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CHALLENGES FOR THE CHEMICAL SCIENCES IN THE 21ST CENTURY NVI NM N ORGANIZING COMMITTEE FOR THE WORKSHOP ON THE ENVIRONMENT COMMITTEE ON CHALLENGES FOR THE CHEMICAL SCIENCES IN THE 21 ST CENTURY BOARD ON CHEMICAL SCIENCES AND TECHNOLOGY DIVISION ON EARTH AND LIFE STUDIES NATIONAL RESEARCH COUNCI L OF THE NATIONAL ACADEMIES THE NATIONAL ACADEMIES PRESS Washington, D.C. www.nap.edu

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THE NATIONAL ACADEMIES PRESS 500 Fifth Street, N.W. Washington, D.C. 20001 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Insti- tute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. Support for this study was provided by the National Research Council, the U.S. Department of Energy (DE-AT-OlOEE41424, BES DE-FG-02-OOER15040, and DE-AT01-03ER15386), the National Science Foundation (CTS-9908440), the Defense Advanced Research Projects Agency (DOD MDA972-01-M-0001), the U.S. Environmental Protection Agency (R82823301 and X83080801), the American Chemical Society, the American Institute of Chemical Engineers, the Camille and Henry Dreyfus Foundation, Inc. (SG00-093), the National Institute of Standards and Technology (NA1341-01-2-1070 and 43NANB010995), the National Institutes of Health (NCI-NO1-OD-4-2139 and NIGMS-NO1-OD-4-2139), the Green Chemistry Institute, and the chemical industry All opinions, findings, conclusions, or recommendations expressed herein are those of the authors and do not necessarily reflect the views of the organizations or agencies that provided support for this project. International Standard Book Number 0-309-08719-8 (Book) International Standard Book Number 0-309-52666-3 (PDF) Additional copies of this report are available from: The National Academies Press 500 Fifth Street, N.W. Box 285 Washington, DC 20055 800-624-6242 202-334-3313 (in the Washington Metropolitan Area) http://www.nap.edu Copyright 2003 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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THE NATIONAL ACADEMIES Advisers to the Nation on Science, Engineering, and Medicine The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the charter granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Bruce M. Alberts is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meet- ing national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. Wm. A. Wulf is president of the National Academy of . ~ . . . engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the respon- sibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Harvey V. Fineberg is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy's purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Bruce M. Alberts and Dr. Wm. A. Wulf are chair and vice chair, respectively, of the National Research Council. www. nationa l-academies.org

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ORGANIZING COMMITTEE FOR THE WORKSHOP ON THE ENVIRONMENT MAR~o J. Mo~NA, Massachusetts Institute of Technology, Co-Chair JOHN H. SEINFEED, California Institute of Technology, Co-Chair PHILIP H. BRODSKY, Pharmacia (retired) JEAN H. Fumed, Pacific Northwest National Laboratory PARRY M. NOREING, RAND Corporation CHR~sT~NE S. S~oANE, General Motors Corporation ISTAH M. WARNER, Louisiana State University L. . parsons MARK A. BARTEAU, University of Delaware (Steering Committee Liaison) A. WEEFORD CASTEEMAN, JR., The Pennsylvania State University (BCST Liaison) JOSEPH M. DES~MoNE, University of North Carolina, Chapel Hill, and North Carolina State University (BCST Liaison) JEFFREY J. S~Ro~A, Eastman Chemical Company (Steering Committee Liaison) ROBERT M. SUSSMAN, Latham & Watkins (BCST Liaison) Staff JENNIFER J. JACK1W, Program Officer SYBIL A. PAIGE, Administrative Associate DOUGLAS J. RABER, Senior Scholar DAVID C. RASMUSSEN, Program Assistant V

