Anthropogenic Platinum-Group Element Emissions

Springer Berlin Heidelberg New York Barcelona Hong Kong London Milan Paris Singapore Tokyo

Fathi Zereini • Friedrich Alt (Eds.)

Anthropogenic Platinum­Group Element Emissions

Their Impact on Man and Environment

With 49 Figures and 80 Tables

Springer

EDITORS

PD Dr. Fathi Zereini University of Frankfurt Institute of Mineralogy Georg-Voigt-Str.16 60054 Frankfurg a. M. Germany E-mail: zereini@kristall.uni-frankfurt.de

Dr. Friedrich Alt Institute of Spectrochemistry and Applied Spectroscopy Bunsen-Kirchhoff-Str. II 44139 Dortmund Germany E-mail: f alt@isas-dortmundde

ISBN-13: 978-3-642-64080-3 Springer-Verlag Berlin Heidelberg New York

The book was originally published under the title "Emissionen von Platinmetallen. Analytik, Umwelt­und Gesundheitsrelevanz". (© Springer-Verlag Berlin Heidelberg 1999)

Library of Congress Cataloging-in-Publication Data applied for

Die Deutsche Bibliothek - CIP Einheitsaufnahme Anthropogenic platinum-group element emissions: their impact on man and environment / Fathi Zereini; Friedrich Alt (ed.).- Berlin; Heidelberg; New York; Barcelona; Hong Kong; London; Milan; Paris; Singapore; Thkyo: Springer, 2000

Dt. Ausg. u. d. T.: Emissionen von Platinmetallen ISBN-13:97S-3-642-640S0-3 e-ISBN-13:978-3-642-59678-0 DOl: 10.1007/978-3-642-59678-0

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, reuse of illustrations, recitations, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. © Springer-Verlag Berlin Heidelberg 2000 Softcover reprint of the hardcover 1st edition 2000

The use of general descriptive names, 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 general use.

Cover Design: de'blik, Berlin Typesetting: Camera-ready by the editors

SPIN: 10691730 30/3136 - 5 4 3 210 - Printed on acid free paper

Preface

The concentration of platinum-group elements (PGE) in the earth's crust amounts to approximately 1 ppb, i.e. one milligram per ton of rock material. Geochemical processes are able to enrich them by a factor of about 10,000, thus becoming mineable. Processed PGE fmd application in various technological processes, due to their catalytic properties. PGEs are also used in medicine, apparatus technology, jewellery and other fields. The most important application during the last 20 years was their introduction for the catalytic cleaning of automobile exhaust gases. This application results in increasing emissions, caused by anthropogenic sources, of three PGEs (platinum, palladium and rhodium) into the environment.

There has been a vague medical assertion, that the emitted platinum could have adverse health effects for mankind. This vague assertion was the reason to start investigations into the nature and mass of emitted PGEs, especially platinum, and their physiological effects.

To date, profound data has become available. In this book, interdisciplinary contributions from about 58 international authors are collected. This impressive presentation covers a broad array of topics, from the development of suitable and reliable analytical methods to the documentation of the PGE enriclunent in the environment (e.g. dusts, soils, sediments, water, plants). In addition the bioavailability of these elements and their toxicological and allergological potentials have been discussed.

Unfortunately this multi- and interdisciplinary research was promoted only in the first phase by the public authorities in Germany. It is regretable that the problem of contamination of the environment by PGEs does not get further attention, possibly due to political and commercial reasons.

With the above comments in mind, we trust that the data contained herein point to the cumulative contamination of our environment by PGEs. We hope that this book therefore will provide new impulses for futher investigations.

Dortmund, July 1999 Prof. Dr. Dr. h. c. Giinther T6lg

Preface of the Editors

The introduction of catalytic converters in cars in Germany during the 1980's has led to a cumulative increase in the concentration of the three platinum-group elements (PGE) platinum, palladium and rhodium in environmental compartments along roadsides. Besides the undisputed environmental benefits generated by this new technology - a significant reduction in emission of pollutants - the trend mentioned above started a lively discussion on the cumulative adverse side-effects of PGE emissions on the human habitat.

Several university-based groups, especially in Germany, began to investigate the behaviour of anthropogenic PGE in the environment. Emphasis was focused on the following: the development of analytical methods for the detection of ultra­trace concentrations of PGE in environmental matrices, the development of experimental systems to help understand the geochemical behaviour of these elements, their solubility, mobility and bioavailability, and, the estimation of their toxicological and allergological potential.

