Nanotechnology for Environmental Remediation

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1 Nanotechnology for Environmental Remediation

2 Modern Inorganic Chemistry Series Editor: John P. Fackler, Jr., Texas A&M University Current volumes in this series: Extraction of Metals from Soils and Waters D.M. Roundhill Metal Dihydrogen and Sigma-Bond Complexes G.J. Kubas Carbon-Functional Organosilicon Compounds Edited by Vǎclav Chvalovský and Jon M. Bellama Computational Methods for the Determination of Formation Constants Edited by D.J. Leggett Cooperative Phenomena in Jahn Teller Crystals M.D. Kaplan and B.G. Vekhter Gas Phase Inorganic Chemistry Edited by D.H. Russell Homogeneous Catalysis With Metal Phosphine Complexes Edited by Louis H. Pignolet Inorganometallic Chemistry Edited by T.P. Fehlner The Jahn-Teller Effect and Vibronic Interactions in Modern Chemistry I.B. Bersuker Metal Complexes in Aqueous Solutions Arthur E. Martell and Robert D. Hancock Mössbauer Spectroscopy Applied to Inorganic Chemistry Volumes 1 and 2 Edited by Gary J. Long Volume 3 Edited by Gary J. Long and Fernande Grandjean Mössbauer Spectroscopy Applied to Magnetism and Materials Science Volumes 1 and 2 Edited by G.J. Long and F. Grandjean Nanotechnology for Environmental Remediation Sung Hee Joo and I. Francis Cheng Optoelectronic Properties of Inorganic Compounds Edited by D.M. Roundhill and John P. Fackler, Jr. Organometallic Chemistry of the Transition Elements F.P. Pruchnik Translated from Polish by Stan A. Duraj Photochemistry and Photophysics of Metal Complexes D.M. Roundhill

3 Sung Hee Joo I. Francis Cheng Nanotechnology for Environmental Remediation With 79 Illustrations

4 Sung Hee Joo Environmental Engineering Program Civil Engineering Department Auburn University Auburn, AL USA I. Francis Cheng Department of Chemistry University of Idaho Moscow, ID USA Library of Congress Control Number: ISBN-10: e-isbn: ISBN-13: Printed on acid-free paper. C 2006 Springer Science+Business Media, Inc. All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer Science+Business Media, Inc., 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks, and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. While the advice and information in this book are believed to be true and accurate at the date of going to press, neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied, with respect to the material contained herein. Printed in the United States of America. (TB/MVY) springer.com

5 Preface The book covers the recently discovered oxidative process driven by zero-valent iron (ZVI) in the presence of oxygen and a further developed system which is named ZEA (Zero-valent iron, EDTA, Air). Future potential applications for environmental remediation using this process are also discussed. The oxidative process was discovered during the course of molinate (a thiocarbamate herbicide) degradation experiments. Both ferrous iron and superoxide (or, at ph < 4.8, hydroperoxy) radicals appear to be generated on corrosion of the ZVI with resultant production of strongly oxidizing entities capable of degrading the trace contaminant. Fenton oxidation and oxidative by-products were observed during nanosized ZVI (nzvi)- mediated degradation of molinate under aerobic conditions. To assess the potential application of nzvi for oxidative transformation of organic contaminants, the conversion of benzoic acid (BA) to p-hydroxybenzoic acid (p-hba) was used as a probe reaction. When nzvi was added to BA-containing water, an initial pulse of p-hba was detected during the first 30 minutes, followed by the slow generation of additional p-hba over periods of at least 24 hours. The ZEA system showed that chlorinated phenols, organophosphorus and EDTA have been degraded. The mechanism by which the ZEA reaction proceeds is hypothesized to be through reactive oxygen intermediates. The ZVI-mediated oxidation and ZEA system may be useful for in situ applications of nzvi particles and may also provide a means of oxidizing organic contaminants in granular ZVI-containing permeable reactive barriers. The purpose of this book is to provide information on the recently discovered chemical process, which could revolutionize the treatment of pesticides and contaminated water. It also aims to offer significant insights to the knowledge for potential applications of ZVI-based technology. Oxidative degradation of herbicides (e.g., molinate) with its pathway, mechanistic interpretation of the data, modelling/simulation, implication for remediation applications, experimental methodology suitable for pesticides analysis, and ZEA (Zero-valent iron, EDTA, and Air) system with its degradation mechanism are included. v

6 Acknowledgments We would like to deeply acknowledge Dr. Christina Noradoun who contributed her expertise in Chapter 5. Dr. Joo wishes to thank former mentors, Professor David Waite and Dr. Andrew Feitz for their advice during research on this topic. Special thanks go to Dr. Joseph Pignatello who provided insightful comments in preparing the manuscript. Finally we would like to appreciate reviewers comments, which improve the quality of this book and the senior editor, Kenneth Howell who supported us in the preparation of this book. vii

