NATURALLY-PRODUCED ORGANOHALOGENS

ENVIRONMENT & CHEMISTRY

VOLUME 1

Naturally-Produced Organohalogens

edited by

Anders Grimvall LinkOping University, LinkOping, Sweden

and

Ed W.B. de Leer TNO Institute of Environmental Sciences, Delft, The Netherlands

SPRINGER SCIENCE+BUSINESS, MEDIA, B.V.

A C.I.P. Catalogue record for this book is available from the Library of Congress

ISBN 978-94-010-4032-7 ISBN 978-94-011-0061-8 (eBook)

DOI 10.1007/978-94-011-0061-8

Printed an acid-free paper

AII Rights Reserved © 1995 Springer Science+Business Media Dordrecht Origina11y published by Kluwer Academic Publishers in 1995 Softcover reprint ofthe hardcover Ist edition 1995 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permis sion from the copyright owner.

The organisation of the International Conference on Natural-Produced Organohalogens has been made possible by financial contributions from:

National Institute of Public Health and Environmental Protection P.O. Box 1 3720 BA BIL THOVEN The Netherlands

Ministry of Housing, Physical Planning and the Environment Directorate-General for Environmental Protection P.O. Box 30945 2500 GX DEN HAAG The Netherlands

Ministry of Transport, Public Works and Water Management Directorate-General for Water Management, Directorate North Sea P.O. Box 5870 2280 HV RIJSWIJK The Netherlands

TNO Environmental and Energy Research P.O. Box 6010 2600 JA DELFT The Netherlands

Euro Chlor Federation Avenue E. van Nieuwenhuyse 4, Box 2 B-1160 BRUSSEL Belgium

NBM-Bodemsanering BV P.O. Box 16032 2500 BA DEN HAAG The Netherlands

Ned. Vereniging van Zeepfabrikanten Waterigeweg 31 3703 CM ZEIST The Netherlands

Euroglas Voltaweg 22 2627 BC DELFT The Netherlands

Campro Scientific B.V. Postbus 316 3900 AH VEENENDAAL The Netherlands

Contents

List of sponsors

Preface

Chapter 1 General introduction and overview articles

Evidence of naturally produced and man-made organohalogens in water and sediments A. Grimvall

The contribution of natural halogenation processes to the atmospheric halomethane burden D.B. Harper

Origin and occurrence of halogenated organic matter in soil G. Asplund

AOX in groundwater c. Gr0n

Chapter 2 Characterization of organohalogens of natural origin

Isolation of XAD-4 acids from natural waters and their importance as precursors to TOX and TUM upon chlorination R.L. Malcolm, J.P. Crouc and M. Benedicte

Natural AOX in the river Rhine: modelling and trace analysis W.M.G.M. van Loon, 1.1. Boon, B. de Groot and A.-I. Bulterman

v

xiii

3

21

35

49

67

83

viii

Halogenated structural elements in naturally occurring organic matter C. Johansson, H. Boren, A. Grimvall, O. Dahlman, R. Morek, A. Reimann and RL. Malcolm

Chemical characterization of organohalogens in a coniferous forest soil O. Hjelm and G. Asplund

Chemical characterisation of adsorbable organic halogens (AOX) in precipitation K. Laniewski, H. Boren, A. Grimvall, S. Jonsson and L. von Sydow

Naturally produced organic chlorine in the Finnish aquatic environment P.K.G. Manninen and M. Lauren

Chapter 3 Natural production of organohalogens normally considered to be of anthropogenic origin

Are polychlorinated biphenyls produced naturally? Results from recent UK investigations R.E. Alcock, W,A, Lead, A.E. Johnston and K.C. Jones

Formation of organic chlorine compounds of low molecular weight in the chloroperoxidase-mediated reaction between chloride and humic material E.1. Hoekstra, P. Lassen, J.G.E. van Leeuwen, E.W.B. de Leer and L. Carlsen

Chapter 4 Mechanisms for the incorporation of halogens into organic substances

Incorporation of halogenated substances into humic material 1.M. Bollag and 1. Dee

Detoxification of chlorophenols in soils by oxidative transformations on manganese and iron oxides M.D.R Pizzigallo, P. Ruggiero, C. Creeehio and R Mininni

