Atmosphere •Extraterrestrial matter Fertilizers From 238 y in oceanic uwate r BIOTA Land Oceanic wat^r Frosn water I Human Marine ^3 -COAL MINES \ - BENTHIC ORGANISMJy Sediments +-URANIUM MILLING Crust 310 TECHNICAL REPORTS SERIES No, The Environmental Behaviour of Radium Vol.1 im \®pj INTERNATIONAL ATOMIC ENERGY AGENCY, VIENNA, 1990 THE ENVIRONMENTAL BEHAVIOUR OF RADIUM VOLUME 1 The following States are Members of the International Atomic Energy Agency: AFGHANISTAN HAITI PARAGUAY ALBANIA HOLY SEE PERU ALGERIA HUNGARY PHILIPPINES ARGENTINA ICELAND POLAND AUSTRALIA INDIA PORTUGAL AUSTRIA INDONESIA QATAR BANGLADESH IRAN, ISLAMIC REPUBLIC OF ROMANIA BELGIUM IRAQ SAUDI ARABIA BOLIVIA IRELAND SENEGAL BRAZIL ISRAEL SIERRA LEONE BULGARIA ITALY SINGAPORE BYELORUSSIAN SOVIET JAMAICA SOUTH AFRICA SOCIALIST REPUBLIC JAPAN SPAIN CAMEROON JORDAN SRI LANKA CANADA KENYA SUDAN CHILE KOREA, REPUBLIC OF SWEDEN CHINA KUWAIT SWITZERLAND COLOMBIA LEBANON SYRIAN ARAB REPUBLIC COSTA RICA LIBERIA THAILAND COTE DTVOIRE LIBYAN ARAB JAMAHIRIYA TUNISIA CUBA LIECHTENSTEIN TURKEY CYPRUS LUXEMBOURG UGANDA CZECHOSLOVAKIA MADAGASCAR UKRAINIAN SOVIET SOCIALIST DEMOCRATIC KAMPUCHEA MALAYSIA REPUBLIC DEMOCRATIC PEOPLE'S MALI UNION OF SOVIET SOCIALIST REPUBLIC OF KOREA MAURITIUS REPUBLICS DENMARK MEXICO UNITED ARAB EMIRATES DOMINICAN REPUBLIC MONACO UNITED KINGDOM OF GREAT ECUADOR MONGOLIA BRITAIN AND NORTHERN EGYPT MOROCCO IRELAND EL SALVADOR MYANMAR UNITED REPUBLIC OF ETHIOPIA NAMIBIA TANZANIA FINLAND NETHERLANDS UNITED STATES OF AMERICA FRANCE NEW ZEALAND URUGUAY GABON NICARAGUA VENEZUELA GERMAN DEMOCRATIC REPUBLIC NIGER VIET NAM GERMANY, FEDERAL REPUBLIC OF NIGERIA YUGOSLAVIA GHANA NORWAY ZAIRE GREECE PAKISTAN ZAMBIA GUATEMALA PANAMA ZIMBABWE The Agency's Statute was approved on 23 October 1956 by the Conference on the Statute of the IAEA held at United Nations Headquarters, New York; it entered into force on 29 July 1957. The Head quarters of the Agency are situated in Vienna. Its principal objective is "to accelerate and enlarge the contribution of atomic energy to peace, health and prosperity throughout the world". © IAEA, 1990 Permission to reproduce or translate the information contained in this publication may be obtained by writing to the International Atomic Energy Agency, Wagramerstrasse 5, P.O. Box 100, A-1400 Vienna, Austria. Printed by the IAEA in Austria February 1990 TECHNICAL REPORTS SERIES No. 310 THE ENVIRONMENTAL BEHAVIOUR OF RADIUM In two volumes VOLUME 1 INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA, 1990 THE ENVIRONMENTAL BEHAVIOUR OF RADIUM IAEA, VIENNA, 1990 STI/DOC/10/310 ISBN 92-0-125090-8 ISSN 0074-1914 FOREWORD The objective of this publication is to provide an up to date review of the environmental behaviour of radium, including methods for analysis, assessment and control. The need for a reference text on the subject was identified at an early stage of the International Atomic Energy Agency's Co-ordinated Research Programme (CRP) on radium behaviour in relation to uranium mining and milling wastes, which began in 1976. There were two CRPs: (1) The Source, Distribution, Movement and Deposition of Radium in Inland Waterways and Aquifers (1976-1980; final report: IAEA-TECDOC-301, published in 1984). (2) The Environmental Migration of Radium and Other Contaminants Present in Liquid and Solid Wastes from the Mining and Milling of Uranium (1981-1985; final report: IAEA-TECDOC-370, published in 1986). In particular, two CRPs were focused on radium migration in surface and groundwater systems. A forerunner to the present publication was produced at the end of the first CRP (IAEA-TECDOC-301). Although limited in scope and content, the TECDOC attracted the interest of many workers in the field and, as a result of this interest, it became the foundation for the present publication. The present publication had its origin in 1984, towards the end of the second CRP, and has been managed by a small Steering Committee (the members of the Steering Committee and the Advisory Group, as well as the names of the referees, are given in the List of Participants at the end of this report). It was decided that contributors should not be restricted to the members of the CRP, but that partici pation should be invited from known experts in the field. This was seen to have the advantages of ensuring a broader scope for the monograph, rather than being limited entirely to the environmental problems of the uranium mining and milling industry, and of drawing on a larger base of expertise. The Steering Committee reviewed texts as they were received, nominated referees and, at the last (Advisory Group) meeting, made a final review of referees' reports and decided on the acceptance of revised texts. This publication deals with the sources, properties, environmental behaviour and the methods of