Dr. F. Alt (Institute of Spectrochemistry and Applied Spectroscopy, Dortmund) and Prof. Dr. E. Helmers (University of Applied Sciences, Birkenfeld) founded an interdisciplinary and independent "Precious Metal-Forum", to promote the scientific exchange between the different groups. The annual meetings of the forum - 1999 will be the 6th meeting in Frankfurt am Main - saw the presentation of a great number of important and thought-provoking papers which layed the foundation of this book. Last year the publishers of Springer, most notably Dr. W. Engel and Mr. Ch. Witschel, guided the publication of a first book ("Emissionen von Platinmetallen: Analytik, Umwelt- und Gesundheitsrelevanz," in German) on anthropogenic PGE in the environment. This edition, written by 42 authors, contained 27 original papers. Its interdisciplinary approach includes authoritative related work in: geoscience, chemistry, biology and medicine.

The warm reception by the scientific community for the first book encouraged the editors to publish a second book on the same subject in English. This second book targets an even more international circle of researchers and readers. The enthusiastic response of the participants attested to the great interest for this young environmental field. Within one year, 29 papers from 58 authors have come from Austria, Belgium, Canada, Germany, Great Britain, Japan, Sweden, and Spain, many of them new and different from those already published in the German edition. The absence of works from the U.S.A., although Dr. G. Rosner (Consulting Toxicology & Environmental, Freiburg) has thankfully tried to promote this with great engagement, is due to a stop of scientific work on that subject since the mid-1980s.

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The present book offers for the ftrst time a state-of-the-art in-depth view on anthropogenic PGE emissions into the environment. The many scientiftc approaches currently under investigation are mirrored by works from chemists, geoscientists, biologists and physicians. They all discuss different aspects of the environmental impact these emissions have and will have in the future. The main subjects covered are: sources of PGE emissions; occurrence, geochemical behaviour and fate of PGE in the environment; analytical methods for detecting PGE in environmental matrices; bioavailabiIity and biomonitoring of PGE; health risk ofPGE; car exhaust catalysts; pollutant reduction and emission balance.

The editors are well-aware that this book could only present an up-to-date snapshot of a lively scientific fteld, although it is covering the related science work of the last 10-15 years; but they are convinced that it contains directiones for future investigations. Since the types of catalytic converters in use are changing with regard to their structure and composition, continuous vigilence is imparative to assure environmental safety. An unbiased and objective discussion of evolving scientiftc trends will be supported by this book.

The editors thank the many contributors as well as peer reviewers for their dedication to on-time delivery. Additionally, the editors are indebted to the following individuals for their help in completing this book: Dr. G. Rosner (Consulting Toxicology & Environmental, Freiburg), Dr. B. Skerstupp (Institute of Mineralogy, Frankfurt), Dr. K. Kiimmerer (Institute of Environmental Medicine and Hospital Epidemeology, Freiburg), Dr. S. Lustig (GSF-National Research Center for Environment and Health, Institute for Ecological Chemistry, Neuherberg)) and Dr. J.-D. Eckhardt (Institute of Petrography and Geochenistry, Karlsruhe). Our sincere thanks go to Springer, for enabling publication and again to Dr. W. Engel and Mr. Ch. Witschel.

Frankfurt, Dortmund, July 1999 PD Dr. Fathi Zereini Dr. Friedrich Alt

Contents

1 Sources of PGE emissions

1.1 The automobile catalyst as an important source of PGE in the environment M A. Palacios, M Moldovan and M M Gomez .......................................... .3

1.2 Sources and sinks of anthropogenic platinum fluxes E. Helmers and K. Kiimmerer ....................................................................... 15

1.3 Traffic-borne platinum pollution in municipal sewage treatment plants D. Laschka and M Nachtwey ....................................................................... 25

1.4 Engine test bench experiments to determine platinum emissions from three-way catalytic converters S. Artelt, K. Levsen, H.-P. Konig and G. Rosner .......................................... 33

2 Occurrence, geochemical behaviour and fate in the environment

2.1 Environmental PGE contamination in Southwest Germany J-D. Eckhardt, J Schafer, H. Puchelt and D. Stiiben ................................. .47

2.2 Changes in platinum concentrations in soils and dusts from UK cities E. J Hutchinson, M E. Farago and P. R. Simpson ..................................... 57

2.3 Biomonitoring of platinum immissions from motor vehicles C. Dietl, D. Laschka, M Waber and L. Peichl ............................................. 65

2.4 Anthropogenic emission of platinum-group elements (Pt, Pd and Rh) into the environment: concentration, distribution and geochemical behaviour in soils F. Zereini, B. Skerstupp, K. Rankenburg, F. Dirksen, J-M Beyer, T Claus and H. Urban ................................................................................. 73

