Color profile: Disabled Composite 150 lpi at 45 degrees Fluorides in the Environment A4662 - Weinstein - Vouchers - VP10 #K.prn 1 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:50 PM Color profile: Disabled Composite 150 lpi at 45 degrees A4662 - Weinstein - Vouchers - VP10 #K.prn 2 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:50 PM Color profile: Disabled Composite 150 lpi at 45 degrees Fluorides in the Environment Effects on Plants and Animals Professor L.H. Weinstein Boyce Thompson Institute for Plant Research Tower Road Ithaca NY 14853 USA and Professor A. Davison School of Biology Ridley Building University of Newcastle Newcastle upon Tyne NE1 7RU UK CABI Publishing A4662 - Weinstein - Vouchers - VP10 #K.prn 3 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:51 PM Color profile: Disabled Composite 150 lpi at 45 degrees CABI Publishing is a division of CAB International CABI Publishing CABI Publishing CAB International 875 Massachusetts Avenue Wallingford 7th Floor Oxon OX10 8DE Cambridge, MA 02139 UK USA Tel: +44 (0)1491 832111 Tel: +1 617 395 4056 Fax: +44 (0)1491 833508 Fax: +1 617 354 6875 E-mail: [email protected] E-mail: [email protected] Web site: www.cabi-publishing.org ©L.H. Weinstein and A. Davison 2004. All rights reserved. No part of this publication may be reproduced in any form or by any means, electronically, mechanically, by photocopying, recording or otherwise, without the prior permission of the copyright owners. A catalogue record for this book is available from the British Library, London, UK. Library of Congress Cataloging-in-Publication Data Weinstein, Leonard H., 1926- Fluorides in the environment / by L.H. Weinstein and A. Davison. p. cm. Includes bibliographical references and index. ISBN 0-85199-683-3 (alk. paper) 1. Fluorides--Environmental aspects. I. Davison, Alan. II. Title. TD196.F54W44 2004 363.738--dc21 2003013590 ISBN 0 85199 683 3 Typeset by AMA DataSet Ltd, UK. Printed and bound in the UK by Biddles Ltd, King’s Lynn. A4662 - Weinstein - Vouchers - VP10 #K.prn 4 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:51 PM Color profile: Disabled Composite 150 lpi at 45 degrees Contents Preface vi Acknowledgements viii 1.The History of Fluorine and Sources of Fluorides in the Environment 1 2.Uptake, Transport and Accumulation of Inorganic Fluorides by Plants and Animals 21 3.Effects of Inorganic Fluorides on Animals 56 4.Effects of Inorganic Fluorides on Plants and Other Organisms 86 5.Some Case Histories Involving Fluoride Contamination 119 6.Monitoring and Identifying Effects of Fluoride in the Field 147 7.Environmental Standards to Protect Humans, Other Animals and Plants 181 8.Natural Organofluorine Compounds 191 9.Manufactured Organofluorine Compounds 218 References 242 Index 281 The colour plate section can be found following p. 118 v A4662 - Weinstein - Vouchers - VP10 #K.prn 5 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:51 PM Color profile: Disabled Composite 150 lpi at 45 degrees Preface Fluoride emissions from volcanoes and the natural occurrence of excessive amounts of fluoride in drinking water have affected the health of humans and livestock for centuries, if not millennia. In addition to these natural sources, the use of fluoride as a flux, as a feed material in the chemical industry, its occurrence as a contaminant in phosphates and coal, and its use in a myriad of organic compounds have led to widespread air pollution and environmental damage. For over a century inorganic fluoride emissions damaged crops, forests and natural vegetation, and they caused fluorosis in factory workers, livestock and wild mammals. There is no doubt that inorganic fluoride was one of the major air pollut- ants of the 20th century but in the last 40 years there have been enormous improvements in the containment and scrubbing of emissions, so at the present time modern fluoride- emitting industries generally have little or no environmental impact outside the factory fence. Very few organofluorides were manufactured until the 1930s then CFCs (chloro- fluorocarbons) transformed refrigeration and air conditioning, leading to enormous social changes in regions with hot climates. Later they were found to be the cause of ozone deple- tion in the stratosphere and contributors to climate forcing. They are being phased out but over a million organofluorides are known, including agrochemicals, surfactants, insulating materials, fabrics and life-saving pharmaceuticals such as anaesthetics and antibiotics. They are a vital part of modern society but their effects on the environment are still largely unexplored. There are thousands of publications that relate to fluorides in the environment but most are specialized, and there is no recent text that attempts to provide an introduction to this large, complex subject; thus the main aim of this book is to provide a source of information for