analysis, control and assessment of 226Ra. It is an outgrowth of Agency programmes directed towards the environmental problems involved in uranium mining and milling. The emphasis in several of the sections reflects these origins. For example, many of the contributions in Volume 2 of this report on technologically enhanced sources of radium (Part 1), methods of control and abatement (Part 2) and the impact on man (Part 3) are concerned with uranium mining and milling. In Volume 1, coverage of the natural distribution (Part 2), analytical methods (Part 3), environmental migration (Part 4) and biological uptake (Part 5), is more general. It is likely that the reader will find the information needed on the environmental behaviour of radium in this report, or will at least find references to other, more appropriate, texts contained in it. Throughout the period of preparation of this publication, the Agency has taken the advice of the members of the Steering Committee. Their support is gratefully acknowledged, in particular, A.R. Williams, P. Benes, R.J. Kirchmann and G.M. Ritcey should be mentioned. The help provided by the referees in reviewing and commenting on the draft contributions is also acknowledged. The project was managed by IAEA staff members J. Molinari (from 1984-1985) and G. Linsley (from 1985 until the present), of the Division of Nuclear Fuel Cycle and Waste Management. EDITORIAL NOTE The papers have been edited by the editorial staff of the IAEA to the extent considered necessary for the reader's assistance. The views expressed remain, however, the responsibility of the named authors or participants. In addition, the views are not necessarily those of the governments of the nominating Member States or of the nominating organizations. Although great care has been taken to maintain the accuracy of information contained in this publication, neither the IAEA nor its Member States assume any responsibility for consequences which may arise from its use. The use of particular designations of countries or territories does not imply any judge ment by the publisher, the IAEA, as to the legal status of such countries or territories, of their authorities and institutions or of the delimitation of their boundaries. The mention of names of specific companies or products (whether or not indicated as registered) does not imply any intention to infringe proprietary rights, nor should it be construed as an endorsement or recommendation on the part of the IAEA. The authors are responsible for having obtained the necessary permission for the IAEA to reproduce, translate or use material from sources already protected by copyrights. Material prepared by authors who are in contractual relation with governments is copyrighted by the IAEA, as publisher, only to the extent permitted by the appropriate national regulations. CONTENTS PART 1. INTRODUCTION 1-1. Radium — A historical introduction A.R. Williams, R.J. Kirchmann 1-2. The chemistry and radiochemistry of radium and the other elements of the uranium and thorium natural decay series 11 J. Molinari, W.J. Snodgrass PART 2. DISTRIBUTION AND GLOBAL CYCLING 2-1. The natural distribution of radium 59 M.A.R. Iyengar 2-2. Sources and the global cycle of radium 129 Z. Jaworowski PART 3. ANALYTICAL METHODS 3-1. Introduction 145 P. Benes 3-2. Methods for measuring radium isotopes: Emanometry 149 H.F. Lucas, F. Markun, R. Boulenger 3-3. Methods for measuring radium isotopes: Alpha particle spectrometry 173 C.J. Bland 3-4. Methods for measuring radium isotopes: Gamma spectrometry 189 A. Canet, R. Jacquemin 3-5. Methods for measuring radium isotopes: Gross alpha and beta counting 205 J.M. Godoy 3-6. Methods for measuring radium isotopes: Liquid scintillation .... 213 W.J. McDowell 3-7. Methods for measuring radium isotopes: Coincidence methods 223 J.M. Godoy 3-8. Methods for measuring radium isotopes: Track detection 229 G. Somogyi 3-9. Sampling and selection of analytical methods for radium 257 G. Smithson 3-10. Speciation procedures 273 P. Benes 3-11. Error analysis: Evaluation of interlaboratory comparisons against a precision model 301 A.R. Williams PART 4. ENVIRONMENTAL MIGRATION 4-1. Radium in soil 323 M.J. Frissel, H. W. Koster 4-2. Radium in groundwater 335 B.L. Dickson 4-3. Radium in (continental) surface water 373 P. Benes 4-4. Radium isotopes in estuaries and coastal water 419 W.S. Moore 4-5. Radium in oceans and seas 429 T. Okubo PART 5. BIOLOGICALUPTAKE 5-1. Radium uptake by marine plants 451 S. Bonotto 5-2. Uptake of radium by marine animals 467 M.A.R. Iyengar, K. Narayana Rao 5-3. Radium uptake by freshwater plants 487 A.R. Williams 5-4. Radium uptake by freshwater invertebrates 509 R.A. Jeffree 5-5. Radium uptake by freshwater fish 529 J. Justyn, B. Havlflc 5-6. Biological uptake of radium by terrestrial plants 545 S.L. Simon, S.A. Ibrahim