2.5 Routes for bioaccumulation and transformation of platinum in the urban environment S. Rauch and G. M Morrison ....................................................................... 85

2.6 Platinum bioaccumulation in plants and overview of the situation for palladium and rhodium S. Lustig and P. Schramel ............................................................................. 95

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2.7 Determinants of the phytotoxicity of platinum H. -J. Ballach, F. Alt, 1. Messerschmidt and R. Wittig ...... .......................... 105

2.8 A contribution to the enology and ecology of noble metals H. R. Eschnauer .......................................................................................... 115

3 Analytical methods for PGE in the environment

3.1 Preconcentration/separation methods for the determination of trace platinum in environmental samples by ICP-MS K. Akatsuka and1. W. McLaren ................................................................. 123

3.2 PGE emissions of automobile catalysts - identifying their track in the environment. A challenge to analytical strategy and assessment E. Helmers .................................................................................................. 133

3.3 Voltammetric determination of ultra trace platinum and rhodium in biological and environmental samples K. Hoppstock and F. Alt ............................................................................. 145

3.4 PACEPAC: A road dust as a certified reference material for the quality assurance in the analysis of Pt, Pd and Rh in environmental samples S. Lustig, P. Schramel and Ph. Quevauviller ............................................ .153

3.5 Platinum speciation using on-line hyphenation of capillary electrophoresis to ICP-MS B. Michalke and P. Schramel .................................................................... .161

3.6 Determination of palladium in environmental samples M. Schuster, M. Schwarzer and G. Risse .. ................................................. 173

3.7 Speciation of platinum in plant material. A combination of chromatography, elemental mass spectrometry and electrochemistry G. Weber, N. Jakubowski and D. Stuewer .................................................. 183

3.8 Plasma source mass spectrometric techniques and highly efficient sample introduction systems as tools for the ultratrace detennination ofPGE H. Wildner .................................................................................................. 191

3.9 Reliability of and measurement uncertainty for the determination of Au, Pd, Pt and Rh by ICP-MS in environmentally relevant samples M. Zischka and W. Wegscheider ................................................................ 201

4 Bioavailability and biomonitoring of PGE

4.1 Bioavailability of finely dispersed platinum as emitted from automotive catalytic converter: A model study

XI

S. Artelt and K. Levsen ............................................................................... 217 4.2 Internal platinum and palladium exposure of the general population

with emphasis on the exposure from automobile exhaust and dental restorative alloys 1. Begerow and L. Dunemann .................................................................... 227

4.3 Urinary biomonitoring of platinum in occupational medicine R. Schierl .................................................................................................... 237

5 Health risk potential of PGE

5.1 Toxicology of platinum, palladium, rhodium, and their compounds T. Gebel ...................................................................................................... 245

5.2 Occupational platinum salt allergy. Diagnosis, prognosis, prevention and therapy R. Merget .................................................................................................... 257

5.3 Evaluation of the health risk of platinum emissions from automotive emission control catalysts G. Rosner and R. Merget ............................................................................ 267

6 Car exhaust catalysts: pollutant reduction and emission balance

6.1 Pollution reduction in motor car exhaust gases by regulation of the fuel mixture with the lambda-sensor H. R. Eschnauer .......................................................................................... 285

6.2 Screening life cycle inventory of PGEs and its influence on the overall emission balance of cars fitted with catalytic converters C. Hochfeld and W. Jenseit ........................................................................ 293

Index ..................................................................................................................... 301

List of Contributors

Akatsuka, K., Prof. Dr. Department of Applied and Environmental Chemistry Kitami Institute of Technology 165 Koen-cho, Kitarni, Hokkaido, 090-8507 Japan

Alt, F., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-440 13 Dortmund

Artelt, S., Dr. Innovation Relay Centre Gewerbemuseurnsplatz 2 D-90403 Niirnberg

Ballach, H.-J, PD Dr. Department of Geobotany and Plant Ecology, J. W. Goethe University, Frankfurt Siesmayerstr. 70 D-60323 Frankfurt am Main

Begerow, J., Dr. Medical Institute of Environmental Hygiene, Department of Analytical Chemistry, University Dusseldorf P.O. Box 103751 D-40028 Dusseldorf

Beyer, J. M., DipI. GeoI. Institute of Mineralogy, J. W. Goethe-University

Georg-Voigt-Str. 16 D-60054 Frankfurt am Main

Claus, T., DipI. GeoI. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str.16 D-60054 Frankfurt am Main

Dietl, C., DipI. BioI. Bavarian State Office for Environmental Protection Munich ' Rosenkavalierplatz 3 D-81925 MUnchen

