© 2009 by Taylor & Francis Group, LLC Nanotechnology and the Environment 60198.indb 1 6/12/08 1:31:28 PM © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of the Taylor & Francis Group, an informa business Boca Raton London New York Nanotechnology and the Environment Kathleen Sellers Christopher Mackay Lynn L. Bergeson Stephen R. Clough Marilyn Hoyt Julie Chen Kim Henry Jane Hamblen 60198.indb 3 6/12/08 1:31:28 PM © 2009 by Taylor & Francis Group, LLC CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487‑2742 © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid‑free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number‑13: 978‑1‑4200‑6019‑5 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher can‑ not assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copy‑ right.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978‑750‑8400. CCC is a not‑for‑profit organization that pro‑ vides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging‑in‑Publication Data Nanotechnology and the environment / authors, Kathleen Sellers [et al.]. p. cm. Includes bibliographical references and index. ISBN 978‑1‑4200‑6019‑5 (alk. paper) 1. Nanotechnology‑‑Environmental aspects. I. Sellers, Kathleen. II. Title. T174.7.N373193 2008 620’.5‑‑dc22 2008019075 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com 60198.indb 4 6/12/08 1:31:28 PM © 2009 by Taylor & Francis Group, LLC v Contents Acknowledgments vii About the Authors ix Chapter 1 Introduction 1 Kathleen Sellers Chapter 2 Nanoscale Materials: Denition and Properties 11 Kathleen Sellers Chapter 3 Overview of Manufacturing Processes 33 Julie Chen and Kathleen Sellers Chapter 4 Developing Environmental Regulations Pertinent to Nanotechnology 49 Lynn L. Bergeson Chapter 5 Analyses of Nanoparticles in the Environment 99 Marilyn Hoyt Chapter 6 Environmental Fate and Transport 123 Chris E. Mackay and Kim M. Henry Chapter 7 Treatment of Nanoparticles in Wastewater 155 Kim M. Henry and Kathleen Sellers Chapter 8 The Potential Ecological Hazard of Nanomaterials 169 Stephen R. Clough Chapter 9 Toxicology and Risk Assessment 193 Chris E. Mackay and Jane Hamblen 60198.indb 5 6/12/08 1:31:29 PM © 2009 by Taylor & Francis Group, LLC vi Nanotechnology and the Environment Chapter 10 Nanoparticle Use in Pollution Control 225 Kathleen Sellers Chapter 11 Balancing the Risks and Rewards 249 Kathleen Sellers 60198.indb 6 6/12/08 1:31:29 PM © 2009 by Taylor & Francis Group, LLC vii Acknowledgments The authors gratefully acknowledge the scientists and engineers who reviewed drafts of this manuscript and provided valuable perspective, including: Larry S. Andrews, Ph.D., Rohm & Haas Janis Bunting, General Dynamics Stefanie Giese-Bogdan, Dr.rer.nat., 3M Laurie Gneiding, AMEC Martin P. A. Grifn, Wisconsin Department of Natural Resources Kimberly A. Groff, Ph.D., AMEC Richard Johnson, Ph.D., Oregon Health and Science University Maria Victoria Peeler, Washington State Department of Ecology Nora Savage, Ph.D., U.S. Environmental Protection Agency John Schupner, AMEC Jack Spadaro, Ph.D., AMEC The authors appreciate the assistance of the following contributors: Robin Weinbeck, AMEC Beth Auerbach, Bergeson & Campbell, P.C. Ira Dassa, Bergeson & Campbell, P.C. Elizabeth Algeo, AMEC Kevin Haines, AMEC Denise Ladebauche, AMEC Elizabeth Martin, AMEC Finally, the AMEC team gratefully acknowledges the support for this project under the AMEC Technical Council’s Research and Development Program. 60198.indb 7 6/12/08 1:31:29 PM © 2009 by Taylor & Francis Group, LLC ix About the Authors Kathleen Sellers, PE, has worked on developing solutions to a variety of environ- mental problems during her 20 years of experience. She is particularly intrigued with exploring emerging environmental issues and their solutions. An environmen- tal engineer and chemist, Sellers’ work has ranged from analysis and bioassay of environmental samples through comprehensive eld characterizations, and extended to treatment process development, permitting, and negotiation of regulatory solu- tions. Sellers published an engineering textbook entitled Fundamentals of Hazard- ous Waste Site Remediation (CRC Press/Lewis Publishers, 1999), then edited and co-authored Technical Brief: Endocrine Disrupting Compounds and Implications for Wastewater Treatment (Water Environment Research Foundation, 2005) and Perchlorate: Environmental Problems and Solutions (Taylor & Francis / CRC Press, 2006) before editing and co-writing this book. Chris E. Mackay, PhD, is an environmental chemist and toxicologist with more than 10 years of experience conducting site, product, and chemical compliance assessments. Mackay has worked extensively at the interface of industrial, pharma- ceutical, and agricultural chemistry and environmental biology. To answer challeng- ing environmental and toxicology questions, he has constructed statistical models such as quantitative structure-activity