparticles for Enhanced In Situ Destruction of Chlorinated Solvents in Soils and Groundwater Introduction Stabilization of zero-valent iron nanoparticles using polysaccharides Reactivity of starch- or carboxymethyl-cellulose-stabilized zero-valent iron nanoparticles 496 References 499

15 xvi Contents CHAPTER 32 Reducing Leachability and Bioaccessibility of Toxic Metals in Soils, Sediments, and Solid/Hazardous Wastes Using Stabilized Nanoparticles Reductive immobilization of chromate in soil and water using stabilized zero-valent iron nanoparticles Introduction Reduction and removal of Cr(VI) in water Reduction and immobilization of Cr(VI) sorbed in soil In situ immobilization of lead in soils using stabilized vivianite nanoparticles Mechanisms of nanoparticle stabilization by carboxymethyl cellulose Conclusions 510 References 510 PART 5 SOCIETAL ISSUES CHAPTER 33 Introduction to Societal Issues: The Responsible Development of Nanotechnology for Water 515 References 517 CHAPTER 34 Nanotechnology in Water: Societal, Ethical, and Environmental Considerations Introduction Responsible development: ethical, social, and environmental concerns Access, parity, and effects of technology deployment Human health and environmental effects Public engagement: what role should the public have? Conclusions 527 References 527 CHAPTER 35 Competition for Water Introduction Population and technological impacts on water 531

16 xvii 35.3 Water access Corruption, mismanagement, and overconsumplion Climate change and global warming Patents: parity and access issues Political demands Conflict Biofuels Biofuels introduction Worldwide biofuels policy Biofuels: solution to or creation of a problem? Possible ways forward for biofuels Bottled water Future trends Conclusions 549 Notes 550 References 550 CHAPTER 36 A Framework for Using Nanotechnology to Improve Water Quality Introduction Superordinate goals Trading zones Interactional expertise Boundary object Moral imagination Adaptive management Anticipatory governance Expert elicitation as a method for facilitating anticipatory governance Potters for peace Conclusions 568 Acknowledgments 570 References 570 CHAPTER 37 International Governance Perspectives on Nanotechnology Water Innovation Introduction Diagnosing the need The role for policy Conclusions 580 References 580

17 xviii Contents CHAPTER 38 Nanoscience and Water: Public Engagement at and below the Surface Introduction Water and the public Nanotechnology treatment strategies Modalities Municipal systems Point-of-use systems Targeted systems 38.5 Water and public engagement Municipal systems Point-of-use strategies Conclusions 593 Acknowledgments Notes 593 References CHAPTER 39 How Can Nanotechnologies Fulfill the Needs of Developing Countries? Nanotechnologies and developing countries How can nanotechnologies deliver public value? Nanodialogues in Zimbabwe Balancing risk and opportunity Future directions 607 References 608 CHAPTER 40 Challenges to Implementing Nanotechnology Solutions to Water Issues in Africa Introduction Community involvement or ownership Community need for the technology Community water quality monitoring Infrastructure Capacity development Improvements in quality of life Commercialization of nanotechnologies Conclusions 620 References 620

18 xix CHAPTER 41 Life Cycle Inventory of Semiconductor Cadmium Selenide Quantum Dots for Environmental Applications Introduction Applications and synthesis of quantum dots Methodology Life cycle inventory of synthesis of CdSe quantum dots Conclusions and future perspective 639 Acknowledgments 639 References 639 PART 6 OUTLOOK Nanotechnology Solutions for Improving Water Quality 647 Index 651