95

105

113

131

141

149

161

171

ix

On the possible role of humic materials in the environmental organohalogen 183 budget: The enzymatically mediated incorporation of 4-chlorophenol into humic acids P. Lassen, A. Randall, O. J0rgensen, P. Warwick and L. Carlsen

Reaction mechanism and 3-dimensional structure of bacterial non-haem haloperoxidases K.-H. van Pee, H.-J. Hecht, T. Haag, O. Pfeifer, R. Bantleon, H. Sobek, I. Pelletier and

J. Altenbuchner

Structures of aquatic humic substances responsible for the reaction with chlorine 1. Hejzlar, H. Boren and A. Grimvall

193

201

Incorporation of haloalkanes into long chain fatty acids by the chloroalkane- 213 degrading bacterium Rhodococcus rhodochrous NCIMB 13064 J.T.G. Hamilton, O. Flynn, M.1. Larkin and D.B. Harper

Kinetic control of the biogeochemical formation of halogenated humic acids 221 J. Dolfing and W. Salomons

ChapterS Occurrence and production of organohalogens in the terrestrial environment

The natural chlorinated plant hormone of pea, 4-chloroindole-3-acetic acid, an endogenous herbicide? K.C. Engvild

Biosynthesis and metabolic role of chloromethane in fungi D.B. Harper

Occurrence of fluoroacetate, a naturally-produced organohalogen in plants T. Vartiainen, K. Takala and P. Kauranen

Significant fungal biogenesis of physiologically important chlorinated aromatics in natural environments E. de Jong. J.A. Field. H.-Eo Spinnler. A,E. Cazemier and J.A.M. de Bont

Naturally produced organohalogens: AOX-monitoring in plants and sediments G. Nkusi and G. MUller

227

235

245

251

261

x

Biosynthesis of fluoroacetate and 4-fluorothreonine by Streptomyces cattleya K.A. Reid, R.D. Bowden and D.B. Harper

Chapter 6 Occurrence and production of organohalogens in the marine environment

Marine phytoplankton as a natural source of volatile organohalogens R.M. Moore. R. Tokarczyk, V.K. Tait, M. Poulin and e. Geen

Iodinated CI-C4 hydrocarbons released from ice algae in Antarctica E. Fogelqvist and T. Tanhua

Occurrence of halogenated fatty acids in bivalve lipids e. Wesen. H. Mu. P. Sundin, O. Ringstad and G. Odham

Formation and distribution of halogenated volatile organics in sea water K. Abrahamsson. A. Ekdahl, J. Collen and M. Pedersen

The natural formation of trichloroethylene and perchloroethylene in sea water K. Abrahamsson. A. Ekdahl. J. Collen, E. Fahlstrbm and M. Pedersen

Occurrence of organic halogens in marine mammals M. Kawano, H. Yoshioka. Y. Tejima and R. Tatsukawa

Origin of organohalogens found in Baltic Sea sediments S. 10nsson. I. Pavasars, e. Johansson. H. Boren and A. Grimvall

Bromoperoxidase from a marine red alga, Corallina pi/uli/era Y. Izumi and R. Wever

Chapter 7 Reactive chlorine and halogenated organic compounds in the atmosphere

Inorganic CI cycling in the marine boundary layer: a review w.e. Keene

269

283

295

307

317

327

333

339

353

363

Production of a photolytic precursor of atomic CI from aerosols and CI- in the presence of 03 W. Behnke, V. Scheer and C. Zelzsch

Biogenic emission of organobromine compounds to the Arctic Ocean and atmosphere W.T. Sturges and G.F. COla

Chlorinated Cl- and C2-hydrocarbons in the needles of Scots Pine (Pinus sylvestris L.) in three forests of Northern Britain R.H.A. Brown, IN. Cape and J.G. Farmer

Chapter 8 Policy aspects

From 'is' to 'ought' J.A. Wesseldijk

Occurrence and toxicology of natural and anthropogenic organohalogens and relevance to environmental protection R.L. Stringer and P.A. Johnston

xi

375

385

397

405

415

What is the opinion of a policy-maker on naturally produced organohalogens? 429 The governmental point of view M. Bovenkerk

