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Stable Isotope Hydrology

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Stable Isotope Hydrology TECHNICAL REPORTS SERIES No. Stable Isotope Hydrology Deuterium and Oxygen-18 in the Water Cycle „ INTERNATIONAL ATOMIC ENERGY AGENCY. VIENNA. 1981 Cover picture: Allegory of Water, etching by CRISTOFORO DALL’ACQUA (1734-1787). By courtesy of Collezione Libreria Marsilio, Padua, Italy. STABLE ISOTOPE HYDROLOGY Deuterium and Oxygen-18 in the W ater Cycle The following States are Members of the International Atomic Energy Agency' AFGHANISTAN H O L Y SEE PHILIPPINES ALBANIA HUNGARY POLAND ALGERIA ICE LAN D PORTUGAL ARGENTINA INDIA QATAR AUSTRALIA INDONESIA ROMANIA AUSTRIA IRAN SAUDI ARABIA BANGLADESH IRAQ SENEGAL BELGIUM IRELAND SIERRA LEONE BOLIVIA ISRAEL SINGAPORE BRAZIL ITALY SOUTH AFRICA BULGARIA IVORY COAST SPAIN BURMA JAMAICA SRI L A N K A BYELORUSSIAN SOVIET JAPAN SUDAN SOCIALIST REPUBLIC JORDAN SWEDEN C A N A D A KENYA SWITZERLAND CH ILE KOREA, REPUBLIC OF SYRIAN ARAB REPUBLIC C O LO M B IA K UW AIT THAILAND COSTA RICA LEBANON TUNISIA CU B A LIBERIA TURKEY CYPRUS LIBYAN ARAB JAMAHIRIYA UGANDA CZECHOSLOVAKIA LIECHTENSTEIN UKRAINIAN SOVIET SOCIALIST DEMOCRATIC KAMPUCHEA LUXEMBOURG REPUBLIC D E M O C R A TIC PEOPLE’ S MADAGASCAR UNION OF SOVIET SOCIALIST REPUBLIC OF KOREA MALAYSIA REPUBLICS DENMARK MALI UNITED ARAB EMIRATES DOMINICAN REPUBLIC M AU RITIU S UNITED KINGDOM OF GREAT ECUADOR MEXICO BRITAIN AND NORTHERN EGYPT MONACO IR E L A N D EL SALVADOR MONGOLIA UNITED REPUBLIC OF ETHIOPIA MOROCCO C A M E R O O N FINLAND NETHERLANDS UNITED REPUBLIC OF FRANCE NEW ZEALAND T A N Z A N IA GABON NICARAGUA UNITED STATES OF AMERICA GERMAN DEMOCRATIC REPUBLIC NIGER U R U G U A Y GERMANY, FEDERAL REPUBLIC OF NIGERIA VE N E ZU E L A GHANA NORWAY V IE T NAM GREECE PAKISTAN YUGOSLAVIA GUATEMALA PANAMA ZA IR E HAITI PARAGUAY ZAMBIA PERU 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 Headquarters 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, 1981 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 December 1981 TEC H N IC A L REPORTS SERIES No. 210 STABLE ISOTOPE HYDROLOGY D euterium and Oxygen-18 in the W ater Cycle A MONOGRAPH PREPARED UNDER THE AEGIS OF THE IAEA/UNESCO WORKING GROUP ON NUCLEAR TECHNIQUES IN HYDROLOGY OF THE INTERNATIONAL HYDROLOGICAL PROGRAMME Scientific editors: J.R. Gat, R. Gonfiantini INTERNATIONAL ATOMIC ENERGY AGENCY VIENNA, 1981 STABLE ISOTOPE HYDROLOGY: DEUTERIUM AND OXYGEN-18 IN THE WATER CYCLE IAEA, VIENNA, 1981 •STI/DOC/10/210 ISBN 92-0-145281-0 FOREWORD The preparation of this monograph was recommended by the IAEA/ UNESCO Working Group on Nuclear Techniques in Hydrology of the Inter­ national Hydrological Programme at its session in 1973. As was originally suggested by the Working Group, this monograph is mainly intended for hydrologists, hydrogeologists and geochemists who want to become acquainted, rapidly but in some]detail, with the theoretical background of stable isotope fractionation in natural physico-chemical processes involving fresh water, with the isotopic differences actually encountered in natural waters and with their use for practical hydrological purposes. Throughout the monograph, and in particular in the last chapter, a series of examples are discussed, giving the results obtained with stable isotope techniques in current hydrological and hydrogeological investigations or, more generally, in water resources explora­ tion and assessment! One chapter is also dedicated to the techniques for measuring D/H and 180/160 ratios in water. It is hoped that the book will fill a gap in the scientific literature. The sponsoring' organizations would like to thank all the authors who 0 contributed to this monograph: B. Amason (Iceland), J.Ch. Fontes (France), P. Fritz (Canada), J.R. Gat (Israel), R. Gonfiantini (IAEA), M. Magaritz (Israel), C. Panichi (Italy), B.R. Payne (IAEA) and Y. Yurtsever (IAEA). Thanks are also due to W. Dansgaard (Denmark), L. Merlivat (France), K.O. Munnich (Federal Republic of Germany) and E. Roth (France), who read and criticized parts of the manuscript and made fruitful suggestions for improvement of the text. The members of the IAEA/UNESCO Working Group on Nuclear Tech­ niques in Hydrology participated in the preparation of the monograph and gave generously of their advice and encouragement. They are: G.H. Davis (USA), V.T. Dubinchuk (USSR), E. Eriksson (Sweden), V.I. Ferronsky (USSR), J.Ch. Fontes (France), W.H. Gilbrich (UNESCO), J. Guizerix (France), J.S.G. McCulloch (United Kingdom), H. Moser (Federal Republic of Germany), K.O. Munnich (Federal Republic of Germany), A. Nir (Israel), F.J. Pearson, Jr. (USA), S.M. Rao (India), D.B. Smith (United Kingdom), R. Tiburtini (UNESCO) and E. Tongiorgi (Italy). The present and past staff of the Agency’s Section of Isotope Hydrology helped in many ways, in particular W. Giggenbach and C.B. Taylor. In addition to these, the scientific editors would like to thank their colleague G.M. Zuppi, whose assistance and co-operation has been most useful. The Nier mass spectrometer, 1947 (by courtesy of Professor A.O. Nier). CONTENTS CHAPTER 1. HISTORICAL INTRODUCTION....................................... 