relationships (QSAR) and physiologically based pharmacokinetics (PBPK), as well as rst principal models for stochastic competition and thermodynamic energy transfer. These models have been applied to illustrate and predict not only the transport, fate, and impact of chemical and biological stresses to human populations and aquatic and terrestrial wildlife, but also to optimize industrial and agricultural productivity and economy. Along with providing technical guidance in product and patent development, Mackay has been involved in designing chemical and toxicological assessments to support product development and to comply with regulatory requirements under various consumer and environmental protection statutes in both the United States and Europe. He also has considerable experience in regulatory chemistry and toxicology. Lynn L. Bergeson is Managing Director of Bergeson & Campbell, P.C. (B&C), a Washington, D.C. law rm concentrating on conventional and engineered nanoscale chemical, pesticide, and other specialty chemical product regulation and approval matters, domestic and foreign chemical classication, chemical product litigation, Food and Drug Administration-regulated product approval, and associated business issues. Bergeson is also president of The Acta Group, L.L.C. and The Acta Group EU, Ltd., B&C’s consulting afliates, with ofces in Washington, DC and Man- chester, UK, respectively. She counsels clients on health, safety, science policy, and related legal and regulatory aspects of traditional domestic chemical regulatory pro- grams under the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) and 60198.indb 9 6/12/08 1:31:29 PM © 2009 by Taylor & Francis Group, LLC x Nanotechnology and the Environment the Toxic Substances Control Act (TSCA), as well as issues pertinent to nanotech- nology and other emerging transformative technologies. Stephen R. Clough, PhD, DABT, gr aduated from the University of Michigan with an MS in Water Quality (1984) and a PhD in Toxicology (1988). His career experi- en ce includes the design and management of mammalian and aquatic toxicology laboratories for the planning and analysis of safety evaluation studies addressing both commercial products and industrial waste streams. He was later certied as a Diplomate by the American Board of Toxicology and has since served more than 20 years as a senior environmental toxicologist. He specializes in benthic bioas - se ssments and the evaluation of point and non-point impacts to the aquatic macro- in vertebrate community. Clough has worked at more than 50 hazardous waste sites where he has evaluated the fate, exposure and ecological effects of a wide range of toxicants in various types of media, including heavy metals, pesticides, dioxins/ furans, perchlorate, polycyclic aromatic hydrocarbons, and residuals from chemical, pharmaceutical, pulp/paper/forestry, mining, and automotive industries. He has a broad understanding of projects and/or regulations that fall under CERCLA, RCRA, TSCA, FIFRA, and the Clean Water Act, particularly in US EPA Regions I through IV. Marilyn Hoyt ha s more than 25 years of experience in materials science and envi- ronmental consulting. She has provided chemical measurement support for the research and development of strategic defense systems as part of a multidisciplinary team, as well as managed numerous environmental measurement programs. Hoyt has directed a full service environmental laboratory and has managed studies requir- in g original research with data collection and interpretation. She is familiar with the full array of characterization and instrumental measurement techniques applicable to nanoparticle measurement, as well as the particular challenges involved in envi- ro nmental analyses as compared to laboratory studies. Julie Chen, PhD, is currently one of the three co-directors of the University of Massachusetts Lowell Nanomanufacturing Center. She is responsible for the Nano- ma nufacturing Center of Excellence (NCOE), a state-funded center with the mission of fundamental scientic and applied, industry-collaborative research on environ- me ntally benign, commercially viable manufacturing with nanoscale control. Chen is also the co-director of the Advanced Composite Materials and Textile Research Laboratory at the University of Massachusetts Lowell, where she is a professor of mechanical engineering. Chen was the program director of the Materials Processing and Manufacturing and the Nanomanufacturing Programs in the Division of Design, Manufacture, and Industrial Innovation at the National Science Foundation from 2002 to 2004. Chen has been on the faculty at Boston University, a NASA-Langley Summer Faculty Fellow, a visiting researcher at the University of Orleans and Ecole Nationale Supérieure d’Arts et Métiers (ENSAM-Paris), and an invited participant in the National Academy of Engineering, Frontiers of Engineering Program (US, 2001, US-Germany, 2005, and Indo-US, 2006). 