Preface

The idea of organizing an international conference on naturally produced organohalogens was conceived within an international research project! on natural halogenation of organic macromolecules in the terrestrial environment. Investigations carried out by scientists from the participating organizations (Linkoping University, Sweden; TNO, Delft, the Netherlands; the Technical University of Denmark; and the National Environmental Research Institute, Roskilde, Denmark) had provided new evidence of remarkable discrepancies between the amounts of organohalogens found in the environment and the possible contributions from known anthropogenic emissions of chlorinated, brominated and iodinated organic compounds. Large-scale natural production of organohalogens was an obvious explanation for the observed data, and the project high-lighted the role of halogenation processes in the terrestrial environment. However, it was also found that important knowledge about the cycling of such substances within and between different environmental compartments had been accumulated in a large number of disciplines, e.g. analytical chemistry, biochemistry, microbiology, soil science, marine biology and atmospheric chemistry. Therefore, a conference was organized at TNO in Delft, the Netherlands, to bridge the gap between the different disciplines and to bring together scientists who have a common interest in natural halogenation.

Some of the research papers presented at the conference were selected to give an overview of the occurrence and natural production of organohalogens in different environmental compartments. Other contributions were chosen because they represented significant progress in the search for mechanisms underlying the indicated production and in the determination of the chemical structure of detected compounds. In addition, a special session was devoted to contributions from participants representing industry, regulating agencies and the environmental movement.

Several recently published articles and review papers have emphasized the great variety of fluorinated, chlorinated, brominated and iodinated metabolites produced by different types of organisms. The Delft conference reported in this book focused on organohalogens that are naturally produced in such quantities that they can make substantial contributions to the total amount of organically bound halogens detected in unpolluted soil, water or air. Special

STEP CT-90 0026, Commission of the European Communities

xiv

attention was paid to the two groups of organohalogens that have appeared as the dominating naturally produced organohalogens, i.e. halogenated humic substances and halomethanes.

The crucial role of humus or humus-like substances in the cycling of organohalogens in the environment was also emphasized in the contributions on characterization of organohalogens of natural origin. Several halogenated structures have been identified in humic substances, and this group of organic macromolecules is now being recognized as the main cause of the widespread occurrence of organohalogens at remote sites. Chlorinated structures seem to be most widespread in soil and freshwater, whereas brominated or iodinated structures are ubiquitous in marine environments. The identity and origin of the major fractions of organohalogens found in precipitation are still largely unknown.

The great variety of organohalogens produced in nature has raised the question whether or not there is a significant difference between organohalogens of anthropogenic and natural origin. The Delft conference provided new evidence that there is a considerable natural production of compounds, or structural elements of macromolecules, that are known from chlorine bleaching of pulp and disinfection of drinking water. The natural production of the highly toxic PCB's and PCDDIF was also discussed and, in fact, the biogenic production of PCDDIF from chlorinated phenols was clearly demonstrated. However, in soil the biogenic production of PCB and PCDD/F is probably negligible as compared to the anthropogenic input.

The past few years of research has resulted in considerable knowledge about the occurrence of organohalogens in different media and the magnitude of the natural production of such compounds. In addition, the conference provided several examples of natural halogenation mechanisms, in particular enzyme-mediated reactions, that may underlie the observed production. However, there is still substantial uncertainty about the relative importance of the different halogenation mechanisms, and it is not unlikely that important mechanisms have not yet been revealed. The organisms or abiotic reactions responsible for the large natural production of chloromethane, for example, are still unidentified, and the same holds true for the mechanisms underlying the so-called arctic bromine pulse. In the terrestrial environment, a majority of the organically bound halogens are found in macromolecules, but at least two different mechanisms for the incorporation of halogens into such molecules were proposed during the conference: (i) enzyme-mediated oxidation of inorganic halides to reactive chlorine species that subsequently react with the macromolecules; (ii) enzyme-mediated incorporation of low-molecular-weight organohalogens into naturally occurring macromolecules. The conference contributions regarding reactive chlorine in the atmosphere further illustrate the great variety of challenging research problems that have not yet been clarified. However this uncertainty can not obscure the main conclusion of the conference, i.e. that the release, transport and transformation of man-made organohalogens is only part of a much more extensive cycling of these compounds, in which natural production in terrestrial and aquatic environments, and possibly also in the atmosphere, plays a much more important role than was previously assumed.