engineers, regulators, academics, students and the public. However, the literature is dominated by publications on industrial air pollution and fluoridation of water supplies so it has a bias towards the problems encountered in the more developed countries. There is much less information available about the immense problems caused by excessive amounts of natural fluoride in water supplies in the less developed countries and about the effects of organofluorides, so a second aim is to redress the balance and provide a more global picture. Finally, anyone looking at the literature for the first time, and especially if they use the Internet, will immediately become aware of the controversy surrounding fluoridation of public water supplies. Since fluoridation was introduced in 1945, there has been strong support from its proponents but strenuous opposition from a vocal minority of opponents. Scientific debate is essential to all environmental matters but the problem is that the anti- fluoridation lobby does not use robust science, relies too heavily on non-peer reviewed documents and resorts to conspiracy theories and scaremongering. The Internet is awash vi A4662 - Weinstein - Vouchers - VP10 #K.prn 6 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:51 PM Color profile: Disabled Composite 150 lpi at 45 degrees Preface vii with web sites that claim that fluoridation constitutes a plot to dispose of waste industrial fluoride, and a communist plot to weaken the moral and physical fibre of developed nations (epitomized by the movie Dr Strangelove). A recent (July 2003) article included at the top of its list of reasons for not fluoridating water, a statement declaring that ‘. fluoride is the active ingredient in most pesticides . .’. This is, of course, nonsense but it is this kind of falsehood that may confuse the reader who has little knowledge of chemistry or pesticides, so our final aim is to provide background information to allow readers to make more informed judgements about environmental questions relating to fluoride. A4662 - Weinstein - Vouchers - VP10 #K.prn 7 Z:\Customer\CABI\A4642 - Weinstein\A4662 - Weinstein - Vouchers - VP10 #K.vp Monday, November 10, 2003 3:35:51 PM Color profile: Disabled Composite 150 lpi at 45 degrees Acknowledgements Books are rarely written without lots of help, and this book is no exception. For example, whenever we had a need for the latest information or to review the chapter on naturally occurring organofluorine compounds in plants, we turned to our guru, Dr Laurie Twigg of the Western Australia Department of Agriculture, whose responses were always immediate and thorough. For questions relating to biochemistry, we thank Dr Gary W. Winston, a Chief Toxicologist with the Ministry of Health in Jerusalem, Israel, and a very close confidant to LHW. We thank Robert E. Feder, Esq. of Cuddy & Feder, White Plains, NY, who is not only a dear friend to both of us, and legal advisor to LHW, but also obtained the transcripts of the actions in the several Martin v. Reynolds legal actions, and gave gener- ously of his time to clarify the legal lingua. David Doley of the University of Queensland in Brisbane, Australia, our friend and a fine plant physiologist, provided the list of Australian and New Zealand plant species given in Table 6.1. His book complements several aspects of this publication. Answers to several questions relating to effects of fluoride on teeth were generously provided by Dr Gary Whitford of the University of Georgia Medical College, Augusta, GA. When it came to writing the chapter on fluorocarbons, Archie McCulloch (Marbury Consulting) provided masses of information and useful comments on the draft. Thanks are due to the Boyce Thompson Institute for its generous support. Kathleen Kramer, the Boyce Thompson Institute librarian, went far beyond any reasonable expecta- tions by poring through web sites and libraries to acquire references, reprints and copyright permissions. Joan Curtis and Elaine van Etten, of the Boyce Thompson Institute Computer Services, kept one of us relatively computer literate and Dr Richard C. Staples, Emeritus Plant Pathologist at BTI, gave one of us (LHW) almost daily computer advice. Bernard Willson (ex-Alcan, UK) and the late Serge Friar (Alcan, Canada) were responsible for the authors’ first meeting and the start of a lasting friendship that resulted in this book. Both Bernard and Serge were excellent sources of information about the aluminium industry, emissions and regulation. We must also thank the late James Alcock for his advice and information about fluoride effects on animals. Field work will never be the same without Jim’s acerbic comments and constant stories about veterinary life. The chapter on animals would not have been the same without the sterling work of one of AWD’s first graduate students, Professor John Cooke, and Professor Mike Johnson and their excellent team of workers.