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COMMITTEE ON CHALLENGES FOR THE CHEMICAL SCIENCES IN THE 21ST CENTURY RONALD BRESEOW, Columbia University, Co- Chair MATTHEW v. TIRRELL, University of California at Santa Barbara, Co-Chair MARK A. BARTEAU, University of Delaware JACQUELINE K. BARTON, California Institute of Technology CAROLYN R. BERTOZZI, University of California at Berkeley ROBERT A. BROWN, Massachusetts Institute of Technology ALICE p. GAST,1 Stanford University IGNACIO E. GROSSMANN, Carnegie Mellon University JAMES M. MEYER,2 DuPont co. ROYCE w. MURRAY, University of North Carolina at Chapel Hill PAUL J. REIDER, Amgen, Inc. WILLIAM R. ROUSH, University of Michigan MICHAEL L. SHULER, Cornell University JEFFREY J. SITROLA, Eastman Chemical Company GEORGE M. WHITESIDES ~ Harvard University PETER G. WOLYNES, University of California, San Diego RICHARD N. ZARE, Stanford University Stay JENNIFER J. JACK1W, Program Officer CHRISTOPHER K. MURPHY, Program Of fleer SYBIL A. PAIGE, Administrative Associate DOUGLAS J. RABER, Senior Scholar DAVID c. RASMUSSEN, Program Assistant iCommittee member until July 2001; subsequently the Board on Chemical Sciences and Tech- nology (BCST) liaison to the committee in her role as BCST co-chair. 2Committee member until March 2002, following his retirement from DuPont. v

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BOARD ON CHEMICAL SCIENCES AND TECHNOLOGY ALICE p. GAST, Massachusetts Institute of Technology, Co-Chair WILLIAM KEEMPERER, Harvard University, Co- Chair ARTHUR I. BIENENSTOCK, Stanford University A. WEEFORD CASTEEMAN, JR., The Pennsylvania state University ANDREA w. CHOW, Caliper Technologies Corp. THOMAS M. CONNALLY, JR., E. I. du Pont de Nemours & co. JEAN DE GRAEVE, Institut de Pathologic, Liege, Belgium JOSEPH M. DESIMONE, University of North Carolina, Chapel Hill, and North Carolina state University CATHERINE FENSEEAU, University of Maryland JON FRANKLIN, University of Maryland MARY L. GOOD, University of Arkansas, Little Rock RICHARD M. GROSS, Dow Chemical Company NANCY B. JACKSON, Sandia National Laboratory SANGTAE KIM, E1i Lilly and Company THOMAS J. MEYER, Los Alamos National Laboratory PAUL J. REIDER, Amgen, Inc. ARNOLD F. STANCEEE, Georgia Institute of Technology ROBERT M. SUSSMAN, Latham & Watkins JOHN c. TULLY, Yale University CHI-HUEY WONG, Scripps Research Institute Stay JENNIFER J. JACK1W, Program Officer CHRISTOPHER K. MURPHY, Program Officer SYBIL A. PAIGE, Administrative Associate DOUGLAS J. RABER, Senior Scholar DAVID c. RASMUSSEN, Program Assistant ERIC L. SHIPP, Postdoctoral Associate DOROTHY ZOEANDZ, Director v!

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Preface The Workshop on the Environment was held in Irvine, California, on No- vember 17-19, 2002. This workshop was the third in a series of six workshops that make up the study Challenges for the Chemical Sciences in the 21 st Century. The task for each of the workshops was defined as follows: Each workshop and its subsequent report will address a series of com- mon themes: Discovery: Identify major discoveries or advances in the chemical sci- ences during the last several decades. Interfaces: Identify the major discoveries and challenges at the interfaces between chemistry/chemical engineering and such areas as biology, environmen- tal science, materials science, medicine, and physics. Challenges: Identify the grand challenges that exist in the chemical scat ences. . Infrastructure: Identify the issues and opportunities that exist in the chemi- cal sciences to improve the infrastructure for research and education, and demon- strate the value of these activities to society. The Workshop on the Environment brought together a diverse group of participants (Appendix F) from the chemical sciences who were addressed by invited speakers in plenary session on a variety of issues and challenges for the chemical sciences as they relate to environmental science and technology (Ap- pendix C). These presentations served as a starting point for discussions and com- ments by the participants. The workshop participants were then divided into small groups that met periodically during the workshop to further discuss and analyze . . via