60198.indb 10 6/12/08 1:31:30 PM © 2009 by Taylor & Francis Group, LLC About The Authors xi Chen received her PhD, MS, and BS in Mechanical Engineering from MIT. She has more than 20 years of experience in the mechanical behavior and deformation of ber structures, ber assemblies, and composite materials, with an emphasis on composites processing and nanomanufacturing. Examples include analytical model- ing and novel experimental approaches to electrospinning and controlled patterning of nanobers, and nanoheaters, as well as forming, energy absorption, and failure of textile reinforcements for structural (biomedical to automotive) applications. Kim Henry brings her experience as a hydrogeologist to the fate and transport of nanoparticles in the environment, and the application of those principles to waste- water treatment. She has a BA in geological sciences from Harvard University and an MS in environmental science and engineering from Rice University. Henry has more than 20 years of experience in characterizing and remediating environmental contaminants at a variety of sites, including former manufactured gas plants, rail yards, gasoline stations, bulk storage terminals, chemical reneries, and military facilities. She has negotiated highly controversial projects with regulatory agencies and presented the ndings of site investigations at public meetings and press confer- ences. Henry is intrigued by the concept of science writing, of presenting leading scientic issues accurately and evocatively to the public. She is also the author of four children’s books. Jane Hamblen has more than 28 years of experience in risk assessment, environ- mental health, and biology. As a senior health scientist, Hamblen is responsible for managing risk assessment projects and for technical assistance on a variety of human health projects. Hamblen’s expertise lies in exposure assessment, specializ- ing in both deterministic and probabilistic analyses. Most recently, she has applied those skills to the assessment of nanomaterials and the identication of toxic effects from exposure to nanomaterials. In addition, she has evaluated the public health impacts associated with PCBs, chlorinated organics, mercury, resorcinol, pesticides, gasoline spills, and ash generated by power plants. Hamblen has also developed risk- specic chemical concentrations used to derive clean-up goals, and evaluated public health risks associated with remedial alternatives. She has co-authored several pub- lished technical papers, including articles on the use of Monte Carlo methodology in exposure assessment. Hamblen’s extensive project experience has included human health risk assessments conducted under CERCLA and RCRA. Her project man- agement experience ranges from baseline risk assessments to dose reconstruction projects. She has managed toxic tort cases that allege health effects from chemical exposure and worked in the area of regulatory compliance for worker and commu- nity right-to-know legislation. 60198.indb 11 6/12/08 1:31:30 PM © 2009 by Taylor & Francis Group, LLC 1 1 Introduction Kathleen Sellers ARCADIS U.S., Inc. In early 2007, the United Nations reported that nanotechnology, which then accounted for approximately 0.1% of the global manufacturing economy, would grow to 14% of the market by 2014. This m arket share would correspond to $2.6 trillion in U.S. dollars [1]. What accounts for this explosive growth? And what does it mean for our environment? This book provides perspective on those questions based on the cur- rent state of the science. Nanotechnology is a eld of applied science concerned with the control of mat- ter at dimensions of roughly 1 to 100 nanometers (nm) [1]. (1 nm is one-billionth of a meter.) At the particle size of 1 to 100 nm, nanoscale materials may have differ- ent molecular organizations and properties than the same chemical substances in a larger size. Nano-sized chemicals can have different properties due to [2]: Increased relative surface area per unit mass, which can increase physical strength and chemical reactivity In some cases, the dominance of quantum effects at the nanometer size, which changes basic material properties These unique properties offer revolutionary means to optimize a variety of prod- ucts, including electronics, textiles, paintings and coatings, pharmaceuticals, and personal care products. And these unique properties mean that nanoscale materials can behave differently in the human body and the environment than the correspond- ing macro-scale materials. Similarly, revolutionary developments during the past two centuries offer caution- ary tales. In the 1800s, gaslights illuminated the Industrial Revolution. Engineers had devised ways to manufacture gas from the pyrolysis of coal or oil. A hundred years later, the residuals of that process stained soils bright blue with cyanide compounds • • CONTENTS 1.1 Potential Rewards 2 1.2 Possible Risks and Public Concerns 3 1.3 About This Book 8 References 9 60198.indb 1 6/12/08 1:31:30 PM [...]