Dirksen, F., DipI. GeoI. Institute of Mineralogy, J. W. Goethe-University

Georg-Voigt-Str.16 D-60054 Frankfurt am Main

Dunemann, L., Prof. Dr. Medical Institute of Environmental Hygiene, Department of Analytical Chemistry, University Dusseldorf P.O. Box 103751 D-40028 Dusseldorf

Eckhardt, J. D., Dr. Institute of Petrography and Geochemistry, University Karlsruhe KaiserstraBe 12 D-76128 Karlsruhe

Eschnauer, H. R., Prof. Dr. Institute of Enology Stiegelgasse 49 D-552180ber-Ingelheiml Rhein

XIV

Farago, M. E., Prof. Dr.

Environmental Geochemistry Research Group, The T.H. Huxley School for the Environment, Earth Science and Engineering, Imperial College of Science Technology and Medicine, Royal School of Mines, London, SW7 2BP, UK

Gebel, T., Dr. Medical Institute of General Hygiene and Environmental Health, University of Gottingen Windausweg 2 0-37073 Gottingen

Gomez, M. M., Prof. Dr. Dpto. de Quimica Analitica, Fac. de Quimica, Universidad Complutense 28040 Madrid, Spain

Helmers, E., Prof. Dr. Environmental Campus University of Applied Sciences P.O. Box 13 80 0-55761 Birkenfeld

Hochfeld, Ch., Dipl.-Ing. Institute for Applied Ecology Elisabethenstr. 55-57 0-64283 Darmstadt

Hoppstock, K., Dr. Research Center of Jfilich GmbH Institute of Applied Physical Chemistry, ICG 7 0-52425 Jfilich

Hutchinson, E. J., Research Student. Environmental Geochemistry Research Group, The T.H. Huxley School for the Environment, Earth Science

and Engineering, Imperial College of Science Technology and Medicine, Royal School of Mines, London, SW7 2BP, UK

Jakubowski, N., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.o. Box 10 13 52 0-44013 Dortmund

Jenseit, W., Dr. Institute for Applied Ecology Elisabethenstr. 55-57 0-64283 Dannstadt

Konig, H.-P., Prof. Dr. Hochschule Bremen FB 3 Neustadtwa1l30 0- 28199 Bremen

Kfimmerer, K., Dr. Institute of Environmental Medicine and Hospital Epidemiology, University of Freiburg 0-79106 Freiburg

Laschka, D., Dr. Bavarian State Office for Water Management Postfach 190241 0-80602 MUnchen

Levsen, K., Prof. Dr. Fraunhofer Institute for Toxicology and Aerosol Research Nikolai-Fuchs-Str. 1 0-30625 Hannover

Lustig, S., Dr. GSF-National Research Center for Environment and Health Institute for Ecological Chemistry P.O. Box 1129 D-85758 Neuherberg

McLaren, 1.W., Dr. Institute for National Measurement Standards, NRC Ottawa KIA OR6, Canada

Merget, R., PD Dr. Research Institute for Occupational Medicin P.O. Box 100250 D-44702 Bochum

Messerschmidt, 1., Dipl. Ing. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-440 13 Dortmund

Michalke, B., Dr. GSF-National Research Center for Environment and Health Institute for Ecological Chemistry P.O. Box 1129 D-85758 Neuherberg

Moldovan, M., Dr. Dpto. de Quimica Analitica, Fac. de Quimica, Universidad Complutense 28040 Madrid, Spain

Morrison, G. M., Prof. Dr. Chalmers University of Technology, Department of Sanitary Engineering SE-41296 Goteborg, Sweden

Nachtwey, M., Dipl. Ing. Bavarian State Office for Water Management Postfach 190241 D-80602 Munchen

Palacios, M. A., Prof. Dr. Dpto. de Quimica Analitica, Fac. de Quimica, Universidad Complutense 28040 Madrid, Spain

Peichl, L., Dr. Bavarian State Office for Environmental Protection, Munich Rosenkavalierplatz 3 D-81925 MUnchen

Puchelt, H., Prof. Dr. Institute of Petrography and Geochemistry, University Karlsruhe KaiserstraBe 12 D-76128 Karlsruhe

Quevauviller, Ph.,Dr. European Commission, SM&T, Rue de Loi 200 B-I049 Brussels, Belgium

Rauch, S., M.Sc. Chalmers University of Technology, Department

xv

of Sanitary Engineering SE-41296 Goteborg, Sweden

Rankenburg, K., Dipl. Geol. Institute of Mineralogy, J. W. Goethe-University Senckenberganlage 28 D-60054 Frankfurt am Main

