Biodegradation of Dioxins and Furans

292 Pages·1998·8.687 MB·English

by  Rolf-Michael Wittich (auth.), Rolf-Michael Wittich (eds.)

Springer-Verlag Berlin Heidelberg GmbH
Rolf-Michael Wittich (Ed.)
Biodegradation
of Dioxins and Furans
, Springer
Rolf-Michael Wittich (Ed.)
GBF-National Research Center for Biotechnology
Braunschweig, Germany
ISBN 978-3-662.-000]0-4
Environmental Intelligence Unit
Library of Congress Cataloging-in-Publication data
Biodegradation of dioxins and furans / [edited by) Rolf-Michael Wittich.
p. cm. - (Environmental intelligence unit)
Includes bibliographical references and indeL
ISBN 978-3-662-06070-4 ISBN 978-3-662-06068-1 (eBook)
DOI 10.1007/978-3-662-06068-1
1. Dioxins-Biodegradation. 2. Furans-Biodegradation.
1. Wittich, Rolf-Michael. II. Series.
QH 545.D55B55 1998
628.5-dc2.1 97-53086
CIP
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=====PREFACE =====
R
etrospectively we can say that the so-called Seveso Accident in 1976
at the occasion of which several kilograms of the highly toxic 2,3,7,8-
tetrachlorodibenzo-p-dioxin were released has led to an increased
awareness of environmental pollution in the public. As a consequence
intensive efforts have been made to develop and improve physical and
chemical technologies for remediation of the class of dioxins and re
lated compounds. In parallel research on biological mechanisms of
transformation, detoxification and bio-degradation of dioxins increased
dramatically. The results of these investigations over the past twenty
years extended significantly our knowledge and understanding ofbio
logical reactions of eukaryotic and prokaryotic cells. This will help us
in the design of biological techniques for applications of degradation
of dioxins by bacterial and fungal biocatalysts in laboratory systems
and in the field.
The authors of the chapters of this book reviewed the present
state of knowledge in their own and related disciplines. In many cases
they have incorporated new and unpublished results from their work.
They have considered aspects of aerobic degradation of dioxins which
is still limited to non-halogenated dibenzo-p-dioxin and dibenzofuran
and low-halogenated derivatives. The elucidation of the genetic back
ground of the aerobic dioxin degradation pathways will provide the
necessary information and help to overcome those limitations by means
of molecular biotechnology techniques for the generation of genetic
tools for improvement of degradative enzymes. Both aerobic and
anaerobic microorganisms then can be combined in a two-stage pro
cess for reductive dehalogenation of highly chlorinated congeners and
the subsequent aerobic mineralization of intermediate products.
Since fungi producing peroxidases can attack and at least par
tially degrade almost all organic compounds their biological activity
deserves particular attention. Other eukaryotic enzymes such as P-450
oxidases transform dioxins to less toxic compounds and provide acti
vation by hydroxylation of stable aromatic structures for further deg
radation processes in the environment. Biodegradation, however, will
be efficient only if biocatalysts and target molecules can interact pro
ductively. The migration of organisms and compounds of concern in
the subsurface therefore plays an important role. Mathematical mod
eling of biological activity with regard to structural elements to be de
graded and the elucidation and improvement of the bioavailability
therefore are treated as well. So to speak a promising outlook is pre
sented in the last chapter on the biodegradation of diaryl ether-based
pesticides.