... (e.g., Pesticide and Chemical News) Values for 2007 in Figure 1. 1 were estimated by doubling the numbers of articles published between January 1 and June 30, 2007 © 2009 by Taylor & Francis Group, LLC 6 019 8.indb 4 6 /12 /08 1: 31: 31 PM  Introduction 14 00 Articles in Academic Journals 12 00 10 00 800 600 400 200 0 19 97 19 98 19 99 2000 20 01 2002 2003 2004 2005 2006 2007 19 97 19 98 19 99 2000 20 01 2002 2003 2004... containing nanomaterials when the potential benefits are high, even if there are health and safety risks [15 ] Respondents perceived that nanotechnology offered benefits on the order of the benefits from food preservatives and chemical disinfectants, albeit at lower risk [14 ] © 2009 by Taylor & Francis Group, LLC 6 019 8.indb 7 6 /12 /08 1: 31: 42 PM  Nanotechnology and the Environment Table 1. 1 (Continued) Public... Surveyed Knowledge of Nanotechnology 2003 10 05 people over the age of 15 in Great Britain 2004 10 11 Japanese adults in the Tokyo area Year Perception of Risk Other Findings Ref 26% of respondents had heard of nanotechnology and 19 % could define the term 68% of respondents believed nanotechnology would improve life in the future; 13 % believed that the consequences would depend on how nanotechnology was... applied, these materials should be considered hazardous until shown otherwise.” — Greenpeace Environmental Trust, 2003 [10 ] As nanotechnology penetrates the marketplace and receives some press coverage (Figure 1. 1 [11 , 12 ]), the public is just beginning to develop opinions about nanotechnology Those opinions will shape the market for consumer goods containing nanotechnology They may affect the concerns... References 1 United Nations Environment Programme 2007 GEO Year Book 2007: An Overview of our Changing Environment Emerging Challenges — Nanotechnology and the Environment ISBN: 97 8-9 2-8 0 7-2 76 8-9 http://www.unep.org/geo/yearbook/yb2007/ (Accessed February 20, 2007) 2 U.S Environmental Protection Agency 2007 Nanotechnology White Paper EPA /10 0/ B-07/0 01 Prepared for the U.S Environmental Protection... government agencies, NGOs, and corporations engaged in nanotechnology, will help shape the public’s opinions as they evolve Those opinions, in turn, will influence the marketplace and regulatory developments For now, public concerns over © 2009 by Taylor & Francis Group, LLC 6 019 8.indb 5 6 /12 /08 1: 31: 42 PM  Nanotechnology and the Environment Table 1. 1 Public Perceptions Regarding Nanotechnology Based on... terms of the nanotechnology- related information is the highest (54%) among NGO, Industry, government, TV and other media And the government received the lowest trust (22.5%).” [19 ] © 2009 by Taylor & Francis Group, LLC 6 019 8.indb 6 6 /12 /08 1: 31: 42 PM  Introduction Table 1. 1 (Continued) Public Perceptions Regarding Nanotechnology Based on Opinion Polls Year Population Surveyed Knowledge of Nanotechnology. .. 6 019 8.indb 8 6 /12 /08 1: 31: 43 PM Introduction  written in a few years, would contain much more detail and could address technical questions more fully But the community of scientists, engineers, regulators, and the public cannot wait for the results of mature research; given the possible risks and rewards of nanotechnology, we must explore what is known about the ramifications of nanotechnology and the environment. .. Occupational Safety and © 2009 by Taylor & Francis Group, LLC 6 019 8.indb 3 6 /12 /08 1: 31: 31 PM  Nanotechnology and the Environment Health (BAuA), Federal Institute for Risk Assessment (BfR), Federal Environment Agency (UBA), Germany, 2006 [9] • “Knowing the basics about the dangers of new materials is a prerequisite for effective environmental responsibility With cause for concern, and with the precautionary... opinion influences the development of regulations Given the possible weight and effects of public opinions, they are worth examining in this Introduction Public surveys between 2003 and 2007 showed some common themes and some different perceptions regarding nanotechnology around the world Table 1. 1 shows the results of six surveys of people in the U.S., Great Britain, and Japan between 2003 and 2007 This . magazines and academic journals regarding “nanotechnol- ogy,” 19 97–2007 [11 , 12 ]. 6 019 8.indb 5 6 /12 /08 1: 31: 42 PM © 2009 by Taylor & Francis Group, LLC 6 Nanotechnology and the Environment TABLE 1. 1 Public. exposure and worked in the area of regulatory compliance for worker and commu- nity right-to-know legislation. 6 019 8.indb 11 6 /12 /08 1: 31: 30 PM © 2009 by Taylor & Francis Group, LLC 1 1 Introduction Kathleen. Hamblen 6 019 8.indb 5 6 /12 /08 1: 31: 29 PM © 2009 by Taylor & Francis Group, LLC vi Nanotechnology and the Environment Chapter 10 Nanoparticle Use in Pollution Control 225 Kathleen Sellers Chapter 11