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Applications of Analytical Chemistry to Oceanic Carbon Cycle Studies Committee on Oceanic Carbon Ocean Studies Board Commission on Geosciences, Environment, and Resources National Research Council 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 Institute of Medicine. The members of the committee responsible for the report were chosen for their special compe¬ tencies and with regard for appropriate balance. This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The National Academy of Sciences is a private, nonprofit, self-perpetuating society of dis¬ tinguished 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. Frank Press 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 meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. Robert M. White 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 responsibility given to the National Academy of Sciences by its congressional charter to be an advisor to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Kenneth I. Shine 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 the general policies determined by the Academy, the Council has become the principal operat¬ ing agency of both the National Academy of Sciences and the National Academy of Engineer¬ ing 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. Frank Press and Dr. Robert M. White are chairman and vice-chairman, respec¬ tively, of the National Research Council. The work upon which this publication is based was performed pursuant to contracts with the Department of Commerce/NOAA (#50-DGNC-9-00139), the Department of Energy (#DE-FG05- 90ER60934), and the National Science Foundation (#OCE-9021694). Such support does not constitute an endorsement of the views expressed in this report by the sponsors. Library of Congress Catalog No. 93-84415 International Standard Book Number 0-309-04928-8 Additional copies of this report are available from: National Academy Press, 2101 Constitution TARO TAKAHASHI, Lamont-Doherty Earth Observatory, Chair ROBERT BERNER, Yale University PETER BREWER, Monterey Bay Aquarium Research Institute ELLEN DRUFFEL, Woods Hole Oceanographic Institution HUGH DUCKLOW, University of Maryland CHARLES D. KEELING, Scripps Institution of Oceanography JORGE SARMIENTO, Princeton University SHARON SMITH, Brookhaven National Laboratory, Department of Energy ERIC SUNDQUIST, U.S. Geological Survey, Woods Hole PIETER TANS, National Oceanic and Atmospheric Administration DAVID WALT, Tufts University RAY F. WEISS, Scripps Institution of Oceanography JAMES YODER, University of Rhode Island Additional Contributors KENNETH S. JOHNSON, Moss Landing Marine Laboratory PETER JURS, Pennsylvania State University MARK E. MEYERI-IOFF, University of Michigan GEORGE H. MORRISON, Cornell University JANET G. OSTERYOUNG, North Carolina State University RICHARD THOMPSON, University of Maryland EDWARD S. YEUNG, Iowa State University ALBERTO ZIRINO, Naval Ocean Systems Center Staff EDWARD R. URBAN, JR., Staff Officer CARL I. WUNSCH, Massachusetts Institute of Technology, Chair DONALD F. BOESCH, University of Maryland PETER G. BREWER, Monterey Bay Aquarium Research Institution KENNETH BRINK, Woods Hole Oceanographic Institution ROBERT CANNON, Stanford University SALLIE W. CHISHOLM, Massachusetts Institute of Technology BILIANA CICIN-SAIN, University of Delaware WILLIAM CURRY, Woods Hole Oceanographic Institution GORDON EATON, Lamont-Doherty Earth Observatory RANA FINE, University of Miami MICHAEL FREILICH, Oregon State University EDWARD A. FRIEMAN, Scripps Institution of Oceanography ARNOLD L. GORDON, Lamont-Doherty Earth Observatory GORDON GREVE, Amoco Production Company WILLIAM MERRELL, Texas A&M University ARTHUR R.M. NOWELL, University of Washington DENNIS A. POWERS, Stanford University FRANK RICHTER, University of Chicago BRIAN ROTHSCHILD, University of Maryland PAUL STOFFA, University of Texas at Austin Staff MARY HOPE KATSOUROS, Director EDWARD R. URBAN, JR., Staff Officer ROBIN RICE, Staff Associate DAVID WILMOT, Research Associate MARY PECHACEK, Administrative Associate LAVONCYE MALLORY, Senior Secretary AND RESOURCES M. GORDON WOLMAN, The Johns Hopkins University, Chair PATRICK R. ATKINS, Aluminum Company of America PETER S. EAGLESON, Massachusetts Institute of Technology EDWARD A. FRIEMAN, Scripps Institution of Oceanography HELEN M. INGRAM, University of Arizona W. BARCLAY KAMB, California Institute of Technology GENE E. LIKENS, The New York Botanical Garden SYUKURO MANABE, NOAA Geophysical Fluid Dynamics Laboratory JACK E. OLIVER, Cornell University FRANK L. PARKER, Vanderbilt/Clemson University DUNCAN T. PATTEN, Arizona State University RAYMOND A. PRICE, Queen’s University at Kingston, Canada MAXINE L. SAVITZ, Garrett Ceramic Components LARRY L. SMARR, University of Illinois, Urbana-Champaign STEVEN M. STANLEY, The Johns Hopkins University WARREN WASHINGTON, National Center for Atmospheric Research EDITH BROWN WEISS, Georgetown University Law Center IRVIN L. WHITE, Battelle Pacific Northwest Laboratories Staff STEPHEN RATTIEN, Executive Director STEPHEN D. PARKER, Associate Executive Director JEANETTE SPOON, Administrative Officer ROBIN LEWIS, Senior Project Assistant Acknowledgments The committee was aided in preparation of this report by a group o expert contributors—analytical chemists and oceanographers—listed on th committee page of this report. These individuals contributed the technics information about the measurement technologies described in this repot and provided recommendations for actions necessary to bring closer intei actions between the fields of chemical oceanography and analytical chemis try. This report would have been impossible without their efforts. Contents SUMMARY 1 Summary of Recommendations, 2 The Federal Government’s Role, 3 The Role of Academic Scientists, 4 INTRODUCTION 5 Need for New Applications of Analytical Chemistry to Oceanography, 9 OCEANOGRAPHIC MEASUREMENTS 13 Priority Analytes, 13 Priority 1 - Quantifying the Anthropogenic Carbon Input, 18 Priority 2a - Understanding the Biological Pump, 21 Priority 2b - Tracing Water Masses, 23 Priority 3 - Other Analytes of Interest, 24 Present Status of Measurements, 26 The Ideal In Situ Sensor, 31 TECHNOLOGIES FOR CHEMICAL MEASUREMENTS 33 Mass Spectrometry, 33 L-ouiometry, 4U Spectrophotometry, 42 Absorbance, 42 Infrared, 44 Luminescence, 45 Raman, 48 Fiber Optics, 50 Refractive Index, 52 Piezoelectric Mass Sensors, 53 New Chemistry, 54 Immunochemistry, 54 Polymers and New Materials, 56 Recognition Chemistry, 57 Chromatography and Electrophoresis, 61 Flow Injection Analysis and Continuous Flow Analysis, 63 Robotics, 65 Chemometrics, 68 Communications, 70 RECOMMENDATIONS AND IMPLEMENTATION The Federal Government’s Role, 73 Research and Development Needed, 74 Standards and Calibration, 75 Resources for Instrument Development, 75 The Role of Academic Scientists, 78 Priority Setting by the Oceanographic Community, 78 Education and Training, 78 REFERENCES