Douglas G. Brookins. Eh-pH Diagrams. for. Geochemistry. With 98 Figures and 61 Tables. Springer -Verlag Berlin Heidelberg New York London Paris Tokyo

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2 Douglas G. Brookins Eh-pH Diagrams for Geochemistry With 98 Figures and 61 Tables Springer -Verlag Berlin Heidelberg New York London Paris Tokyo

3 Dr. Douglas G. Brookins Department of Geology University of New Mexico Albuquerque. NM 87 t 3 t. USA ISBN-13 : DOl: / e-isbn-13 : Library of Congress Cataloging-in-Publication Data. Brookins, Douglas G. Eh-pH diagrams for geochemistry. Includes Index. I. Geochemistry, Analytic. 2. Hydrogen-ion concentration. l. Title. QE516.3.B This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, re-use of illustrations, recitation, broadcasting, reproduction on microfilms or in other ways, and storage in data banks. Duplication of this publication or parts thereof is only permitted under the provisions of the German Copyright Law of September 9, 1%5, in its version of June 24, 1985, and a copyright fee must always be paid. Violations fall under the prosecution act of the German Copyright Law. Springer-Verlag Berlin Heidelberg 1988 Softcover reprint of the hardcover 1st edition 1988 The use of registered names, trademarks. etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. 1Ypesetting: K+V Fotosatz GmbH, Beerfelden ()"543210

4 Preface Eh-pH diagrams have been in moderate use since the late 1950s in the fields of geochemistry, metallurgy, and chemical engineering; more recently, they have been popular in addressing aspects of radioactive and other hazardous waste disposal problems. Yet in many instances these diagrams are outdated and incomplete. In other cases the behaviour of the chemical elements in pure water is considered, yet no attention is given to the possible presence of dissolved sulfur and/or carbon dioxide species. In still other cases the data used are old, and lead to erroneous diagrams. In this book I have attempted to prepare generic Eh-pH diagrams for the chemical elements and their species in the presence of water and with, where relevant, the presence of dissolved sulfur and carbon dioxide. Some 75 elements are covered here; only the alkali elements, the noble gases, and a few radioactive elements for which there are insufficient thermodynamic data, have been omitted. I include here those elements with more than one valance in natural waters, and those monovalent elements are sensitive to sulfide-sulfate redox conditions. In addition, I have plotted the stability fields of solids and aqueous species of phdependent only elements in Eh-pH space so that the reader may compare these conditions for a great variety of species stable under the Eh-pH limits of water. For many years I have been bothered by the fact that Eh-pH diagrams, and the data used to construct them, are scattered throughout a large volume of literature. This book attempts to gather all the good to very good thermodynamic data useful for the 75 elements considered, and to construct the appropriate Eh-pH diagrams. A brief text accompanies each element that is designed to explain the diagram for that element, but is not in any sense intended to be a comprehensive discussion of the geochemistry of the elements. In many cases I have added a brief text on the importance of various elements to problems of hazardous waste disposal. The diagrams have been constructed for 25 C and 1 bar pressure conditions. A forthcoming project will address Eh-pH conditions at higher temperatures and pressures, as I do not feel the thermodynamic data base is adequate to do this yet for many elements. The thermodynamic data base used for this book is, admittedly, uneven, in that some older and less precise data are used as well as recent and high quality data. This, of course, is necessary to allow the calculation of the diagrams, but will result in revisions of many of the diagrams as never and more refined data become available. The goal of this book is also to allow the reader an opportunity to inspect the role of redox reactions in nature, and to compare various mineral assemblages and/or aqueous species in Eh-pH space. This will allow a greater appreciation of the utilization of these diagrams in geochemistry and other fields, especially since it is all packaged in one place. Albuquerque, February 1988 Douglas G. Brookins v

5 Acknowledgments Modern Eh-pH diagrams are built on the foundation provided by M. Pourbaix (pourbaix 1966) and R.M. Garrels (Garrels 1959; Garrels and Christ 1965), and I respectfully and gratefully acknowledge their monumental efforts on this subject. Partial fmancial support was made available for some of this project by the Oak Ridge National Laboratory, where I spent part of my sabbatical leave, and from the University of New Mexico Research Allocations Committee. Mr. D. Lopez drafted many of the figures. This project could not have been completed without the painstaking yet expeditious efforts of Ms. Judith Binder of the University of New Mexico, who prepared the final manuscript and co-checked proofs. Her efforts are especially appreciated. VI

6 Contents Introduction... 1 Previous Studies... 2 Eh Versus pe... 2 Eh-pH Diagrams: Background... 3 lypes of Boundaries in Eh-pH Space... 4 Thermodynamic Data and Uncertainties... 7 Use of Eh-pH Diagrams at Other Temperatures and Pressures... 8 Stability Limits for Water Natural Waters... 9 Presentation of the Elements and Elements Covered Iodine and Other Halides Iron Sulfur Palladium Selenium Rhodium Tellurium Ruthenium Polonium Platinum Nitrogen Iridium Phosphorus Osmium Arsenic Manganese Antimony Technetium Bismuth Rhenium Carbon Chromium Silicon Molybdenum Germanium Tungsten Tin Vanadium Lead Niobium Boron Tantalum Aluminum Titanium Gallium Zirconium Indium Hafnium Thallium Scandium Zinc Yttrium and the Rare Cadmium Earth Elements (REE) Mer.cury Americium Copper Plutonium Silver Neptunium Gold Uranium Nickel Thorium Cobalt Beryllium VII

7 Magnesium Calcium Strontium Barium Radium References Subject Index VIII

ICP/ICP-MS Standards. High Purity Standards for ICP/ICP-MS

ICP/ICP-MS Standards. High Purity Standards for ICP/ICP-MS ICP/ICP-MS Fisher Brand AA/ICP MS Fisherbrand ICP/ICP-MS Catalog No. Catalog No. Concentrationion Size ml Concentration Size ml 36 102 7820 Aluminum 36 102 7821 Antimony 36 102 7823 Arsenic 36 102 7824