7 Contents Preface... Acknowledgments... Abbreviations and Symbols... v vii xiii Chapter 1. Introduction Objectives Outlines... 3 Chapter 2. Literature Review Zero-Valent Iron (ZVI) Iron Use in the Environment Nanoparticulate Bimetallic and Iron Technology Permeable Reactive Barrier (PRB) Using Granular ZVI PRB and ZVI Colloids Use of ZVI, H 2 O 2, and Complexants Nanosized ZVI (nzvi) Pesticides and Contamination Introduction Characteristics of Pesticides and Their Environmental Effects Commonly Used Pesticides Pesticides Treatment and Management Practices Summary Chapter 3. Nanoscale ZVI Particles Manufacture and Analytical Techniques Synthesis of Nanoscale ZVI Particles ZVI Particle Characterization Analytical Techniques Solid-Phase Microextraction GC/MSD HPLC Analysis of Benzoic Acid and p-hydroxybenzoic Acid 34 ix

8 x Contents Measurement of Ferrous Iron Concentrations Measurement of Hydrogen Peroxide (H 2 O 2 ) Concentrations Procedures Used in nzvi-mediated Degradation Studies Molinate Degradation Benzoic Acid Degradation Experimental Setup Used in ZEA System Studies Determination of ZVI Surface Products by XRD Measurements in the Presence of Molinate Measurements in the Absence of Molinate Chapter 4. Oxidative Degradation of the Thiocarbamate Herbicide, Molinate, Using Nanoscale ZVI Introduction Results Effect of the Presence of Air/Oxygen Effect of Molinate and ZVI Concentration Effect of ph Ferrous Iron Generation Effect of DO Hydrogen Peroxide Generation Catalase and Butanol Competition Degradation By-products Molinate Degradation by Combined ZVI and H 2 O Effect of ZVI at Fixed Hydrogen Peroxide Concentration Effect of Hydrogen Peroxide at Constant ZVI Degradation By-products by Combined ZVI and H 2 O Fe(II) Generation from Coupled ZVI/H 2 O 2 in the Presence of Molinate Molinate Degradation Using Fenton s Reagent Degradation By-products of Molinate Using Fenton s Reagents Comparison of ZVI, Coupled ZVI/H 2 O 2 and Fenton s Process at High ph XRD and XPS Analysis Results of XRD Analysis XPS Results Discussion Evidence of Oxidation Pathway Reaction Mechanism Kinetics of Fe(II) and H 2 O 2 Generation Overview of the ZVI-Mediated Oxidative Technology Conclusion... 80

9 Contents xi Chapter 5. Molecular Oxygen Activation by Fe II/III EDTA as a Form of Green Oxidation Chemistry Oxygen Activation Xenobiotic Degradation by ZEA System Mechanism of Degradation Rate-Determining Step Iron Chelation and Chelate Geometry Influence Reactivity Form of Reactive Oxygen Intermediate Species Conclusion Chapter 6. Quantification of the Oxidizing Capacity of Nanoparticulate Zero-Valent Iron and Assessment of Possible Environmental Applications Introduction Results p-hydroxybenzoic acid (p-hba) Formation Cumulative Hydroxyl Radical Formation over Long Term Effect of Fe(II) as Oxidant Scavenger Effect of ZVI Concentrations on Oxidant Yield Effect of ph Selectivity of Oxidant Effect of ZVI Type on Oxidant Yields Comparison Study on Standard Fenton Oxidation of Benzoic Acid Effect of Pure O 2 on Oxidant Yield Discussion Conceptual Kinetic Modeling Conclusion Chapter 7. Conclusions and Future Research Needs Column Studies Further Applications of the ZVI-Mediated Oxidative Process Summary of Results Overview of nzvi Research and Further Research Needs Chapter 8. References Appendix A: XRD Analysis of ZVI Collected from Four Different Samples Appendix B: XRD Analysis of ZVI Collected from Four Different Samples

10 xii Contents Appendix C: ELISA Analysis Methodology Appendix D: Oven Programs for GC/MS Analysis of Pesticides Appendix E: Experimental Conditions for Pesticides and Preliminary Screening Studies Using Nanoscale ZVI Index

11 Abbreviations and Symbols ZVI ZEA PRB SPME GC MS HPLC ELISA SOD SEM TEM XRD XPS Zero Valent Iron Zero-valent iron, EDTA, and Air Permeable Reactive Barrier Solid-Phase MicroExtraction Gas Chromatography Mass Spectrometer High Performance Liquid Chromatography Enzyme Linked Immuno Sorbent Assays Superoxide Dismutase Scanning Electron Microscope Transmission Electron Microscope X-Ray Diffraction X-ray Photoelectron Spectroscopy xiii

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