1 (J.R. Gat) 1.1. Discovery of the oxygen isotopes................................................... 1 1.2. Discovery of deuterium................................................................. 2 1.3. Early measurement techniques...................................................... 3 1.4. Early work on isotope hydrology................................................... 3 References to Chapter 1 ......................................................................... 5 CHAPTER 2. PROPERTIES OF THE ISOTOPIC SPECIES OF WATER: THE ‘ISOTOPE EFFECT’ ................................................ 7 (J.R. Gat) 2.1. The isotopes of hydrogen and oxygen: Nomenclature and definitions................................................................................... 7 2.2. Physical and transport properties ................................................... 7 2.3. Equilibrium isotope effects............................................................ 9 2.4. Kinetic isotope effects.................................................................. 17 References to Chapter 2 ......................................................................... 18 CHAPTER 3. ISOTOPIC FRACTIONATION.......................................... 21 (J.R. Gat) 3.1. General....................................................................................... 21 3.2. Equilibrium processes................................................................... 22 3.3. Non-equilibrium fractionation: Evaporation of surface waters........ 25 References to Chapter 3 ......................................................................... 32 CHAPTER 4. THE 5-NOTATION AND THE MASS-SPECTROMETRIC MEASUREMENT TECHNIQUES...................................... 35 (R. Gonfiantini) 4.1. The 6-notation for expressing stable isotope ratio variations............ 35 4.1.1. Definition of 5................................................................... 35 4.1.2. The reference standard: SMOW and V-SMOW...................... 36 4.1.3. Other water samples for intercalibration............................... 38 4.1.4. The PDB reference standard............................................... 40 4.1.5. References and notations other than 5 ................................. 42 4.2. The Nier mass spectrometer.......................................................... 43 4.2.1. Ion source........................................................................ 45 4.2.2. Magnetic field................................................................... 46 4.2.3. Ion collectors.................................................................... 46 4.2.4. Double inlet system.......................................................... 47 4.2.5. Measuring the difference between the isotopic ratios of reference and sample.......................................................... 50 4.2.6. Instrumental corrections..................................................... 53 4.2.7. Corrections specific to C02 isotopic analyses...................... 55 4.2.8. Corrections specific to H2 isotopic analyses......................... 57 4.3. Determination of the oxygen isotope composition of natural waters......................................................................................... 60 4.3.1. The C02 equilibration method .......................................... 60 4.3.1.1. Sample preparation .............................................. 60 4.3.1.2. Correction for equilibration with C02 .................... 63 4.3.1.3. Correction for salts dissolved in water.................... 64 4.3.1.4. Example of 6iaO calculation for a water sample....... 66 4.3.1.5. 5180 calculation using two different laboratory standards............................................................. 69 4.3.2. Other methods of determining the oxygen isotope composition of natural waters............................................. 69 4.3.2.1. Method of reduction of water over graphite............ 70 4.3.2.2. Method of water fluorination................................. 70
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