Rolf-M. Wittich
Braunschweig
November, 1997
CONTENTS
1. Aerobic Degradation by Bacteria of Dibenzo-p-Dioxins,
Dibenzofurans, Diphenyl Ethers and Their Halogenated
Derivatives ...................................................................................... 1
Rolf-Michael Wittich
Introduction ................................................................................. 1
Natural Dioxin-Like Compounds .............................................. 3
Biotransformation of Dibenzo-p-Dioxins and
Dibenzofurans by Bacteria Incapable of Mineralization ..... 5
Regioselective Co-oxidations by Bacteria Degrading
Aromatic Compounds ............................................................. 5
Mineralization of Nonhalogenated and of Hydroxylated
Diaryl Ethers by Newly Isolated Bacteria .............................. 7
Co-Oxidation of Halogenated Diaryl Ethers .......................... 14
Degradation by Mixed Cultures ................................................ 17
Conversion of Higher Halogenated DDs and DFs ................. 20
Conclusions ............................................................................... 22
2. Anaerobic Bacterial Dehalogenation of Polyh alogenated
Dioxins and Furans ..................................................................... 29
Merel Toussaint, Rene van Herwijnen and John R. Parsons
Introduction ............................................................................... 29
Measurements in Sediment ....................................................... 31
Measurements in Soil ................................................................ 38
Laboratory Experiments on Reductive Dechlorination
of Dioxins and Dibenzofurans ............................................. 39
Conclusions ............................................................................... 52
3. Biodegradation of Dioxin and Dioxin-Like Compounds
by White-Rot Fungi ..................................................................... 61
Steven D. Aust and James D. Stahl
Introduction ............................................................................... 61
Fungal Biodegradation of Dioxin ............................................ 66
Fungal Biodegradation of Pentachloroanisole ....................... 69
Future Applications ................................................................... 71
4. Molecular Genetics of the Degradation of Dioxins
by Bacteria .................................................................................... 75
Jean Armengaud and Kenneth N. Timmis
Introduction ............................................................................... 75
Sphingomonas sp. RWI as a Model Dibenzo-p-Dioxin
Degrader ................................................................................. 76
Characterization of the Ring-Cleaving Dioxygenase,
DbfB ........................................................................................ 81
Characterization of the Initial Dioxin Dioxygenase .............. 88
The Genetic Organization of Sphingomonas Sp. RWl
Degradative Genes Differs from That of Other Aromatic
Degraders ............................................................................. 107
Genetic Characterization of Degraders of Dioxin and
Dioxin-Related Compounds ............................................... 109
Concluding Remarks and Perspectives .................................. 113
5. Biotransformation of Dioxin-Like Compounds
by Eukaryotic Cells ..................................................................... 125
Rolf-Michael Wittich
Introduction .............................................................................. 125
Biotransformations by Fungal Cells ....................................... 125
Biotransformations by Higher Eukaryotes (Mammals) ....... 127
Biotransformations of Chlorinated DFs ................................ 128
Biotransformations of Chlorinated DDs ............................... 130
6. Bioavailability of Dioxin-Like Compounds for Microbial
Degradation ................................................................................. 135
Hauke Harms
Introduction .............................................................................. 135
Biological Factors Affecting Bioavailability .......................... 137
Environmental Factors Affecting Bioavailability ................. 142
Degradation of Dioxin-Like Compounds .............................. 147
Environmental PCDD/PCDF Fluxes and Evolution
of Degradation Pathways ..................................................... 153
Dioxin Contamination-Subject to Bioremediation? .......... 156
Conclusive Remarks ................................................................. 158
7. Structure-Biodegradability Relationships for Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans ................................. 165
lirf Damborsky, Mary Lynam and Michal Kuty
Introduction .............................................................................. 165
Basic Principles of (Q)SBR ..................................................... 166
Progress in Structure-Biodegradability Modeling ............... 170
Methodology for Development of Quantitative Models ...... 174
QSBR for Aerobic Transformation of Chlorinated
Dibenzo-p-Dioxins and Dibenzofurans ............................ 197
Molecular Orbital Calculations to Understand Anaerobic
Transformation of Chlorinated Dibenzo-p-Dioxins ........ 209
8. Biodegradation of Diaryl Ether Pesticides ............................ 229
Stefan Schmidt
Introduction ............................................................................. 229
Diaryl Ether Pesticides-An Overview ................................. 230