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. . . vile PREFACE the relevant issues. Each group reported its discussions to the workshop as a whole. This report is intended to reflect the concepts discussed and opinions ex- pressed at the Workshop on the Environment and is not intended to be a compre- hensive overview of all of the potential challenges that exist for the chemical sciences in the areas of environmental science and technology. The organizing committee has used this input from workshop participants as a basis for the con- clusions expressed in this report. However, sole responsibility for these conclu- sions rests with the organizing committee. Although much progress has been achieved toward detailed mechanistic understanding in all environmental sciences, the greatest advances appear to have occurred in the atmospheric chemistry field, reflecting most likely the greater complexity of aquatic and terrestrial systems and their biological components. This study was conducted under the auspices of the National Research Council's Board on Chemical Sciences and Technology, with assistance provided by its staff. The committee acknowledges this support. A number of our colleagues across the chemical sciences community pro- vided the committee with helpful input. The committee thanks Patrick G. Hatcher, Robert G. Keesee, Karl T. Mueller, and Paul Ziemann. Mario J. Molina and John H. Seinfeld, Co-Chairs, Organizing Committee for the Workshop on the Environment Challenges for the Chemical Sciences in the 21st Century

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Acknowledgment of Reviewers This report has been reviewed in draft form by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures ap- proved by the National Research Council's (NRC's) Report Review Committee. The purpose of this independent review is to provide candid and critical com- ments that will assist the institution in making the published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and responsiveness to the study charge. The review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their participation in the review of this report: Heather C. Allen, The Ohio State University Liese Dallbauman, Gas Technology Institute Thom H. Dunning, Jr., Oak Ridge National Laboratory and University of r ~ . . ennessee William H. Glaze, Oregon Health & Science University George M. Hornberger, University of Virginia Henry T. Kohlbrand, The Dow Chemical Company Stephen G. Maroldo, Rohm and Haas Company Peggy O'Day, University of California, Merced Ed Young, Iowa State University Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recommendations nor did they see the final draft of the report before its release. Six

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x ACKNOWLEDGMENT OF REVIEWERS The review of this report was overseen by George E. Keller II (Union Carbide, retired). Appointed by the National Research Council, he was responsible for making certain that an independent examination of this report was carried out in accordance with institutional procedures and that all review comments were care- fully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution.

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Contents EXECUTIVE SUMMARY INTRODUCTION SUCCESSES AND DISCOVERIES IN ENVIRONMENTAL CHEMICAL SCIENCE Analytical Capabilities, 10 Fundamental Chemical Science, 11 Models and Databases, 12 Pollution Control, Remediation, and Purification, 12 Pollution Prevention: Synthesis, Manufacturing, and Process Advances, 15 Identification of Problems, 17 Atmosphere, 17 Water, 20 Soil, 20 Interdisciplinary Discoveries, 20 7 10 3 CHALLENGES IN ENVIRONMENTAL CHEMICAL SCIENCE 22 Fundamental Understanding, 25 Human Influence on the Natural Environment, 25 Water and Sediment Chemistry, 26 Gas-to-Particle Conversion and Combustion Aerosol Formation, 30 Putting It All Together: Understanding Biogeochemical Cycles, 32 x~

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xt! Instrumentation and Research Tools, 33 Measurement Tools, 35 Modeling, Simulation, and Computational Chemistry, 41 Approaches to Solutions, 44 Pollution Prevention: Green Process Technology, 44 Remediation, 46 Cost-effectiveness, 48 Interfaces and Infrastructure, 48 4 CONCLUSIONS AND KEY OPPORTUNITIES APPENDIXES STATEMENT OF TASK B BIOGRAPHIES OF THE ORGANIZING COMMITTEE MEMBERS C WORKSHOP AGENDA D WORKSHOP PRESENTATIONS James G. Anderson, 66 Thomas W. Asmus, 75 Ruben G. Carbonell, 80 Uma Chowdhry, 85 Barry Dellinger, 97 David A. Dixon, 102 William H. Farland, 113 Janet G. Hering, 119 Charles E. Kolb, 127 Francis M.M. Morel, 136 Michael K. Stern, 140 Mark H. Thiemens, 144 E BIOGRAPHIES OF WORKSHOP SPEAKERS F WORKSHOP PARTICIPANTS G REPORTS FROM BREAKOUT SESSION GROUPS Discovery, 158 Interfaces, 162 Challenges, 168 Infrastructure, 172 H LIST OF ACRONYMS CONTENTS 50 57 58 62 149 155 158 176