CHEMICAL REFERENCE MATERIALS

SETTING THE STANDARDS FOR OCEAN SCIENCE

Committee on Reference Materials for Ocean Science

Ocean Studies Board

Division on Earth and Life Studies

NATIONAL RESEARCH COUNCIL OF THE NATIONAL ACADEMIES

THE NATIONAL ACADEMIES PRESS
Washington, D.C. www.nap.edu



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Chemical Reference Materials: Setting the Standards for Ocean Science CHEMICAL REFERENCE MATERIALS SETTING THE STANDARDS FOR OCEAN SCIENCE Committee on Reference Materials for Ocean Science Ocean Studies Board Division on Earth and Life Studies NATIONAL RESEARCH COUNCIL OF THE NATIONAL ACADEMIES THE NATIONAL ACADEMIES PRESS Washington, D.C. www.nap.edu

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Chemical Reference Materials: Setting the Standards for Ocean Science THE NATIONAL ACADEMIES PRESS 500 Fifth Street, NW Washington, DC 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 Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. This material is based upon work supported by the National Science Foundation (NSF grant number OCE-0096792). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. International Standard Book Number: 0-309-08500-4 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 2002 by the National Academy of Sciences. All rights reserved. Printed in the United States of America.

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Chemical Reference Materials: Setting the Standards for Ocean Science 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 meeting 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 responsibility 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.national-academies.org

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Chemical Reference Materials: Setting the Standards for Ocean Science This report is dedicated to the memory of our colleague John Hedges and his many contributions to oceanography and organic geochemistry. (1946-2002)

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Chemical Reference Materials: Setting the Standards for Ocean Science COMMITTEE ON REFERENCE MATERIALS FOR OCEAN SCIENCE ANDREW DICKSON Chair, Scripps Institution of Oceanography, La Jolla, California ROBERT BIDIGARE, University of Hawaii, Honolulu JOHN HEDGES, University of Washington, Seattle* KENNETH JOHNSON, Monterey Bay Aquarium Research Institute, Moss Landing, California DENISE LEBLANC, National Research Council of Canada, Nova Scotia, Canada CINDY LEE, Stony Brook University, Stony Brook, New York ANN McNICHOL, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts FRANK MILLERO, University of Miami, Miami, Florida JAMES MOFFET, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts WILLARD MOORE, University of South Carolina, Columbia EDWARD PELTZER, Monterey Bay Aquarium Research Institute, Moss Landing, California STAN VAN DEN BERG, University of Liverpool, United Kingdom Staff JOANNE BINTZ, Ocean Studies Board, Study Director DARLA KOENIG, Ocean Studies Board, Senior Project Assistant The work of this committee was overseen by the Ocean Studies Board. *   Deceased July 2002

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Chemical Reference Materials: Setting the Standards for Ocean Science OCEAN STUDIES BOARD NANCY RABALAIS (Chair), Louisiana Universities Marine Consortium, Chauvin ARTHUR BAGGEROER, Massachusetts Institute of Technology, Cambridge JAMES COLEMAN, Louisiana State University, Baton Rouge LARRY CROWDER, Duke University, Beaufort, North Carolina G. BRENT DALRYMPLE, Oregon State University RICHARD B. DERISO, Scripps Institution of Oceanography, La Jolla, California EARL DOYLE, Shell Oil (Retired), Sugar Land, Texas ROBERT DUCE, Texas A&M University, College Station WAYNE R. GEYER, Woods Hole Oceanographic Institution, Massachusetts D. JAY GRIMES, University of Southern Mississippi, Ocean Springs MIRIAM KASTNER, Scripps Institution of Oceanography, La Jolla, California CINDY LEE, Stony Brook University, Stony Brook, New York RALPH S. LEWIS, Connecticut Geological Survey, Hartford BONNIE MCCAY, Rutgers University, New Brunswick, New Jersey JULIAN P. McCREARY, Jr., University of Hawaii, Honolulu JACQUELINE MICHEL, Research Planning, Inc., Columbia, South Carolina RAM MOHAN, Gahagan & Bryant Associates, Inc., Baltimore, Maryland SCOTT NIXON, University of Rhode Island, Narragansett JON SUTINEN, University of Rhode Island, Kingston NANCY TARGETT, University of Delaware, Lewes PAUL TOBIN, Armed Forces Communications and Electronics Association, Fairfax, Virginia Staff MORGAN GOPNIK, Director SUSAN ROBERTS, Senior Program Officer DAN WALKER, Senior Program Officer JOANNE C. BINTZ, Program Officer JENNIFER MERRILL, Program Officer TERRY SCHAEFER, Program Officer JOHN DANDELSKI, Research Associate ROBIN MORRIS, Financial Officer

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Chemical Reference Materials: Setting the Standards for Ocean Science SHIREL SMITH, Office Manager JODI BACHIM, Senior Project Assistant NANCY CAPUTO, Senior Project Assistant DENISE GREENE, Senior Project Assistant DARLA KOENIG, Senior Project Assistant JULIE PULLEY, Project Assistant ALISON SCHRUM, Project Assistant

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Chemical Reference Materials: Setting the Standards for Ocean Science Acknowledgments The committee would like to acknowledge the contributions and support of its sponsor, the National Science Foundation. This report was also greatly enhanced by the input of the invited representatives from government agencies with experience in oceanic reference materials who gave talks at the planning meetings: Don Rice, National Science Foundation; Adriana Cantillo, National Oceanic and Atmospheric Administration; John Fassett, National Institute of Standards and Technology; and Scott Willy, National Research Council of Canada. Input was also solicited through e-mail from a broad cross-section of the marine community world-wide, with help from the American Society of Limnology and Oceanography. This report has been reviewed in draft form by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the National Research Council’s Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the institution in making its 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 review of this report: Dr. Richard T. Barber (Duke University), Dr. Edward Boyle (Massachusetts Institute of Technology), Dr. Thomas S. Bianchi (Tulane University), Dr. Katherine H. Freeman (Penn State), Dr. Dennis A. Hansell (University