Risse, G., Dr. Institute of Inorganic Chemistry, TU Munchen Lichtenbergstr.4 D-85747 Garching

Rosner, G., Dr. Consulting Toxicology & Environment Bachelhurst 39 D-79249 Merzhausen

XVI

Schafer, 1., Dr. Institute of Petrography and Geochemistry, University Karlsruhe Kaiserstral3e 12 D-76128 Karlsruhe

Schierl, R., Dr. Institute for Occupational and Environmental Medicine, University Munich Ziemssenstr. 1 D-80336 Miinchen

Schramel, P., Prof. Dr. GSF-National Research Center for Environment and Health Institute for Ecological Chemistry P.O. Box 1129 D-85758 Neuherberg

Schuster, M., Prof. Dr. Institute of Inorganic Chemistry, TV Miinchen Lichtenbergstr. 4 D-85747 Garching

Schwarzer, M., Dr. Institute of Inorganic Chemistry, TV Miinchen Lichtenbergstr.4 D-85747 Garching

Simpson, P., R., Dr. Prof. British Geological Survey, Keyworth, Nottingham, NG12, 5GG, UK

Skerstupp, B., Dipl. Min. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str. 16 D-60054 Frankfurt am Main

Stuewer, D., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-440 13 Dortmund

Stiiben, D., Prof. Dr. Institute of Petrography and Geochemistry, University Karlsruhe KaiserstraBe 12 D-76128 Karlsruhe

Urban, H., Prof. Dr. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str. 16 D-60054 Frankfurt am Main

Waber, M., Dr. Bavarian State Office for Environmental Protection, Munich Rosenkavalierplatz 3 D-81925 Miinchen

Weber, G., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-440 13 Dortmund

Wegscheider, W., Prof. Dr. Institute for General and Analytical Chemistry University of Leoben Franz-Josef-Strasse 18 A-8700 Leoben Austria

Wildner, H., Dr. PLANSEEAG, Technology Center, Materials Analysis A-6600 ReuttelTyrol Austria

Wittig, R., Prof. Dr. Department of Geobotany and Plant Ecology, J. W. Goethe University, Frankfurt Siesmayerstr. 70 D-60323 Frankfurt am Main

Zereini, F., PD Dr. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str.16 D-60054 Frankfurt am Main

Zischka, M., Dr. Institute for Analytical Chemistry, Micro- and Radiochemistry Technical University Graz Technikerstrasse 4 A-8010 Graz Austria

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List of Referees

Alt, F., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-44013 Dortmund

Ballach, H.-J., PD Dr. Department of Geobotany and Plant Ecology, J. W. Goethe University, Frankfurt Siesmayerstr. 70 D-60323 Frankfurt am Main

Dunemann, L., Prof. Dr. Medical Institute of Environmental Hygiene, Department of Analytical Chemistry, University Dusseldorf Postfach 103751 D-40028 Dusseldorf

Helmers, E., Prof. Dr. Environmental Campus University of Applied Sciences P.O. Box 13 80 D-55761 Birkenfeld

Hoppstock, K., Dr. Research Center of Jiilich GmbH Institute of Applied Physical Chemistry, ICG 7 D-52425 Jiilich

Lustig, S., Dr. GSF-National Research Center for Environment and Health Institute for Ecological Chemistry, Neuherberg P.O. Box 1129 D-85758 OberschleiBheim

Puttmann, W., Prof. Dr. Institute of Mineralogyl Environment Analysis 1. W. Goethe-Universitat Georg-Voigt-Str.16 D-60054 Frankfurt am Main

Schramel, P., Prof. Dr. GSF-National Research Center for Environment and Health Institute for Ecological Chemistry, Neuherberg P.O. Box 1129 D-85758 OberschleiBheim

Schuster, M., Prof. Dr. Institute of Inorganic Chemistry, TV Miinchen Lichtenbergstr.4 D-85747 Garching

Stuewer, D., Dr. Institute of Spectrochemistry and Applied Spectroscopy P.O. Box 10 13 52 D-440 13 Dortmund

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Thiemeyer, H., Prof. Dr. Institute of Physical Geography J. W. Goethe-University Georg-Voigt-Str.16 D-60054 Frankfurt am Main

Tolg, G., Prof. Dr. Dr. h.c. In der Schlage 53 D-58313 Herdecke

Urban, H., Prof. Dr. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str. 16 D-60054 Frankfurt am Main

Zereini, F., PD Dr. Institute of Mineralogy, J. W. Goethe-University Georg-Voigt-Str. 16 D-60054 Frankfurt am Main