Environmental Impact of Diaryl Ether Pesticides ............... 234
Environmental Fate of Diaryl Ether Pesticides .................... 238
Color Figures ........................................................................................ 283
Index ...................................................................................................... 285
r;:::::::==================ED ITO RS
====================~
Rolf-Michael Wittich
GBF-National Research Center for Biotechnology
Braunschweig, Germany
Chapters 1, 5
1======= CONTRIBUTORS ======1
Jean Armengaud Mich~Kuty
DepanrnnentofEnvrronment~ Laboratory of Structure and
Microbiology Dynamics of Biomolecules
GBF-Nation~ Research Center Faculty of Science
for Biotechnology Masaryk University
Braunschweig, Germany Bmo, Czech Republic
Chapter 4 Chapter 7
Steven D. Aust Mary Lynam
Biotechnology Center Laboratory of Structure and
Utah State University Dynamics of Biomolecules
Logan, Utah, U.S.A. Faculty of Science
Chapter 3 Masaryk University
Brno, Czech Republic
Jid Damborsky Chapter 7
Laboratory of Structure and
Dynamics of Biomolecules John R. Parsons
Faculty of Science Depanrnnent of Environment~
Masaryk University and Toxicologic~ Chemistry
Bmo, Czech Republic Amsterdam Research Institute
Chapter 7 for Substances in Ecosystems
University of Amsterdam
Hauke Harms Amsterdam, The Netherlands
Department of Microbiology Chapter 2
EA WAG -Swiss Feder~ Institute
for Envrronment~ Science and Stefan Schmidt
Technology Depanrnnent of Microbiology
Duebendorf, Switzerland Institute of Gener~ Botany
Chapter 6 and Botanic~ Garden
University of Hamburg
Hamburg, Germany
Chapter 8
James D. Stahl Merel Toussaint
Biotechnology Center Department of Environmental
Utah State University and Toxicological Chemistry
Logan, Utah, U.S.A. Amsterdam Research Institute for
Chapter3 Substances in Ecosystems
University of Amsterdam
Kenneth N. Timmis Amsterdam, The Netherlands
Department of Environmental Chapter 2
Microbiology
GBF-National Research Center Rene van Herwijnen
for Biotechnology Department of Environmental
Braunschweig, Germany and Toxicological Chemistry
Chapter 4 Amsterdam Research Institute
for Substances in Ecosystems
University of Amsterdam
Amsterdam, The Netherlands
Chapter 2
1
CHAPTER
Aerobic Degradation by Bacteria
of Dibenzo-p-Dioxins,
Dibenzofurans, Diphenyl Ethers
and Their Halogenated Derivatives
Rolf-Michael Wittich
Introduction
P
olychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are not
produced on a massive scale like basic chemicals, plastic material, dyes, explo
sives, pesticides and other materials. Rather, this class of compounds is generated
during combustion of chlorine-containing organic material. Bleaching of paper
pulp with chlorine as well as the production of sodium hydroxide and chlorine
generate highly contaminated effluents and deposited material. Another major
concern is their contamination of haloorganic pesticides and flame retardants.
PCDD/Fs are found at relatively high concentrations (ppm level) in technical pen
tachlorophenol (PCP), polychlorinated biphenyls (PCBs), chlorophenols and
List of abbreviations
DF Dibenzofuran
DD Dibenzo-p-dioxin
DE Diphenyl ether
C- (mono-) chloro-
DC- Dichloro-
TrC- Trichloro-
TC- Tetrachloro-
PC- Pentachloro-
HeC- Hexachloro-
HpC- = Heptachloro-
OC- = Octachloro-
PC Polychloro
PCBs Polychlorinated biphenyls
PAHs Polyaromatic hydrocarbons
Biodegradation of Dioxins and Furans, edited by Rolf-Michael Wittich.
© 1998 Springer-Verlag and R.C. Landes Company.
2 Biodegradation ofD ioxins and Furans
Fig. 1.1. Structures of polychlori
nated dibenzo-p-dioxins (PCDDs),
dibenzofurans (PCDFs) and diphe cr~:b
PCDDs 8 -....;:::: :/'" 2
nyl ethers (PCDEs). The number
of possible congeners is given in 71 ~60 4Q~ 13
[75]
brackets. Reproduced from CI ~ CI
m6 4 n
BioEngineering 1, 1994, pp 33-40,
with permission.
8 9 1 2
PCDFs Clm~CI"
7~!. ~;';;3
[135]
6 60 0 40 4
5
5'0;.0:0'
PCDEs
1 1
I'
[209] 4' ~ 2' 6 ~ 4
3'
Clm 5Cln
chlorophenoxy herbicides. They have entered the environment as a result and there
still persist due to their high chemical stability and recalcitrance towards micro
bial breakdown.
The structures of these tricyclic or heterocyclic aromatic compounds, includ
ing the subclass of polychlorinated diphenyl ethers (PCDEs), which are also pro
duced during incineration, are shown in Figure 1.1. Polybrominated DEs have been
produced in bulk in order to replace PCBs as technical flame retardants, but are
not addressed in this chapter; the same is true of diaryl ether-based pesticides.
Carboxy-and methyl-substituted diaryl ethers are considered in this chapter, how
ever, because of the central ether bond as a common feature.
The high toxicity of this class of compounds when chlorinated more or less
exclusively at the lateral positions is still of strong interest with regard to political,
environmental, and health aspects. Consequently, it is essential to reduce anthro
pogenic generation and release on the one hand, and to restore better environ
mental conditions by remediation of environmental pollutants on the other hand.
Since the incineration of huge masses of polluted soil, sediment or other matrices
is not an ideal option due to tremendous costs, limited containment and storage
techniques and many other reasons, alternative biological strategies are being
considered. In principle, the combination of anaerobic dehalogenation and aero
bic treatment of the lower halogenated products seems feasible. Microbial consor
tia have been established and have worked properly in laboratory systems; these
results have encouraged the future development of more sophisticated
bioremediation technologies.