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Chemical Reference Materials: Setting the Standards for Ocean Science of Miami), Dr. Susan Libes (Coastal Carolina University), Dr. Steven E. Lohrenz (University of Southern Mississippi), Dr. Jay Pinckney (Texas A&M University), and Dr. Thomas Torgersen (University of Connecticut). 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. The review of this report was overseen by Dr. Kenneth H. Brink, Woods Hole Oceanographic Institution. 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 carefully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution. Maggie Sheer provided valuable assistance with copy-editing. The artwork and cover were designed by Van Nguyen.

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Chemical Reference Materials: Setting the Standards for Ocean Science Preface Chemical Reference Materials: Setting the Standards for Ocean Science is part of an evolving body of work being conducted by scientists and research sponsors interested in ensuring the quality control of oceanographic data. Chemical data collected during ongoing and future global oceanographic studies and time-series efforts must be comparable over time and among laboratories. A wide range of scientific opportunities will result from such long-term observations, such as a better understanding of the role of ocean chemistry in climate dynamics; also improved stewardship of the ocean’s natural resources. The large investment of time, money, and equipment needed for such chemical oceanographic measurements demands that the data collected be of the highest quality achievable. Chemical reference materials play a critical role in the verification of the quality of these measurements. To this end, the National Research Council Committee on Reference Materials for Ocean Science (Appendix A) was charged with the difficult tasks of identifying the most critically needed reference materials, and recommending the most appropriate approaches for their development. The committee gave careful consideration to keeping their recommendations within the context of current and future oceanographic efforts throughout this process. Committee members were chosen for their wide variety of scientific expertise and experience in production and certification of reference materials. In addition, members with proficiency in the use of reference materials for the analysis of trace metals, radioisotopes, nutrients, carbon, and organic matter were represented. The committee met on four sepa-

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Chemical Reference Materials: Setting the Standards for Ocean Science rate occasions to discuss and to plan this report. One of these meetings was a workshop held in September of 2001 in Islamorada, Florida at which about 30 invitees from the ocean science community (Appendix B) listened to keynote presentations, and discussed which reference materials, if available, would enhance the ability of ocean scientists to address key research topics. In addition, workshop participants were asked to identify which materials they felt represented the highest priority for development and research. Workshop participants, posters, and discussions helped set the stage for the fruitful committee discussions that followed. The committee also relied on written comments provided by workshop participants, on an email survey of members of the American Society of Limnology and Oceanography, and on the National Science Foundation’s report on the Future of Ocean Chemistry in the U.S. (1999), which set research priorities in marine chemistry. As this report went to press, the committee was saddened by the unexpected death of a committee member, Dr. John Hedges. Dr. Hedges’ extensive and thoughtful input to this report reflected his deep interest in this topic and his hopes that this report would meaningfully further the use of reference materials in the ocean sciences. His death is a great loss to the many individuals who knew him personally and to the chemical oceanography community as a whole. Committee on Reference Materials for Ocean Science

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Chemical Reference Materials: Setting the Standards for Ocean Science Contents     EXECUTIVE SUMMARY   1 1   INTRODUCTION   7     Background to the Study,   7     Benefits of Chemical Reference Materials to Ocean Science,   11     Report Structure,   14 2   IMPROVING CHEMICAL OCEANOGRAPHIC DATA   17     Matrix Dependence of Reference Materials,   17     How Reference Materials Work,   18     Limitations of Reference Materials,   20     Benefits of Reference Materials,   22 3   SEAWATER   29     Nutrients,   29     Trace Metals,   33     Radionuclides,   37     Carbon Isotopes in Dissolved Inorganic Carbon (DIC),   41     Dissolved Organic Matter (DOM),   43     Dissolved Gases,   46

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Chemical Reference Materials: Setting the Standards for Ocean Science 4   CHEMICAL REFERENCE MATERIALS FOR THE ANALYSIS OF PARTICULATE AND SEDIMENT SAMPLES   47     Rationale for Sediment and Particulate Matter Analysis,   47     Influence of Matrix Composition on Chemical Determinations,   57     Reference Materials Currently Available for the Analysis of Sediment and Particulate Samples,   66     Recommended Reference Materials,   72     Potential Long-Term Needs for Additional Reference Materials,   75 5   PRODUCTION AND DISTRIBUTION OF CHEMICAL REFERENCE MATERIALS   77     Introduction,   77     Requirements of Reference Materials,   78     Reference Material and Certified Reference Material Production,   78     Methods Employed to Characterize Reference Materials and Certified Reference Materials,   81     Preparation of Recommended New Reference Materials and Certified Reference Materials for Ocean Science,   82     Costs of Producing and Distributing Reference Materials and Certified Reference Materials,   85     A Strategy for the Production of New Reference Materials for the Ocean Sciences,   86     Education,   87 6   CONCLUSIONS AND RECOMMENDATIONS   89     Recommendations for Reference Materials for Ocean Science,   90     Recommendations for Community Participation,   95     Statement of Top Priorities,   96     REFERENCES CITED   99     APPENDIXES     A   COMMITTEE AND STAFF BIOGRAPHIES   111 B   WORKSHOP PARTICIPANTS   115 C   GLOSSARY   116 D   ACRONYM LIST AND CHEMICAL TERMINOLOGY   122 E   REFERENCE MATERIALS LISTED WITHIN THIS REPORT   126